Is current generation of polychlorinated biphenyls exceeding peak production of the 1970s?

Polychlorinated biphenyls (PCBs) are man-made chemicals that were once widely produced as commercial mixtures for various industrial applications. PCBs were later recognized as environmental pollutants and health hazards, leading to their global phase-out and strict regulations on their production, use, and disposal. Most investigations on PCBs focus on measuring the specific PCBs present in commercial mixtures or marker compounds representing those mixtures. However, there are new sources of PCBs that are gaining more attention. These 'by-product PCBs' are inadvertently produced in certain chemical and product formulations. Our estimates show that U.S. legislation currently permits the generation of more by-product PCBs (~100 million lb. (~45,000 Tonnes) per year) than during peak commercial production of the 1970s (85 million lb. (~39,000 Tonnes) per year). These PCBs are currently going un-detected in most investigations. Therefore, they may be a posing a growing, unmonitored environmental and human health risk. Most people assume PCBs to be legacy pollutants from historically formulated commercial mixtures. However, our research suggests that due to the emergence of by-product PCBs they may need to be reconsidered as an emerging pollutant of concern.

Polychlorinated biphenyl (PCB) half-lives in humans: A systematic review.

This manuscript presents a systematic review of PCB half-lives reported in the scientific literature. The review was completed in accordance with PRISMA guidelines and included a review of almost 1000 peer-reviewed publications. In total, 26 articles were found to report half-lives in humans, with the majority of data coming from studies performed in North America on individuals suspected to have been exposed to PCBs. Terminology for reporting PCB half-lives was inconsistent, so we have attempted to consolidate this and recommend using either "apparent half-life" or "intrinsic half-life" in future studies. Within the literature, values for reported half-lives varied considerably for different PCBs. Less chlorinated PCBs generally have shorter half-lives than more chlorinated PCBs. It was interesting to note the large variability of half-lives reported for the same PCB. For example, the reported half-life for PCB 180 varied by nearly 3 orders of magnitude (0.34 years-300 years). Our review identified that the half-lives estimated were largely dependent on the studied cohort. We discuss the importance of PCB body burden, degree of chlorination and PCB structure, gender, age, breastfeeding, BMI, and smoking status on half-life estimations. We also identified significantly shorter half-lives for some PCBs in occupationally exposed individuals compared to results reported from the general population. PCB half-lives are not the same for every PCB or every individual. Therefore, careful consideration is needed when these values are used in human exposure studies.

Source apportionment of polychlorinated biphenyls (PCBs) using different receptor models: A case study on sediment from the Portland Harbor Superfund Site (PHSS), Oregon, USA.

Multivariate modelling techniques are used by a wide variety of investigations in environmental chemistry. It is surprisingly rare for studies to show a detailed understanding of uncertainties created by modelling or how uncertainties in chemical analysis impact model outputs. It is common to use untrained multivariate models for receptor modelling. These models produce a slightly different output each time they are run. The fact that a single model can provide different results is rarely acknowledged. In this manuscript, we attempt to address this by investigating differences that can be generated using four different receptor models (NMF, ALS, PMF & PVA) to perform source apportionment of polychlorinated biphenyls (PCBs) in surface sediments from Portland Harbor. Results showed that models generally had a strong agreement and identified the same main signatures that represented commercial PCB mixtures, however, subtle differences were identified by; different models, same models but with a different number of end members (EM), and the same model with the same number of end members. As well as identifying different Aroclor-like signatures, the relative proportion of these sources also varied. Depending on which method is selected it may have a significant impact on conclusions of a scientific report or litigation case and ultimately, allocation on who is responsible for paying for remediation. Therefore, care must be taken to understand these uncertainties to select a method that produces consistent results with end members that can be chemically explained. We also investigated a novel approach to use our multivariate models to identify inadvertent sources of PCBs. By using a residual plot produced from one of our models (NMF) we were able to suggest the presence of approximately 30 different potentially inadvertently produced PCBs which account for 6.6 % of the total PCBs in Portland Harbor sediments.

A review of the mechanisms of by-product PCB formation in pigments, dyes and paints.

