ARE MARINE SPONGES AN EFFICIENT TOOL FOR MONITORING TRACE ELEMENTS CONTAMINATION IN COASTAL ENVIRONMENTS?
Anna Maria Orani a,b, Aurélie Barats a, Emilia Vassileva b, Olivier P. Thomas a,c
a Université de Nice Sophia Antipolis, CNRS, IRD, Observatoire de la Côte d’Azur, Géoazur UMR 7329, 250 rue Albert Einstein, Sophia Antipolis 06560 Valbonne, France
b International Atomic Energy Agency, Environment Laboratories, 4 Quai Antoine 1er, Monaco
c National University of Ireland Galway, Marine Biodiscovery, School of Chemistry, University Road, Galway, Ireland
Trace elements (TE, metals and metalloids) originating from both natural and contaminated sources, enter marine ecosystems through direct discharges of wastewaters, rivers, atmospheric depositions, and through land run-off. The level of TE pollution is usually assessed by analyses of water, sediments and marine organisms. However seawater chemical analysis presents measurement limitations due to very low analyte levels and high salinity of the matrix. Sediments are more appropriate to be monitored but are not always available in coastal areas, especially in rocky shores. For these reasons, living organisms are of great interest to characterize the quality of a marine ecosystem. Sponges are convenient organisms for that purpose as they possess all the characteristics of good bioindicators (sessile filter feeders and large occurrence in coastal areas like the Mediterranean Sea). Sponges can thus concentrate a wide range of pollutants from both the suspension and dissolved phases, with high bio-concentration factors. These organisms have also shown capability to transform some chemical species, representing a promising tool in a bioremediation context.
In this work, we propose a full study on TE bioaccumulation and biotransformation in four species of Mediterranean sponges (Haliclona fulva, Cymbaxinella damicornis, Chondrilla nucula and Acanthella acuta) collected in the bay of Villefranche-Sur-Mer, southern France. These species present different morphological features and, as a consequence, they may have different accumulation and biotransformation processes. In this study the intra- and inter-specimen variability, as well as the inter-specific variations in TE accumulation have been evaluated.
Although the total TE concentrations can offer valuable information on overall pollution levels, it is not sufficient to accurately evaluate the TE availability and toxicity. Additional analytical methodologies have been developed and applied to sponges samples in order to distinguish and quantify TE species (As and Hg speciation), as well as to trace the pollution sources (Pb isotope ratios).
DETERMINATION OF TOTAL ARSENIC IN FISH BY HYDRIDE-GENERATION ATOMIC ABSORPTION SPECTROMETRY: METHOD VALIDATION, TRACEABILITY AND UNCERTAINTY EVALUATION
Nugraha, Willy Cahya; Elishian, Christine; Katarina, Rosi Ketrin
Indonesian Institute of Sciences, Indonesia
Determination of total arsenic in fish has been carried out. Fish is one of the important indicators for arsenic contamination in a body of water. The high level of arsenic in the body of fish are because of absorption and accumulation of arsenic in their habitant. Hydride generation (HG) coupled with atomic absorption spectrometric (AAS) detection is one of the most popular techniques employed for arsenic determination in a variety of matrices including fish. In this study, determination of total arsenic in fish by HG-AAS has been developed and validated using Certified Reference Material DORM 3 Fish Protein for trace metals for ensuring the accuracy and the traceability of the results. The sources of uncertainty of the method also has been evaluated.
THE EFFECTS OF SOOT ON THE ENVIRONMENT
University of ABBES Laghrour - Khenchela - Algeria, Algeria
Soot formation remains a subject of challenge in the field of combustion. Carbon emissions from the U.S.A alone reached approximately 1.6 Mt (megaton / year) which contributes greatly to air pollution and global warming the Earth. On the other hand, for many combustion processes, the formation of soot is an indication of incomplete combustion and hence a shortfall in the use of chemical energy. The fundamental challenge in predicting the formation of soot comes from the fact that this training involves a heterogeneous sequence.
A new chemical mechanism designed to study the process of forming the first aromatic ring (benzene) and polycyclic aromatic hydrocarbons (PAH) from a flame of acetylene (C2H2) has been developed. The mechanism developed, contains 50 chemical species involved in 268 reversible elementary reactions. The comparison between the results from modelling and experimental measurements allowed us to test the validity of the postulated mechanism in specific experimental conditions. Kinetic analysis of the flame by calculating the maximum rates for each elementary reaction, allowed us to identify key reactions pathways of consumption and formation of main precursors of soot.
METAL SORPTION AND ITS MOBILITY CAPACITY IN ROADSIDE SAMPLES IN A CITY OF NORTHERN NIGERIA
Okunola, Oluwole & Joshua
Federal University, Dutsin-Ma, Katsina State, Nigeria, Nigeria
The aim of the study is to assess the impact of traffic volume on metal (Cd and Pb) concentration and to evaluate the mobility of the metals using sequential extraction. Particulate dust fall-out and roadside surface soil samples were collected from ten (10) locations along major roads in the Kano metropolis, Nigeria in four seasons: cool and dry, hot and dry, warm and wet, and warm and dry. The samples collected were digested using standard methods and analysed using flame atomic absorption spectrophotometer. The results of metal inter-relation analysis on both samples revealed positive correlations, an indication of common source of these metals. . Positive correlation between the metals and traffic confirmed the fact that automobiles are major source of the presence of these metals in the roadside environment. The results also showed that the concentrations in the mobile phase (water soluble, exchangeable and carbonate bound fractions) were generally high for Cd (29.49 – 92.7%) and Pb (26 – 76.4%) with the highest obtained during warm and wet, and warm and dry seasons. The results suggests potential toxicity to residential and food vendors’ adjacent to major roads in Kano metropolis which could be either direct or indirect pathways of metal in humans.
DETERMINATION OF LINEAR PROGRAMMED TEMPERATURE GAS CHROMATOGRAPHY RETENTION INDICES FOR SOME PLASTICIZERS
Halaimia, Farhi (1); Lakehal, Imane (2)
1: University badji Mokhtar - Annaba, Algeria; 2: University badji Mokhtar - Annaba, Algeria
A method which allows the determination of retention indices in programmed temperature gas chromatography (P.T.G.C) is described. The method, based on cubic spline interpolation, does not require the presence of a complete homologous series of n-alkanes in the sample. Its application to some plasticizers, eluted on two columns of different polarity, shows that the indices obtained behave more linearly than those determined by the classical method.
PHOTODEGRADATION OF CARBAMAZEPINE INDUCED BY FE(III)CITRATE COMPLEX IN AQUEOUS SOLUTION
Ghoul, Imen (1,2); Dekkiche, Besma Anfel (1); Debbache, Nadra (1); Canle López, Moisés (2)
1: Laboratoire des Sciences et Technologies de l’Environnement, département de chimie, Faculté des sciences exactes, Université Mentouri Constantine, 25000 Constantine, Algéria; 2: Chemical Reactivity and Photoreactivity Group, Department of Physical Chemistry and Chemical Engineering, University of A Coruna, Rua da Fraga 10,E-15008 A Coruna, Spain
Pharmaceutically active compounds are considered as emerging environmental problem due to their continuous input and persistence to the aquatic ecosystem even at low concentrations. Among them, Carbamazepine (CBZ) an anti-epileptic pharmaceutical agent has been detected at the highest frequency, which ends up in aquatic systems via wastewater treatment plants among other sources. Many treatment technologies, including advanced oxidation processes (AOPs) have been developed in order to degrade CBZ in wastewater and wastewater sludge. Fenton reaction with using ferric citrate complex was employed in this work to study the photocatalytic degradation of Carbamazepine in aqueous solution.
Before to start the photochemical study, the behavior of the mixture in the absence of light and at room temperature have been followed to highlight the existence of eventual reaction between the complex and CBZ in aqueous solution.
Upon irradiation of the mixture CBZ-Fe(III)Citrate, CBZ disappears rapidly in the beginning of irradiation and the free process is enhanced at acidic medium. The influence of parameters such as the substrate concentration and that of the complex on the kinetics of the reaction was also studied. The results show that the process is very effective when CBZ and Fe(III)Citrate complex have a low and higher concentration respectively.
Mechanistic aspect of the photochemical process was also taken account by studying the effect of oxygen, chloroform and isopropanol.
To make evidence for the complete mineralization of CBZ, TOC (Total Organic Carbon) experiments were undertaken, the mixture CBZ- Fe( III) Citrate is exposed to artificial irradiation at acidic pH when the process is faster and .The result obtained shows that 70% of TOC was removed after 7 hours of Irradiation.
MOLECULARLY IMPRINTED SORBENT FOR THE ANALYSIS OF CHLORPHENAPYR IN AGRICULTURAL RUN-OFF.
Manzoor, Suryyia; Abbas, Naseem; Fatima, Hira; Jamal, Umair
Bahauddin Zakariya University, Multan, Pakistan
Many of the farm chemicals – pesticides – are infamous because of their hazardous effect on the human health, who ingest food and water contaminated with these pesticides. This problem is of high concern at international level and Pakistan has also suffered many outbreaks of acute pesticide poisoning during last few decades resulting in serious causalities. The major reasons were excessive spray, inadequate precautionary measures and lack of awareness among population. One of the commonly used pesticides is chlorphenapyr applied on a wide range of crops. The pesticide enters the water reservoirs through agricultural runoff. A molecularly imprinted polymer for the analysis of chlorphenapyr was synthesized by non-covalent approach to deal with the analysis of this chemical in water samples. The precipitation polymerization was followed using three functional monomers i.e. acrylic acid, acrylonitrile and vinyl acetate and standard chlorphenapyr as template. A control polymer was also synthesized through same procedure without the addition of template for the purpose of comparison. The resulting polymers were characterized using SEM, IR and TGA. The sorption capacity of synthesized imprinted polymer showed that it has potential to be applied as a sorbent in HPLC columns for the determination of the pesticide in contaminated aqueous samples
Mobility of Metallic Trace Elements (MTE) in Water and Sediment of the Rivers. Case of Nil River (North-eastern Algerian)
Benessam, Sihem (1,2); Debieche, Taha-Hocine (1); Amiour, Souad (1); Chine, Amel (1); Khelili, Smaïl (3)
1: Water and Environmental research team, Geological Engineering Laboratory, Faculty of Nature and Life Sciences, University of Mohamed Seddik Benyahia - Jijel, Algeria; 2: Department of Chemistry, Faculty of Exact and computer Sciences, University of Mohamed Seddik Benyahia - Jijel, Algeria; 3: , Pharmaceutical chemistry and Ecotoxicology laboratory, Faculty of Exact and Computer Sciences, University of Mohamed Seddik Benyahia - Jijel, Algeria
The metallic trace elements (MTE) are present in water and sediments of the rivers with weak concentrations. Several physicochemical parameters (Eh, pH and oxygen dissolved) and chemical processes (adsorption, absorption, complexation and precipitation) as well as nature of the sediments control their mobility. In order to determine the effect of these factors on the mobility of some MTE (Cd, Cr, Cu, Fe, Pb and Zn) in water of the rivers, a two-monthly monitoring of the physicochemical parameters and chemistry of water and sediments of the nil wadis (Algeria) was carried out during the period from November 2013 to January 2015.
The results show that each MTE has its own conditions of mobility and generally are very influence by the variations of the pH and Eh. Under the natural conditions, neutral pH with basic and medium oxidizing, only the lead presented in water with raised values, indicating its solubility in water and its salting out of the sediments. The others MTE present raised concentrations in the sediments, indicating their trapping by adsorption and/or chemical precipitation. The chemical form of each ETM was given by Eh-pH diagrams. The spatio-temporal monitoring of these ETM shows the effect of the rains, the dry periods and the rejects in the variation of their concentrations.
Keywords: Chemistry, metallic trace elements, sediment, water
TOTAL REFLECTION X-RAY FLUORESCENCE ANALYSIS: A FAST AND SIMPLE METHOD FOR THE QUANTIFICATION OF TRACE METAL NANOPARTICLES ?
Woerle, Katharina; Leopold, Kerstin
Ulm University, Germany
Metal nanoparticles (NP) are due to their size-related properties widespread used in technical, medical, and consumer products. The emission of such materials into the aquatic system is increasing, however, expected concentrations are in the sub-µg/L range. For separation and preconcentration of NPs from waters several techniques have been suggested, like e.g. solid phase or cloud point extraction. Total reflection X-ray fluorescence analysis (TXRF) is a non-destructive multi-element detection technique for trace analysis with detection limits in the low µg/L range. An advantage of this technique is the straightforward sample preparation and fast quantification due to internal one-point-calibration. However, several conditions have to be fulfilled to achieve reliable data. These include a particle size limitation, homogeneous suspensions and homogeneous distribution of analyte and standard on the sample carriers. In this study, we have examined the applicability of TXRF for quantification of Au and Ag NPs in aqueous suspensions investigating step-by-step the above-mentioned preconditions and their influences on the found concentration. A size-independent underestimation for aqueous NP suspensions was observed and possible sources of error were identified. Finally, two strategies/approaches are proposed overcoming these problems and providing accurate quantification.
Development of nanogold-modified dipsticks for mercury accumulation from natural waters
Schlathauer, Maria; Leopold, Kerstin
Ulm University, Germany
Mercury (Hg) is a hazardous and toxic pollutant that harms human health and the environment. Due to its high mobility Hg naturally cycles in the atmosphere, terrestrial and aquatic systems and therefore is ubiquitously present. Since mercury is known for its extremely high bioaccumulation factors (up to 1 million), highly sensitive analytical methods with low quantification limits are required to monitor Hg traces in aquatic Systems.
In this work several approaches for the preparation of nanogold-modified sensor/accumulation chips (“dipsticks”) are presented. First, the surface of quartz glass slides was coated with a thin gold film by vapor plating. By use of an annealing process, the smooth gold film was nano-structured. Investigation by atomic force microscopy confirmed successful formation of gold “islands” or “rods” in the nano-scale and a significant increase in the surface roughness of the carrier. Furthermore, AFM images show that the size of the nanogold particles could easily be affected by variation of temperature and heating time. In order to prove the feasibility of the prepared dipsticks for mercury accumulation, several exposition experiments in Hg(II) aqueous solutions were performed. After accumulation, Hg was released from the dipstick by thermal desorption and measured by atomic fluorescence spectrometry. Moreover, additional experiments were performed to investigate how the size of gold nanoparticles affects the adsorption efficiency of different Hg species.
Mobility and Speciation of Iron in the Alluvial Sheet of Nil River (North-Eastern Algerian)
Benessam, Sihem (1,2); Debieche, Taha-Hocine (1); Amiour, Souad (1); Chine, Amal (1); Khelili, Smail (3)
1: Water and Environmental research team, Geological Engineering Laboratory, Faculty of Nature and Life Sciences, University of Mohamed Seddik Benyahia - Jijel. Algeria; 2: Department of Chemistry, Faculty of Exact and computer Sciences, University of Mohamed Seddik Benyahia - Jijel. Algeria; 3: Pharmacology, Pharmaceutical chemistry and Ecotoxicology laboratory, Faculty of Exact and Computer Sciences, University of Mohamed Seddik Benyahia - Jijel. Algeria
Iron is naturally present in groundwater, it comes from the dissolution of the geological formations (clay, schist, mica-schist, gneiss…). Its chemical form and mobility in water are controlled mainly by two physicochemical parameters (Eh and pH). In order to determine its spatio-temporal evolution in groundwater, a two-monthly monitoring of the physicochemical parameters and major elements in the water of the alluvial sheet of Nil river (North-eastern Algerian) was carried out during the period from November 2013 to January 2015.
The results show that iron is present with weak concentrations in the upstream part of the alluvial sheet and with raised concentrations, which can exceed the standard of potable drinking water (0.2 mg/L), in the central and downstream parts of the alluvial sheet. This variation of the concentrations is related to the important variation of Eh between the upstream part (200 mV) where the aquiver is unconfined (oxidizing medium) and the central and downstream parts (-100 mV) where the aquifer is confined (reducing medium). Iron in the oxidizing part is presented with the complexes form, where it precipitates or/and adsorbed by the geological formations. On the other hand, in the reducing parts, it is released in water. In this study one will discuss also the mobility and the chemical forms of iron according to the rains and pumping.
Biological denitrification using microorganisms collected from the waste-water treatment plant : Enterobacter hormaechei
Aouati, M.Khelil (1); Kebabi, Brahim (2); Ouled Haddar, Houria (3); Sifour, Mohamed (3); Aissaoui, Salima (3)
1: Ecole Normale Supérieur (ENS), université Constantine3, Algérie.; 2: Laboratoire pollution et traitement des eaux(LPTE), Université Constantine1,Algérie.; 3: Laboratoire de toxicologie moléculaire (LTM), Université de jijel, Algérie.
The aim of the present work was to explore bacterial diversity and bio indication in ecosystems by isolate and characterize the denitrifier bacterium for reducing nitate in wastewater. Microbial research has generally involved bacteria that are culturable. However, it is estimated that only a small portion of all bacteria are culturable. Two denitrifier bacteria with nitrate removal activities were isolated from activated sludge wastewater. One of the bacterium displayed the highest reduction of nitrate, and transforming carbonaceous matter in to carbon dioxyde, both transformation processes being carried out in anaerobic condition. The strain was preliminarily identified using biochimical tests and further identified based on similarity of PCR- 16S rRNA using universal primers. 16S rRNA gene sequence analysis indicated that the strain was most closely related to Enterobacter hormaechei with sequence similarities of 99%.The strain utilizes various carbon sources. The experiments showed the ability of bacterial strain to rapidly remove nitrate and also concerns a method for treating wastewater using said microorganism. The microorganisms according to our research is represented by the N5 N6 strains and filed September 23, 2014 at GenBank. The submission of data to GenBank nucleotide sequences was under the accession numbers: BankIt1760650 Seq1: KM604662 and BankIt1760650 Seq2: KM604663.
The lead isotopes of aeolian dust observed at Saitama area (Japan) and their genetic implications
Takahashi, Kazuya (1); Obi, Yuri (1,2); Tanaka, Miho (2)
1: RIKEN, Japan; 2: Tokyo University of Marine Science and Technology
Aeolian dust derived from Eurasian continent has been considered to be a source of environmental pollution. Especially, some of adducts in dust, represented by heavy metal such as Pb, have been regarded as harmful materials. In order to investigate chemical characteristics and the origin of adducts in aeolian dust which is brought to Japan, we have performed chemical analyses and Pb isotope measurements for the aeolian dust collected at Saitama area and several soil samples from north west China and Kanto region in Japan.
Aeolian dust samples were collected at Wako-shi using ADVANTEC HE-40T Air-dust sampler with 0.31μm filter in 2013. For comparison with aeolian dust, sand samples from Xinjang (north west of China) and soil samples in Kanto region (Japan) were also collected. North west of China has been regarded as the “birth-place” of aeolian dust brought to Japan. These samples were chemically decomposed. The decomposed sample solutions were divided into two portions; one was diluted for trace element analyses by ICP-MS (Agilent 7700) and the other was used for the multi-stage ion exchange processes to obtain lead fraction for the measurements of Pb isotopes by TIMS (VG Sector-54).
In all dust samples, the concentrations of As, Se and Pb are significantly higher than those for the soil samples from Xinjang area. Furthermore, for the dust collected from May to July, the concentration of Hg also became high. These observations imply the adducts of the component like fly-ash. Lead isotope compositions in dust samples collected from July to August are similar to those in the airborne particulate matter (NIES 28) and the other dust samples exhibited the lead isotope compositions like to those in fly-ash matter (NIES 19). These observations imply that significant amount of matter containing heavy metals adducts to the aeolian dust during the movement from the Eurasian continent to Japan.
DETERMINATION OF TRACES OF PLATINUM GROUP METAL IN ROADSIDE SOILS
Rommel, Dimitri; Müller, Cara; Schindl, Roland; Huber, Lars; Leopold, Kerstin
Ulm University, Germany
Platinum group metals (PGM), especially palladium (Pd), rhodium and platinum, are used in car exhaust catalytical converts. Because of high temperature and mechanical stress, these metals are emitted into the environment. Concentrations of PGM in road-side soils have increased within the last 30 years, i.e. since the introduction of car catalytic converters. This indicates certain retention of PGMs in the topsoil. Nevertheless, a final evaluation of migration, mobility, and bioavailability of PGMs in/from roadside soils requires further systematic investigation since only few data exists. Unfortunately, quantification of PGMs at trace level in soil samples is still a challenging analytical task. Schuster and Schwarzer first described in 1996 a highly selective ligand-assisted pre-concentration and separation strategy for Pd traces from digests of complex environmental samples. Here, this strategy was further developed in order to simultaneous pre-concentrate and detect PGMs in roadside soils. This method is based on a microwave-assisted total digestion and pH dependent complexation with a chelating reagent, followed by pre-concentration on an RP-C18 micro-column. Enriched PGMs in the eluent are then measured by total reflection X-ray fluorescence (TXRF) and high-resolution continuum source atomic absorption spectrometry (HR-CS-AAS). In addition to PGMs, traces of the precious metals gold and silver can be detected by this method in soil samples.
