Results of WEPAL-QUASIMEME/NORMANs first global interlaboratory study on microplastics reveal urgent need for harmonization.

To survey the conformity and quality of results among laboratories for microplastics determination worldwide, an international laboratory intercomparison and development exercise was organized. The 34 participants were requested to determine the polymer type and number or mass of polymer particles in 12 samples, i.e. six samples containing of pre-production pellets, five dissolvable soda tablets containing different (smaller) polymer particles and one blank soda tablet. A novel method for providing the test materials in aluminium strips was used. Thirty laboratories (88%) submitted data using their own method of choice, resulting in a variety of identification and quantification methods (n = 7). The majority of the labs (53-100%) correctly identified the type of polymer in all samples but one. The performance of the laboratories in quantifying and weighing the pellets was very good. The analysis of the number of the particles in the soda tablets varied considerably between laboratories (29-91%). The results of this study highlight the complexity of microplastics analysis and the need for harmonization of both reporting format and methods. Continued development and assessment of the comparability among analytical methods and laboratories are urgently needed to support monitoring programmes, research and decision-making.

The association between p,p'-DDE levels and left ventricular mass is mainly mediated by obesity.

BACKGROUND AND OBJECTIVES: The pesticide metabolite p,p'-DDE has been associated with left ventricular (LV) mass and known risk factors for LV hypertrophy in humans and in experimental models. We hypothesized that the associations of p,p'-DDE with LV hypertrophy risk factors, namely elevated glucose, adiposity and hypertension, mediate the association of p,p'-DDE with LV mass. METHODS: p,p'-DDE was measured in plasma from 70-year-old subjects (n = 988) of the Prospective Study of the Vasculature in Uppsala Seniors (PIVUS). When these subjects were 70-, 75- and 80- years old, LV characteristics were measured by echocardiography, while fasting glucose, body mass index (BMI) and blood pressure were assessed with standard clinical techniques. RESULTS: We found that p,p'-DDE levels were associated with increased fasting glucose, BMI, hypertension and LV mass in separate models adjusted for sex. Structural equation modeling revealed that the association between p,p'-DDE and LV mass was almost entirely mediated by BMI (70%), and also by hypertension (19%). CONCLUSION: The obesogenic effect of p,p'-DDE is a major determinant responsible for the association of p,p'-DDE with LV mass.

Per- and polyfluorinated compounds (PFCs) in house dust and indoor air in Catalonia, Spain: implications for human exposure.

A total of 27 per- and polyfluorinated compounds (PFCs) were determined in both house dust (n=10) and indoor air (n=10) from selected homes in Catalonia, Spain. Concentrations were found to be similar or lower than those previously reported for household microenvironments in other countries. Ten PFCs were detected in all house dust samples. The highest mean concentrations corresponded to perfluorodecanoic acid (PFDA) and perfluorononanoic acid (PFNA), 10.7 ng/g (median: 1.5 ng/g) and 10.4 ng/g (median: 5.4 ng/g), respectively, while the 8:2 fluorotelomer alcohol (FTOH) was the dominating neutral PFC at a concentration of 0.41 ng/g (median: 0.35 ng/g). The indoor air was dominated by the FTOHs, especially the 8:2 FTOH at a mean (median) concentration of 51 pg/m(3) (median: 42 pg/m(3)). A limited number of ionic PFCs were also detected in the indoor air samples. Daily intakes of PFCs were estimated for average and worst case scenarios of human exposure from indoor sources. For toddlers, this resulted in average intakes of ∑ionic PFCs of 4.9ng/day (0.33 ng/kg(bw)/day for a 15 kg toddlers) and ∑neutral PFCs of 0.072 ng/day (0.005 ng/kg(bw)/day) from house dust. For adults, the average daily intakes of dust were 3.6 and 0.053 ng/day (0.05 and 0.001 ng/kg(bw)/day for a 70 kg adult) for ∑ionic and ∑neutral PFCs, respectively. The average daily inhalation of ∑neutral PFCs was estimated to be 0.9 and 1.3 ng/day (0.06 and 0.02 ng/kg(bw)/day) for toddlers and adults, respectively. For PFOS, the main ionic PFC detected in indoor air samples, the median intakes (based on those samples where PFOS was detected), resulted in indoor exposures of 0.06 and 0.11 ng/day (0.004 and 0.002 ng/kg(bw)/day) for toddlers and adults, respectively. Based on previous studies on dietary intake and drinking water consumption, both house dust and indoor air contribute significantly less to PFC exposure within this population.

Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment.

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm(3). In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.

Uncertainty assessment of polychlorinated dibenzo-p-dioxins and dibenzofuran and dioxin-like polychlorinated biphenyl analysis in stationary source sample emissions in accordance with the impending European standard EN-1948 using fly ashes.

The analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) present in stack gas emissions and solid residues from incinerators will be mandatory in the foreseeable future. European standard EN-1948 is in the process of being updated through the addition of a new Part 4 related to the analysis of the 12 dl-PCBs. Therefore, either a comprehensive and reliable method capable of analyzing all of these 29 compounds (12 dl-PCBs and 17 2,3,7,8-PCDD/Fs) needs to be developed, or the existing PCDD/F analytical procedure must be adapted to include the dl-PCBs. This study has taken the latter approach of modifying PCDD/F methodology and in particular the fractionation step, by isolating dioxins and dl-PCBs into separate fractions ready for high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC/HRMS) analysis. Results obtained from the analysis of Certified Reference Materials (CRM-490 and CRM-615) and fly ashes from the European Committee for Standardization (CEN) intercalibration study demonstrated that the proposed methodology is appropriate to determine the dl-PCBs in accordance with the impending European standard EN-1948. Uncertainty values obtained during the validation of the analytical methodology were 13% total I-TEQ (International Toxic Equivalent) for PCDD/Fs and 31% total WHO-TEQ (World Health Organization Toxic Equivalent) in the case of dl-PCBs. In addition, 'real' samples such as emissions and fly ashes were successfully analyzed following the proposed analytical method.

Determination of 2,4,6-trichloroanisole and 2,4,6-tribromoanisole in wine using microextraction in packed syringe and gas chromatography-mass spectrometry.

A selective and fast method for the quantitative determination of 2,4,6-trichloroanisole (TCA) and 2,4,6-tribromoanisole (TBA) in wine was developed. Microextraction in packed syringe (MEPS) was optimized for the extraction and preconcentration of the analytes using extremely small volume samples (0.1-1 mL). For GC-EI-MS, the limit of detection (LOD) for red and white wine was in the range 0.17-0.49 microg L(-1) for TCA and TBA. In addition to GC-EI-MS both GC-NCI-MS and GC-HRMS were used to further improve both selectivity and sensitivity. The lowest LODs were achieved using GC-HRMS in the EI mode. In red and white wine samples the LODs were between 0.22-0.75 ng L(-1) for TCA and TBA. The reproducibility and linearity for the GC-HRMS method was good, with RSD-values of 4-10% for spiked red wine samples at 1 ng L(-1) and linearity with R (2) > 0.962 over a concentration range of 1 to 100 ng L(-1).

Multivariate characterisation and quantitative structure-property relationship modelling of nitroaromatic compounds.

A multivariate model to characterise nitroaromatics and related compounds based on molecular descriptors was calculated. Descriptors were collected from literature and through empirical, semi-empirical and density functional theory-based calculations. Principal components were used to describe the distribution of the compounds in a multidimensional space. Four components described 76% of the variation in the dataset. PC1 separated the compounds due to molecular weight, PC2 separated the different isomers, PC3 arranged the compounds according to different functional groups such as nitrobenzoic acids, nitrobenzenes, nitrotoluenes and nitroesters and PC4 differentiated the compounds containing chlorine from other compounds. Quantitative structure-property relationship models were calculated using partial least squares (PLS) projection to latent structures to predict gas chromatographic (GC) retention times and the distribution between the water phase and air using solid-phase microextraction (SPME). GC retention time was found to be dependent on the presence of polar amine groups, electronic descriptors including highest occupied molecular orbital, dipole moments and the melting point. The model of GC retention time was good, but the precision was not precise enough for practical use. An important environmental parameter was measured using SPME, the distribution between headspace (air) and the water phase. This parameter was mainly dependent on Henry's law constant, vapour pressure, logP, content of hydroxyl groups and atmospheric OH rate constant. The predictive capacity of the model substantially improved when recalculating a model using these five descriptors only.

