Analysis Of Persistent Organic Pollutants Research Articles

Carbon, Hydrogen and Chlorine Stable Isotope Fingerprinting for Forensic Investigations of Hexachlorocyclohexanes.

Multielemental stable isotope analysis of persistent organic pollutants (POPs) has the potential to characterize sources, sinks, and degradation processes in the environment. To verify the applicability of this approach for source identification of hexachlorocyclohexane (HCHs), we provide a data set of carbon, hydrogen, and chlorine stable isotope ratios (δ13C, δ2H, δ37Cl) of its main stereoisomers (α-, β-, δ- and γ-HCHs) from a sample collection based on worldwide manufacturing. This sample collection comprises production stocks, agricultural and pharmaceutical products, chemical waste dumps, and analytical-grade material, covering the production time period from the late 1960s until now. Stable isotope ratios of HCHs cover the ranges from -233‰ to +1‰, from -35.9‰ to -22.7‰, and from -6.69‰ to +0.54‰ for δ2H, δ13C, and δ37Cl values, respectively. Four groups of samples with distinct multielemental stable isotope fingerprints were differentiated, most probably as a result of purification and isolation processes. No clear temporal trend in the isotope compositions of HCHs was found at the global scale. The multielemental stable isotope fingerprints facilitate the source identification of HCHs at the regional scale and can be used to assess transformation processes. The data set and methodology reported herein provide basic information for the assessment of environmental field sites contaminated with HCHs.

Automated milk fat extraction for the analyses of persistent organic pollutants.

We have utilized an automated acid hydrolysis technology, followed by an abbreviated Soxhlet extraction technique to obtain fat from whole milk for the determination of persistent organic pollutants, namely polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls. The process simply involves (1) pouring the liquid milk into the hydrolysis beaker with reagents and standards, (2) drying the obtained fat on a filter paper and (3) obtaining pure fat via the modified Soxhlet extraction using 100mL of hexane per sample. This technique is in contrast to traditional manually intense liquid-liquid extractions and avoids the preparatory step of freeze-drying the samples for pressurized liquid extractions. Along with these extraction improvements, analytical results closely agree between the methods, thus no quality has been compromised. The native spike (n=12) and internal standard (n=24) precision and accuracy results are within EPA Methods 1613 and 1668 limits. While the median (n=6) Toxic Equivalency Quotient (TEQ) for polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans and the concentration of the marker polychlorinated biphenyls show a percent difference of 1% and 12%, respectively, compared to 315 previously analyzed milk samples at the same laboratory using liquid-liquid extraction. During our feasibility studies, both egg and fish tissue show substantial promise using this technique as well.

PCDD, PCDF, dl-PCB and organochlorine pesticides monitoring in São Paulo City using passive air sampler as part of the Global Monitoring Plan

The persistent organic pollutants (POPs), such as organochlorine pesticides and PCBs, are ordinarily monitored in the aquatic environment or in soil in the environmental quality monitoring programs in São Paulo, Brazil. One of the core matrices proposed in the POPs Global Monitoring Plan (GMP) from the Stockholm Convention list is the ambient air, which is not a usual matrix for POPs monitoring in the country. In this study POP levels were evaluated in the air samples from an urban site in São Paulo City over five years, starting in 2010 as a capacity building project for Latin America and the Caribbean region for POP monitoring in ambient air using passive samplers. Furthermore, after the end of the Project in 2012, the monitoring continued in the same sampling site as means to improving the analytical capacity building and contribute to the GMP data. The POPs monitored were 17 congeners of 2,3,7,8 chloro-substituted PCDDs and PCDFs, dioxin-like PCBs, indicator PCBs, organochlorine pesticides and toxaphene. The results show a slight decrease in PCDD/F, dl-PCBs and indicator PCBs levels along the five years. The organochlorine pesticide endosulfan was present at its highest concentration at the beginning of the monitoring period, but it was below detection level in the last year of the monitoring. Some other organochlorine pesticides were detected close to or below quantitation limits. The compounds identified were dieldrin, chlordane, α-HCH, γ-HCH, heptachlor, heptachlor epoxide, hexachlorobenzene and DDTs. Toxaphene congeners were not detected. These results have confirmed the efficacy of passive sampling for POP monitoring and the capacity building for POP analysis and monitoring was established. However more needs to be done, including expansion of sampling sites, new POPs and studies on sampling rates to be considered in calculating the concentration of POPs in ambient air using a passive sampler.