DIRECT DETECTION OF METAL NANOPARTICLES WITH HIGH RESOLUTION CONTINUUM SOURCE GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY
Brandt, Anja; Tarren, Holly; Leopold, Kerstin
Ulm University, Germany
Metal nanoparticles (MNPs) are nowadays widely used in science, industry and technology due to their unique physical and chemical properties. They are applied, for instance in car industry, electronical devices, medical, and consumer products. Usage and disposal of nanomaterials may release MNPs into the environment. However, detection of MNPs in complex matrices, like environmental or biological samples, is challenging and yet there are no established analytical methods for this purpose. Hence, the development of robust and reliable analytical methods for NP detection is important in order to assess potential risks arising from nanotechnology.
Recently, our group proposed solid sampling high resolution continuum source graphite furnace atomic absorption spectroscopy (SS HR-CS GFAAS) as a potential technique to directly detect silver NPs in biological samples. The method is based on differences in the atomization time of Ag ions and Ag NPs, which is used as a significant indicator for distinguishing both species. Here, we present new results obtained by investigating size-depending effects on the atomization delay in order to identify the smallest detectable / distinguishable NP size. For this purpose, again new strategies for signal interpretation were evaluated. Moreover, the technique was applied to further relevant MNPs, like gold or palladium, using the novel evaluation strategy.
FIRST INVESTIGATIONS ON THE MECHANISM OF ATOMIZATION DELAY OF SILVER NANOPARTICLES IN SOLID SAMPLING GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY
Brucker, Dominic; Leopold, Kerstin
Ulm University, Germany
Nowadays silver nanoparticles (Ag NP) are used in a wide range of consumer products due to the antibacterial, antifugal and antiviral effects of silver. At the same time, concerns about migration, accumulation, or transport of Ag NPs released from these products into our environment and food occur. Assessment of this risk may only be possible by provision of suitable analytical monitoring methods. At present, there is no established, robust and valid method for monitoring Ag NP in complex and/or solid samples.
A promising technique to distinguish between Ag NP and ionic Ag in solid samples, such as food matrices, is solid sampling high-resolution-continuum source graphite furnace atomic absorption spectrometry (SS HR-CS GFAAS). Our group recently showed that Ag species show different atomization behaviour making a distinction between NPs and ions possible by calculating the so-called atomization delay. However, little is known about the mechanism for the atomizations delays (tad) of Ag+ and Ag NP and the influence of sample preparation on this event. Studies now show a dependency of tad on the matrix composition (protein, carbohydrate, water content). Hence, it can be assumed that the differences in tad of silver species are related to different interactions of the silver species with the functional groups of the matrix. First investigations by thermo-gravimetric analysis and electron microscopy confirm this hypothesis.
Leachability, Bioaccessibility and Risk Mitigation of Heavy Metals in an E-Waste Contaminated Soil after EDDS Washing Combined with Selective Dissolution or Soil Stabilization
Beiyuan, Jingzi; Tsang, Daniel C.W.
The Hong Kong Polytechnic University, Hong Kong S.A.R. (China)
To address the problem resulting from heavy metals in an e-waste contaminated soil (mainly contaminated by Cu, Pb and Zn), a 2-h biodegradable ethylenediaminedisuccinic acid (EDDS) washing combined with additional treatments (2-month stabilization or 2-h selective dissolution) were investigated for its low extraction efficiency and the increased leachability. Multiple endpoints of leachability, bioaccessibility and risk assessment were evaluated. For the stabilization, a dosage equated to 150 ton ha-1 of agricultural wastes (biochars produced in two temperatures: 300 and 700 oC) and an industrial by-product (coal fly ash) and their mixtures were studied. Subsequent immobilization decreased metal leachability, while EDDS was responsible for removing large bioaccessible metals before the stabilization. The human health risks (chiefly caused by Pb) calculated based on the result of metal mobility and bioaccessibility were reduced to an acceptable level in water consumption and by half in soil ingestion pathway for children. For the selective dissolution part, four types of reagents (reductants, oxidants, alkaline solvents and ligands) were examined, with the aim to dissolve the Fe/Mn oxide and/or organic matter in soil before the EDDS washing. After the two-step washing, both the leachability and bioaccessibility of metals increased by the strong reagents, especially for the ligands. The additional washing by EDDS was proved necessary because the ligands released more metals which re-adsorbed on the surface of soil minerals. Similar human health risks results achieved for acidified NH2OH-HCl and citrate method by metal bioaccessibility. The ligands showed much lower impact on the soil properties in terms of microbial activity, cytotoxicity, and available nitrogen and phosphorous. Because these ligands naturally exist in soil and the pH of reagents was not that intensive as acidified hydroxylamine hydrochloride. These endpoints acted as useful tools for us to make a better informed decision on the recycling/recovery of remediated soil.
Simulation of metabolic transformation products of pesticides by EC-LC-MS
Mekonnen, Tessema Fenta (1); Koch, Matthias (1); Panne, Ulrich (1,2)
Among major food contaminants agrochemicals (including insecticides, fungicides and herbicides) are a threat for food safety in many countries. Once they entered the food chain or the environment, the parent compound can be transformed into different products by manmade and natural processes. The transformation products (TPs) might be more toxic and stable than the parent compound. In addition to this the transformation products might undergo conjugation with different compounds and/or changed to phase II metabolites.
Conventional in-vivo or in-vitro methods to study phase I and II metabolism have drawbacks of long-time sample preparation and matrix complexity. Online coupling of an electrochemical cell with liquid chromatography-mass spectrometry (EC–LC–MS) is a promising technique to study metabolites, fate and transformation products of pesticides [1, 2]. The new approach enables to identify metabolic transformation products by oxidizing analyte of interest on the EC, separate the metabolites on HPLC and identifying them by MS .
The aim of the present study is to identify/mimic pesticides phase I metabolites using electrochemical cell coupled to liquid chromatography-mass spectrometry (EC-LC-MS). Metabolic transformed products of two model compounds, fluopyram (fungicide) and glyphosate (herbicide) were studied by EC upfront with MS. The results of EC-LC-MS are compared and discussed with those derived from in-vitro assays and the metabolites identified by LC-MS/MS.
 H. Faber, M. Vogel, U. Karst, Electrochemistry/mass spectrometry as a tool in metabolism studies - a review. Anal Chim Acta 2014, 834, 9-21.
 W. Lohmann, R. Dötzer, G. Gütter, S. M. Van Leeuwen, U. Karst, Online electrochemistry/liquid chromatography mass spectrometry for the simulation of pesticide metabolism. J Am Soc Mass Spectrom 2009, 20, 138-145.
 S. Jahn and U. Karst, Electrochemistry coupled to (liquid chromatography) mass spectrometry - current state and future perspectives. J Chromatogr A 2012, 1259, 16-49.
VOLATILE ORGANIC COMPOUND EMISSIONS FROM AGROMATERIALS RESULTING FROM A CORIANDER BIOREFINERY
Burianova, Klara; Uitterhaegen, Evelien; Merah, Othmane; Talou, Thierry; Evon, Philippe; Simon, Valérie
In the context of sustainable development, the reduction of environmental impacts has become a priority in numerous sectors such as the building industry, which is marked by an important use of non-renewable raw materials. It is then essential to develop innovative building materials with low environmental impact, such as renewable biomaterials, that may be applied for economical, safe and sustainable constructions.
This study focuses on agromaterials resulting from the biorefinery of coriander (Coriandrum sativum L.), an annual crop belonging to the Apiaceae. The fruits are characterized by their potential to provide both an essential and a vegetable oil. While the former fraction is traditionally obtained through hydrodistillation, the latter may be extracted by twin-screw extrusion. This further renders a press cake that could be valorized through its transformation into renewable particleboards using thermopressing, which have shown potential for use as building materials, e.g. load bearing boards. However, this could present a substantial source of indoor emissions of volatile organic compounds (VOCs). The assessment of such VOCs emissions is of great importance because of their negative impact on human health.
Two types of particleboards were examined in an environmental chamber. As self-bonded boards, no formaldehyde emission was observed, making them environment-friendly materials. VOC emissions were mainly a result of the presence of essential oil in the press cake. Linalool was the most abundant compound, while γ-terpinene, camphor and limonene emissions were also detected. Emission rates were evaluated depending on temperature and relative humidity and compared to emission rates of traditional building materials.
Use of alkyl esters of p-hydroxybenzoic acid (parabens) in baby teethers: Analysis via gas chromatography-quadrupole mass spectrometry (GC-qMS) using a stable isotope dilution assay (SIDA)
Potouridis, Theodoros (1); Berger, Elisabeth (1,2); Püttmann, Wilhelm (1)
1: J.W. Goethe-University Frankfurt am Main, Germany; 2: Senckenberg Research Institute and Natural History Museum Frankfurt, Germany
Alkyl esters of p-hydroxybenzoic acid (parabens) are commonly used as preservatives in pharmaceuticals, cosmetics and food products. However, parabens and their salts are not permitted in foods for infants and young children and their overall use in foodstuff in the European Union is regulated. Parabens are known to act as endocrine disruptors. Thus, an application of parabens in consumer goods, particularly in products for infants and young children should be considered as critical and be thoroughly investigated; at least if an intake into the body cannot be excluded.
The plastic baby teethers examined in the present study were filled with cooling gel. Due to the high water content in a gel, microbial growth is possible. Thus, it was conceivable that preservatives such as parabens were added to the gel-fillings. For analysis, samples of plastic and gel material were prepared using ultrasonic assisted extraction with methanol. Gas chromatography-quadrupole mass spectrometry was applied on trimethylsilylated derivatives of methyl-, ethyl- and n-propylparaben. Quantification was based on a stable isotope dilution assay and showed good validation results. Parabens were present in all considered plastic and gel samples in the range of 0.3 to 1.2 mg g-1. Furthermore, in all gel samples the derivatized (2E,4E)-hexa-2,4-dienoic acid (sorbic acid) was identified as additional preservative.
TREATMENT OF WASTEWATER BY ADSORPTION ON RAW ORE GRAPHITE (DEPOSIT POINT 214-AREA SIDI BOUOTHMANE- MARRAKECH)
Faculty of science Ben M'sik University Hassan II Casablanca, Morocco
This work has allowed us to study the adsorption phenomenon of BM methylene blue on raw ore graphite (deposit point 214 sidi bouothmane region Marrakech).
At the beginning of this work, we conducted a series of experiments to study this phenomenon methylene blue playing on a number of parameters, namely: The pH of the medium, the particle size, the mass of graphite, the concentration of methylene blue, the main results of this study are:
The adsorption is done in a first time in a monolayer when the initial concentration of methylene blue does not exceed 10mg / l. Once this concentration limit is outdated, a new multilayer adsorption phenomenon began to appear according to the concentration put out. Otherwise, the saturation of a monolayer of 1 g of GP214 with 10 mg of (BM) has confirmed by two models (Langmuir, Freundlich)
We are planning into perspective to continue our trials multilayer adsorption subject to try to discover the farthest upper boundary layer of the support and which could result in improvement, the adsorption capacity of the GP214 natural material.
Application of cysteine terminus-molecularly imprinted Nano-polymers for selective recognition and identification of hepatotoxic microcystins in a freshwater reservoir.
Eguzozie, Kennedy Uchenna; Mavumengwana, Vuyo; Kayitesi, Eugenie
University of Johannesburg, South Africa
About 80% of microcystins (MCs) congeners reported in literature consist of cysteine conjugates (glycine-cysteine and γ-glutamyl-cysteine). Molecularly imprinted polymers (MIPs) bearing glycine-cysteine terminus cavities were successfully synthesized using glycine as a template. Non-imprinted polymers (NIPs) were also synthesized for control purposes. The surface area, total pore volume and average pore diameter of MIPs and NIPs were 270.15 m2/g, 0.68 cm3/g and 92.42Å; 250.42 m2/g, 0.54 cm3/g and 89.28Å respectively. The synthesized molecularly imprinted nanostructured polymers were investigated for selective recognition and microextraction of [cysteine]-MCs in an environmental freshwater sample employing liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). Three distinct MCs variants (MC-YR, MC-LR and MC-RR) were isolated, identified and quantified. Additionally, two minor microcystin congeners (MC-(H4) YR), (D-Asp3, Dha7) MC-RR) were also identified. Variant dominance followed the order MC-LR > MC-RR > MC-YR across the sampling sites. Analysis of maximum and minimum concentrations of quantified MCs variants showed 270.7, 14.10 (µg/g), 141.5, 1.43 (µg/g) and 72.28, 0.15 (µg/g) for MC-LR, MC-RR and MC-YR respectively. This implies there was quantitative variations of microcystin congeners across the sampled sites. Significant differences between means were assessed by an analysis of variance (ANOVA) with P < 0.05 being considered significant. The analysis showed that there was significant difference between mean MCs concentrations across sampling sites (P < 0.05). The study demonstrated that nanostructured molecularly imprinted polymers have potential application for the selective detection and identification of microcystins (with amino acid-and lipid conjugates) in water.
 K. Eguzozie, V. Mavumengwana, D. Nkosi, E. Kayitesi, E. C. Nnabuo-Eguzozie, Bioaccumulation and Quantitative Variations of Microcystins in the Swartspruit River, South Africa. Arch Environ Contam Toxicol 2016, 71, 286-96.
ULTRASOUND AND MAGNETIC FIELDS IN THE DETERMINATION OF DNA IN SOIL
Dzhenloda, Rustam (1); Petrov, Dmitry (2); Shkinev, Valeriy (1); Spivakov, Boris (1)
1: Vernadsky Institute of Geochemistry and Analytical Chemistry of Russian Academу of Sciences, Russian Federation; 2: Institute for Analytical Instrumentation of the Russian Academy of Sciences, Russian Federation
Recovery of DNA in molecular biological techniques is one of important stages in the analysis of environmental samples. DNA isolation is complicated because of high contents of various organic compounds such as humic acids (HA). HA are inhibitors of the polymerase chain reaction (PCR) which is used for DNA identification and detection. Previously proposed columns using a suspension in standing ultrasonic waves were applied to the recovery of metals from aqueous solutions. In this work, the first attempt was made to recover DNA from aqueous extracts of soil in a slurry (suspension) column, allowing to keep magnetic sorbents in a combined acoustic and magnetic fields. The use of slurry columns allows to intensify and automate the process of DNA sorption. It was possible to achieve better extraction of DNA from aqueous extracts of soil and to obtain samples suitable for PCR analysis. The use of magnetic field provides the retention of a greater sorbent mass than in the case of acoustic field alone. A sod-podzolic sandy loam (SPSL) and a typical black earth loam (TBEL) were taken as soil samples containing plasmid DNA of M.tuberculosis. It has been shown that the DNA recovery from SPSL and TBEL can reach 80 and 60% respectively that is sufficient for DNA detection. Thus, we proposed a new flow method for sorption preconcentration of DNA from soil extracts with subsequent elution in an on-line mode and determination by PCR analysis.
The authors are grateful for the financial support of RFBR (No 16-33-00214, No 16-03-00106).
SIMULTANEOUS ANALYSIS OF 4 POLYCYCLIC AROMATIC HYDROCARBONS IN EDIBLE OIL BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY - FLUORESCENCE DETECTOR
Pamukkale University, Turkey
Polycyclic aromatic hydrocarbons (PAHs) are composed of two or more fused aromatic rings and can be introduced into the food chain from environmental sources. Furthermore, food can be contaminated by different food preparation and manufacturing practices (e.g. drying, smoking, roasting, baking, and frying). Edible oils and fats might contribute significantly to human exposure to PAHs due to their lipophilic nature. European legislation requires the control of the contents of four PAHs (4PAHs), particularly BaP, benzo[a]anthracene (BaA), benzo[b]fluoranthene (BbF) and chrysene (CHR) [EC1881/2006]. Benzo[a]pyrene (BaP) was classified by the International Agency for Research on Cancer (IARC) as a human carcinogen (class 1) [IARC 2010, 2012]. To minimize human exposure, the European Union has set a maximum levels for 4PAHs in edible oils and fats to 2 µg kg-1 for BaP and 10 µg kg-1 for the sum of BaP, BaA, BbF and CHR (EC 835/2011). This study focused on the determination of 4PAHs in edible oil samples (sesame, maize, sunflower and olive oil), according to the method performance characteristics required by EU legislation. The analysis method is based on saponification of the edible oil, extraction of the PAHs by LLE followed by HPLC-FLD. The limit of detection and quantification of four PAHs ranged from 2.1 pg g-1 to 4.1 pg g-1 and 4.2 pg g-1 to 8.2 pg g-1, respectively and recovery rates higher than 72.8% were achieved for all four PAHs. The applicability of the method to routine samples was evaluated based on a limited number of commercial edible oil samples.
DETERMINATION OF COBALT WITH METHOD OF CLOUD POINT EXTRACTION
Divrikli, Umit (1); Soylak, Mustafa (2); Elci, Latif (3)
1: Pamukkale University Faculty of Art and Science, Turkey; 2: Erciyes University, Science Faculty, Department of Chemistry, Kayseri, Turkey; 3: Pamukkale University Faculty of Art and Science, Turkey
Separation and preconcentration procedures are considered of great importance in analytical and environmental chemistry. Cloud point extraction is a separation and preconcentration procedure that has been extensively applied for trace metal determination in several different matrices. Its major advantages are simple experimental procedures, low cost, high preconcentration factors, and environmental safety. These aspects include it in a set of analytical methods in agreement with the “green chemistry” principles [1,2].
In this study, cloud point extraction method was developed for the determination of trace amount of cobalt by flame atomic absorption spectrometry detection for separation and preconcentration. The method of optimization chosen was a chemometric method using a factorial design. The average recoveries were in the range of % 96,0 - 98,4 and the relative standard deviation was in the range of % 0,8-1,9. The detection limit (3s, N=12) was found to be 0,14 µg L-1, the quantitative limit was found to be 0,38 µg L-1 (10s, N=12). The method was applied to various water samples, dry mint and B12 Vitamine.
 L. H. Willie, E. Pramauro, Critical Reviews in Analytical Chemistry 1993, 24, 133-177.
 C. Vandecasteele, C. B. Block, Modern Methods for Trace Element Determination 1-7, 1997.
REMOVAL OF TEXTILE DYE WITH DIFFERENT ORGANISMS AND ASSESMENT OF SOME FACTORS EFFECT
Ardag Akdogan, Hatice (1); Dayi, Bugra (2)
1: Pamukkale University Faculty of Art and Science, Turkey; 2: Pamukkale University Faculty of Art and Science, Turkey
Water pollution control has obtained great importance in recent years. Synthetic dyes are widely used in many sectors and these may include textile, painting, printing, leather industry and many others. Although synthetic dyes have great industral value, they are also a big cause to serious environmental problems. Their us threatens the life of living organisms in the surrounding enviroment. Today, there are physical, chemical and biological methods to solve these problems. However, physical and chemical methods are somewhat expensive and therefore biological methods have become the alternative. White-rot fungi have been considered by far the most efficient dye decolorizing microorganisms. In recent years, biological methods such as non-specific extracellular ligninolytic enzymes of white rot fungi have been shown to have a strong capability in the over throw of synthetic dyes [1, 2].
First of all four different white rot fungus (Pleurotus osteratus, Coprinus plicatilis, Morchella esculenta, Tramates versicolor) were investigated for removal of dye or paint. Best results demonstrated Coprinus plicatilis (% 97,32). This fungus by using reactive orange 16 dye with aspartic acid, salt (NaCl) and detergents (Triton X-100) the removal yield was research. The data obtained in accordance, decolorization decreased with the concentration increase of the amount of materials in the Environment.
 Kanu, Ijeoma, O. K. Achi, Industrial effluents and their impact on water quality of receiving rivers in Nigeria. Journal of Applied Technology in Environmental Sanitation 2011, 1, 75-86.