There has been an increased awareness of paints and pigments as a source of by-product PCBs in the environment. The majority of existing work has focused only on reporting the presence of the main PCBs in different products with a specific focus on the most PCB congeners, PCB11 and PCB209. This gives the impression that only a handful of PCBs are found in paints. However, this is not the case. PCB profiles in paints and pigments can be just as complex as commercial technical mixtures. This review identified the presence of 149 different PCBs in paint samples. For reference, only 141 different PCBs have been reported in all of the 5 main commercial Aroclor formulations (A1016, A1242, A1248, A1254 (early & late) and A1260). The total PCB concentrations in some paint samples can be substantial, with concentrations as high as 919 mg kg-1 reported in azo pigments. When trying to identify sources of PCBs in the environment, pigments, dyes and paints are often overlooked. In this manuscript, we have compiled congener profiles from 140 different samples from the available scientific literature and presented this in the supplementary information as valuable resource for others to use in source identification applications. We have also proposed detailed mechanisms for the formation of PCBs in pigments, dyes and paints. In many cases, the PCB congeners predicted by these mechanisms provide an excellent match for what has been observed in the scientific literature. We have also identified several additional classes of pigments that are expected to contain PCBs but have yet to be verified by experimental data.

Polychlorinated biphenyl (PCB) concentrations and profiles in marine mammals from the North Atlantic Ocean.

Polychlorinated biphenyls (PCBs) can provide crucial information into the bioaccumulation and biomagnification of POPs in marine mammals. Muscle tissue samples were obtained for detailed PCB congener specific analysis of all 209 PCBs in 11 species of marine mammals stranded across the coast of the UK between 2010 and 2013. At least 145 PCB congeners were found in each individual. The highest concentrations of PCBs were recorded in a killer whale (318 mg/kg lipid) and the highest toxic equivalent in a Risso's dolphin (1687 pg/g TEQ2005 wet). Concentrations of PCBs in the majority of samples exceeded toxic thresholds (9 mg/kg lipid) for marine mammals, highlighting the health risk they face from PCB exposure. Many PCB profiles did not fit typical 'Aroclor' signatures, but instead indicated patterns of congeners that are resistant to biotransformation and elimination. However, this study identified a novel PCB signature in a sei whale that has not yet been previously observed in marine mammals. The whale had a PCB profile that included lighter and inadvertent PCB congeners such as PCB 11, suggesting that the main source of exposure was through atmospheric deposition, rather than terrestrial discharges. Seven subsamples were chosen for chiral analysis of PCB 95, 136 and 149. The enantiomer fractions (EFs) of C-PCBs 95 and 149 were non racemic suggesting there may be enantiomer selective metabolism in marine mammals. Although there has been a shift in the literature towards emerging pollutants, this study acts as a stark reminder that PCBs continue to pose a significant risk to wildlife.

Comparison of different approaches to quantify substituted polycyclic aromatic compounds.

Unlike native polycyclic aromatic hydrocarbons (PAHs), quantitation of substituted polycyclic aromatic compounds (PACs) has been a challenge in the environmental industry. The challenge can be attributed in part to the large number of theoretically possible isomers and the lack of authentic standards for quantitation. In addition, the lack of a unified approach to the quantitation of these compounds has led to poor interlaboratory accuracy. Because these compounds are often used for toxicology studies or to delineate sources and fingerprinting, it is vital that a standardized approach to quantify them is established. This study evaluated different quantitation approaches to quantify both 16 individual PACs and 32 groups/clusters of substituted PACs in three standard reference materials (SRM 1944 - New York / New Jersey waterway sediments, SRM 1597 - a coal tar sample and SRM 2779 - Gulf of Mexico crude oil). The methods employed include: (1) external calibration taking into account recovery correction factor for each analyte, (2) an average relative response factor (ARRF) of PACs obtained with a recovery correction, (3) ARRF of PACs obtained using uncorrected peak areas (i.e., no recovery correction), (4) ARRF of PACs calculated by normalization to deuterated PAHs and (5) ARRF of native PAHs to quantify substituted PACs. The evaluation of concentrations of individually substituted PACs from the different quantitative approaches compared to the certified/reference values showed that methods 1, 2 and 3 performed best. The average percentage of compounds that fell within our acceptable limit (±30%) using methods 1, 2 and 3 for SRM-1944, -1597a and -2779 was 87, 75 and 100%, respectively. Using native PAHs to quantify their substituted analogs resulted in data of the poorest quality. Irrespective of the approach used, there were significant systematic errors in measurements on clusters/groups PACs most notably C1 and C2-benzanthracenes/ chrysenes/triplenylenes, and C2- and C3-dibenzothiophenes being consistently greater than 100% of the stated value. Commerical availability of more substituted PACs will mitigate the biases associated with the quanititation of PAC clusters/groups.