United Nations Environment Programme Capacity Building Pilot Project--training and interlaboratory study on persistent organic pollutant analysis under the Stockholm Convention.

Within the framework of a United Nations Environment Programme (UNEP) Capacity Building Project for training of laboratory staff in developing countries on persistent organic pollutant (POP) analysis, an interlaboratory study was organised following an initial evaluation of the performance of laboratories (reality check) and a series of training sessions. The target compounds were polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP). Seven laboratories from five countries (Ecuador, Uruguay, Kenya, Moldova, and Fiji) participated. Most of the laboratories had no experience in determining PCBs. Although chromatograms improved considerably after the training and installation of new gas chromatographic (GC) columns at participating laboratories, the level of performance in the interlaboratory study was essentially on par with the moderate performance level achieved by European POP laboratories in the 1980s. Only some individual results were within +/-20% of the target values. The relative standard deviations (R.S.D.s) in POP concentrations determined by laboratories in a sediment sample were >200% in a number of cases. The results for a certified herring sample were better with at least some R.S.D. values below 50% and most below 100%. Clean up was as one of the main sources of error. After inspection it was ascertained that training of laboratory staff and investments in simple consumables such as glassware and GC columns would help to improve the quality of the analysis more than major investments in expensive instrumentation. Creating an effective network of POP laboratories at different continents together with a series of interlaboratory studies and workshops is suggested to improve the measurements of POPs in these countries.

Analysis of nitroaromatic compounds in complex samples using solid-phase microextraction and isotope dilution quantification gas chromatography-electron-capture negative ionisation mass spectrometry.

A solid-phase microextraction (SPME) method using gas chromatography-electron-capture negative ionisation mass spectrometry (GC-ECNI-MS) and isotope dilution quantification for the analysis of nitroaromatic compounds in complex, water based samples has been optimised. For ionisation, ECNI was the most sensitive and selective method. SPME was compared to solid-phase extraction (SPE) and found to be more sensitive for these small volume samples. LODs were in the range 0.02-38ngL(-1) for SPME and 6-184ngL(-1) for SPE, respectively. The SPME method was applied on samples in the ngL(-1) level from artificial reed beds treated with sludge containing residues from explosives and pharmaceuticals.

Levels of brominated flame retardants in blood in relation to levels in household air and dust.

Levels of tri- to decabrominated diphenyl ethers (BDEs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and 1,2-bis(pentabromophenyl)ethane (DeBDethane) were determined in air, sedimentary dust and human plasma from five households in Sweden. The levels of the individual BDEs in the plasma samples were in the same order of magnitude as in other studies of the general population in Scandinavia, and varied between non-detectable (<0.41 ng g(-1) l.w.) to 17 ng g(-1) (l.w.). BDE#28 and #47 were present in all air samples, with mean values of 0.015 and 0.12 ng m(-3), respectively, except for one sample where the BDE#47 concentration was below the limit of detection (<0.17 ng m(-3)). BDE#209 was found in one of the five air samples at a concentration of 0.26 ng m(-3). DeBDethane was also detected in one sample, in which the BDE#209 level was below LOD (<0.021 ng m(-3)), at a level of 0.023 ng m(-3). All the target compounds were found in the sedimentary dust samples at levels from 0.51 to 1600 ng g(-1), the highest concentration representing BDE#209. The most abundant components in plasma, air and dust were BDE#47, #99 and #209. In the plasma samples BDE#207 and #206 were also present at similar concentrations as BDE#47. In the sedimentary dust samples, DeBDethane was also among the most abundant BFRs. A positive relationship was found for the sumBDE concentrations in dust and plasma, although the relationship was strongly dependent on one of the five observations. BFR levels in dust and air were not dependent on the house characteristics such as living area, floor material or number of electronic devices.