 D. Wesenberg, I. Kyriakides, S. N. Agathos, White-rot fungi and their enzymes for the treatment of industrial dye effluents. Biotechnology Advances 2003, 22, 161–187.
Analysis of Contaminants in Surface Water using SPE–GC×GC–HR-ToF MS
Wendt, Juergen (1); de Koning, Sjaak (2)
1: LECO European Application&Technology Centre,Berlin,Germany; 2: Da Vinci Laboratory Solutions, Cairostraat 10, 3047BC Rotterdam, Netherlands
The monitoring of water samples for the presence of organic pollutants at trace level requires sensitive and selective analytical methods. Because (inter)national directives tend to become more stringent each year, new methods have to be developed. To meet the present day’s demands, the determination of organic substances in water commonly has to involve trace enrichment of the compounds of interest. If possible, this preconcentration step is combined with capillary gas chromatography (GC), mainly because of the excellent separation efficiency. For selective and sensitive detection, the mass spectrometer (MS) is the preferred choice. In the 1990s, much attention has been paid to the development of on-line techniques for water analysis, which combine sample preparation and separation plus detection in one, fully automated set-up. For such systems, solid-phase extraction (SPE) is generally preferred over liquid–liquid extraction as the isolation technique, because it is less laborious, uses less organic solvent, yields better analyte enrichment and is easier to couple on-line to the chromatographic technique to be used. Various systems for water analysis based on on-line sample preparation with subsequent GC analysis have been described in the literature. In these systems large volume injection (LVI) techniques hold a key position. In most of these studies, on-column LVI was used to transfer the extract to the GC system after SPE.
In recent years GC×GC is introduced to routine laboratories and also high-resolution massspectrometry is finding its position there. This poster shows the analysis of surface water using SPE–LVI–GC×GC–HR-ToF MS. The advantage of coupling of all these techniques to one on-line system is highly sensitive and selective combined target/screening analysis of water samples is one run.
Lichens as biomonitors of spatial distribution of PAH atmospheric deposition in a Pyrenean site.
Foan, Louise; Roudière, Audrey; Simon, Valérie
Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants emitted through incomplete combustion of organic material by industries, waste incineration, domestic heating and traffic. Due to their slow rates of degradation, their toxicity and potential for both long-range transport and bioaccumulation in living organisms, PAHs are monitored in the entire Environment.
This study was carried out to determine the distribution of atmospheric PAH deposition in the Irati Forest, one of the largest and best preserved beech and fir forest in Europe located in the Western Pyrenees in the Northeast of the Basque Country by using lichens as passive samplers. Lichens (Parmelia caperata, Parmelia sulcata, Hypogymnia physodes and Lobaria pulmonaria) were collected during November 2010 in 50 sites which altitude varies between 400m and 1600m.
Samples were freeze-dried, grounded to form homogenous samples and stored in amber glass vials at 4°C until analysis. PAHs were extracted by pressurized liquid extraction followed by a solid phase extraction clean-up and analyzed by high-performance liquid chromatography associated with fluorescence detection. Optimization of the analytical purification procedure was conducted by testing several SPE phases generally used for organic matrix clean-up: Florisil, NH2, Silica and Alumina. The SPE choice influenced PAH recoveries. However, some adsorbents clearly eliminated more interferences, facilitating PAH analysis. The accuracy of the methodology used in this study was evaluated by analyzing the reference material IAEA-140/OC together with the samples.
Total PAH concentrations (13 PAH quantified) vary between 50 and 200 ng/g dry weight. Fluorene and phenanthrene are the main compounds. PAH diagnostic ratios are used to investigate the identification of pollution emission sources. Impact of altitude is discussed.
SURFACE MODIFICATION OF LIPOSOMES FOR ANALYTICAL APPLICATIONS
Figalist, Carola (1); Dechantsreiter, Susanne (1); Roth, Guenter (2); Hirsch, Thomas (1); Baeumner, Antje J. (1)
1: University of Regensburg, Institute of Analytical Chemistry, Chemo-and Biosensors, Germany; 2: ZBSA, University of Freiburg, Germany
Bioanalytical sensors based on liposomes have demonstrated that nanovesicles lower the limit of detection of bioassays by orders of magnitude and simultaneously increase the assay sensitivity. For practical application in bioanalysis, conjugation of biological molecules to the liposome surface is of utmost importance. Ideally, a simple and highly reliable surface modification strategy that does not negatively impact yield and concentration of a liposome stock is desirable. In this study two different principles for the modification of liposomes with biotin were tested. The first concept is based on the incorporation of an already modified lipid to the liposome composition during synthesis. The second principle is achieved by an insertion-method, which was investigated for three different molecules, a biotinylated lipopeptide, Dipalmitoylphosphatidylethanolamine-biotin and cholesterol-biotin. The resulting liposomes were characterized and compared with respect to their size, ζ-potential, encapsulation efficiency and binding capability. All types of modification resulted in colloidally stable liposome dispersions with vesicle diameters of around 160 nm and ζ potentials more negative than 15 mV. It was found that the insertion-method is most efficient in case of the biotinylated lipopeptide. Those liposomes also show a more reliable binding capability and higher encapsulation efficiencies than liposomes modified directly during synthesis. The insertion-method makes the preparation not only simpler and faster but also provides the ability to test different concentrations or types of biorecognition elements on the nanovesicle surface at the same time using a single batch of liposomes. Direct modification of the lipopeptide with biorecognition elements will be a versatile tool for its application with liposomes and other lipid-layer approaches for analytical applications.
ONLINE-DETECTION SYSTEM FOR ENGINEERED NANOPARTICLES OF DIAMETERS LESS THAN 30 NM
Hermann, Cornelia A.; Hirsch, Thomas; Baeumner, Antje J.
University of Regensburg, Institute of Analytical Chemistry, Chemo- and Biosensors, Germany
Engineered nanoparticles are ubiquitously used in products of our everyday life, which leads to their massive entry into the environment, tending to exhibit negative effects on flora and fauna. Therefore, the development of an online detection system for metallic nanoparticles is highly desirable.
A concept of such a system based on the surface plasmon resonance (SPR) technique was developed. Iron oxide nanoparticles were used as example and a protocol for the synthesis of Fe3O4 nanoparticles was established. By thermal decomposition of iron oleate monodisperse particles have been obtained, with adjustable diameter from 8 to 15 nm. Through the growth of a shell of the same material around the particles the diameter can be further increased. In addition to particle size also their surface coating is an important parameter influencing their toxicity. Thus, two different surface modifications have been prepared by either forming an additional capping layer with an amphiphilic polymer, or by introducing small capping molecules via the ligand-exchange technique.
It was found that the change in the bulk refractive index of such small nanoparticles is too low to be detected by SPR spectroscopy. Thus, a thin receptor layer needed to be designed to accumulate the nanoparticles from solution. A polydimethylsiloxane film containing Fe3O4 nanoparticles was created. Upon dissolving these nanoparticles from the film using hydrochloric acid, a receptor layer with pores in the size of the nanoparticles was generated.
The polymer was immobilized on an SPR sensor chip and changes in refractive index were monitored. Finally, this sensor may enable the discrimination of nanoparticles with different sizes and surface modifications in environmental samples´.
DETERMINATION OF RARE EARTH METALS IN WINE USING SORBENT SILASORB SPH C18 MODIFIED WITH BIS(2-ETHYL-HEXYL)PHOSPHORIC ACID (HDEHP)
Shkinev, Valeriy (1); Danilova, Tatiana (1); Dzhenloda, Rustam (1); Malofeeva, Galina (1); Karandashev, Vasiliy (2); Spivakov, Boris (1)
1: Vernadsky Institute of Geochemistry and Analytical Chemistry of Russian Academу of Sciences, Russian Federation; 2: Institute of Microelectronic Technology and Ultra-High-Purity Materials, RAS
The identification of wines is possible on the basis of the concentrations of rare elements (e.g. rare-earth elements, REE) because different artifacts can exert noticeable effects on the identification if common elements are used as markers. Direct determination of REE in wine using ICP-MS or AES could be possible only after wine dilution but the element concentrations in wine are too low for reliable detection. This is why other variants of sample preparation (mineralization or acid treatment, frequently in an autoclave) are needed, however large sample volumes should be used in this case. Solid-phase extraction (SPE) and preconcentration of analytes should make it possible to enrich trace elements before their detection.
In this work, we studied SPE of REE by sorbent Silasorb SPH C18 after modification with HDEHP in order to use it in batch and dynamic modes. In the latter case, we used a flow version of SPE using an ultrasonic column with a loosen layer of the sorbent.
As samples, we applied a dry table white Aligote (Russia) and a dry red wine Barolo (Franco Serra, Italy). It has been shown that the use of 50-100 mg of the sorbent allows to achieve full extraction of REE. Total desorption is achieved using 2M HNO3 or 6M HCl as eluent. This enables the subsequent determination of REE by ICP-MS or AES to be performed.
The authors are grateful for the financial support of RFBR (project No 16-33-00214, project No 16-03-00106)
A Rapid and Cost-efficient Method for the Measurement of Arsenic in Rice
Gross, Armin; Stosnach, Hagen
Bruker Nano GmbH, Germany
Almost half of the world’s population eats rice every day, in many cases several times per day. Therefore, it is considered that rice is the dominant source of inorganic arsenic in the human diet. Rice contains significant amounts of inorganic arsenic with concentrations often between 0.1 to 0.4 mg arsenic/kg dry mass or higher.
Although it is known that chronic arsenic exposure is linked with cancers of the bladder, lungs, skin and prostate, as well as heart disease, only a few countries have established maximum levels (MLs) for total arsenic in food. In 2011 the World Health Organisation (WHO) has published a recommendation showing a maximum level of 200 µg/kg of inorganic As in polished Rice.
The accurate detection if low levels of As in food by common atomic spectroscopy methods requires a dedicated laboratory infrastructure with sample preparation equipment (microwave digestion), cooling water and gas supplies. In contrast to that Total Reflection X-Ray Fluorescence (TXRF) spectrometry is an easy-to-use method which requires minimum sample preparation and no gases or any other media for an accurate multi-elements analysis in the ppb-range.
This paper describes the successful application and method development for the measurement of As in rice by TXRF. An improved spectrometer with a 50W micro focus tube and a 60 mm² XFlash silicon drift detector offers detection limits below 50 µg/kg after a rapid sample preparation without any digestion. TXRF is therefore a suitable method for food analysis in the field or at remote Locations.
PURIFICATION PROCESS BY SYNERGISM EXTRACTION OF THE HEAVY METALS. APPLICATION TO TREATMENT EFFLUENT CONTAINING OF LEAD
Hassaine-Sadi, Fatma (2); Chelouaou, Sihem (1)
1: University of sciences and technology, USTHB, Algeria; 2: University of sciences and technology, USTHB, Algeria
The conventiel processes to treat this kind of wastewater such as as separation processes. In this work, a purification technique by synergism applied to the systems: Pb2+, H3O+, Cl-. The solvent extraction is largely used, it became one of the techniques which experienced the most significant development, consequently to the rise of the raw material prices mineral and to the generalized preoccupation with an environmental protection. It is profitable for recovery, the separation and the purification of heavy metals with low grade.
The reactions for the extraction of Pb2+ from chlorhydric acid are quite complicated, because various Pb(II) species may be present. Lead tends to form aqueous species such as hydroxyl PbOH +, Pb (OH) 2 (aq) and Pb (OH) 3 – , also the lead can also form aqueous complexes with ligands chlorides, Note however that the various forms of Pb(II) and chlorhydric acid solution: PbCl+, PbCl2; PbCl3- in the aqueous phase were taken into account in the analysis of the extractions.
The chemical parameters have allowed us to obtain the variables giving the optimum extraction efficiency for diluted solutions of lead. The fundamental parameters influencing the extraction synergism by mixing different extractants of lead from chlorhydric acid solutions have been examined. The extraction synergism by the mixture: Extractant cation exchanger / solvating extractant; extractant cation exchanger / anion exchanger extractant; Extractant anion exchanger / solvating extractant; two extractants cation exchangers; two extractants anion exchangers and two extractants solvating dissolved in kerosene were investigated.
The process purification by extraction synergism would be particularly judicious in the case of the treatments of the industrial wastes containing heavy metals, it is very sparing out of water and raw materials by recycling of the reagents and extractants.
POTENTIAL USE OF MIXED FRUIT PULP AS A LOW-COST ADSORBENT FOR REMOVAL OF REACTIVE BLUE 19 DYE
Karamfil, Ece; Demirhan, Elçin
Yildiz Technical University, Department of Chemical Engineering, Davutpasa Campus, 34210, Esenler/Istanbul, Turkey
Textile mill effluents present a high pollution potential and health risk. These effluents require prior treatment before being discharged back into the environment. The release of hazardous synthetic dyes into industrial effluents has emerged as an environmental problem requiring remediation. This research focused on the development of a new and environmentally-friendly process for the remediation of aqueous media containing dye.
In recent years, research on the production of low cost adsorbents alternative to commercially available activated carbon has increased. Therefore, in the present study it was aimed to investigate the potential use of mixed fruit pulp (kiwi, apple, carrot, pineapple) for reactive blue 19 removal from aqueous solutions. The effect of several parameters such as pH, adsorbent concentration and temperature was studied and adsorption mechanisms were evaluated. Overall, dyes removal by adsorption on mixed fruit pulp is presented as a promising technology due to the low cost and easy availability of the precursor, as well as the straightforward generation, the satisfactory characteristics and the proved adsorption capacity of the adsorbent.
TRANSPORT THROUGH A MEMBRANE OF CHROME (III) AND CHROME (VI) FROM SULFATE MEDIUM USING TRI-N-OCTYLAMINE AS EXTRACTANT
Hassaine-Sadi, Fatma (2); Zakmout, Asmâa (1)
1: University of sciences and technology, USTHB,Algeria; 2: University of sciences and technology, USTHB,Algeria
Many industrial wastewater streams contain metal cations, one can quote primarily: chrome, lead, copper.…etc. contained in the galvanic rejections they have an impact on the plants and the products for current human consumption, even with low contents. The conventiel process to treat this kind of wastewater such as solvent extraction. In this work, this technique applied to transport through a membrane (extractant+ diluent) of the valuable metal ions: trivalent chromium and hexavalent chromium by Tri-n-octylamine (TOA) from sulfates solutions. The extraction of ions total chromium (Cr(III) + Cr(VI) ) from aqueous solutions has always been a problem for treatment of the wastes in particular releases from the tannery industries.
The chemical parameters have allowed us to obtain the variables giving the optimum extraction efficiency for diluted solutions of Cr(III) and Cr(VI) from sulfuric middle by the Tri-n-octylamine (TOA) dissolved in kerosene were investigated.
A chemical modelization has allowed us to suggest the extraction mechanism. The classical behaviour obtained in surroundings has been found, with an anion exchanger mechanism.
The transport by membrane would be particularly judicious in the case of the treatments of the industrial wastes containing toxic heavy metals ions, this allows an effective protection of the environment while being profitable.
DISPERSIVE SOLID-PHASE EXTRACTION AS A SIMPLE AND LOW-COST CLEAN-UP TECHNIQUE FOR THE DETERMINATION OF PARABENS IN SEDIMENTS AND SOILS
Garrido, Eva; Abril, Concepción; Martín, Julia; Santos, Juan Luis; Aparicio, Irene; Alonso, Esteban
University of Seville, Spain
Parabens are a group of phenols widely used as preservatives in many cosmetics, pharmaceuticals, personal care products and food because of their bactericide and fungicide properties. Due to their ongoing wide use and continuous introduction into the environment through domestic and industrial wastewater, their presence in water, soil, sediment and fish has been reported. To reduce matrix effect and interferences in the determination of parabens in environmental solid samples, a clean-up step after sample extraction is highly recommended. Clean-up of environmental samples is commonly carried out by using solid-phase extraction cartridges. In this work, the use of dispersive solid-phase extraction (DSPE) for the clean-up of sample extracts in the determination of methylparaben, ethylparaben and propylparaben in sediments and soils is proposed. The main advantages of DSPE are its simplicity, low cost and speed. Several solid phases and salts were tested. Best extraction recoveries (up to 92%) were achieved using ultrasonic extraction with acetonitrile and DSPE with C18 as sorbent material. Analysis was carried out by liquid chromatography-triple quadrupole mass spectrometry. The method was validated in soils and sediments. Precision values were lower than 11% and limits of detection were between 0.006 and 0.010 ng/g dry matter. The method was successfully applied to real samples. Methylparaben was detected in sediment and soil samples.
The authors wish to thank financial support received from the Ministerio de Economía y Competitividad, Spain (Project No. CGL2013-44402-R).
INVESTIGATION OF METHYLENE BLUE DYE REMOVAL USING MIXED FRUIT PULP AS AN ECO-FRIENDLY BIOSORBENT
Balta, İdil; Demirhan, Elcin
Yildiz Technical University, Department of Chemical Engineering, Davutpasa Campus, 34210, Esenler/Istanbul, Turkey
The textile industry plays a part in the economy of several countries around the world. Dyeing is a fundamental operation during textile fiber processing. This operation causes the production of more or less colored wastewater, depending on the degree of fixation of the dyestuffs on the substrates, which varies with the nature of the substances, the desired intensity of coloration, and the application method. Natural materials that are available in large quantities may have potential as inexpensive sorbents. Due to their low-cost, after these materials have been expended, they can be discarded without expensive regeneration. The abundance and availability of agricultural by-products make them good sources of raw materials.
In recent years, research on the production of low cost adsorbents alternative to commercially available activated carbon has increased. Therefore, in the present study it was aimed to investigate the potential use of mixed fruit pulp (kiwi, apple, carrot, pineapple) for methylene blue removal from aqueous solutions. The effect of several parameters such as pH, adsorbent concentration and temperature was studied and adsorption mechanisms were evaluated. In conclusion, the present study demonstrated that the fruit pulp as a biosorbent could be employed as an effective and eco-friendly alternative for the cleanup of dye-polluted aqueous media.
Disadvantage in freezing seawater for determination of silicic acid
Tanaka, Miho (1); Takahashi, Kazuya (2)
1: Tokyo Univ. of Marine Sci. and Tech., Japan; 2: Riken, Japan
Silicic acid is important for the preparation of diatoms and maintaining the silica cycle in the marine environment. Freezing of the sample is the most common procedure for the preservation of nutrients to be determined away from sampling site. The frozen samples are completely thawed prior to the molybdate yellow method of determination of silicic acid. However, values determined for silicic acid decreased considerably, especially in seawater samples. This discrepancy was observed between the original seawater sample and the same sample when frozen for preservation.
Pure water begins to freeze and the salinity increases when seawater samples approach freezing point. Seawater contains 0.5 mol/L (M) sodium chloride, this concentration is the critical point of “salting-out effect” of silicic acid. At higher concentrations of sodium chloride, more silicic acid precipitates in solution.
Fast-atomic bombardment mass spectrometry (FAB-MS) is used to measure the “dissolution states of silicic acid” in solution. At sodium chloride concentrations of lower than 0.5 M, silicic acid tends to be stable, but at higher concentrations hydrolyzation occurs. Sodium chloride precipitates above 3.5 M at 20oC, in oversaturated sodium chloride solutions polymerization of silica complexes are present. Therefore, reproducibility for determination of silica is obtained in frozen seawater at low concentrations of silicic acid, but at high concentrations, there is a discrepancy. Also, the hydrolysis of silicic acid is not complete by the precipitation procedure, where large molecules of silicic acid are formed. Sulfuric acid used in the molybdate yellow method is not sufficient for the hydrolyzation process. We thus conclude that freezing seawater for determination of silicic acid is not recommended. Another alternative would be to freeze seawater samples at a higher pH, which when thawed releases all silicic acid for its determination.