Profiling and Spatial Variation Analysis of Persistent Organic Pollutants in South African Delphinids.

The continuous disposal of persistent organic pollutants (POPs) in South Africa (SA) warrants concern about their detrimental effects on humans and wildlife. We surveyed six dolphin species (n = 90) incidentally captured in shark net installations or stranded off the SA east and south coast from 2005 to 2009 to study the POP exposure. Sousa plumbea, an inshore and estuarine species, was found to be the most contaminated by total POPs (21 100 ng g(-1) lw) of all the dolphins off SA, followed by Tursiops aduncus (19 800 ng g(-1) lw), Lagenodelphis hosei (13 600 ng g(-1) lw), and Delphinus capensis (5500 ng g(-1) lw), whereas POP levels in the offshore or pelagic delphinids were much lower. In all delphinids, dominant pollutants were dichlorodiphenyltrichloroethanes (DDTs), which represented more than 60% of the total concentration of total POPs, followed by polychlorinated biphenyls (PCBs, 30%). Concentrations of DDTs in S.plumbea and T.aduncus off SA were among the highest levels reported in delphinids globally. Approximately half of the adult T.aduncus had PCB concentrations above the effect threshold for impairment of immune functions. The concentrations of Mirex and Dieldrin in SA delphinids were higher than those found in species from other regions of the Southern Hemisphere.

Occurrence and levels of chemical contaminants and their effect on disease susceptibility and reproductive performance on Tilapia species from Lake Kariba in Zambia

Event Abstract Back to Event Occurrence and levels of chemical contaminants and their effect on disease susceptibility and reproductive performance on Tilapia species from Lake Kariba in Zambia Chalumba K. Simukoko1, 2*, Kaampwe Muzandu2, Stephen Mutoloki3, Øytein Evensen3 and Jan Ludvig Lyche1 1 Norwegian Uiversity of Life Sciences, Food Safety and Infection Biology, Norway 2 University of Zambia, School of Veterinary Medicine, Zambia 3 Norwegian University of Life Sciences, Basic science and Aquatic Medicine, Norway The objective of this study was to assess occurrence and levels of chemical contaminants in farmed and free living Tilapia on Lake Kariba in Zambia. Lake Kariba is located in the southern part of Zambia. The study covered the four strata (divisions) of the lake. Strata 1 and 2 are located near a coalmine, has a considerable number of fishing boats (500), farming activities, with a sizable human population. Likewise, stratum 4 has a high human population, fishing boats and several commercial fish farms while stratum 3 has very little human activity. The aim of the study was to assess a potential association between the human activity in stratum 1, 2 and 4, and contamination of the fish as well as association between the level of contamination and adverse health effects. Strata 3 with low human activity serve as reference (control).Fish were sampled from each stratum and parameters including sex, weight and length were recorded. Tissues (organs and blood) and water samples were collected and fixed for various toxicological analysis. Persistent organic pollutants (POPs), pharmaceuticals, and heavy metals were measured using GC-MS and AAS in liver tissue and water respectively. Results showed a difference in sex ratios between strata (skewed towards females (Stratas 1 and 3); and towards males (strata 4). Examination of water samples showed no elevated levels of Heavy metals (As, Cd, Cr, Co, Fe, Pb, Mn, Hg, Ni and Zn) in all sites. The analyses of POPs and pharmaceuticals are under processing. Toxicological analyses are under way. The implications of the findings will be presented and discussed. Acknowledgements The work was funded by NORAD Project number (TAN13/0027) Keywords: Persistent Organic Pollutants, Tilapia, Sex Ratios, Zambia, Aquaculture Conference: AquaEpi I - 2016, Oslo, Norway, 20 Sep - 22 Sep, 2016. Presentation Type: Poster Topic: Aquatic Animal Epidemiology Citation: Simukoko CK, Muzandu K, Mutoloki S, Evensen Ø and Lyche J (2016). Occurrence and levels of chemical contaminants and their effect on disease susceptibility and reproductive performance on Tilapia species from Lake Kariba in Zambia. Front. Vet. Sci. Conference Abstract: AquaEpi I - 2016. doi: 10.3389/conf.FVETS.2016.02.00006 Copyright: The abstracts in this collection have not been subject to any Frontiers peer review or checks, and are not endorsed by Frontiers. They are made available through the Frontiers publishing platform as a service to conference organizers and presenters. The copyright in the individual abstracts is owned by the author of each abstract or his/her employer unless otherwise stated. Each abstract, as well as the collection of abstracts, are published under a Creative Commons CC-BY 4.0 (attribution) licence (https://creativecommons.org/licenses/by/4.0/) and may thus be reproduced, translated, adapted and be the subject of derivative works provided the authors and Frontiers are attributed. For Frontiers’ terms and conditions please see https://www.frontiersin.org/legal/terms-and-conditions. Received: 23 Aug 2016; Published Online: 14 Sep 2016. * Correspondence: Mr. Chalumba K Simukoko, Norwegian Uiversity of Life Sciences, Food Safety and Infection Biology, Oslo, 0454, Norway, chalumba@yahoo.com Login Required This action requires you to be registered with Frontiers and logged in. To register or login click here. Abstract Info Abstract The Authors in Frontiers Chalumba K Simukoko Kaampwe Muzandu Stephen Mutoloki Øytein Evensen Jan Ludvig Lyche Google Chalumba K Simukoko Kaampwe Muzandu Stephen Mutoloki Øytein Evensen Jan Ludvig Lyche Google Scholar Chalumba K Simukoko Kaampwe Muzandu Stephen Mutoloki Øytein Evensen Jan Ludvig Lyche PubMed Chalumba K Simukoko Kaampwe Muzandu Stephen Mutoloki Øytein Evensen Jan Ludvig Lyche Related Article in Frontiers Google Scholar PubMed Abstract Close Back to top Javascript is disabled. Please enable Javascript in your browser settings in order to see all the content on this page.