Evaluation of the effectiveness of different indicator PCBs to estimating total PCB concentrations in environmental investigations.

Polychlorinated biphenyls (PCBs) are one of the most widely studied group of persistent organic pollutants (POPs). There are 209 different PCBs, however not all 209 can currently be individually quantified in one analytical run. This means that a subset of PCBs congeners are often determined and reported. Some of the most commonly reported subsets are the 7 indicator PCBs (28, 52, 101, 118, 138, 153 and 180) and the WHO 12 PCBs (77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169 and 189). The WHO 12 congeners are co-planar 'dioxin like' PCBs that are effective for establishing health risks. The 7 indicator PCBs were selected as some of the most common PCBs across the compositional range of the most common technical mixtures (such as Aroclors), and are used to give an indication of the total PCB concentrations. These groups of indicator PCBs were established several decades ago. However, in the environment commercial mixtures are subject to weathering and fractionation processes, and additional sources of non-Aroclor PCBs are also becoming more important. In this manuscript we use existing large scale comprehensive congener specific datasets to evaluate the effectiveness of indicator PCBs to predict total concentrations and establish if they are still fit for purpose. The results indicate that while these traditional indicators are a useful tool to estimate total concentrations in humans with background exposure there are many instances where they are not fit for purpose and can lead to significant under predictions in total PCB concentrations in environmental matrices.

Comprehensive two-dimensional gas chromatography high-resolution mass spectrometry for the analysis of substituted and unsubstituted polycyclic aromatic compounds in environmental samples.

Polycyclic aromatic compounds (PACs) consists of multiple compounds and the number of theoretically possible isomers can reach into the thousands. Currently each PAC group is quantified collectively as a single group of compounds. However, individual PACs can reveal important information on how the PACs were formed and this information may be used to determine sources of PACs in environmental samples, It is hypothesized that many of the limitations with characterizing alkylated PACs with one dimensional gas-chromatography (1D GC) can be circumvented using GC × GC (two dimensional gas chromatography). Here we apply comprehensive GCxGC coupled to high-resolution time of flight mass spectrometry (GC × GC-HFTOF-MS) to aid in the separation, identification and quantitation of APACs in three environmental matrices: mussel tissue (Mytilus edulis), lubricating oil and coal. In the absence of authentic analytical standards, differences in the mass spectral fragmentation pattern of isomers were used to confirm the identity of isomers within a PAC group. The method was validated according to the EURACHEM guidelines and used to quantify a biological standard reference material (SRM 2974a). The method met all the standard method performance requirements such as trueness, precision and measurement of uncertainty and is fit for quantifying these compounds in biota. Furthermore, the method was used to identify and quantify additional PAC compounds in the SRM 2974a material which to date have not been certified. With appropriate statistical analytical tools, the described GC × GC method can be used as a tool for more robust source fingerprinting and source apportionment of PACs in the environment.

Snapping Turtles (Chelydra serpentina) from Canadian Areas of Concern across the southern Laurentian Great Lakes: Chlorinated and brominated hydrocarbon contaminants and metabolites in relation to circulating concentrations of thyroxine and vitamin A.