LC/MS/MS DETERMINATION OF EMERGING POLLUTANTS IN SURFACE WATER. OCCURRENCE AND ENVIRONMENTAL RISK IN GUADIAMAR RIVER BASIN (SOUTH OF SPAIN)
Garrido, Eva; Santos, Juan Luis; Martín, Julia; Aparicio, Irene; Alonso, Esteban
University of Seville, Spain
The increasing usage of soaps, fragrances, deodorants, prescribed drugs, plastic materials, among other daily products, has resulted in continuous discharges to the aquatic environment of hundreds of chemical pollutants, mainly through wastewater. To prevent damage to aquatic ecosystems is necessary to obtain information about their presence and distribution in the aquatic media. To achieve that aim, and because of matrix complexity and the low concentrations expected, sensitive and accurate analytical methods are needed. In this work, an analytical method for the determination of thirty-five of the most problematic emerging pollutants, due to their continuous discharge to the aquatic environment, persistence and/or toxicity, in surface water is proposed. Target compounds included surfactants, parabens, hormones, pharmaceutical compounds, perfluorinated compounds, a plasticizer and a brominated flame retardant. Recoveries achieved, for most of the selected pollutants, were in the range between 62 and 102 %. Precision, expressed as relative standard deviation, was lower than 18 %. Limits of detection ranged from 0.04 to 98 ng/L. Nineteen of the target compounds were found in the analyzed samples. The compounds at the highest concentration levels were the plasticizer (concentration up to 930 ng/L), caffeine (up to 623 ng/L) and salicylic acid (up to 318 ng/L). The analytical method has been applied to evaluate their occurrence and potential ecotoxicological risk on Guadiamar River basin (South of Spain).
The authors wish to thank financial support received from the Ministerio de Economía y Competitividad, Spain (Project No. CGL2013-44402-R).
SOLVENT SELECTION FOR CHLOROPHENOLS EXTRACTION WITH MULTICRITERIA DECISION ANALYSIS
Tobiszewski, Marek Wiktor; Bigus, Paulina
Gdańsk University of Technology, Poland
Method optimization in analytical chemistry often involves selection of proper solvent. Solvents are chosen to offer good extraction efficiency, while other important factors, like their environmental impacts are neglected. In this study the combination of both factors is proved to be possible with application of multicriteria decision analysis. MCDA analysis allowed to select the most suitable pair of dispersive and extraction solvents applied in dispersive liquid-liquid microextraction for chlorophenols extraction. The criteria applied were extraction efficiency, coefficient of variance for three repetitions and toxicological and environmental persistence parameters of solvents. The presented approach allowed to consider contradictory criteria in the method optimization, to select the most appropriate pair of solvents and to rank the remaining ones. The most beneficial was acetone as the dispersive solvent and heptane as extraction one. The methodology is easy to be applied and has the great potential to be applied as a part of experimental design plans.
This research was financed by Ministry of Science and Higher Education under „Iuventus Plus” program in years 2015 – 2017, project number IP2014 048173.
BENZO(A)ANTHRACENE BIOAVAILABILITY IN VEGETABLES
Marigliano, Laura (1,2); Esposito, Mauro (2); Chiaiese, Pasquale (1); Rao, Maria A. (1)
1: Università di Napoli Federico II, Italy,; 2: Istituto Zooprofilattico Sperimentale del Mezzogiorno, Italy
Polycyclic aromatic hydrocarbons (PAHs) are a group of chemical compounds produced during the incomplete combustion or high-temperature pyrolysis of organic materials. PAHs are classified as carcinogenic and/or mutagenic, able to significantly contribute to human cancer. Food consumption is identified as the major pathway for human exposure to environmental contaminants, accounting for >90% intake as compared to inhalation or dermal routes. Vegetables and fruits are important constituents of Mediterranean diet, therefore their chemical contamination could affect the public health.
The benzo(a)anthracene B[a]A is a one of four PAHs that European Food Safety Authority (EFSA) recommended of monitor for to verify their level contamination.
The aim of this study was to evaluate the B[a]A root uptake and mobilization to the epigeal organs in various species. Tomato (Solanum lycopersicum), broccoli (Brassica rapa var. esculenta), lettuce (Lactuca sativa), artichoke (Cynaria scolymus), strawberry (Fragaria vesca) were grown in both axenic conditions (in vitro) and soil (in vivo) in the presence of different B[a]A concentrations.
This study allowed better understanding the B[a]A bioavailability, its translocation from soil to root and leaf tissue of different vegetables, and the effects on the plant growth.
PESTICIDE RESIDUE ANALYSIS IN PROPOLIS WITH DUAL-LAYER SOLID PHASE EXTRACTION BY LIQUID CHROMATOGRAPHY–MASS SPECTROMETRY
University of Hohenheim, Germany
Propolis is a resinous material collected by honeybees from different leaf buds, exudates, and plants. The composition of propolis is directly related to the composition of the collected bud exudates. Chemically, propolis is a very complex mixture of substances. Thus, the brownish material is a rather challenging matrix for pesticide residue analysis. Besides resins, flavonoids and phenols, high amount of wax is co-extracted resulting in huge matrix effects.
In this study a solid phase extraction (SPE) clean-up was developed for pesticide residue analysis in propolis with high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS). The clean-up success was quickly and easily monitored by high-performance thin-layer chromatography with several detection possibilities. The method consists of the extraction of propolis with acetonitrile based on the QuEChERS method, followed by an effective purification of extracts on dual-layer SPE cartridges with spherical hydrophobic polystyrene-divinylbenzene resin/primary secondary amine as sorbent and a mixture of toluene/acetone for elution. Thereby, fat-soluble components like waxes, flavonoids, and terpenoids, and additionally more polar compounds like organic acids and fatty acids were effectively removed. Method performance was suitable, determined by recovery experiments at two spiking levels (n = 5) for fourteen pesticides that are relevant for bee products. Mean recoveries determined by HPLC–MS and calculated against matrix-matched standards provided recoveries of 79–104% for all pesticides under study. The results were well repeatable since relative standard deviations were below 9%.
Thus, the developed dual-layer SPE clean-up method allows the reliable pesticide residue analysis in propolis.
Pharmaceutical contamination of Slovene wastewaters
Klančar, Anita; Trontelj, Jurij; Roškar, Robert
Faculty of pharmacy, University of Ljubljana, Slovenia
Environmental contamination by pharmaceuticals has been identified as a potential risk to aquatic biota. Recent reports have confirmed the presence of several pharmaceuticals in wastewater treatment plant (WWTP) effluents . Demographics profile, lifestyle, and healthcare may differ across various regions significantly. For getting a broader picture of pharmaceutical contaminants entering the surface waters in Slovenia, an overview of approximately 10 WWTP effluents from rural and urban regions has been undertaken.
A method capable of monitoring 111 pharmaceuticals from multiple therapeutic groups was applied to wastewater samples (250 mL) which were processed by a semi-automated solid-phase extraction system (SPE-DEX 4790, Horizon) using HLB discs as the sorbent. The obtained extracts were analysed by a UHPLC-MS/MS (Infinity 1290 + 6460 QQQ, Agilent Technologies). The chromatographic separation was performed on a Poroshell C18 100 × 3.0 mm, column (Agilent Technologies) by a gradient elution using 0.05% formic acid and acetonitrile.
The preliminary results based on 5 WWTP 24-hours composite effluent samples revealed a high incidence of discharged pharmaceuticals from WWTPs. Briefly, 90% of all considered pharmaceuticals were detected in at least one effluent, 64% in at least three effluents and 38% in each effluent. The highest average concentrations were measured as follows: analgesic drug tramadol (21 µg/L), antidiabetic drug metformin (19 µg/L), antibiotic azithromycin (3.4 µg/L), anticonvulsant lamotrigine (2.2 µg/L), vasodilator valsartan (1.3 µg/L), analgesic drug diclofenac (1.2 µg/L), antibiotic ciprofloxacin (1.1 µg/L) and stimulant caffeine (1.0 µg/L). Slightly lower concentrations were observed for diuretic furosemide and antiepileptic carbamazepine (0.8 µg/L). Overall, the majority of detected compounds were below 100 ng/L.
The present study demonstrates the necessity to systematically monitor these pollutants in order to systematically evaluate the risks and support the future protection measures.
 E. N. Evgenidou, I. K. Konstantinou, D. A. Lambropoulou, Sci Total Environ 2015, 505, 905-926.
Authentication of maize as feed material using non-targeted FT-IR spectroscopy on ground maize and extracted oil
Achten, Elisabeth (1); Schütz, David (2); Fischer, Markus (2); Lahrssen-Wiederholt, Monika (1); Fauhl-Hassek, Carsten (1); Riedl, Janet (1)
1: Federal Institute for Risk Assessment, Germany; 2: University of Hamburg, Hamburg School of Food Science, Institute of Food Chemistry, Germany
Rising numbers of food and feed fraud incidents in recent years have drawn the public attention to the authenticity of products. In addition to established traceability systems based on records it becomes more and more preferable to verify the authenticity with analytical methods on the product itself. To confirm the geographical origin as one feature of authenticity, non-targeted approaches that use spectroscopic or spectrometric techniques are considered to complement classical targeted methods like stable isotope analysis as they are alone not in all cases sufficient to discriminate samples according to their geographical origin. Non-targeted approaches generally use the whole spectral information, a characteristic fingerprint of the sample, for interpretation. By applying multivariate statistics to create classification models the geographical origin of unknown samples can be verified.
The presented project focusses on the verification of the geographical origin of grain maize as maize has great relevance on the international feed market. We present first results from a sample set from different regions in Germany. We used attenuated total reflection Fourier transform infrared spectroscopy with two different types of sample preparation, on the one hand ground maize directly, on the other hand the extracted oil fraction. The results will be compared and discussed. In future other spectroscopic and spectrometric methods will accompany FTIR spectroscopy for complementary data acquisition and advanced multivariate statistics for model building and validation.
Oregano authentication by Fourier transform infrared spectroscopy
Horn, Bettina; Riedl, Janet; Conradi, Florian P.; Pfister, Michael K.-H.; Fauhl-Hassek, Carsten
Federal Institute for Risk Assessment, Germany
Spices and herbs have been used since ancient times to flavor foods and beverages. As spices and herbs are typically high-price commodities and spice consumption is increasing world-wide, fraudulent practices promise high economic profit. Therefore, it is not surprising that spices and herbs are among the top notifications in the European Rapid Alert System for Food and Feed. The main objective of the EU project SPICED is to secure the spices and herbs commodity chain against deliberate, accidental or natural biological and chemical contamination. For the purpose of ensuring the authenticity of these commodities and detecting adulteration of spices and herbs with chemical agents, non-targeted fingerprinting techniques are evaluated and improved. The techniques involve a spectroscopic or spectrometric method combined with multivariate statistical data analysis. The basic idea of the fingerprinting approach is to capture as many features or compounds as technically possible within one measurement and to provide a comprehensive insight into the composition of the food sample.
In this study, a representative set of oregano samples was investigated by Fourier transform infrared (FTIR) spectroscopy and principal component analysis (PCA) to (i) determine the data space of non-adulterated samples and (ii) to identify oregano adulteration with common adulterants such as olive leaves. The results of the study demonstrate the potential of FTIR spectroscopy for authentication and fraud detection of spices and herbs.
ASSESSMENT OF TRACE ELEMENTS ACCUMULATION IN NATIVE PLANTS GROWING AROUND THE PUCHUNCAVÍ-VENTANAS INDUSTRIAL AREA IN CENTRAL CHILE
SalmaniGhabeshi, S (1); Fadic, X (2); Calvo-Blázquez, L (1); Palomo-Marín, M.R (1); Bernalte, E (1); Rueda-Holgado, F (1); Miro Rodriguez, C (3); Cereceda-Balic, F (2,4); Pinilla-Gil, E (1)
1: Dep. Química Analítica and Instituto de Agua, Cambio Climático y Sostenibilidad (IACYS). Universidad de Extremadura, Avda. de Elvas, s/n, E-06006 Badajoz, Spain; 2: Dep. Química; 3: Dep. de Física Aplicada. Av. Universidad s/n E-10071-Cáceres, Spain; 4: Centro de Tecnologías Ambientales, Universidad Técnica Federico Santa María. Av. España, 1680, Valparaíso, Chile
As a part of a long-term integrated environmental assessment project in the heavily impacted industrial area of Puchuncaví-Ventanas (central Chile) including the study of atmospheric deposition, soil and biomonitors, we present here preliminary data of uptaking of trace elements from soil by selected native plants (namely Oenothera Affinis, OA; Sphaeralcea Velutina, SV and Argemone Subfusiformis, AS) growing in the area. The study area include major emission sources as a copper refinery and coal fired power plants, and a set of other 14 different industrial facilities. Native plants have been previously investigated as potential biomonitors but mainly for copper impact. We are enriching the information about the biomonitoring potential of the selected plants by analyzing a set of trace elements (Cu, Sb, As, Pb, Cd, Zn, Cr, Mn, Ni, V, and Co) in biomass samples taken from specific locations with different degree of impact at a range of distances from the pollution sources, including a background site. Plant samples (aerial parts) were washed, dried, grounded and digested by a microwave-assisted protocol before assaying by ICP-MS. Our preliminary results show a significant enrichment of trace elements in OA, SV and AS samples, especially in those taken at most impacted places close to the industrial sources. OA shows higher accumulation in whole aerial parts than in leaves. The effect of environmental parameters such as soil nutrients, pH, organic matter, and clay content is discussed. Work is in progress to estimate trace elements transfer factors and potential use of native plants for phytoremediation purposes.
Acknowledgements: Spanish Ministry of Science and Innovation (project CTQ2014-52309-P), Spanish Agency of International Cooperation for Development (AECID project A1/037813/11), Junta de Extremadura (GR15087), FEDER and AES-GENER (Puchuncaví-Ventanas).
DETERMINATION OF ARSENIC SPECIES IN WINE SAMPLES USING ION PAIR CHROMATOGRAPHY HYPHENATED TO INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY ANALYSIS
Food Research Division, Bureau of Chemical safety, Food Directorate, Health Product and Food Branch, Health Canada, Ottawa, Ontario, Canada
As a naturally occurring element, trace amounts of arsenic are always found in the water and soil, and from there it enters the food chain. Recently, arsenic in food and beverage products have attracted much attention because elevated concentrations of arsenic have been detected in certain food and beverage samples (e.g. rice, apple juice), which may represent a potential health hazard to the consumer. Each arsenic species is different in relative toxicity, so it is important to measure each of the arsenic species rather than total arsenic in food and beverage samples for accurate assessment of human exposure to arsenic. For instance, inorganic arsenic has been identified as a human carcinogen, and AsIII (arsenite) is more toxic than AsV (arsenate). For these reasons, there is a need to implement a rapid and accurate method for the routine analysis of arsenic species. Hence, the current presentation reported a rapid analytical technique for the determination of arsenic species (AsIII(arsenite), AsV(arsenate), AsB(arsenobetaine), MMA(monomethylarsenate) and DMA(dimethylarsenite)), in wine samples.
A high performance liquid chromatograph coupled to inductively coupled plasma mass spectrometer (HPLC-ICP-MS) was used to separate and detect arsenic speciation in water samples. The separation of arsenic species was performed on an anion exchange column (Hamilton, PRP-X110S) with a step gradient elution (20 mM NH4HCO3 and 50 mM NH4HCO3). The arsenic species were detected at m/z 75 with an Agilent 7500cx ICP-MS. The method limit of detection (LOD) ranged from 0.03-0.08 µg∙L-1and limit of quantification (LOQ) ranged from 0.09-0.24 µg∙L-1. A total of 35 wine samples were analyzed, which included 16 white wines, 18 red wines and 1 rose wine. The results showed that the levels of arsenic found in these wine samples were all below the current drinking water guideline, with an average of 1.97 µg∙L-1, and ranging from <0.14 to 5.65 µg∙L-1. Inorganic arsenic was found to constitute 84± 16% of the total arsenic in the wine samples. This work is a contribution toward accurately assessing Canadian exposure to arsenic through diet.
HETEROGENEOUS PHOTODEGRADATION OF AMOXICILLIN BY GOETHITE UP ON ARTIFICIAL AND NATURAL IRRADIATION
Benachrine, Mohamed Mehdi; Debbache, Nadra; Dekkiche, Anfel; Sehili, Taher
Frères Mentouri University, Algeria
The photo-degradation of Amoxicillin (AMX) was investigated in heterogeneous phase with Goethite (a-FeOOH), in aqueous solution, at different experimental conditions. The Behavior of AMX-Goethite system in absence of irradiation has shown that AMX disappear when the solution ages and the phenomenon is less pronounced when the medium became acid.
The irradiation was provided by 365 nm UV lamps or sunlight give evidence for AMX transformation. Indeed, a significant modification has been noticed on UV-Visible spectra where an isosbestic point was detected at 247 nm. Moreover, the band at 230nm is marked by a greater decrease for long time while at 272 nm; the increase in absorption is noted.
Kinetic investigation is carried out allowing that AMX photodégradation followed a pseudo-ﬁrst order kinetics with rate constants k=1.52 ×10-2 h-1. The AMX mineralization reaches 42 % after 90 hours of irradiation. Some parameters affecting mechanistic way of reaction have been examined. The photodegradation of AMX in the mixture AMX-Goethite under solar light was significantly accelerated in comparison with artificial irradiation at 365nm.
DEPENDENCE OF TAR CONCENTRATION IN BIOGAS ON THE TYPE OF BIOMASS
Osipovs, Sergejs; Pučkins, Aleksandrs
Daugavpils University, Latvia
The aim of the present research is to find out if the difference in the type of biomass the concentration of tar in the produced synthesis gas. For research, the two Circulating Fluidised Bed gasifiers situated in eastern Latvia (Rēzekne region) were chosen. The gasifiers differ in the diameter of their reactors, temperature, hence the difference in the conditions of biomass gasification in them. Chinese tea waste, peat, and wood cheeps were employed as biomass.
Tar was sampled at the producer gas temperature reaching 250°С. In the present work, a solid-phase adsorption (SPA) method for determining the concentration of tar compounds has been chosen. The sampling device consists of 500 mg of amino-phase sorbent and 100 mg of activated coconut charcoal. The sampling volume is 100 – 200 mL.
If wood cheeps were used as biomass, the total tar concentration is biggest than Chinese tea waste and peat were used as biomass. The resulting composition of tar contains Benzene, Naphthalene, Acenaphthylene, and over 27 other compounds.
It is concluded that less total tar and lower range of volatile organic compounds such as Benzene were obtained in the latter case, whereas the percentage of the heavy tar is higher.
Simultaneous analysis of mono-, di-, and tri-ethanolamine in cosmetic products using liquid chromatography coupled tandem mass spectrometry
Chungbuk National University, Korea, Republic of (South Korea)
The purpose of this study was to develop a simultaneous quantification method for measurement of MEA, DEA, and TEA in cosmetic products. Liquid chromatography coupled tandem mass spectrometry (LC–MS/MS) was performed using a hydrophilic interaction liquid chromatography (HILIC) column with isocratic elution containing acetonitrile and 5 mM ammonium formate in water (88:12, v/v). Identification and quantification of alkanolamines were performed using MS/MS monitoring to assess the transition from precursor to product ion of MEA (m/z, 61.1 ? 44.0), DEA (m/z, 106.1 ? 88.0), TEA (m/z, 150.1 ? 130.0), and the internal standard triethylamine (m/z, 102.2 ? 58.0). Alkanolamines extractions were simplified using a single extraction with acetonitrile in the cosmetic matrix. Performance of the method was evaluated with quality parameters such as specificity, carry-over, linearity and calibration, correlation of determination (R2), detection limit, precision, accuracy, and recovery. Calibration curves of MEA (2.9–1000 ppb), DEA (1–1000 ppb), and TEA (1–1000 ppb) were constructed by plotting concentration versus peak-area ratio (analyte/internal standard with a correlation coefficient greater than 0.99). The intra- and inter-assay accuracy ranged from 92.92 to 101.15 % for all analytes. The intra- and inter-assay precision for MEA, DEA, and TEA showed all coefficients of variance were less than 9.38 % for QC samples. Limits of detection and limits of quantification were 2.00 and 15.63 ppb for MEA, 0.49 and 1.96 ppb for DEA, and 0.49 and 1.96 ppb for TEA, respectively. This novel quantification method simplified sample preparation and allowed accurate and reproducible quantification of alkanolamines in the ng/g cosmetic weight (ppb) range for several cosmetic products.
AN IONIC LIQUID-BASED SENSOR FOR DETERMINATION OF DICLOFENAC IN WATER
Brennan, Emma; Schazmann, Benjamin; Cassidy, John
The presence of endocrine disrupting chemicals (EDCs) in the environment has been heavily scrutinised, particularly in recent years. These are compounds that interfere with the endocrine system of animals, and are generally drug or pesticide residues. One such compound is diclofenac, an anti-inflammatory drug. The objective of this study is to develop an electrochemical method for diclofenac determination, which can be used in the lab or the field for rapid analysis.
An ion-pair immobilisation modification is utilised in this investigation – an electrode surface is modified with sensing material that elicits a potential in the presence of diclofenac ions. This is known as an ion selective electrode (ISE).