Evaluation of pesticide residue analysis of dieldrin in soil using a high resolution gas chromatograph/mass spectrometer (HR-GC/MS)

The objective of this study was to evaluate the effectiveness of using HR-GC/MS for the rapid screening of dieldrin residues in soils. Persistent organic pollutants (POPs) of organochlorine pesticides such as dieldrin, were analyzed in sedimentary rock and granite rock collected from greenhouses, Niigata, Japan. Dieldrin remains in Japanese farming soils, more than 40 years after their use as insecticides was prohibited. The averages in soil moisture ranged from 2.79% to 7.20% in soils derived from sedimentary rock and from 25.59% to 31.40% in soils derived from granite rock. Mean concentrations of dieldrin residues in sedimentary rock and granite rock were 39.7 ng g-1 and 40.51 ng g -1 , respectively. Dieldrin residue was detected at a slightly higher concentration in granite rock than sedimentary rock samples. There was no consistency between the two soils or between surface and subsurface soils. The coefficients of variation of the two soils were 10.6% and 8.7%, respectively. These results suggest that our high-resolution mass spectrometry detector (HR-GC/MS) is effective at analyzing residual organochlorine pesticides in soil. In order to increase the precision and sensitivity for chemical analysis of POPs, high-resolution gas chromatography coupled with a HR-GC/MS is highly recommended.

Pop, heavy metal and the blues: secondary analysis of persistent organic pollutants (POP), heavy metals and depressive symptoms in the NHANES National Epidemiological Survey

ObjectivesPersistent environmental pollutants, including heavy metals and persistent organic pollutants (POPs), have a ubiquitous presence. Many of these pollutants affect neurobiological processes, either accidentally or by design. The aim of...