The metabolites of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), as well as other halogenated phenolic contaminants (HPCs) have been shown to have endocrine-disrupting properties, and have been reported with increasing frequency in the blood of wildlife, and mainly in mammals and birds. However, little is known about the persistence, accumulation and distribution of these contaminants in long-lived freshwater reptiles. In the present study, in addition to a large suite of chlorinated and brominated contaminants, metabolites and HPCs, we assessed and compared hydroxylated (OH) PCBs and OH-PBDEs relative to PCBs and PBDEs, respectively, in the plasma of adult male common snapping turtles (Chelydra serpentina). Blood samples were collected from 62 snapping turtles (2001-2004) at 12 wetland sites between the Detroit River and the St. Lawrence River on the Canadian side of the Laurentian Great Lakes of North America. Turtles were sampled from sites designated as Areas of Concern (AOCs) and from a relatively clean reference site in southern Georgian Bay (Tiny Marsh), Lake Huron. Plasma concentrations of Σ46PCB (10-340 ng/g wet weight (ww)) and Σ28OH-PCB (3-83 ng/g ww) were significantly greater (p<0.05) in turtles from the Turkey Creek and Muddy Creek-Wheatley Harbour sites in Lake Erie compared with the reference site turtles. The HPC, pentachlorophenol (PCP), had a mean concentration of 9.6±1.1 ng/g ww. Of the 28 OH-CB congeners screened for, 4-OH-CB187 (42±7 ng/g ww) was the most concentrated of all HPCs measured. Of the 14 OH-BDE congeners examined, four (4'-OH-BDE17, 3-OH-BDE47, 5-OH-BDE47 and 4'-OH-BDE49) were consistently found in all plasma samples. p,p'-DDE was the most concentrated of the 18 organochlorine pesticides (OCPs) examined. The mean concentrations of circulating total thyroxine (TT4), dehydroretinol and retinol in the plasma of the male snapping turtles regardless of sampling site were 5.4±0.3, 81±4.7 and 291±13 ng/mL, respectively. Significant (p<0.05) negative (e.g. cis-chlordane) or positive (e.g. BDE-99) correlations between some of the target contaminants and TT4, dehydroretinol or retinol were observed. To our knowledge, we report for the first time on HPC (e.g. OH-PCBs) and methylsulfonyl- (MeSO2-) PCB metabolite contaminants in the plasma of any freshwater turtle or freshwater reptilian species. Our findings also show that the accumulation of OH-PCBs, MeSO2-PCBs, OH-PBDEs and some OCPs in the snapping turtles from Lake Erie and Lake Ontario (in 2001-2004) had the potential for eliciting endocrine disruption. Exposure to these contaminants and associated adverse effects on the endocrine system in freshwater reptiles and the related mechanisms require further investigation.

Elucidating the structural properties that influence the persistence of PCBs in humans using the National Health and Nutrition Examination Survey (NHANES) dataset.

In human exposure studies involving Polychlorinated Biphenyls (PCBs), it is useful to establish when an individual was potentially exposed. Age dating PCB exposure is complex but assessments can be made because different PCB congeners have different residence times in the human body. The less chlorinated congeners generally tend to have shorter residence times because they are biotransformed and eliminated faster than more chlorinated congeners. Therefore, the presence of high proportions of less chlorinated congeners is often indicative of recent exposure. The 2003-04 National Health and Nutrition Examination Survey (NHANES) dataset contains results for the concentration of 37 PCBs in a sub-sample of the US population. Multivariate statistical analysis of the NHANES data showed that less chlorinated congeners are not always biotransformed faster than higher chlorinated compounds. For example, PCB 28 (a tri-chlorobiphenyl) appears to be more resistant to biotransformation than PCB 101 and 110 (penta-chlorobiphenyls). Using statistical analysis of the NHANES data in conjunction with previously published studies on PCB persistence in humans, it was possible to identify the structural relationships that determine if a PCB is likely to be from a recent exposure (termed 'episodic') or from steady state exposure. Congeners with chlorine atoms in the 2,5- and 2,3,6-positions appear to be more susceptible to biotransformation whereas congeners with chlorine bonds in the 2,3,4- 2,4,5- 3,4,5- and 2,3,4,5-positions appear to be more persistent. This work shows that future investigations to date PCB exposure would benefit from the analysis of a wide range of congeners, including the selection of key congeners based not only on the degree of chlorination but also on the positions of the chlorine atoms on the biphenyl.

Thyroid hormone levels of pregnant inuit women and their infants exposed to environmental contaminants.