An imidazolium-diclofenac complex was immobilised in a PVC/plasticiser membrane, in a classical ISE format – however, this compartmentalised ISE design can be bulky and fragile. Instead, the work primarily focuses on development of planar solid-state electrodes, which are compact, more robust, and ideal for transferral to field analysis applications.
The suitability of the solid-state system was verified by applying sodium and perchlorate-selective membranes onto carbon electrodes, and characterising. The diclofenac sensor was fabricated similarly, applying the imidazolium-diclofenac complex as a membrane. The electrode chips are cheap to prepare and small in size, making them ideal for fieldwork with a suitably sized potentiometer and reference electrode chip.
Monitoring of Polychlorinated Biphenyls in Processed Food in Korea
Kim, Hye Jeong; Kang, Youngwoon; Jeong, Youngjin; Ahn, Ji Eun; Yang, Jinseong; Kim, Sheen Hee; Kim, Dongsul
Ministry of Food And Drug Safety, Korea, Republic of (South Korea)
Soxhlet and ASE were compared with the content of PCBs in extracted fat, which is commercially merchandised from domestic market. Also, the determination of PCBs was checked by analyzing CARP-2 which is certified reference materials (CRM) in various ASE conditions. This study was performed to survey for levels of indicator-Polychlorinated biphenyls (PCBs) in 102 samples of livestock products from 5 cities of Korea using developed method. To analyze indicator-PCBs, the extracted solution was cleaned by multi-layer silica column and analyzed by a gas chromatography combined with mass spectrometer (GC/MS). The recoveries were measured in 50.7~116.9% for 13C-labeld standards. As a results, the levels of indicator-PCBs were 0.77 ng/g fat in ham, 0.42 ng/g fat in sausage, 0.94 ng/g fat in canned ham, 0.61 ng/g fat in fried chicken, 0.52 ng/g fat in bacon, 1.39 ng/g fat in pork cutlet and sweet and sour pork with sauce, 0.22 ng/g fat in grilled seasoned beef, 4.02 ng/g fat in sliced beef with sauce and dried, 1.69 ng/g fat in Sundae (a sausage made of pork and beancurd stuffed in pig intestine), 0.38 ng/g wet in beef tallow, 0.48 ng/g fat in lard, and so the total average of indicator-PCBs was 1.24 ng/g fat. The results of this study showed lower level compared to regulation limit of PCBs from European union (EU, 2011) of 40.0 ng/g fat of meat and meat products.
TWO-DIMENSIONAL LIQUID CHROMATOGRAPHY AND ITS ADDED VALUE IN PHYSICO-CHEMICAL CHARACTERISATION
Reingruber, Eva; Opmeer, Leon; Baltussen, Erik; Noij, Theo
Department of Analytical and Physical Chemistry, WIL Research - A Charles River Company
Two-dimensional liquid chromatography (2D LC) promises benefits for chromatographic laboratories due to its excellent separation power. 2D LC can add chromatographic selectivity for demanding applications, where 1D LC even in combination with selective detection (i.e. mass spectrometry) fails. Furthermore 2D LC allows carrying out orthogonal separations within one chromatographic analysis: two independent characteristics of a sample can be investigated simultaneously. In this way 2D LC can refine the determination of physico chemical parameters to be used in models for (for instance) environmental partitioning and human and environmental toxicity.
This poster illustrates the potential of 2D LC for the determination of physico-chemical parameters using both a mix of reference substances and a real-life sample and off-line as well as online 2D LC. Firstly, a set of reference substances was analyzed with comprehensive 2D LC. In this way the interrelation of two physico-chemical characteristics was investigated: the partition coefficient (determined according to OECD 117 guideline) and the adsorption coefficient (determined according to OECD 121 guideline). Secondly the number of separated peaks of a complex real-life sample was optimized. The added value of 2D LC was evaluated in course of the determination of the water solubility of the real-life sample.
Determination of etrogens in effluent from wastewater treatment plant using method of passive sampling.
Škodová, Alena; Šimek, Zdeněk; Vrana, Branislav
Masaryk University, Czech Republic
Wastewaters are significant source of organic contaminants. These substances are released into the environment as a result of the metabolism of organisms. Although wastewaters are treated in wastewater treatment plants (WWTP), organic contaminants may be found in environmentally relevant concentrations also at the output from WWTP. They can act as endocrine-disrupting compounds. EDCs include a wide range of chemicals; estrogens are among the most important.
Most aquatic monitoring programmes rely on collecting spot or bottle samples of water, where pollutants could be present at a given time. In the last few years passive sampling techniques were presented for the monitoring of micropollutants. Analytes are trapped in a medium within the passive sampler.
Accumulation in the sampler is driven by a difference in chemical activity of the substance dissolved in water and in the receiving phase of the sampler, initially free of the contaminant of interest . These techniques can be used to determine the time-weighted average (TWA) concentrations of a wide range of environmental contaminants over extended sampling periods, and are capable of concentrating trace contaminants to detectable levels .
To predict TWA water concentrations of contaminants from levels accumulated in passive samplers, calibration studies are necessary to determine the uptake of chemicals under various exposure conditions.
Our study was carried out in WWTP Modřice, Czech Republic. The facility is equipped with a device for measuring the quantity and quality of water discharged. Passive samplers were exposed in effluent. During the exposure, samples of water were collected at the same place. Extracts of samplers and samples of water were analyzed by LC-MS-MS after the precolumn derivatization with dansyl chloride. Concentrations of estrogens in water are presented along with results of sampling rates, mass transfer coefficients of steroids to passive samplers and sorption distribution coefficients.
 Harman et al. 2012
 Arditsoglou et al. 2008
Optimization of novel automated sample preparation systems for elemental and isotopic analysis of environmental samples via (MC) ICP-MS
Zimmermann, Tristan (1,2); Retzmann, Anika (3); Irrgeher, Johanna (1); Prohaska, Thomas (3); Pröfrock, Daniel (1)
1: Helmholtz Zentrum Geesthacht, Germany; 2: University of Hamburg, Germany; 3: University of Natural Resources and Life Sciences, Vienna
Over the past decades (MC) ICP-MS has become a powerful tool for the quantification of trace metals and the precise measurement of isotopic ratios in various kinds of environmental samples. Due to their potentially high content of matrix components and low concentrations of the targeted analytes (μg/L to ng/L) the analysis of such samples remains challenging. In most cases, a time-consuming sample preparation prior to analysis is necessary.
Within this work optimized sample preparation protocols based on two automated sample preparation systems provided by Elemental Scientific (Omaha, Nebraska, USA) have been evaluated:
The seaFAST® system is dedicated to the ultra-trace analysis of undiluted seawater via ICP-MS. Since many trace elements play an important role in the oceans, their precise quantification is vital for understanding oceanic biochemistry or anthropogenic influences. The seaFAST® system allows on-line matrix removal and preconcentration of the targeted elements directly coupled to an ICP-MS, utilizing a chelating resin containing iminodiacetic acid and ethylenediaminetriacetic acid functional groups (Nobias Chelate PA-1®). The system enables time-reduced sample preparation and minimizes risk of contamination. The successful application of an optimized protocol to North Sea water samples and the precise quantification of heavy metal and rare earth elements at lowest concentration levels (low ng/L to sub ng/L) are presented. The ESI prepFAST-MC® is a fully automated, column based chromatographic extraction system which enables the separation of targeted analytes in matrix rich samples. During the last decades isotopic compositions of Sr, Pb and Nd (amongst others) have been widely used in different fields of application such as ecochemistry and geochemistry. Since precise isotopic measurements suffer from isobaric and matrix-based interferences and/or low analyte concentrations sample preparation is vital. First results on the optimization of a sample preparation protocol for the simultaneous separation of Sr, Pb and Nd are shown.
OCCURRENCE OF PHARMACEUTICALS IN DIFFERENT SOLID ENVIRONMENTAL MATRICES
Golovko, Oksana (1); Fedorova, Ganna (1); Koba, Olga (1); Randak, Tomas (1); Grabic, Roman (1); Kodesova, Radka (2); Klement, Ales (2); Fer, Miroslav (2); Nikodem, Antonin (2)
1: University of South Bohemia in Ceské Budejovice, Czech Republic; 2: Czech University of Life Sciences Prague, Department of Soil Science and Soil Protection
Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a simple and fast analytical method was applied for pharmaceuticals tracing in two possible water contamination pathways. One assumed scenario included sediments from fish pond dominated by wastewater treatment plants (WWTP). The sediments are formed from soil transported to pond from surrounding fields. Another one included soil from an experimental field which was annually enriched with WWTP sludge. Concentrations of the pharmaceuticals ranged between 0.83 ng/g and 223 ng/g dry weight. The samples, which can be assigned as sources of contamination (WWTP effluent and applied sludge), had significantly higher levels of studied compounds compared to the assumed targets of transport.
Engineering bacteriophage for the ultrasensitive detection of foodborne and animal pathogens
Hinkley, Troy; Nugen, Sam
University of Massachusetts Amherst, United States of America
The top 14 foodborne pathogens in the United States create almost 9 million infections per year and almost half (~46%) are linked to leafy green produced contaminated from soiled agricultural water. As a result, we have developed a bacteriophage-based detection system to identify and quantify bacterial contaminants. Bacteriophages are viruses that exclusively infect bacteria through attachment and subsequent injection of genetic material. They utilize the cell’s replication resources to produce progeny phage that lyse the cell to repeat the infection cycle. The coliphage T7 was genetically engineered to carry the phoA gene to force overexpression of alkaline phosphatase in E. coli to serve as an enzymatic signal. Colorimetric assays utilizing p-nitrophenyl phosphate (pNPP) provided a sensitive substrate for bacterial quantification. Introduction of two specific point mutations in the phoA gene resulted in a hundred-fold increase in enzymatic activity and thus lower detection limits. Confirmation of successful genetic engineering was confirmed by PCR. The corresponding bacterial lysates were added to the pNPP substrate and significant differences in signal at 405nm were observed. Our bacteriophage-based detection platform was successful in laboratory conditions and serves as a proof of principle for agricultural systems.
Removal of Uranium Ions from Aqueous Solution by Brown Macro Alga Cystoseira sp.
Gök, Cem (1); Aytaş, Sule (2); Sezer, Hasan (2)
1: Pamukkale University, Turkey; 2: Ege University, Izmir
The aim of the present work was to determine applicability of raw and modified brown macroalga Cystoseira sp. as a biosorbent material for the sorption of uranium ions from aqueous solutions. Organic leaching is important problem for industrial applications in the biosorption studies of heavy metals and radionuclides by raw biosorbents. In this work, alkali chemicals, acids, cross linkers, organic compounds, salts and oxidizing agent were used for modification of raw brown macroalga Cystoseira sp. in order to increase uranium (U) biosorption capacity and decrease the organic leaching from macroalga. The loss in biomass of the biosorbent due to treatment was recorded at each step. Biosorption and desorption of uranium ions was investigated as a function of some parameters. The effect of each treatment on the removal efficiency was evaluated in comparison with the raw and modified biosorbents. Surface properties and the possible binding sites of the macroalga were evaluated by instrumental analysis using Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD). The maximum experimental uranium biosorption capacity of Cystoseira sp. biomass modified with 0.2% glutaraldehyde in water was 428.4 mg/g and the percentage of desorbed uranium loaded biosorbent was (99±1)% with 1 mol/L HCl. Equilibrium of uranium biosorption was analyzed under isotherm models and thermodynamic parameters of the process were calculated. Recovery of uranium from acidic mine wastewater was also applied. The mechanism of biosorption was discussed considering experimental data and theoretical models. The bioremoval efficiency of modified biomass was higher than that of raw biomass and theoretical biosorption capacity of modified biosorbent calculated to be 468.01 mg U/g. This work suggests promising biosorption potential of modified Cystoseira sp. biosorbent for recovery of uranium ions. Overall the first report of Cystoseira sp. on the sorption studies was presented.
SAMARIUM REMOVAL BY HYDROXYAPATITE COMPOSITES
Pamukkale University, Turkey
The removal and recovery of lanthanides has become important because of its wide application in industry and also for environment. The necessity for these elements requires the selective and effective separation technique. In this study, batch adsorption method as a green technology has been investigated for removal and recovery of samarium (Sm) using hydroxyapatite composite adsorbent. According to results, the maximum adsorption capacities of Sm were calculated as 370.37 mg/g, respectively. Different types of adsorption isotherms and kinetic models were used to describe the Sm adsorption behavior, and the experimental results fitted Langmuir model and the pseudo-second-order kinetic models well. The adsorption of Sm was founded as endothermic and spontaneous process with respect to obtained thermodynamic parameters. Recovery of adsorbed lanthanides and reusability of adsorbent was tested. Possible adsorption mechanisms were also discussed. The proposed adsorbent has good adsorption ability and high sorption capacity for Sm with a chemisorption mechanism.
REACTIVE TEXTILE DYES BIODEGRADATION IN DENIZLI BY IMMOBILIZED FUNGAL ORGANISM
Ardag Akdogan, Hatice; Topuz, Merve C.; Akdogan, Abdullah; Mercan Dogan, Nazime
Pamukkale University Faculty of Art and Science, Turkey
Different dyes and pigments are used in dyeing and printing industries. The total world colorant production is estimated to be 8,00,000 tons per year and at least 10% of the used dyestuff enters the environment through wastes. To achieve a high efficiency of color removal from dyestuff wastewater, both the microbial consortium and pure isolates were investigated in scientific studies. Many studies have focused on microorganisms that are able to degrade dyes, suggesting bioremediation as an environmentally friendly and cost-competitive alternative for dyed wastewater treatment [1, 2].
In this project, we aimed on the biodegradation of textile dyes (remazol violet 5R, reactif orange 16, reactif red 123, reactif orange 107 which contaminates the environment and will design a new batch shaking system. At first, selected dyes removals investigated by free Coprinus plicatilis. Afterwards, this organism immobilized on different supports. After selecting best support for the organism, Biodegradation of dyes studied. During experimental studies, selected textile dyes and metabolites detected by ESI-MS.
PRESENCE OF PHARMACEUTICALS IN A HOSPITAL EFFLUENT
Klančar, Anita (1); Trontelj, Jurij (1); Kristl, Albin (1); Čater, Maša (2); Rozina, Tinkara (2); Zupančič Justin, Maja (2); Roškar, Robert (1)
1: University of Ljubljana, Faculty of Pharmacy, Aškerčeva cesta 7, 1000 Ljubljana, Slovenia; 2: Arhel d.o.o., Pustovrhova ulica 15, 1000 Ljubljana, Slovenia
Hospital activities such as patient care, diagnostics and laboratory testing require intense and permanent use of pharmaceutical compounds which consequently enter into hospital wastewater. Therefore, hospital effluents have been identified as a relevant source of pharmaceuticals entering the environment . Our aim was to monitor 10 target pharmaceuticals (atorvastatin, bisoprolol, carbamazepine, ciprofloxacin, clofibric acid, diclofenac, fluoxetine, imatinib, metoprolol and sertaline) in the outflow from a hospital wastewater treatment plant.
Wastewater effluents from a hospital with approximately 200 beds were sampled as 24-hour composite sample. Five samplings were carried out in weekly intervals in May 2015 and the target pharmaceuticals were quantified by a sensitive validated analytical method (LOQs in low ng/L range). Extraction of 250 mL wastewater was carried out on the extraction system SPE-DEX 4790 (Horizon Technology) and subsequently analysed by the 1290 Infinity UHPLC coupled to 6460 Triple Quad Mass Spectrometer (Agilent Technologies).
Seven out of ten pharmaceuticals were quantified in all obtained samples, while fluoxetine (2), imatinib (1) and clofibric acid (0) occurred less frequently. The highest concentrations were measured for diclofenac and ciprofloxacin (0.9-3.5 µg/L), carbamazepine (150-600 ng/L) and bisoprolol (200-400 ng/L). While sertraline and metoprolol were present at more or less constant concentrations, the majority of monitored pharmaceuticals showed a high inter-sample variability (RSDs were up to 68.9%).
The results showed that hospital effluents may have a substantial contribution to the load of pharmaceuticals into the aquatic environment and should be considered in ecotoxicological risk assessment as well as for implementation of specific wastewater treatment Solutions.
Acknowledgment: This work was supported by the LIFE+ project: LIFE13ENV/SI/000466.
T. S. Oliveira, M. Murphy, N. Mendola, V. Wong, D. Carlson, L. Waring, Characterization of Pharmaceuticals and Personal Care Products in Hospital Effluent and Waste Water Influent/Effluent by Direct-Injection LC-MS-MS. Sci. Total Environ. 2015, 518–519, 459-478.
DEGRADATION OF CHLORPROMAZINE IN RIVER WATER UNDER NON-STRESS LABORATORY CONDITIONS. IDENTIFICATION OF TRANSFORMATION PRODUCTS AND EVOLUTION OVER TIME.
Jimenez, Juan Jose (1); Muñoz, Beatriz E. (2); Sánchez, Isabel (2); Pardo, Rafael (1); Vega, María del Sol (1)
1: Department of Analytical Chemistry, Faculty of Sciences, University of Valladolid, Spain; 2: Department of Analytical Chemistry, School of Industrial Engineers, University of Valladolid, Spain
Chlorpromazine is a phenothiazine drug with antipsychotic and neuroleptic activity prescribed for the treatment of mental and behavioral disorders. It is considered as a non-biodegradable compound and there is concern for the influence of its residues in the environment: harmful and allergic effects on biomolecules, bacteria, protozoans and Daphnia magna have been reported.
In this context, the degradation of chlorpromazine in river water kept in glass containers at laboratory temperature, exposed to sunlight under the natural day-night cycle, is monitored for 20 weeks to simulate the concurrent natural processes in a body of water, avoiding stress conditions. Sunlight UV irradiation promotes the degradation of chlorpromazine but the glass absorbs partially the UV radiation. Thus, the behavior of chlorpromazine kept in glass container is comparable to that in a mass of water where the penetration of solar UV radiation is diminished with depth.
The residues were weekly monitored by a UPLC/Q-TOF/MS system after solid-phase extraction, and the structures of the found degradation products were tentatively proposed from the molecular formulae and fragmentation observed in high-resolution tandem mass spectra. So, chlorpromazine half-life was estimated in 0.44 weeks (first-order kinetics) and some benzo[1,4]thiazin-6-ol derivatives were found to be the major degradation products at the end of the study. A prediction of toxicity in aquatic ecosystems by the TEST software from the US Environmental Protection Agency suggests that some degradation products have toxicities similar, or even higher, than chlorpromazine.
FAST AND SIMPLE DETERMINATION OF FREE AMINO ACIDS IN BEER
Schad, Gesa Johanna; Bollig, Brigitte; Ludwig, Robert; Erxleben, Björn Thoralf
Shimadzu Europa GmbH, Germany
With an annual consumption of approximately 200 million kiloliters, beer is one of the most popular beverages world-wide. It comes in a huge variety of styles and flavors, with or without alcohol, pure or as a mixed drink, as ale, lager, pils, wheat-beer, Kölsch or Alt, just to name a few. Apart from the risks of overindulging in alcoholic beverages beer is not all-bad. It is easily digestible and offers an important source of vitamins, as well as potassium, magnesium, phosphor and other trace elements, proteins as well as free amino acids.
The composition of beer wort is largely dependant on the raw materials and the style of brewing used in the production. The contribution of specific amino-acids in the formation of off-flavors as well as a positive effect of others on fullness and drinkability has been established. Also the significance of amino acids as a source of nitrogen for fermentation is indisputable. Therefore, determination of changes in the composition and content of amino acids is an important measure in ensuring the consistency in quality of the end-product.
A rapid and reliable HPLC-MS method for the determination of up to 38 amino acids in 9 minutes, using an automated pre-column derivatization approach has been established. The assay showed good reproducibility of the derivatization procedure. The amount of amino acids in beer depends on the materials and technology used for beer preparation and is partially responsible for nutritional value, quality and stability of beer. The total content of amino acids in the five beer samples tested varied between 5238 – 8074 μmol/L, with significant variability in the amino acid distribution in the different types of beer.
EXTRACTION AND QUANTIFICATION OF MYCOTOXINS IN PEANUT BUTTER USING SFE–SFC–MS
Schad, Gesa Johanna (1); Ogura, Tairo (2); Tanaka, Kenichiro (2)
1: Shimadzu Europa GmbH, Germany; 2: Shimadzu Scientific Instruments Inc., Columbia, United States
Aflatoxins are mycotoxins produced by fungal molds of the Aspergillus species, which prefer a warm and damp climate. Aflatoxins can be produced by fungal infestation during or after harvest of peanuts and can therefore end up in processed products such as peanut butter or satay sauce. In addition to being acutely toxic, they are also known to be carcinogenic. To ensure food safety, manufacturers of food and beverages have to strictly manage risks from such contaminants, and sensitive methods to assay mycotoxins in complex matrices are essential.