Signal Enhancement by Crossing the Sample Flow at a Small Angle against the Laser Beam in Multiphoton Ionization Mass Spectrometry

To enhance sensitivity in multiphoton ionization/time-of-flight mass spectrometry, the sample, in the form of an effusive molecular flow, was introduced at a small angle relative to the laser beam. This approach enlarged the volume of interaction between the sample and the laser beam, thus increasing the number of ions formed by multiphoton ionization. The sensitivity obtained using this technique was compared with that obtained using a previous method based on the off-axis sample introduction technique with detection limits for organic hydrocarbons at the subfemtogram level. The detection limit was examined for dioxins and an improvement of 2.5 ± 0.4 fold was found. The technique developed herein is applicable for practical ultratrace analysis of persistent organic pollutants.

Rapid analysis of persistent organic pollutants by solid phase microextraction in serum samples.

A simple and rapid headspace solid-phase microextraction (HS SPME) based method is presented for the determination of Persistent Organic Pollutants (POPs) in human serum by gas chromatography (GC) coupled to mass detector (MS) with electron impact ionization (EI). As an outcome of the assessment of several polymer phases; the one with the best result was the PDMS fiber (100 μm). A multivariate analysis of variance by permutations (PERMANOVA) was performed to establish the optimal extraction conditions as a function of temperature and time variables. The results were 1 mL serum+200 µL H2SO4 9M+1 mL of deionized water at 600 rpm with a temperature of 80°C for 50 min to expose the fiber. The limits of detection (LOD) for POPs pesticides fell within the 0.22-5.41 ng/mL interval, and within 0.07-1.79 ng/mL for PCBs; a linear method was used with correlation coefficients (r) higher than 0.99. Recovery percentages at low concentrations (15 ng/mL) were 67.8-120.2%, and at high concentrations (75 ng/mL) 80.2-119.2%. Evaluated precision as percentage Relative Standard Deviation (RSD%) of repeatability and reproducibility was within a range of 0.5-9% and 0.3-21%, respectively. This analytical method prevents some of the main problems for quantifying POPs in human serum, such as the elimination of the solvents, sample handling, integration of extraction steps, pre-concentration and introduction of samples; consequently, the time and cost of analyzing the sample can be significantly reduced. The method developed was applied to determine exposure to POPs in samples of children living in different polluted sites in Mexico. In children living in indigenous communities results show exposure to DDE (median 29.2 ng/mL range 17.4-52.2 ng/mL) and HCB (median 2.53 ng/mL range 2.50-2.64 ng/mL); whereas in the industrial scenario, exposure to HCB (median 2.81 ng/mL range 2.61-3.4 ng/mL) and PCBs (median Σ-PCBs 22.2 ng/ml range 8.2-74.6 ng/mL) and finally in petrochemical scenario was demonstrated exposure to HCB (median 2.81 ng/mL range 2.61-3.4 ng/mL) and PCBs (Σ-PCBs median 7.9 ng/mL range 5.4-114.5 ng/mL).

Ecological and spatial factors drive intra- and interspecific variation in exposure of subarctic predatory bird nestlings to persistent organic pollutants

Top predators in northern ecosystems may suffer from exposure to persistent organic pollutants (POPs) as this exposure may synergistically interact with already elevated natural stress in these ecosystems. In the present study, we aimed at identifying biological (sex, body condition), ecological (dietary carbon source, trophic level) and spatial factors (local habitat, regional nest location) that may influence intra- and interspecific variation in exposure of subarctic predatory bird nestlings to polychlorinated biphenyl 153 (CB 153), polybrominated diphenyl ether 47 (BDE 47), dichlorodiphenyldichloroethylene (p,p′-DDE) and hexachlorobenzene (HCB). During three breeding seasons (2008–2010), we sampled body feathers from fully-grown nestlings of three ecologically distinct predatory bird species in subarctic Norway: Northern Goshawk (Accipiter gentilis), White-tailed Eagle (Haliaeetus albicilla) and Golden Eagle (Aquila chrysaetos). The present study analysed, for the first time, body feathers for both POPs and carbon (δ13C) and nitrogen (δ15N) stable isotopes, thus integrating the dietary carbon source, trophic level and POP exposure for the larger part of the nestling stage.Intraspecific variation in exposure was driven by a combination of ecological and spatial factors, often different for individual compounds. In addition, combinations for individual compounds differed among species. Trophic level and local habitat were the predominant predictors for CB 153, p,p′-DDE and BDE 47, indicating their biomagnification and decreasing levels according to coast>fjord>inland. Variation in exposure may also have been driven by inter-annual variation arisen from primary sources (e.g. p,p′-DDE) and/or possible revolatilisation from secondary sources (e.g. HCB). Interspecific differences in POP exposure were best explained by a combination of trophic level (biomagnification), dietary carbon source (food chain discrimination) and regional nest location (historical POP contamination).In conclusion, the combined analysis of POPs and stable isotopes in body feathers from fully-grown nestlings has identified ecological and spatial factors that may drive POP exposure over the larger part of the nestling stage. This methodological approach further promotes the promising use of nestling predatory bird body feathers as a non-destructive sampling strategy to integrate various toxicological and ecological proxies.