BACKGROUND: An increasing number of studies have shown that several ubiquitous environmental contaminants possess thyroid hormone-disrupting capacities. Prenatal exposure to some of them, such as polychlorinated biphenyls (PCBs), has also been associated with adverse neurodevelopmental effects in infants. OBJECTIVES: In this study we examined the relationship between exposure to potential thyroid hormone-disrupting toxicants and thyroid hormone status in pregnant Inuit women from Nunavik and their infants within the first year of life. METHODS: We measured thyroid hormone parameters [thyroid stimulating hormone (TSH), free thyroxine (fT(4)), total triiodothyronine (T(3)), thyroxine-binding globulin (TBG)] and concentrations of several contaminants [PCB-153, hydroxylated metabolites of PCBs (HO-PCBs), pentachlorophenol (PCP) and hexachlorobenzene (HCB)] in maternal plasma at delivery (n = 120), in umbilical cord plasma (n = 95), and in infant plasma at 7 months postpartum (n = 130). RESULTS: In pregnant women, we found a positive association between HO-PCBs and T(3) concentrations (beta = 0.57, p = 0.02). In umbilical cord blood, PCB-153 concentrations were negatively associated with TBG levels (beta = -0.26, p = 0.01). In a subsample analysis, a negative relationship was also found between maternal PCP levels and cord fT(4) concentrations in neonates (beta = -0.59, p = 0.02). No association was observed between contaminants and thyroid hormones at 7 months of age. CONCLUSION: Overall, there is little evidence that the environmental contaminants analyzed in this study affect thyroid hormone status in Inuit mothers and their infants. The possibility that PCP may decrease thyroxine levels in neonates requires further investigation.

Concentration and profile of 22 urinary polycyclic aromatic hydrocarbon metabolites in the US population.

Urinary monohydroxy polycyclic aromatic hydrocarbons (OH-PAHs) are a class of PAH metabolites used as biomarkers for assessing human exposure to PAHs. The Centers for Disease Control and Prevention's National Health and Nutrition Examination Survey (NHANES) uses OH-PAHs to establish reference range concentrations for the US population, and to set benchmarks for future epidemiologic and biomonitoring studies. For the years 2001 and 2002, 22 OH-PAH metabolites were measured in urine specimens from 2748 NHANES participants. Percentages of samples with detectable levels ranged from nearly 100% for metabolites of naphthalene, fluorene, phenanthrene, and pyrene, to less than 5% for metabolites from parent compounds with higher molecular weight such as chrysene, benzo[c]phenanthrene, and benz[a]anthracene. The geometric mean for 1-hydroxypyrene (1-PYR)--the most commonly used biomarker for PAH exposure--was 49.6 ng/L urine, or 46.4 ng/g creatinine. Children (ages 6-11) generally had higher levels than did adolescents (ages 12-19) or adults (ages 20 and older). Model-adjusted, least-square geometric means for 1-PYR were 87, 53 and 43 ng/L for children, adolescents (ages 12-19) and adults (ages 20 years and older), respectively. Log-transformed concentrations for major detectable OH-PAHs were significantly correlated with each other. The correlation coefficients between 1-PYR and other metabolites ranging from 0.17 to 0.63 support the use of 1-PYR as a useful surrogate representing PAH exposure.

Plasma concentrations of selected organobromine compounds and polychlorinated biphenyls in postmenopausal women of Québec, Canada.

BACKGROUND: Brominated flame retardants, especially polybrominated diphenyl ethers (PBDEs), have been widely used in North America, but little is known about the level of exposure of human populations to these compounds. OBJECTIVES: We set out to assess the internal exposure of postmenopausal Canadian women to selected organobromine compounds and to investigate factors associated with this exposure. METHODS: We measured concentrations of four PBDEs, one polybrominated biphenyl, and for comparative purposes, 41 polychlorinated biphenyl (PCB) congeners in plasma samples from 110 healthy postmenopausal women who were recruited at a mammography clinic in 2003-2004. RESULTS: PBDE-47 was the major PBDE congener, with a mean (geometric) concentration of 8.1 ng/g lipids and extreme values reaching 1,780 ng/g. By comparison, the mean concentration of the major PCB congener (PCB-153) was 41.7 ng/g and the highest value was 177 ng/g. PBDEs 47, 99, and 100 were strongly intercorrelated, but weaker correlations were noted with PBDE-153. As the sum of PBDEs (summation operatorPBDEs) increased, the relative contribution of PBDE-47 to the summation operatorPBDEs increased, whereas that of PBDE-153 decreased. PBDE-153 was the only brominated compound correlated to PCB-153. PBDE levels were not linked to any sociodemographic, anthropometric, reproductive, or lifestyle variables documented in the present study. Age and body mass index gain since the age of 18 years were significant predictors of PCB-153 plasma levels. CONCLUSION: Our results suggest that exposure to PBDE-47 likely occurs through direct contact with the penta-PBDE formulation, whereas exposure to PBDE-153 may originate in part from the food chain.