A conventional, manual method for sample extraction of aflatoxins from peanut butter is time consuming. The use of “supercritical” CO2 for extraction as well as chromatographic separation can offer a more efficient extraction process while reducing solvent consumption and the risk of losses or error of measurement during sample preparation.
Furthermore, extraction selectivity can be carefully controlled by adjusting the solvating power of the CO2 through changes in pressure and temperature, making it faster, more efficient and more versatile than liquid and SPE.
The online SFE–SFC–MS approach was successfully used to extract and analyze aflatoxin B1 and B2 from spiked peanut butter samples in only a fraction of the time that a conventional liquid extraction followed by SPE clean-up sample preparation method would take. The procedure was shown to be linear in a concentration range of 0–10 ppm with good reproducibility.
QbD driven Development and validation of an improved LC‑MS/MS method for the quantification of lenalidomide in human plasma
Hasnain, Md Saquib (1); Rishishwar, Poonam (1); Ali, Sadath (2)
1: Shri Venkateshwara University, Gajraula, U.P, India, India; 2: Glocal University, Saharanpur, U.P, India
Purpose: To determine lenalidomide , a novel stability indicating liquid chromatography‑tandem mass spectrometric method was developed and validated to support the clinical advancement in human plasma and optimized with the help of Box-Behnken design. Materials and Methods: For sample preparation, solid‑phase extraction method was used and a quadratic regression (1/x2) was best fitted for the calibration range. The blank plasma screened for any endogenous interference and observed that it was free from any endogenous interference. Box-Behnken design was applied for optimization using design expert 7. Result: The accuracy (% nominal) and precision (%CV) at low limit of quantification LLOQ level for lenalidomide was in prescribed limit. All the stability parameters were in prescribed limit. Conclusion: This method of lenalidomide satisfies all the regulatory requirements for selectivity, sensitivity, precision, accuracy, stability, goodness of fit, and ruggedness for their determination in human Plasma.
COMPREHENSIVE LC X LC ANALYSIS OF FLAVORING INGREDIENTS IN DISTILLED SPIRITS
Schad, Gesa Johanna; Bollig, Brigitte; Ludwig, Robert; Erxleben, Björn Thoralf
Shimadzu Europa GmbH, Germany
Composition of flavoring ingredients in distilled spirits is largely dependent on make and storage of the product after distillation. The so-called “aging” of alcoholic beverages takes place in charred wooden, mostly oak barrels. During this process of maturation, wood components are extracted into the distillate, which has a major effect on their final Aroma.
The complex composition and a distinct change over the period of storage in the cask provide a unique profile for any distilled spirit after “aging”.
Due to anaerobic decomposition of the lignin underneath the wood charcoal layer in the cask, aromatic aldehydes, such as vanillin or p-anisaldehyde are formed. Colour and (poly-)phenol content of the distillate are a result of extractable wood components. Additional flavoring ingredients are formed by oxidative, interactive chemical reactions of the various constituents.
A comprehensive two-dimensional LC method for the simultaneous determination of polyphenols, and a large number of different flavouring substances has been developed. This online 2D approach offers enhanced resolving power compared to a one dimensional run by employing two successive separations, with different selectivities in a single analysis. This LC x LC analysis also allows for 2D pattern profiling for quick and easy quality control and identification of counterfeit products.
MIGRATION OF CHEMICAL COMPOUNDS FROM CARDBOARD FOOD CONTACT MATERIALS INTO FOOD: DEVELOPMENT OF A FAST AND RELIABLE METHOD TO DETECT PHOTOINITIATORS IN DRY FOODSTUFFS
Van Den Houwe, Kathy (1); Van Heyst, Annelies (1); Evrard, Caroline (1); Van Loco, Joris (1); Elskens, Marc (2); Lynen, Frederic (3); Van Hoeck, Els (1)
1: Department food, medicines and consumer safety, Scientific institute of public health, J. Wytsmanstraat 14, B-1050 Brussels; 2: Analytical, Environmental and Geo-Chemistry, VUB, Pleinlaan 2, B-1050 Brussels; 3: Department of Organic Chemistry, Ghent University, Krijgslaan 281, S4, B-9000 Ghent
Food packaging, providing physical protection and extending the shelf life of dry foodstuffs, are becoming increasingly complex in their design and composition. The direct contact, and in many cases the indirect contact, between the food packaging and the food, yield the transfer of relative low molecular weight compounds such as photoinitiators, mineral oil hydrocarbons, phthalates… Photoinitiators are commonly used in the formulation of UV-cured inks for short drying times. However, the photo-initiators are not always completely utilized or removed after the printing process. Food packaging made of recycled materials form another problem for food contamination. Newspapers and other printed materials are recycled to make new food packaging. Unfortunately, the recycling process does not fully eliminate the photoinitiators. As a result, migration can still occur, even though the packaging itself has not been printed with UV-cured inks.
Since migration of contaminants into food may pose a threat for consumers, it has highlighted the need for occurrence data of these contaminants and thus fast and reliable confirmation methods should be developed.
For the determination of photoinitiators such a confirmation method was developed. First, the substances were extracted from the dry food using acetonitrile. Next, the extracts were purified and subsequently analysed for the presence of photoinitiators, using ultra high performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). For the method, an in-house validation was executed, thereby evaluating the following performance characteristics: linearity, recovery, matrix effect, repeatability, reproducibility and sensitivity.
DETERMINATION OF ORGANIC AND INORGANIC CONTAMINANTS IN WINE USING GCMS AND ICPMS SPECTROMETRY
Oppermann, Uwe (1); Knoop, Jan (1); Fromentoux, Ludivine (2)
1: Shimadzu Europa GmbH, Germany; 2: Shimadzu France SAS, France
Wine is one of the oldest cultural products in human history. Wines have been cultivated for over 8000 years. The oldest known archaeological evidence of winemaking is an 8000-year old wine- and fruit press found near Damascus. With approx. 200 million hectolitres per year Europe is a major contributor to the global wine production. That´s why the wine next to water and beer is one of the favourite beverages in European countries.
In order to guarantee a high level of quality, standards are fixed in the national wine regulations such as the German “Weinverordnung”  from 21st April 2012, which includes the classification of wines from different locations but also the production process, alcohol concentrations and the maximum allowable concentrations of elements. A meticulous quality control procedure is essential, and during each stage of the production process analytical methods such as Gas- or Liquid-Chromatography, AAS-, ICP-, FTIR-, and UV-VIS spectroscopy as well as Mass- Spectrometry are applied for quality assurance or for product characterisation in order to guarantee the highest level of food quality as well as food safety.
Wine colour was measured at 520 nm using a UV-VIS spectrophotometer . Quantitative determination of elements has been done with a Shimadzu ICPMS-2030 mass spectrometer with inductively coupled plasma. Ultra fast analysis of resveratrol in red wine was done using the UHPLC- system with an RF-20Axs high-sensitivity fluorescence detector. The undesired 2,4,6-Trichloroanisole (TCA) in wine is detected using the headspace-trap GC/MS QP-2010 Ultra. Experimental data of a variety of methods will be presented.
 Deutsche Weinverordnung, Bundesgesetzblatt Teil 1 S. 827, (2012)
 Compendium of International Wine and Must Analysis, Vol. 2, (2012)
POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) IN FRUITS AND VEGETABLES CULTIVATED IN THE CAMPANIA REGION (ITALY)
Lambiase, Sara; Marigliano, Laura; Cavallo, Stefania; Picazio, Giuseppe; Baldi, Loredana; Esposito, Mauro
Istituto Zooprofilattico Sperimentale del Mezzogiorno, Italy
Polycyclic aromatic hydrocarbons (PAHs) are organic compounds widespread in the environment, many of them showing genotoxic and carcinogenic effects. For this reason it has been recommended that exposure to PAHs should be as low as reasonably achievable. They are primarily formed by incomplete combustion or pyrolysis of organic matter and during various industrial processes. Therefore, PAHs can be present in air, soil or water and environmental pollution can affect food chain and, in particular, vegetables could be the major contributors to the diet intake.
In this study we report the results of PAHs determination in different fruits and vegetables (Cucurbitaceae, Solanaceae, Brassicaceae, Rosaceae) collected from farms over the territory of so called "Land of fires" in Campania Region (Italy). This area is characterized by environmental problems caused by the illegal dumping of industrial or domestic wastes in fields or by the roadside; sometimes these wastes are burned causing the diffusion of organic contaminants.
The PAH concentrations were determined by HPLC-FLD after an extraction procedure of samples. Six PAHs were analyzed as possible indicators of the carcinogenic potency of PAHs in food: benzo[a]anthracene (B[a]A), benzo[b]fluoranthene (B[b]F), chrysene (Chry), benzo[a]pyrene (B[a]P), benzo[k]fluoranthene (B[k]F), dibenzo[a,h]anthracene dB[a,h]A, although only the first four PAHs are considered the most suitable indicators in Food.
Due to the lack of maximum values established by the European legislation for the vegetables, it was not possible to assess compliance of samples but the PAHs levels were very low in comparison to data reported in literature, although some differences of their content in various vegetable species analyzed were found.
BOTANICAL IDENTIFICATION OF ALLERGENIC ANEMOPHILOUS POLLEN BY ITS MORPHOLOGICAL, COLOUR AND VIBRATION SPECTROSCOPIC PROFILES
Shevtsova, Tetiana V.; Bleha, Roman; Synytsya, Andriy
UCT Prague, Czech Republic
Anemophilous pollen is biogenic part of bioaerosols in the air. Pollen grains play a role of the distribution vector for long term transport of fine particulate matters of agricultural or industrial origin, microorganisms, allergens and other agents. In “the century of allergy”, environmental monitoring and effective identification of pollen and concomitant particles are urgent for forecasts and control. The aim of this study is botanical identification of pollen based on their combined morphological, colour and vibrational spectroscopic profiles. Pollen samples from various coniferous and deciduous trees were collected during flowering and pollen maturation. Microscopic image of each pollen population was analysed to obtain morphological and colour parameters for the individual pollen grains. Statistical distribution of these parameters was evaluated for each botanic species. FT-MIR, FT-NIR and FT-Raman spectra of pollen samples were measured and processed by multivariate statistical methods. Elaborated analytical procedure allows separation of pollen originated from related species within the genus or family that enables precise identification of allergenic pollen.
PREPATARION OF NEW SORPTION GEL DICS FOR DETERMINATION OF MERCURY IN FOOD MATRIXES BY DIFFUSIVE GRADIENT IN THIN FILMS TECHNIQUE
Reichstädter, Marek (1,2); Diviš, Pavel (1,2); Pořízka, Jaromír (2)
1: Department of Food Chemistry and Biotechnology, Faculty of Chemistry, Brno University of Technology, Czech Republic; 2: Material Research Centre, Faculty of Chemistry, Brno University of Technology, Czech Republic
Diffusive gradient in thin films technique (DGT) has become a routine tool for speciation analysis of metals in natural waters, sediments and soils. Since its introduction in 1994, more application possibilities appeared - one of them in food chemistry e.g. lead determination in soy sauces. Since the concentration of toxic metals in food matrixes is usually very low, the application of DGT technique with appropriate gel discs is very suitable for their determination. Not only that DGT technique extracts metals from the food matrixes, it has also allowed to determinate very low concentrations of metals due to its preconcentration ability. The usage of DGT technique for determination of some metals in food matrixes requires special types of sorption gel discs, because the commercially available gel discs aren't able to effectively bind these metals from matrixes with high concentration of natural ligands, such as chlorides or organic acids. A typical example of this occurrence is the determination of mercury by DGT technique. In the presented work new sorption gel disc with thiol functional group for DGT technique was prepared by immobilization of L-cysteine on amino-modified silica via reaction with glutaraldehyde. The prepared sorbent was characterized by FTIR-DRIFT technique and also by elemental analysis techniques, incorporated into polyacrylamide hydrogel layer and its performance for determination of mercury in food matrixes by DGT technique was tested.
Characterization of Czech beer: chemical composition and antioxidant properties
Diviš, Pavel (1); Pořízka, Jaromír (2); Jurečková, Zuzana (1)
1: Brno University of Technology, Faculty of chemistry, Department of food chemistry and biotechnology; 2: Brno University of Technology, Faculty of chemistry, Materials research centre
Czechs consider the czech beer a national beverage and part of the cultural heritage. The traditional Czech beer differs from other products in its sensorial properties that are given by specific technology and use of unique raw materials. In the presented work, 51 different czech beers were analysed using HPLC, IC and ICP-OES techniques. The analytes were polyphenolic acids, organic acids and selected elements. In addition to that, total carbohydrate, total protein content, total polyphenols content and antioxidant properties were determined using appropriate UV-VIS spectroscopic methods. Between the analysed samples beers with and without the regional mark “Czech beer” were represented. The aim of the presented work was to study how the beers with EPM 10%, 12% and more than 12% differs in its composition and antioxidant activity and how the beers with and without the regional mark “Czech beer” differs in its composition and antioxidant activity.
MONITORIZATION OF URANIUM AND THORIUM CONCENTRATION AND ISOTOPE RATIOS IN GROUNDWATER FROM A SEMIARID BASIN IN CENTRAL SPAIN BY SINGLE AND MULTICOLLECTOR SECTOR FIELD ICP-MS
Jiménez, Fernando (1); Basdediós, Nuria (1); Martínez-Pillado, Virginia (1); Vega, Marisol (2); Jiménez, Juan José (2); Pardo, Rafael (2); Giménez-Forcada, Elena (3)
1: Centro Nacional de Investigación sobre la Evolución Humana (CENIEH), Spain; 2: Analytical Chemistry Department, Science Faculty, University of Valladolid, Spain; 3: Instituto Geológico y Minero de España – IGME. Unidad de Salamanca, Salamanca, Spain
The radionuclides from uranium and thorium decay series can be used to obtain highly valuable information from aquatic systems due to their physical and chemical properties. Thus, 234U/238U and 232Th/230Th activity ratios in groundwater can be used to investigate transport phenomena and flow relationships in hydrological reservoirs, redox conditions or weathering processes in the aquifer.
Our hypothesis lays on the potentiality of isotope ratios to act as environmental proxies either by themselves or through their consideration as part of multivariate studies. The aim of this work is to develop a simple, fast and sensitive strategy for the measurement and monitoring of U and Th isotope ratios in groundwater samples and apply it for the control of water samples coming from a highly anthropized river basin. Sample measurement strategy consisted on taking two subsamples, the first one was diluted in 2% HNO3 then U, Th and other trace elements were directly measured by ICP-HR-MS (Thermo Element XR), whereas one-step column resin chemistry was applied to the second one in order to separate U and Th fraction and then isotope ratios were measured by MC-ICP-MS (Thermo Neptune).
LASER ABLATION ICP-OES COMBINED TO CARBON PASTE ELECTRODE VOLTAMMETRY FOR MONITORIZATION OF ELECTROACTIVE SPECIES IN FLUVIAL DEPOSITS
Jimenez-Barredo, Fernando (1); Deban, Luis (2); Álvarez-Posada, Claudia (1); Parés, Josep M. (1)
1: Centro Nacional de Investigación sobre la Evolución Humana - CENIEH, Spain; 2: Analytical Chemistry Department. University of Valladolid, Spain
Some of the most favorite settlements for humans are fluvial terraces due to the proximity to water supplies. Thus, these geological formations are highly exposed to anthropogenic effects. Additionally, their geomorphologic evolution is also related to climatic conditions. The most powerful techniques for dating terrace sediments are based on rock magnetism in combination with stratigraphic studies. Here, the presence of ferromagnetic compounds is used to obtain geochronological information. The knowledge of the chemical composition, especially about those species that show magnetic properties, provides complementary information to the acquired by archaeomagnetism techniques, about the magnetic components in the samples.
The objective of this study is to set up a strategy to investigate iron and titanium compound in terms of element composition and oxidation state distribution in terrace sediments from the Duero basin in Spain. Multielement analyses were carried out by Laser Ablation ICP-OES in order to avoid sample digestion. Accuracy was assessed by analysis of several certified reference materials. Iron and titanium electrochemistry was performed by Carbon Paste Electrode Cyclic Voltammetry which allowed us to identify the presence of magnetite and ilmenite in samples additionally to the Fe(II)/Fe(III) system using only a small amount of sample and avoiding any further chemical Treatment.
METHOD DEVELOPMENT IN THE USE OF SOLID PHASE MICROEXTRACTION FOR THE GC-MS ANALYSIS OF PESTICIDE RESIDUES IN BABY FOOD
Buckendahl, Klaus (1); Stenerson, Katherine K. (2); Shirey, Bob (2); Chen, Yong (2); Young, Tyler (2)
1: Sigma-Aldrich Chemie GmbH, a part of Merck, Germany; 2: MilliporeSigma/Supelco, Bellefonte, PA, U.S.A.
Solid phase microextraction (SPME) is a technique that can be used for the analysis of a wide variety of analytes in many different sample matrices. Headspace is the preferred approach, especially for high background samples. However analytes with low volatility, such as pesticides, cannot be extracted from headspace and thus require immersion of the SPME fiber into the sample. High background samples, such as many foods, pose a challenge with this approach due the presence of fats, sugars, pigments and other macromolecules. These can stick to the fiber and reduce its usable life and/or be transferred to the GC, where they may interfere with chromatographic analysis. In this work, we will present data illustrating the development of an SPME method for the GC/MS analysis of pesticide residues from a heavy background food sample – baby food. Ruggedness of the SPME method was found to be improved through the use of an overcoated SPME fiber in combination with a post-extraction wash step. In addition, optimization of parameters in the SPME method such as sample pH adjustment, salt addition, sample dilution, and extraction temperature will be described. Results will be presented showing the final SPME method applied to samples of pureed peas and prunes spiked with pesticides included on the list described as part of EU directive 2006/125/EC for baby food. At a spiking level of 10 ng/g, accuracies of greater than 70% were obtained, with % RSD values of less than 20% for sample replicates. SPME method ruggedness was evaluated by monitoring pesticide response with repeated extractions of spiked baby food samples.
ANALYSIS OF PESTICIDES IN SPAGHETTI SAUCE BY DIRECT IMMERSION SPME USING AN OVERCOATED FIBER
Buckendahl, Klaus (1); Stenerson, Katherine K. (2); Shirey, Bob (2); Chen, Yong (2); Young, Tyler (2)
1: Sigma-Aldrich Chemie GmbH, a part of Merck, Germany; 2: MilliporeSigma/Supelco, Bellefonte, PA, U.S.A.
QuEChERS is a well-established method for analysis of pesticides in many food commodities with minimal use of solvents and cleanup sorbents. However, QuEChERS steps are requiring significant manual intervention. Solid phase microextraction (SPME) is a solvent-less extraction method that is easily automated and does not require the use of solvents or sorbent materials. SPME is often used for headspace extraction prior to GC analysis, especially if the sample matrix is extremely complex. However, many pesticides cannot be sampled in this manner due to their low vapor pressures. If direct immersion is used with complex matrices such as foods, standard SPME fibers can become prematurely fouled, leading to rapid loss in analyte response and contamination of the GC system. A recent advance in SPME fiber technology is the use of a polydimethylsiloxane (PDMS) overcoating on an adsorbent PDMS/divinylbenzene (PDMS/DVB) fiber. The overcoating serves as a barrier between the adsorbent DVB layer and macromolecules in the matrix, but allows smaller analytes to migrate through and be retained. In this work, we utilized this new overcoated fiber in development of an SPME method for analysis of pesticide residues from a complex food matrix- spaghetti sauce. Performance of the fiber with regards to accuracy, reproducibility, durability, and method ruggedness were compared with a standard, non-overcoated fiber of the same chemistry for the analysis of spaghetti sauce samples spiked with pesticides from a variety of classes. Data will also be presented showing a significant improvement in fiber durability and SPME method ruggedness using the overcoated fiber. Finally, results obtained using the optimized SPME method with the overcoated PDMS/DVB fiber were compared to analysis of the same pesticides from spaghetti sauce using a standard QuEChERS method for extraction and cleanup.