Enhanced Electrochemical Sensing for Persistent Organic Pollutants by Nanohybrids of Graphene Nanosheets that are Noncovalently Functionalized with Cyclodextrin

AbstractUsing 3,4,9,10‐perylene tetracarboxylic acid as a bridge to connect mono(6‐ethanediamine‐6‐deoxy)‐β‐cyclodextrin (NH2‐β‐CD) to the surface of graphene, noncovalently functionalized graphene nanosheets (CD‐PTCA‐GNs) are synthesized for the first time. The as‐prepared CD‐PTCA‐GNs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, atomic force microscopy, and electrochemical methods. The electrocatalytic activities toward several persistent organic pollutants (POPs) at the glassy carbon (GC) electrode modified with CD‐PTCA‐GNs were investigated, all of which show a remarkable increase in electrochemical performance relative to the bare GC and GNs/GC electrodes. 1‐aminonaphthalene (1‐NA) was used as the representative analyte to demonstrate the sensing performance of the CD‐PTCA‐GNs. The results show that the linear response range of 1‐NA is 10–550 nM with the detection limit of 1.0 nM (S/N=3), thus implying that the CD‐PTCA‐GNs organic–inorganic nanohybrids will have promising applications in POPs analysis and as sensors.

Analysis of Persistent Organic Pollutants in Sediments of the Wanzhou Section of the Yangtze River

Organochlorine pesticides and polychlorinated biphenyls content can be obtained By measuring Wanzhou of the Yangtze River and Wanzhou Zhuxi River in sediment : Sediment content of organochlorine pesticides and polychlorinated biphenyls are increased the river down. Organochlorine pesticides in sediments are β-HCH> δ-HCH> α-HCH> γ-HCH, and pp'-DDE> pp '-DDD> op'-DDT> pp'-DDT. Organochlorine pesticides and PCBs of Wanzhou of the Yangtze River sediment in the distribution of the sampling points are similar characteristics. The main source of pollution is the direct discharge of industrial wastewater, agricultural pollution and soil erosion of farmland. Although OCPs and PCBs in water environment are very low, the impact on human health can not be ignored. Therefore certain measures are taken to clean emissions from industrial wastewater and agricultural non-point source pollution control.

Analysis of Persistent Organic Pollutants at Sub-Femtogram Levels Using a High-Power Picosecond Laser for Multiphoton Ionization in Conjunction with Gas Chromatography/Time-of-Flight Mass Spectrometry

A low-energy, high-repetition-rate picosecond laser (40 µJ, 20 kHz, 258 nm) was used for multiphoton ionization (MPI) in gas chromatography/time-of-flight mass spectrometry to quantitatively determine dioxins (DXNs) and polycyclic aromatic hydrocarbons (PAHs). The sensitivity of the technique was compared with that obtained using a high-energy, low-repetition-rate femtosecond laser (86 µJ, 1 kHz, 261 nm). The limits of detection (LODs) for the picosecond laser were several femtograms for chlorinated DXNs with low numbers of chloro substituents, and were several times lower than values obtained using a femtosecond laser, although the LODs were increased, reaching values that were nearly identical to those for the femtosecond laser for octachlorodibenzo-p-dioxin (octaCDD) and octachlorodibenzofuran (octaCDF). The LODs were also measured for 16 PAHs specified by the United States Environmental Protection Agency; the values for half of these compounds were at sub-femtogram levels. The procedure was used to analyze a surface-water sample collected from a river.