Environmental contaminants in arctic foxes (Alopex lagopus) in Svalbard: relationships with feeding ecology and body condition.

Adipose tissues from 20 arctic foxes (Alopex lagopus) of both sexes from Svalbard were analysed for polybrominated diphenyl ether (PBDE), polychlorinated biphenyl (PCB), p,p'-dichlorodiphenyltrichloroethane (DDE), chlordane, and hexachlorobenzene (HCB) concentrations. Gender (0.43

Levels of brominated flame retardants in Northern Fulmar (Fulmarus glacialis) eggs from the Faroe Islands.

Eggs from Northern Fulmars (Fulmarus glacialis) were sampled in the Faroe Islands. The content of the brominated flame retardants tri- to decabromodiphenyl ethers (BDEs) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were determined in nine samples in concentrations ranging from non-detectable to 7 ng g-1(l.w.). The BDE levels were similar as in an earlier study of BDE levels in the fulmar eggs from the Faroe Islands but 10-1000 times lower compared to studies of eggs from seabirds and birds of prey from Europe. The two hexaBDEs #153 and #154 were the most abundant congeners, which represented around 50% of the total mean BDE concentration. The levels of BDE #209 were below the limit of detection (1.24 ng g-1 l.w.) except for one sample, which showed a concentration of 7.18 ng g-1 l.w. BTBPE was detected in eight samples and the mean level was 0.11 ng g-1 l.w. This concentration was 150 times lower than the average total BDE concentration (including BDEs #28, #47, #100, #99, #154, #153, #183, #209). BTBPE has only been detected once before in biota. Also other bromo-containing compounds were detected in the fulmar eggs. One group identified was the polybrominated biphenyls (PBBs), but because of the absence of reference standards in the lab, these could not be quantified.

Determination of 2,4,6-trichloroanisole and 2,4,6-tribromoanisole on ng L-1 to pgL-1 levels in wine by solid-phase microextraction and gas chromatography-high-resolution mass spectrometry.

A gas chromatography-high-resolution mass spectrometry (GC-HRMS) method using solid-phase microextraction (SPME) for the determination of 2,4,6-trichloroanisole (TCA) and 2,4,6-tribromoanisole (TBA) in wine at low ng L(-1) levels was developed. A robust SPME method was developed by optimizing several different parameters, including type of fiber, salt addition, sample volume, extraction and desorption time. The quantification limit for TCA and TBA in wine was lowered substantially using GC-HRMS in combination with the optimized SPME method and allowed the detection of low analyte concentrations (ng L(-1)) with good accuracy. Limits of quantification for red wine of 0.3 ng L(-1) for TCA and 0.2 ng L(-1) for TBA with gas chromatography-negative chemical ionization mass spectrometry and 0.03 ng L(-1) for TCA and TBA were achieved using GC-HRMS. The method was applied to 30 wines of which 4 wines were sensorically qualified as cork defected. TCA was found in three of these wines with concentrations in the range 2-25 ng L(-1). TBA was not detected in any of the samples.

Accumulation, metabolism, and food-chain transfer of chlorinated and brominated contaminants in subadult white whales (Delphinapterus leucas) and narwhals (Monodon monoceros) from Svalbard, Norway.