PLANAR PESTICIDE QUANTITATION FROM GREEN FOOD MATRICES USING QUECHERS CLEANUP WITH A NOVEL GRAPHITIZED CARBON BLACK AND ZIRCONIA-BASED ADSORBENT
Buckendahl, Klaus (1); Betz, William (2); Ozanich, Bill (2); Claus, Jennifer (2); Ye, Michel (2); Myers, Pat (2)
1: Sigma-Aldrich Chemie GmbH, a part of Merck, Taufkirchen, Germany; 2: MilliporeSigma/Supelco, Bellefonte, PA, U.S.A.
Pesticides with planar structures, such as hexachlorobenzene and chlorothalonil, are commonly used during the cultivation of spinach and other leafy, green crops. The extraction and analysis of these residues is often complicated by the presence of chlorophyll in green food matrices. In both GC/MS and LC/MS/MS analyses, large pigment molecules, such as chlorophyll, are highly problematic. They accumulate in the inlet and degrade column performance in GC/MS. Chlorophyll is also known to contaminate the LC/MS/MS source. Method EN15662 (QuEChERS) recommends the use of Graphitized Carbon Black (GCB) in sample cleanup methods for the removal of chlorophyll and other pigment interferences. While traditional GCB efficiently removes pigment molecules, it also retains planar pesticides. Recommendations to alleviate this problem include the addition of toluene to the extraction solvent to minimize binding to the GCB as well as the use of smaller amounts of GCB to balance recovery of planar pesticides with color removal. Data shows that neither of these solutions is completely satisfactory. Supel QuE Verde is a unique QuEChERS cleanup mix that contains a zirconia-containing adsorbent, Z-Sep+, in combination with proprietary GCB. It provides recoveries ranging from 70% to 120% of challenging planar pesticides while maintaining >95% chlorophyll removal in green matrices. Spinach and other green matrices will be discussed herein. Color removal will be demonstrated using UV-Vis spectrophotometry. Planar and non-planar pesticide recovery will be determined using a GC/MS/MS Triple Quad. The effects of quantity and surface areas of GCB on color removal and pesticide recovery will also be examined.
PREPARATION AND CHARACTERIZATION OF BIOPOLYMERIC NANO-COMPOSITES FOR RECOVERY OF LANTHANUM
Gök, Cem; Esen Erden, Kadriye; Koizhaiganova, Meruyert; Doruk, Ibrahim; Özcan, Yusu
Pamukkale University, Turkey
Nano-biocomposite materials can be used for many applications in various areas. In this study, prepared biopolymeric nano-composites were used for removal of lanthanum from aqueous solution. In this respect, some physical properties of prepared materials will be determined and characterization studies are carried out by Raman spectrometry, FT-IR, SEM and XRD methods. The physicochemical parameters of biocomposites are also investigated for optimum materials. Sorption mechanisms will be investigated using experimental results and calculated parameters from some models as thermodynamic, isothermal and kinetic. The results suggest that these materials were proven to be potent material for reducing the concentration of lanthanum and some heavy metals with high efficiency in aqueous solution. Due to the high sorption capacity of the prepared material, plus its easy preparation process, economic advantage and environmental friendly nature would make these composites a promising removal and recovery agent for lanthanides.
SYNTHESIS OF NOVEL FUNCTIONALIZED MAGNETIC TITANIUM DIOXIDE NANOCOMPOSITES AS ADSORBENT FOR DYE REMOVAL FROM WASTEWATERS
Shariati, Shahab; Rahnama, Sara
Islamic Azad University, Rasht Branch, Iran, Islamic Republic of
The dye containing wastewaters are very hard to be treated and cause several effects on the human health and environment. For this reason, numerous traditional treatment methods especially, adsorption process have been used to eliminate dyes from wastewaters. In the present study, two novel Fe3O4@SiO2@TiO2-NH2 and Fe3O4@SiO2@TiO2-SO3H nanocomposites were synthesized and their potential as adsorbent for efficient removal of Fuchsine acid (as an anionic) and Methylene blue (as a cationic) dyes from aqueous solutions were investigated. For this aim, TiO2 shell was chemically synthesized on the surface of silica coated magnetite core and functionalized by amine and sulfonic acid groups. The size and chemical structure of the synthesized nanocomposites were evaluated by SEM, FT-IR and XRD. For dyes removal, all of the experimental factors affecting the dye removal efficiency were investigated using L16 Taguchi orthogonal array design and optimal conditions were obtained. The results revealed that more than 99% and 98% removal efficiency of Fuchsine acid and methylene blue was obtained, respectively. Adsorption data were studied using Langmuir and Freundlich models. Also, the sorption kinetics were investigated and the best fit was achieved by pseudo second order kinetic model. The results showed that the newly synthesized nanocomposites exhibited high degree of crystallinity, good chemical stability and excellent magnetic properties at room temperature. Furthermore, they exhibited very fast kinetics and high removal efficiency that make them as a proper recoverable sorbent for removal of anionic and cationic compounds from wastewaters.
PERSISTENT MOBILE ORGANIC CHEMICALS IN THE WATER CYCLE INVESTIGATED BY THE WATER JPI PROJECT PROMOTE
Quintana, José Benito (1); Arp, Hans Peter H. (2); Berger, Urs (3); de Voogt, Pim (4); Gallard, Hervé (5); Knepper, Thomas (6); Neumann, Michael (7); Reemtsma, Thorsten (3)
1: University of Santiago de Compostela, Santiago de Compostela, Spain; 2: Norwegian Geotechnical Institute, Oslo, Norway; 3: Helmholtz Centre for Environmental Research – UFZ, Leipzig, Germany; 4: University of Amsterdam, Amsterdam, The Netherlands; 5: IC2MP UMR 7285 CNRS - University of Poitiers, Poitiers, France; 6: Fresenius University of Applied Sciences, Idstein, Germany; 7: Federal Environment Agency, Dessau-Roßlau, Germany
The quality of surface water and groundwater is affected by the presence of many chemicals. If such compounds are poorly degradable, i.e. persistent, and very mobile (highly hydrophilic), we denote them as PMOCs (persistent mobile organic chemicals). PMOC are particularly relevant in the water context since they can spread though the water cycle, reaching groundwater and surface waters, which afterwards are used for drinking water production, thus potentially becoming a human hazard. Since, by definition PMOC are very polar, containing in many cases ionic groups, current analytical methods mostly relying on reversed-phase liquid chromatography-mass spectrometry (RPLC-MS) may be inefficient for the determination of such pollutants. This gap in analytical methods translates into a lack of information as regards their occurrence and behavior in the water cycle and potential associated risks. The Water JPI funded project PROMOTE (www.promote-water.eu) brings together different European experts in analytical and environmental chemistry, water treatment and chemical regulation and prioritization, as well as relevant stakeholders to: 1) prioritize REACH-registered chemicals and their transformation products which can be PMOC, 2) develop new analytical tools capable of detecting and quantifying PMOC, 3) study their fate, transformation and removal, and finally, 4) provide recommendations on mitigation actions when necessary.
Acknowledgements: The authors thank the European Union Joint Programming Initiative “Water Challenges for a Changing World” (Water JPI) with financial support by the Ministerio de Economía y Competitividad (Spain, JPIW2013‐117), Bundesministerium für Bildung und Forschung (Germany, 02WU1347A/B), Forskningsrådet (Norway, 241358/E50), Office National de l'Eau et des Milieux Aquatiques (France, IC2MP project PROMOTE).
Development of analytical methods of ellagic acid from health functional food of Punica granatum and Psidium guajava fruit extract powder
Moon, Myung-Hee; Lee, Sung-Hye; Hu, Soo-Jung; Kim, Ji-An; Shin, Yong-Woon; Lee, Hwa-Jung; Kang, Yun-Jung; Hwang, Kyung-Mi; Koo, Yong-Eui
Ministry of Food ans Drug Safety, Korea, Republic of (South Korea)
This study was conducted to develop the analytical methods for ellagic acid from health functional food of Punica granatum and Psidium guajava fruit extract powder to help to reduce nasal hypersensitivity and climacteric symptoms. Analytical methods of ellagic acid by HPLC were established through instrumental analytical conditions, and the examination of data such as domestic and foreign reliable methods, and papers of journal. HPLC method analyzing ellagic acid was established using Capcell Pak C18 UG 120 column in 253 nm through test of columns. The validation has been performed on the method to determine linearity, accuracy, limits of quantification (LOQ) and precision for ellagic acid. An excellent linearity (r2=0.996) was observed for ellagic acid in the concentration range (0.1 - 50 µg/mL). Precision for ellagic acid was between 0.7 and 2.8 % relative standard deviation (RSD).
This research was supported by a grant (16161MFDS055) from Ministry of Food and Drug Safety in 2016.
Assessment of sediment bound metal lability and their bioaccumulation in trochus eithraeus in Bushehr coast, Persian Gulf
Mehdinia, Ali (1); Bateni, Fatemeh (2); Sheijooni, Neda (3)
1: Iranian National Institute for Oceanography and Atmospheric Science, Iran, Islamic Republic of; 2: Iranian National Institute for Oceanography and Atmospheric Science, Iran, Islamic Republic of Iran; 3: Iranian National Institute for Oceanography and Atmospheric Science, Iran, Islamic Republic of Iran
In this study, different chemical methods for extraction of the trace metal (total and bioavailable fraction) in sedimentary environment and total trace metal in soft and hard tissues of a gastropod (trochus erithraeus) at seven stations of Bushehr coast, the Persian Gulf, were investigated. To evaluate the bioavailability of metals (cadmium, chromium, cobalt, copper, iron, manganese, zinc, nickel, molybdenum, lead, antimony and yttrium) in sediments, HCl, predict digestive absorption and sequential extraction technique (SET) were used. Sediment contamination degree was calculated by using pollution load index), geoaccumulation index, and enrichment factor. Also an Effects Range-Low and Median were determined. Based on these indexes coastal sediments of the studied area were clean and no enrichment was observed. Also there was no significant difference observed among the stations. As a result, Ni was considered in a range of effect range low (ERL). Bioaccumulation factor (BAF) for essential elements (Zn and Cu) in soft tissues exceed about 12 and 8, respectively, for all stations. In respect of Cd in some stations BAF was about 1 but in others it was about 11. In hard tissue maximum BAF was calculated about 1. In comparison between total concentration of trace metal in sediments and soft tissue, a significant correlation was found between Cr, Ni and Zn concentration in these ambiances. Also there was significant correlation between total concentration of Ni and Zn in hard tissue and sediment samples. Concentration of Ni in single extraction by HCl and also in residual fraction of SET had significant correlation with both soft and hard tissue of the gastropod.
A CLOSER LOOK AT MINERAL OIL FRACTIONS
Leitner, Erich (1); Jurek, Andrea (1); Oppermann, Uwe (2)
1: Graz University of Technology, Austria; 2: Shimadzu Europa GmbH, Duisburg, Germany
A currently heavy discussed theme in the field of packed food concerns mineral oil residues of different sources. The mineral oils fractions can be described by their chemical properties, so a MOSH and a MOAH fraction can be found (MOAH – mineral oil saturated hydrocarbons and MOAH – mineral oil aromatic hydrocarbons).
MOSH consist of linear and branched alkanes, and alkyl substituted cycloalkanes, whilst MOAH include mainly alkyl-substituted polyaromatic hydrocarbons up to four aromatic rings. The main focus is thereby on the aromatic fraction, covering about 15-30% of the whole aromatic fraction, which is suspected to include potential carcinogenic and mutagenic constituents.
Nevertheless the methods which are normally used lacking specific information of the composition of the mineral oils constituents.
A common method uses the combination of HPLC and GC (either on-line or off-line) with non specific FID detection which quantifies only the total concentration of MOSH and MOAH. FID is used due to its universal detection principle which eliminates structural influence of different molecules. In addition the methods uses a large volume injection with quite a steep temperature ramp resulting in broad unresolved humps.
This work is about the identification of individual substances in the MOSH and MOAH fraction using multidimensional chromatography which can be a powerful tool. GCxGC based methods are described and the advantage of increasing chromatographic resolution AND sensitivity is explained.
MULTIVARIATE STATISTICAL INTERPRETATION OF THE DISTRIBUTION OF ARSENIC AND OTHER GEOGENIC TRACE ELEMENTS IN GROUNDWATER FROM A SEMIARID BASIN (CENTRAL SPAIN)
Vega, Marisol (1); Ingignoli, María Sofía (1); Jiménez, Fernando (2); Jiménez, Juan José (1); Pardo, Rafael (1)
1: University of Valladolid, Spain; 2: Centro Nacional de Investigación sobre la Evolución Humana, CENIEH, Spain
The occurrence of high levels of arsenic and other geogenic trace elements in groundwater from the Southern bank of the Duero River basin (Central Spain) has prompted an investigation into groundwater hydrogeochemistry to understand the sources and mobilization pathways of these toxic elements.
More than 70 groundwater samples were collected (2015-2016) from springs and deep wells (>50 m) from an area of 45x25 square kilometers. Hydrochemical parameters determined in the samples included pH, electrical conductivity, E.C., redox potential, Eh, temperature, major ions and trace elements (As, B, Ba, F, Fe, Li, Mn, Sr, U, V and W). The distribution of As in groundwater varies widely: 32% of the samples contained less than 10 µg/L, maximum allowable level in drinking water according to WHO and the Council Directive 98/83/EC, whereas As levels above 100 µg/L occurred in 18% of the samples. Spatial variability was also observed for the rest of trace elements.
The interpretation of the results by multivariate statistical tools (principal component analysis, PCA, and hierarchical agglomerative cluster analysis, HCA) revealed significant correlations amongst groups of variables: As-V-F-W-pH; U-Na-Li-B-bicarbonate; Ca-Mg-sulfate-E.C. The occurrence of trace elements seems to be controlled by two mobilization mechanisms: (i) desorption of As and related elements in alkaline waters (pH>8.5), increased by high concentrations of competing anions (mainly sulfate), and (ii) dissolution of carbonated minerals, abundant in the basin, releasing alkaline elements and uranyl ions. The intensive use of groundwater in agriculture and the high evaporation rates are worsening the quality of groundwater in the Region.
CHARACTERIZATION OF WINES PRODUCED FROM FUNGUS RESISTANT GRAPES
Leitner, Erich (1); Koraimann, Claudia (1); Oppermann, Uwe (2)
1: Graz University of Technology, Austria; 2: Shimadzu Europa GmbH, Duisburg, Germany
The vineyards of the Styrian wine region are located in the southern part of Austria close to the Slovenian border covering approximately 4.500 hectares. Predominantly steep slopes are cultivated with inclinations up to 60%. This area is a classical cool-climate region with an average annual temperature of 10.5°C and precipitation of approximately 1.000 mm per year. Main rainfall months are especially May, June, July & August and September in which 55 to 70% of the annual precipitation falls. The mechanical management of the steep slopes is difficult and quite dangerous, too.
The establishment of fungus- resistant grape varietals can clearly reduce plant protection efforts and also brings economic advantages. First experiments with fungus resistant grape varieties date back to the early '80s. Most varieties of the initial trials were not accepted by the consumers due to their sensory properties. The recent generation of fungus-resistant Grape varietals show much more compromising results and a higher acceptance on the market.
This poster includes both, the results of the sensory analysis by a trained panel of 12 members with specific expertise in wine tasting and the overview on the analytical methods: Quantitative determination of aroma substances using GC-MS/ GC-MSMS and the comprehensive GCxGC-MS for the characterization of the volatile fraction.
DERIVATIVE SPECTROSCOPIC DETERMINATION OF FLORFENICOL IN SOME NATURAL SAMPLES
Fakhre, Nabil Adil
Salahaddin University-Erbil, Iraq
Florfenicol is a member of chloramphenicol and thiamphenicol family. The chemical name is 2, 2-dichloro-N-[(1R, 2S)-3-fluoro-1-hydroxy-1-(4-methanesulfonylphenyl) propan-2-yl] acetamide. Florfenicol was widely used clinically now for the treatment of intestinal infections, respiratory tract infections, typhoid, and so on. Compared to thiamphenicol, florfenicol shows significant superiority in antibacterial spectrum, antibacterial activity, and considerably lower side effect; its antibacterial potency is 10 times higher than that of thiamphenicol. A new, simple, rapid, wide applicable range and reliable derivative spectrophotometric method has been developed for determination of enrofloxacin.
Metabolomic approach for geographical origin discrimination of hazelnuts (Corylus avellana) by UPLC-QTOF-MS
Klockmann, Sven; Reiner, Eva; Fischer, Markus
Hamburg School of Food Science, University of Hamburg, Germany
Ultraperformance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) was used for geographical origin discrimination of hazelnuts (Corylus avellana L.) based on the nonpolar metabolome. 196 authentic hazelnut samples from harvest years 2014 and 2015 (Germany, France, Italy, Turkey, Georgia) were analyzed in a non-targeted approach, followed by selecting and identifying 20 key metabolites with significant differences in abundancy, represented by triacylglycerides, diacylglycerides, phosphatidylcholines, phosphatidylethanolamines with varying fatty acid side chains as well as gamma-tocopherol. Three classification models were created using linear discriminant analysis (PCA-LDA), support vector machine classification (SVM) and a customized statistical model based on confidence intervals of selected metabolite levels, all three combined with soft independent modeling of class analogy (SIMCA) as surveillance analysis for the reduction of false positive assignments, yielding 99.5 % training accuracy at its best. Additionally, 40 hazelnut samples for confectionary industry were subsequently used to estimate as realistic as possible the prediction capacity of the previously developed models.
APTAMERS: APPLICATION STRATEGIES FOR FOOD AND DIAGNOSTIC ANALYSIS
Fischer, Christin; Wessels, Hauke; Frohnmeyer, Esther; Paschke-Kratzin, Angelika; Fischer, Markus
University of Hamburg, Germany
Aptamers are short single stranded DNA or RNA oligonucleotides, which are usually selected from a high diverse oligonucleotide library via the SELEX (systematic evolution of ligands by exponential enrichment) process. Their single stranded conformation enables the aptamers to form distinct three dimensional structures, which are the basis for high affine interactions - comparable to those of antibodies. Aptamers, once generated, can be used in a similar manner for a wide range of applications, like trapping, detection, marking or sensing. Moreover aptamers provide some advantages compared to antibodies, like the ability to be selected towards non-immunogenic or toxic targets or base precise modifiability during aptamer Synthesis.
The present work demonstrates different application strategies of aptamers in food analysis. These promising biomolecules were selected and utilized successful for different trapping applications: e.g. Bacillus cereus spores in different milk samples or metabolites (here: phytosphingosine) in several urine samples. Thus enrichment factors up to 7-fold were reached.
In addition the poster presents the usage of aptamers as capture units in rapid detection test systems like lateral flow devices are. Therefore aptamers with an affinity towards different target classes (i) metabolites, (ii) proteins, and (iii) spores were generated and different competitive and non-competitive lateral flow device assays were implemented. After assay optimization the detection limits of (i) p-aminohippuric acid in urine, (ii) lysozyme in white wine, and (iii) Alicyclobacillus spores in fruit juice were determined.
SULFONIC ACID FUNCTIONALIZED KIT-6 MESOPOROUS SILICA MAGNETITE NANOPARTICLES AS AN EFFICIENT ADSORBENT FOR RHODAMINEB REMOVAL
Shariati, Shahab; Aminianfar, Adineh
Islamic Azad University, Rasht Branch, Iran, Islamic Republic of
Dyes are used in large amount in many industries to color the products. Many dyes are toxic in nature with suspected carcinogenic and mutagenic effects that influence aquatic biota and also human beings. Rhodamine B (RhB), is a synthetically prepared carcinogenic xanthine dye that can affect the skin, eyes and respiratory tract.
In this study, sulfonic acid functional groups were created onto the surface of synthesized KIT-6 mesoporous magnetite nanoparticles to form Fe3O4@SiO2@KIT-6-SO3H) as a recoverable adsorbent for efficient removal of RhB cationic dye from aqueous solutions. For this purpose, magnetite nanoparticles (MNPs) with particle size lower than 21 nm were synthesized via chemical precipitation methods. The surface of bare MNPs was coated with SiO2 layar and then by a highly ordered large pore silica mesoporous KIT-6. After that, mesoporous MNPs were functionalized with SO3H groups. The synthesized nanocomposits were characterized by SEM, TEM, FT-IR, powder XRD and Nitrogen adsorption-desorption isotherms. The various parameters affecting dye removal such as the amount of adsorbent, pH of solution, salt effect, volume of sample and contact time were evaluated using L16 Taguchi experimental design method. Under optimal conditions (sample volume: 10 mL, pH=4.0, sorbent mass: 0.08 g, NaCl content; 0.005 mol L-1and contact time: 20 min) the RhB removal was reached 95.8%. Adsorption data were studied using Langmuir and Freundlich models. Also, the kinetic studies showed the dye followed well with the second-order kinetic model. Ultimately, the efficiency of the synthesized adsorbent for removal RhB from real water samples was successfully confirmed. The results of this study can be used to design an appropriate adsorption treatment plant for removal of Rhodamine B from wastewater samples.