Determination of persistent organic pollutants by gas chromatography/laser multiphoton ionization/time-of-flight mass spectrometry

An authentic mixture of polychlorinated biphenyls was measured using a short wide-bore capillary column for the group separation of major components present in an actual sample of Kanechlor. The limits of detection were improved by ca. 2 fold in comparison with those obtained using a conventional capillary column, since the retention time was reduced and the amount of analytes introduced into the mass spectrometer per unit time could be increased. On the other hand, surface-water and sediment samples containing polycyclic aromatic hydrocarbons (PAHs) were collected from the river located in the vicinity of a waste water treatment plant. Even acenaphthylene, a minor component of the mixture could be measured for the sediment sample, and the concentrations were determined for several heavy PAHs. As demonstrated, a technique involving laser multiphoton ionization/time-of-flight mass spectrometry was useful as a sensitive and selective analytical tool for the trace analysis of persistent organic pollutants in an environmental sample.

Association Between Type 2 Diabetes and Exposure to Persistent Organic Pollutants

OBJECTIVEThe prevalence of type 2 diabetes is increasing alarmingly in both developed and developing countries. Recently, exposure to persistent organic pollutants (POPs) has been associated with the prevalence of type 2 diabetes. The purpose of this cross-sectional study is to examine the association between type 2 diabetes and POP exposure in the Helsinki Birth Cohort Study.RESEARCH DESIGN AND METHODSThe cohort consists of 8,760 people born in Helsinki during 1934–1944, before the global POP emission peak. In 2003, a clinical examination was performed, including blood sampling for laboratory analyses of serum lipids and POPs. Complete data from the examination were available for 1,988 participants. The concentrations of each POP were categorized into four groups on the basis of percentile intervals, and logistic regression was performed to examine diabetes prevalence across the POP categories, adjusting for sex, age, waist circumference, and mean arterial pressure and using the lowest category as the reference group.RESULTSAmong the participants with the highest exposure to oxychlordane, trans-nonachlor, 1,1-dichloro-2,2-bis-(p-chlorophenyl)-ethylene (p,p’-DDE, and polychlorinated biphenyl 153, the risk of type 2 diabetes was 1.64–2.24 times higher than that among individuals with the lowest exposure (Plin = 0.003–0.050, where Plin is the P value for linear trend across POP categories). In the stratified analysis, the associations between type 2 diabetes and oxychlordane and trans-nonachlor remained significant and were strongest among the overweight participants. Exposure to 2,2′,4,4′-tetrabromodiphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromodiphenyl ether (BDE 153) was not associated with type 2 diabetes.CONCLUSIONSThis study confirms the association between type 2 diabetes and adult-only exposure to organochlorine pesticides in a general urban population.

A routine accredited method for the analysis of polychlorinated biphenyls, organochlorine pesticides, chlorobenzenes and screening of other halogenated organics in soil, sediment and sludge by GCxGC-μECD

The analysis of persistent organic pollutants is a real challenge due to the large number of compounds with varying chemical and physical properties. Gas chromatography with electron capture detection or mass spectrometry has been the method of choice for the past 50 years. Comprehensive two-dimensional gas chromatography (GCxGC) coupled with micro-electron capture detector (μECD) is a new method that can analyze polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs) and chlorobenzenes (CBz) in a single analytical run with enhanced selectivity and sensitivity over single column methods and can also be used to screen for other halogenated organics in environmental samples. An accredited routine method using commercially available LECO GCxGC-μECD and a column combination DB-1 × Rtx-PCB has been developed to analyse PCBs/OCs/CBz in soils, sediments and sludges. The method provides quantification of Aroclors and Aroclor mixtures to within 15% of target values and sub-nanogrammes per gramme detection limits.