The concentrations and patterns of polychlorinated biphenyls (PCBs), chlorinated pesticides, and polybrominated diphenyl ethers (PBDEs) were studied in white whales (Delphinapterus leucas) and narwhals (Monodon monoceros) from Svalbard, Norway. In addition, their main food items were included in the study. In the whales, a broad range of pollutants was found in relatively high concentrations. PCBs and pesticides were approximately 3000 and 8000 ng/g lipid, respectively, for white whales and three times higher for narwhals. PBDEs 47 were approximately 70 ng/g lipid for white whales and 170 ng/g lipid for narwhals. Compared with other marine mammals from the same area, contaminant levels are among the highest levels ever measured. These high levels are likely in part because of a decreased capacity to metabolize contaminants. Metabolic indices indicated that most compounds accumulate to the same degree in white whales and narwhals, but for some toxaphenes and chlordanes, narwhals might have a decreased metabolism and consequently a higher accumulation. The three-times-higher contaminant levels in blubber of narwhals was further explained by substantially higher contaminant levels in their more benthic diet. The high levels and broad pattern of accumulating pollutants make white whales and narwhals excellent indicators for a wide range of contaminants in the Arctic.

Polybrominated diphenyl ethers--plasma levels and thyroid status of workers at an electronic recycling facility.

OBJECTIVES: Personnel working with electronic dismantling are exposed to polybrominated diphenyl ethers (PBDEs), which in animal studies have been shown to alter thyroid homeostasis. The aim of this longitudinal study was to measure plasma level of PBDEs in workers at an electronic recycling facility and to relate these to the workers' thyroid status. METHODS: PBDEs and three thyroid hormones: triiodothyronine (T(3)), thyroxin (T(4)) and thyroid stimulating hormone (TSH) were repeatedly analysed in plasma from 11 workers during a period of 1.5 years. RESULTS: Plasma levels of PBDEs at start of employment were <0.5-9.1 pmol/g lipid weight (l.w.). The most common congener was PBDE #47 (median 2.8 pmol/g l.w.), followed by PBDE #153 (median 1.7 pmol/g l.w.), and PBDE #183 had a median value of <0.19 pmol/g l.w. After dismantling the corresponding median concentrations were: 3.7, 1.7 and 1.2 pmol/g l.w., respectively. These differences in PBDE levels were not statistically significant. PBDE #28 showed a statistically significantly higher concentration after dismantling than at start of employment (P=0.016), although at low concentrations (start 0.11 pmol/g l.w. and dismantling 0.26 pmol/g l.w.). All measured levels of thyroid hormones (T(3), T(4) and TSH) were within the normal physiological range. Statistically significant positive correlations were found between T(3) and #183 in a worker, between T(4) and both #28 and #100 in another worker and also between TSH and #99 and #154 in two workers. CONCLUSIONS: The workers' plasma levels of PBDEs fluctuated during the study period. Due to small changes in thyroid hormone levels it was concluded that no relevant changes were present in relation to PBDE exposure within the workers participating in this study.

Polybrominated diphenylethers and methoxylated tetrabromodiphenylethers in cetaceans from the Mediterranean Sea.

Eight tetrabrominated to hexabrominated diphenylethers were present at ppb levels in liver from cetaceans found stranded on the beaches of the Mediterranean Sea, Italy. The highest concentration was found in striped dolphin (sum polybrominated diphenyl ethers [PBDE] 8133 ng/g l.w.) and the lowest concentration in bottlenose dolphin (sum PBDE 66 ng/g lipid weight [l.w.]). The predominant congener in all samples was 2,2',4,4'-tetraBDE (PBDE # 47) followed by, in decreasing order, the pentaPBDE # 99 and 100 and the hexaPBDE # 154 and 153. In 12 of the 14 analyzed samples, 3 different methoxylated PBDEs (MeO-PBDE # 1, 2, and 3) were detected at semiquantitatively calculated concentration ranges of 2 to 14 ng/g l.w.; 5 to 167 ng/g l.w.; and 7 to 628 ng/g l.w., respectively. In addition, several unidentified bromine compounds were seen when screening the samples in negative-chemical ionization (NCI) mode monitoring m/z 79 and 81, which illustrates the importance of running both electron-impact ionization and NCI when analyzing environmental samples. Electron-impact ionization is more specific for monitoring the molecular ion compared with NCI, which might overestimate the concentration of certain PBDE congeners.