OCCURRENCE OF PESTICIDES RESIDUES IN ITALIAN ORGANIC HONEY FROM DIFFERENT AREAS
De Dobbeleer, Inge (1); Galbiati, Fabrizio (2); Panseri, Sara (3)
1: ThermoFisher, Netherlands; 2: Thermofisher. Switzerland; 3: University of Milan, dpt of Veterinary Science and Public Health, Italy
Products, such as honey, are widely consumed as food and consumer interest is currently oriented towards organic foods. Regarding this, the European Commission establishes that the qualification of organic honey and other beekeeping products as being from organic production is closely bound with the characteristics of hive treatments as well as the quality of the environment. Agricultural contamination with pesticides is a challenging problem that needs to be fully addressed, in particular in the field of organic production systems. In this study, the occurrence of different classes of contaminants selected as representative of potential contamination sources were investigated in 59 organic honeys [organochlorines (OCs), organophosphates (OPs), polychlorobiphenyls (PCBs) and polybromodiphenylethers (PBDEs)]. A method based on Accelerated Solvent Extraction with “in-line” clean-up and GC-MS/MS detection was developed to detect contaminants. Residues of many pesticides were found in most of the samples investigated. The majority of honey samples contained at least one of the pesticides, even if their concentrations were found to be lower than its MRL. Diazinon, Mevinphos, Coumaphos, Chlorpyrifos and Quinoxyfen were the residues frequently detected in samples coming from the apple and citrus orchard areas. Furthermore, the results of the present study show that the presence of the residue in organic honey may also be affected by the geographical area (e.g. the presence of an agricultural system) confirming honey bee and beehive matrices as appropriate sentinels for monitoring contamination in the environment. The optimised method proved to be simple and rapid, requiring small sample sizes and minimising solvent consumption, due to the ASE having an “in line” clean-up step.
Differentiation of hazelnut varieties via RAPD
Felbinger, Christine; Kutzsche, Florian; Fischer, Markus
´Hamburg School of Food Science, University of Hamburg, Germany
About 85% of the total hazelnut production is used in the confectionary industry. Thereby certain qualities of hazelnut varieties do play a decisive role. For roasting special varieties are preferred because of certain beneficial flavour components, like sweet and fruity, which come into focus after processing. For the use of whole nuts in chocolates the size of the hazelnut does play an important role. Due to the mentioned reasons above, the price of hazelnut varieties differs vastly and is also depended on harvest yields. For example, in 2014 there were supply shortages of industrial relevant cultivars due to a crop failure in Turkey, the main hazelnut producing country. That led to an increase of the raw material price and therefore adulterations of certain hazelnut varieties are suspected. Adulteration can occur unknowingly when different hazelnuts varieties are harvested on the same field or deliberately to increase the profit margin.
Since hazelnut varieties can be hard to distinguish visually when they are shelled, the origin of the hazelnuts can currently only be tracked via shipping documents. Therefore, in the confectionary industry there is a high demand for solid analytical methods to verify the procured variety and to control possible adulterations. To distinguish between hazelnut cultivars DNA-based methods are best suitable. The DNA is a relatively stable marker and is not affected by external influences. The poster shows a DNA-based non-targeted approach to distinguish between different hazelnut varieties via RAPD (randomly amplified polymorphic DNA).
Optimized fully-automated matrix/Sr separation for Sr isotopic analysis in soil extracts to generate isoscapes of bioavailable Sr for archaeological migration studies
Retzmann, Anika (1); Zimmermann, Tristan (2,3); Irrgeher, Johanna (2); Pröfrock, Daniel (2); Budka, Julia (4); Prohaska, Thomas (1)
1: University of Natural Resources and Life Sciences, Vienna, Austria; 2: Helmholtz-Centre Geesthacht, Germany; 3: University of Hamburg, Germany; 4: Austrian Academy of Sciences, Vienna, Austria
The analysis of systematic variation in the isotopic composition of Sr in the environment is widely used in ecogeochemistry, archaeology and anthropology for tracing various processes such as human and animal migration. However, isotopic measurements using MC ICP-MS can suffer from (isobaric as well as matrix-based) interferences and the concentration is too low for accurate analysis. Hence, the sample matrix has to be separated and the element of interest needs to be pre-concentrated prior to isotopic analysis. These sample preparation steps are usually performed manually and are therefore time-consuming and limit the number of samples.
Separation methods using the fully automated, column based chromatographic extraction system prepFAST-MC® (Elemental Scientific, Omaha, US) were developed to allow isotopic analysis of Sr in bulk samples (e.g. sediments, river- and seawater, carbonates, tissue). Even though the separation scheme using the commercially available DGA resin (TrisKem International, Bruz, France) showed promising results for most sample matrices, the developed separation method suffered from incomplete matrix/Sr separation when ammonium nitrate extracts of soil were processed. These extracts are of major importance since they represent the bioavailable fraction in soils and are a valuable proxy for the autochthonous signal in human/animal migrations studies.
Herein, first results on the application of the developed matrix/Sr separation protocol to soil extracts from Sai Island are shown. The soil samples were taken in the area of the Egyptian settlement on Sai Island in Northern Sudan as part of the “Across ancient borders and cultures”-project (FWF START Y615-G19, Dr. Julia Budka) that investigates the life style, the living conditions and especially the coexistence and merging of cultures in the New Kingdom in Nubia.
The generated isoscape (aka isotope map) of Sai Island will be used as basis for the further interpretation of autochthony or allochthony of the skeletal remains of excavated individuals.
URBAN SURFACE WATER QUALITY: MONITORING NUTRIENT LEVELS AND THREATS TO WATER REUSE
Ximba, Bhekumusa Jabulani; Olatunji, Olatunde; Fatoki, Olalekan; Opeolu, Beatrice
Cape Peninsula University of Technology, South Africa
Introduction: The quality of surface waters traversing through many urban metropolises is under threat of degradation. This is due to indiscriminate disposal of waste from domestic, industrial and agricultural sources into the neural of urban water bodies. As a result, the capacity for self-purification of the water is hampered, and is likely to limit the effectiveness of wastewater treatment procedures in improving their quality [1-3]. Thus water needs to be evaluated in order to determine the effect of organic carbon and inorganic nutrient loads on the water quality using the chemical oxygen demand requirement as an indicator .
Experimental: Water samples were collected from streams, residential, industrial areas. The water samples were process and analysed using standard methods.
Results and discussion: Most of the surface waters were under threat of low oxygen content at circum-neutral pH (6.6 – 6.9), due to high organic and nutrient loads compared to water samples collected from the two peri-urban rivers which served as a control. The nutrient levels in the streams/rivers ranged; Nitrogen, 3.82 – 15.46 mg/L and phosphorus, 1.35 – 5.71 mg/L while Dissolved Organic Carbon ranged between 24.8 and155.4 mg/L. The estimated biochemical oxygen demand and chemical oxygen demand requirement for regeneration of the water quality were 180.81 – 200.62 mg/L, and 250.27 –312.83mg/L, respectively. Variance showed significant differences between sampling sites and seasons, with higher values observed during the dry season.
Conclusion: Thus DO levels in almost all the investigated waters were low and in hypoxic condition. Regulatory intervention are thus needed to ensure compliance to boost the self-regeneration capacity of the water bodies.
 O. S. Olatunde, F. S. Olalekan, O. O.Beatrice, X. J. Bhekumusa, O. O. Zacheaus, A. N. Kehinde, Nutrient Enrichment and Hypoxia Threat in Urban Surface Water. Clean – Soil, Air, Water 2015, 43, 205–209.
 Z. H. Ei Tun , P. Parkpian , R. D. Delaune , R. P. Gambrell, A. Jugsujinda, Cadmium concentration in sea bottom sediment and its potential risk in the upper Gulf of Thailand, J. Environ. Sci. Health, Part A 2009, 44, 244–248.
 A. O. Akinro, I. B. Ologunagba, O. Yahaya, Environmental implications of unhygienic operation of a city abattoir in akure, Western Nigeria. Zeitschrift für Bewässerungswirtschaft 2009, 44, 223–230.
Novel Strategies in Metabolite Identification: Application of 3DCC (3D CrossCorrelation) for the Analysis of Plant-Metabolites
Bollen, Anke (1); Sander, Simon (1); Fischer, Markus (2); Meyer, Bernd (1); Hackl, Thomas (1,2)
1: Institute of organic Chemistry, University of Hamburg, Germany; 2: Hamburg School of Food Science, University of Hamburg, Germany
The Metabolome consists of thousands of Metabolites, which makes it difficult to separate them chromatographically and this culminates in the problem to identify single components.
Therefor the three-dimensional cross correlation (3DCC), first introduced by Behnken et al., is a powerful tool for non-targeted Metabolome Analysis. 
3DCC combines the advantages of MS and NMR and dissects NMR spectra of a mixture into spectra of single components without fully separating the single compounds from each other. The idea of this application is using the fact of compounds occurring at the same retention time in the MS and NMR, which allows to calculate their correlation and to deconvolve the NMR-spectra mathematically to spectra of only one single compound. So far the 3DCC application was only used to separate NMR-Spectra from glycanes by using the advantage of the structural reporter group method.
This work will demonstrate an application to other compounds such as metabolites from plants. A mixture of six compounds was analysed to validate the applicability to other small molecules. Without the complete chromatographic separation, the ESI-MS spectrum and a pure 1H-NMR-spectrum for each individual compound have been obtained.
For many metabolites this data will be sufficient for identification either from a database or assignment of the spectroscopic data. In specific cases the application will facilitate the identification of promising candidates for isolation and further spectroscopic analysis. 3DCC considerably facilitates the search and identification of biomarkers.
 H. N. Behnken, M. Fellenberg, M. P. Koetzler, R. Jirmann, T. Nagel, B. Meyer, Resolving the problem of chromatographic overlap by 3D cross correlation (3DCC) processing of LC, MS and NMR data for characterization of complex glycan mixtures. Anal Bioanal Chem. 2012, 404, 1427-37.
Antibody-based SPR-biosensor for detection of lysozyme in wine
Wesssels, Hauke; Ören, Esma; Mersmann, Lisa; Fischer, Markus; Paschke-Kratzin, Angelika
Hamburg School of Food Science, University Hamburg, Germany
Due to microbial activity, flavor scalping by undesired malolactic fermentation can be observed in wines. For prevention, the products are treated with lysozyme, an enzyme which is capable to hydrolyze peptidoglycanes in cell walls of gram-positive bacteria. Unfortunately, sensitive individuals could be harmed due to allergic reactions caused by the protein which originates from egg. Up to 0.5 g/L are permitted by legislation to stabilize wines, while already 0.25 ppm needs to be labelled in terms of allergen Management.
Currently, antibody-based technologies (e.g. enzyme-linked immunosorbent assay) represent the “gold standard” for the detection of allergens in food. Due to current legislation (Directive 2010/63/EU) and ethical considerations, the use of antibodies should be minimized so far as an equivalent alternative is available.
In the presented work, a reduction of the quantity of antibody was achieved by the use of surface plasmon resonance spectroscopy (SPR). This is possible since the sensor chip can be used numerous times and only a small amount of immunoglobulins is necessary for the preparation. After immobilization of the antibody on the sensor chip surface, an interaction with an injected analyte can be observed by change of the local refractive index. Due to high sensitivity and reproducibility without the necessity of any kind of labelling, this automatable technique provides a promising opportunity for the detection of Antigens.
In the developed system, an antibody towards lysozyme was immobilized and various wines were injected. It was possible to detect and quantify the allergen content from 0.25 to 10 ppm in wines made of different grapes with varying alcohol content. A matrix calibration was performed in three different wines which showed satisfactory results in terms of detection limit (0.25 ppm) and precision Profile.
APPLICATION OF 1H-NMR-SPEKTROSCOPY FOR ANALYSIS OF THE GEOGRAPHICAL ORIGIN OF HAZELNUTS
Bachmann, René (1,2); Klockmann, Sven (2); Fischer, Markus (2); Hackl, Thomas (1,2)
1: University of Hamburg, Institute of Organic Chemistry, Germany; 2: University of Hamburg, Hamburg School of Food Science, Germany
Considering the increasing globalization and the growing interest in local produced products, the determination of the origin of food becomes more and more important. Today Turkey is the largest hazelnut producer with about 75% of the world production. The second largest hazelnut producer is Italy with significant differences in production conditions and qualitative marketing. Therefore a unique method of determination of the products origin would be desirable.
In this study different hazelnut samples from Turkey, Italy, Georgia and Germany were analyzed by 1H-NMR-spectroscopy and the multivariate data analysis methods such as PCA and PLS-DA. The PCA showed a good clustering of samples according to their geographic origin. Especially Georgian samples differed significantly from Italian and German samples. The corresponding Loadings-Plots show the important buckets which are responsible for separation of the sample groups. In the next step a discriminant analysis was performed, which showed the total separation of the samples by their origin. It appears that the approach of using 1H-NMR-Spectroscopy together with PCA and PLS-DA delivers a fast and accurate determination of the geographical origin of hazelnuts.
NANOFABRICATION OF FLUID DEVICES AND THEIR ENVIRONMENTAL APPLICATIONS
Zanjanchi, Pegah; Zarrabi, Ali
Isfahan University, Iran, Islamic Republic of Iran
Nanofluidics is the study of the behavior, manipulation, and control of fluid flow in transport phenomena of fluids and particles in nanochannels / nanopores, devices that are confined to structures of nanometer (typically 1-100 nm) characteristic dimensions. This paper describes the present state of research in this field and discusses possible directions of developments with emphasis on its environmental applications. There are three important strategies for nanofabrication of fluid devices including nanolithography, micro electromechanical system based techniques (MEMS) and methods using various nanomaterials that are briefly discussed in this paper. Subsequently, an overview is given for the different phenomena happening on the nanoscale and their present environmental applications and after that some possible future applications are discussed. As a whole, nanofluidics is a fascinating field that is facing considerable challenges today. It possesses a formidable potential and offers much space for creative ground breaking ideas.
QUANTITATIVE DETERMINATION OF 30 PLASTICIZERS IN FOOD PRODUCTS
Meiss, Ernst; Ruthenschroer, Ansgar; Reichel, Mareike; Schulz, Claudia
Eurofins WEJ Contaminants, Germany
Plasticizers like phthalates or adipates are widely used in plastics and packaging materials. Because of migration into the environment plasticizers can be found in food, feed, soil and even air samples.
This ubiquitous contamination of plasticizers in environment has become an important source of plasticizers in foods, in addition to direct migration from food packaging materials. It is well known that some phthalates, like diethylhexyl phthalate (DEHP), are suspected of being carcinogenic. As most plasticizers are lipophilic they commonly can be found in fatty foods. Therefore a simple, sensitive and accurate method for the analysis of plasticizers in food products is needed. In this study, a scheduled MRM LC-ESI-MS/MS method for the quantitative determination of 30 plasticizers in food products is presented. For sample preparation, the homogenized food sample is extracted with acidified acetonitrile and a simple clean up procedure was also included. For LC separation of analytes a phenyl-hexyl reversed phase column was chosen. For MS measurement, the [M+H]+ precursor ion was isolated for each analyte and two product ions were selected for data acquisition. Calculation was carried out using calibration standards of defined concentrations by correction with internal Standards.
Metabolic Profiling of Asparagus officinalis for Discrimination of the Geographical Origin based on ultra-high resolution Mass Spectrometry
Creydt, Marina; Arndt, Maike; Wrage, Jasmin; Cain, Nicolas; Fischer, Markus
University of Hamburg, Hamburg School of Food Science, Grindelallee 117, 20146 Hamburg, Germany
The geographical origin of food is of high priority for German consumers, who are prepared to accept higher prices for the valuable characteristics from certain geographical areas. As a consequence, indicating the origin of goods can have significant influence on purchasing decisions and thus offers a special incentive for food fraud. Food labeling with incorrect information is a known problem these days, particularly in the asparagus production. However, there are currently no reliable methods to obtain objective evidence. Within the scope of this project, funded by BMWi/AiF/FEI, a simple and reliable LC-MS/MS-method is intended to develop for routine Analysis.
The presented work is based on a metabolomics approach. The principle of this strategy is the assumption that the metabolom of raw material differs considerably in accordance to location and growing conditions. Due to their high diversity it is not possible to detect all metabolites with a single analytical method. The higher the resolution and performance of the technology, the more molecules can be discovered. This is particularly important for hypothesis free non-targeted metabolomics studies as they offer a way to detect simultaneously as many metabolites as possible and therefore increase the likelihood of identifying relevant compounds. Currently, one of the most widespread analytical platforms for non-targeted metabolomics approaches is liquid chromatography coupled to electrospray ionization-quadrupole-time-of-flight-mass spectrometer. To maximize the coverage of the metabolome, it is essential to optimize LC-MS-parameters as well as extraction procedure. The presented results illustrate the workflow for the development of non-targeted analysis, which ultimately aim at a substantial improvement of data quality by choosing appropriate columns, eluents and ionization improving substances, an appropriate sample preparation and extraction procedure up to the final dataset.
DETERMINATION OF THE GEOGRAPHIC ORIGIN OF WHITE ASPARAGUS USING FT-NIR AND CHEMOMETRIC METHODS
Richter, Bernadette; Klare, Juliane; Creydt, Marina; Fischer, Markus
Hamburg School of Food Science, Hamburg, Germany
The geographic origin of food is of great importance as European consumers show an increasing interest in local products. This especially applies for white asparagus, which is one of the main cultivation products in Germany. Consequently, there is a need for reliable and standardised analytical methods to distinguish asparagus samples from different regions.
The aim of this study is to find a method to determine the geographic origin of white asparagus from an unknown provenance. To this end, FT-NIR as a fast technique suitable for routine screening was chosen for sample Analysis.
Accordingly, 113 white asparagus samples from 13 German regions and 20 foreign samples from China, Peru, Greece, Spain, France, Belgium and Poland were analysed. All samples were harvested in 2014 and 2015. Prior to data analysis, different pre-processing methods were compared. Principal component analysis (PCA) was used for dimensionality reduction. Hierarchical clustering was applied for visualization of the results and to identify similarities between individual samples. A multivariate classification model was built using a support vector machine (SVM).
German and foreign asparagus samples showed different trends in the principal components and in the hierarchical clustering analysis. However, a clear separation of regions within Germany was not possible. Our classification model was able to detect foreign asparagus samples with sensitivity and specificity of more than 85 % in both training and test group. The determination of regions within Germany was only achievable with lower accuracy.
Our results demonstrate that FT-NIR can be a rapid and easy to handle method to identify whether an asparagus sample originates from Germany or not. However, for the classification of samples to specific regions within Germany, other analytical tools should be applied.
COLOR-SENSOR FOR STRAIGHTFORWARD QUALITY ASSESSMENT OF NANOGOLD-COATED SILICA AS ADSORBENT FOR METHYLMERCURY PRECONCENTRATION
Przewodnik, Alexander Maximilian
Ulm University, Germany
Methylmercury is a highly toxic organometallic compound which is produced in biomethylation-reactions from inorganic mercury. Its high bioaccumulation in the aquatic food chain requires monitoring by sensitive analytic methods.
Our group developed a reagent-free flow-injection analysis system for preconcentrating aqueous mercury-species from waters coupled to an atomic fluorescence spectrometer for detection of mercury. The preconcentration is based on solid-phase extraction onto nanogold-coated silica. However, reproducible synthesis of the sorbent material is a critical point and characterization of each batch requires bulky analytical instruments, like transmission electron microscopy and extraction of gold for determination of gold load by e.g. atomic absorbance spectrometry.
In the present study, a straightforward and simple to handle color-sensor was constructed and used to optimize the synthesis of nanogold-coated, colored collector material. Differently shaded materials were synthesized by variation of reaction parameters and their Hg retention efficiency determined in a flow injection analysis system. The obtained results show a dependence of retained methylmercury and the fraction of red light reflected from the material. Pink and purple materials show a higher retention than red material, whereas blue material shows barely any retention.