Development of Rapid Pretreatment Method Using Microwave-Assisted Extraction with Biphasic Organic-Aqueous System for Analysis of Persistent Organic Pollutants in Soil

Development of Rapid Pretreatment Method Using Microwave-Assisted Extraction with Biphasic Organic-Aqueous System for Analysis of Persistent Organic Pollutants in Soil

Fractionation of persistent organic pollutants in fish oil by high-performance liquid chromatography on a 2-(1-pyrenyl)ethyl silica column

The analysis of persistent organic pollutants in foodstuffs has become necessary for control of their levels in products for human and animal consumption. These analytical procedures usually require a fractionation step in order to separate the different families of pollutants to avoid interferences during the instrumental determination. In this study the separation was carried out on a 2-(1-pyrenyl)ethyl silica column, where analyte fractionation was based on differences in planarity and aromaticity. The fractionation of several types of persistent organic pollutants found in fish oil samples was studied; the pollutants included polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls, polybrominated diphenyl ethers, and some organochlorine pesticides. Fractions were analyzed by high-resolution gas chromatography with electron-capture detection and high-resolution gas chromatography-high resolution mass spectroscopy. Finally, the whole method (including the purification, fractionation, and instrumental determination steps) was validated and successfully applied to the analysis of several samples of fish oil.

Risk‐based analysis of polychlorinated biphenyl toxicity in harbor seals

Persistent organic pollutants (POPs) have been associated with adverse health effects in marine mammals. However, the complex mixtures to which free-ranging populations are exposed constrain the elucidation of cause-and-effect relationships between specific POPs and the observed health risks. In this study, we 1) assembled data from studies showing polychlorinated biphenyl (PCB)-associated effects on the health of free-ranging harbor seals in the northeastern Pacific Ocean, 2) carried out additional POP analyses on seal samples to broaden the available data on contaminant residues, and 3) derived estimates of individual POPs and their toxic risks. Taken together, these components were used to generate a new toxicity reference value (TRV) for the protection of marine mammal health. In this case study of seals in British Columbia, Canada, and Washington State, USA, PCBs were the single most abundant POP and were correlated with several adverse health effects. PCB exposures consistently exceeded regulatory toxicity thresholds for fish-eating wildlife. Nursing seal pups were at particular risk, reflecting their greatly increased dietary intake of PCBs and their sensitivity to developmental toxicity. Based on the collective evidence obtained, we propose TRVs (consisting of 5% tissue residue concentration and dose) of 1.3 mg/kg lipid weight tissue residue in blubber and 0.05 mg/kg lipid weight tolerable daily intake in prey. Insofar as the TRVs are lower than previously established TRVs and regulatory guidelines, our study highlights the current underestimation of risks associated with PCBs in high-trophic-level wildlife.

Automated Analysis of Persistent Organic Pollutants in the Gas Phase by Laser Ionization Mass Spectrometry

Persistent organic pollutants (POPs) are toxic chemicals that adversely affect human health and the environment around the world. The detection and evaluation of small amounts of POPs require methods with both high precision and high chemical selectivity. Conventional methods involve a number of preparatory steps and time-consuming analysis and are not suitable for the abovementioned purposes. Hence, new automated analysis methods are required for on-line detection and rapid analysis of POPs. In this paper, mass spectrometry with resonance-enhanced multi-photon ionization (REMPI) is performed to obtain information about the automated analysis of POPs in the gas-phase with on-line detection. Dynamic trapping time-of-flight mass spectrometry (TOFMS) was performed with sufficient selectivity and sensitivity for rapid analysis of polychlorinated biphenyls (PCBs) in the gas phase. Compared to normal trapping, the use of dynamic trapping enabled ion signal intensity to be increased by a factor of greater than 10. The detection limit at 1 min was <1 ppbV, and the accuracy also correlated well with the results of conventional analysis. Based on these results, an automated monitoring system was developed for automated analysis of PCBs. It was confirmed that this monitoring system was capable of analyzing PCB concentration without being influenced by main gas components or various coexisting substances, even under conditions characterized by exhaust gas and the work environment atmosphere. PCB concentration in PCB waste plants, which is substantially lower than the 0.10 mg/m3N specified in statutory regulations, could be analyzed within 1 min. It was possible to make continuous long-term analysis for over 2,000 h (120,000 points).