Degradation of toxaphene in water during anaerobic and aerobic conditions.

The degradation of technical toxaphene in water with two kinds of bioreactors operating in sequence was studied. One packed bed reactor was filled with Poraver (foam glass particles) running at anaerobic conditions and one suspended carrier biofilm reactor working aerobically. Chemical oxygen demand (COD), chloride, sulphate, pH, dissolved oxygen, total toxaphene and specific toxaphene isomers were measured. After 6 weeks approx. 87% of the total toxaphene was degraded reaching 98% by week 39. The majority of the conversion took place in the anaerobic reactor. The concentrations of toxaphene isomers with more chlorine substituents decreased more rapidly than for isomers with less chlorine substituents.

Case-control study on concentrations of organohalogen compounds and titers of antibodies to Epstein-Barr virus antigens in the etiology of non-Hodgkin lymphoma.

A rapid increase in incidence of non-Hodgkin lymphoma (NHL) has been reported from many countries. Exposure to certain pesticides and organochlorines has been shown to be risk factors. Epstein-Barr virus (EBV) is a human herpesvirus that has been associated with some subgroups of NHL, such as Burkitt lymphoma and lymphomas related to severe immunosuppression. In this study, we measured lipid adjusted blood concentrations of 36 congeners of polychlorinated biphenyls (PCBs), p,p'-dichlorodiphenyl-dichloroethylene (p,p'-DDE), hexachlorobenzene (HCB), four different subgroups of chlordanes (trans-nonachlordane, cis-nonachlordane, MC6 and oxychlordane) and 2,2',4,4'-tetrabrominated diphenyl ether (TBDE) in incident cases of NHL and controls from the general population. Titers of antibodies to the Epstein-Barr early antigen (EA) were correlated to concentrations of organochlorines. We found a significant difference in lipid adjusted blood concentrations of total PCBs and TBDE between cases and controls. Titers of antibodies to EA IgG > 80 were correlated to an increased risk for NHL with odds ratio (OR) = 1.9, 95% confidence interval (CI) =0.94-3.8. This risk was further increased in those with a level above the median value of "sum of PCBs" (OR=4.0, CI=1.2-14), HCB (OR=5.3, CI=1.6-19), sum of chlordanes (OR=4.0, CI=1.2-14) and TBDE (OR=21, CI=4.6-124), suggesting an interaction between EBV and a higher concentration of these chemicals. Also for the "sum of immunotoxic PCBs" increased risk was found in that group (OR=6.4, CI=1.9-24). Subdivision of NHL in histological types yielded highest risks for low-grade B-cell NHL.

Adipose tissue concentrations of dioxins and dibenzofurans, titers of antibodies to Epstein-Barr virus early antigen and the risk for non-Hodgkin lymphoma.

A rapid increase in the incidence of non-Hodgkin lymphoma (NHL) has been reported in many countries. Exposure to certain pesticides or organochlorines has been shown to be a risk factor. Epstein-Barr virus (EBV) is a human herpesvirus that has been associated with some subgroups of NHL, such as Burkitt lymphoma and lymphomas related to severe immunosuppression. In this study we measured concentrations of dioxins and dibenzofurans in 33 NHL cases and 39 surgical controls. For 23 of the cases and 32 of the controls EBV titers were also available. Median titer of antibodies to EBV early antigen (EA) IgG was higher in patients than in controls. Concentrations of dioxins and dibenzofurans were divided into two groups according to the median concentration for the controls. Unconditional logistic regression analysis was performed adjusting for sex, age, and body mass index. For several higher chlorinated congeners increased risk was found for patients in the high-concentration and high-titer group. For toxic equivalency factor >27.79 and EA>80 an odds ratio of 2.8 with 95% confidence interval 0.52-18 was calculated. These results indicated that current exposure to certain organochlorines in combination with EBV might increase the risk for NHL.