Automated solid-phase extraction method for measuring urinary polycyclic aromatic hydrocarbon metabolites in human biomonitoring using isotope-dilution gas chromatography high-resolution mass spectrometry.

In order to perform comprehensive epidemiological studies where multiple metabolites of several PAHs are measured and compared in low-dose urine samples, fast and robust methods are needed to measure many analytes in the same sample. We have modified a previous method used for measuring polycyclic aromatic hydrocarbon (PAH) metabolites by automating the solid-phase extraction (SPE) and including an additional eight metabolites. We also added seven new carbon-13 labeled standards, which improves the use of isotope-dilution calibration. Our method included enzyme hydrolysis, automated SPE and derivatization with a silylating reagent followed by gas chromatography (GC), coupled with high-resolution mass spectrometry (HRMS). Using this method, we measured 23 metabolites, representing 9 parent PAHs, with detection limits in the low pg/mL range. All steps in the clean-up procedure were optimized individually, resulting in a method that gives good recoveries (69-93%), reproducibility (coefficient of variation for two quality control pools ranged between 4.6 and 17.1%, N>156), and the necessary specificity. We used the method to analyze nearly 3000 urine samples in the fifth National Health and Nutrition Examination Survey (NHANES 2001-2002).

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis.

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.

A reassessment of the nomenclature of polychlorinated biphenyl (PCB) metabolites.

Polychlorinated biphenyls (PCBs) are a widespread class of persistent organic chemicals that accumulate in the environment and humans and are associated with a broad spectrum of health effects. PCB biotransformation has been shown to lead to two classes of PCB metabolites that are present as contaminant residues in the tissues of selected biota: hydroxylated (HO) and methyl sulfone (MeSO2) PCBs. Although these two types of metabolites are related structures, different rules for abbreviation of both classes have emerged. It is important that a standardized nomenclature for the notation of PCB metabolites be universally agreed upon. We suggest that the full chemical name of the PCB metabolite and a shorthand notation should be adopted using the International Union of Pure and Applied Chemistry's chemical name/original Ballschmiter and Zell number of the parent congener, followed by the assignment of the phenyl ring position number of the MeSO2- or HO-substituent. This nomenclature provides a clear, unequivocal set of rules in naming and abbreviating the PCB metabolite structure. Furthermore, this unified PCB metabolite nomenclature approach can be extended to the naming and abbreviation of potential metabolites of structurally analogous contaminants such as HO-polybrominated biphenyls and HO-polybrominated diphenyl ethers.

New high-resolution mass spectrometric approach for the measurement of polychlorinated biphenyls and organochlorine pesticides in human serum.

To increase our analytical throughput for measuring polychlorinated biphenyls (PCBs) and organochlorine (OC) pesticides without sacrificing data quality, we have developed and validated a combined PCB/OC pesticide gas chromatography-high-resolution mass spectrometry (GC-HRMS) analysis. In a single GC-HRMS analysis, both selected PCBs and OC pesticides are detected and quantified. Previously, this has been difficult, if not impossible, because of the major difference in masses of the most abundant electron-impact ions. However, we have identified slightly less abundant ions to monitor that allow us to successfully combine these analytes into a single analysis without sacrificing any analytical sensitivity or instrument reliability. Consequently, we have been able to double our analytical throughput by modification of mass spectrometric parameters alone. Our new methodology has been validated against our current GC-HRMS method, which entails using two separate injections, one for PCB analysis and one for OC pesticide analysis. The two methods differ by less than 4% overall, with no systematic bias. We used this method to analyze approximately 350 serum samples over a period of several months. We found that our new method was as reliable in automated, overnight runs as our current method.

Comprehensive solid-phase extraction method for persistent organic pollutants. Validation and application to the analysis of persistent chlorinated pesticides.

The Centers for Disease Control and Prevention (CDC) is involved in many epidemiological studies regarding the measurement of chlorinated pesticides and polychlorinated biphenyls in specimens obtained from humans. In addition to these commonly determined analytes, there is a need to include additional persistent organic pollutants (POPs) in our analyses, which further stresses the analyses because sample volumes remain small. Thus, a single method of analysis for all POPs in human serum is needed. CDC has recently developed a semiautomated and comprehensive solid-phase extraction method for POPs. The method is comprehensive since it was optimized for the extraction of many different POP compound classes. We then developed a purification and fractionation scheme that allows (a) separation of different compound classes by particular functionalities and (b) purification of those fractions to remove coextracted interferences. This paper describes the first step in the semiautomated comprehensive extraction and multiple fractionation method developed by CDC for monitoring POPs. In this paper, we validate the analysis of the persistent chlorinated pesticides, a compound class difficult to examine because of their structural diversity, in human plasma. The method was validated against an existing CDC method by using a spiked quality-control serum pool. The concentrations determined for all analytes using both methods were within 2%-14% relative standard deviations. A multilevel (i.e., 3-4 point) matrix spike showed good linearity for the analytes tested (r2 = 0.978-0.999). The method was then applied to 40-year-old archived plasma samples for the quantitative analysis of selected chlorinated pesticides. Mean recoveries of the 13C-labeled internal quantification standards ranged from 64% to 123% for the 11 monitored pesticides. The overall method proved to be robust by handling old coagulated plasma samples. It allowed faster throughput of samples than our previous methods and provided cleaner samples with less frequent interferences or background as analyzed by high-resolution mass spectrometry. The method represents a preliminary step in establishing an automated, comprehensive multiresidue analysis method for POPs in human serum.

Pentachlorophenol and hydroxylated polychlorinated biphenyl metabolites in umbilical cord plasma of neonates from coastal populations in Québec.

Concentrations of polychlorinated biphenyls (PCBs), hydroxylated metabolites of PCBs (HO-PCBs) and octachlorostyrene (4-HO-HpCS), and pentachlorophenol (PCP) were determined in umbilical cord plasma samples from three different regions of Québec. The regions studied included two coastal areas where exposure to PCBs is high because of marine-food-based diets--Nunavik (Inuit people) and the Lower North Shore of the Gulf of St. Lawrence (subsistence fishermen)--and a southern Québec urban center where PCB exposure is at background levels (Québec City). The main chlorinated phenolic compound in all regions was PCP. Concentrations of PCP were not significantly different among regions (geometric mean concentration 1,670 pg/g, range 628-7,680 pg/g wet weight in plasma). The ratio of PCP to polychlorinated biphenyl congener number 153 (CB153) concentration ranged from 0.72 to 42.3. Sum HO-PCB (sigma HO-PCBs) concentrations were different among regions, with geometric mean concentrations of 553 (range 238-1,750), 286 (103-788), and 234 (147-464) pg/g wet weight plasma for the Lower North Shore, Nunavik, and the southern Québec groups, respectively. Lower North Shore samples also had the highest geometric mean concentration of sum PCBs (sum of 49 congeners; sigma PCBs), 2,710 (525-7,720) pg/g wet weight plasma. sigma PCB concentrations for Nunavik samples and southern samples were 1,510 (309-6,230) and 843 (290-1,650) pg/g wet weight plasma. Concentrations (log transformed) of sigma HO-PCBs and sigma PCBs were significantly correlated (r = 0.62, p < 0.001), as were concentrations of all major individual HO-PCB congeners and individual PCB congeners. In Nunavik and Lower North Shore samples, free thyroxine (T4) concentrations (log transformed) were negatively correlated with the sum of quantitated chlorinated phenolic compounds (sum PCP and sigma HO-PCBs; r = -0.47, p = 0.01, n = 20) and were not correlated with any PCB congeners or sigma PCBs. This suggests that PCP and HO-PCBs are possibly altering thyroid hormone status in newborns, which could lead to neurodevelopmental effects in infants. Further studies are needed to examine the effects of chlorinated phenolic compounds on thyroid hormone status in newborns.