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.

Microbead beating extraction of avian eggs for polycyclic aromatic compounds.

Due to their relatively high trophic position and importance as a food source for many communities in the circumpolar north, seabird eggs are an important matrix for monitoring contaminant levels. In fact, many countries, including Canada, have established long-term seabird egg contaminant monitoring programs, with oil related compounds a contaminant of emerging concern for seabirds in several regions. Current approaches to measuring many contaminant burdens in seabird eggs are time-consuming and often require large volumes of solvent. Here we propose an alternative approach, based on the principle of microbead beating tissue extraction using custom designed stainless-steel extraction tubes and lids, to measure a suite of 75 polycyclic aromatic compounds (polycyclic aromatic hydrocarbons (PAHs), alkyl-PAHs, halogenated-PAHs and some heterocyclic compounds) comprising a wide-range of chemical properties. Our method was conducted in strict accordance with ISO/IEC 17025 guidelines for method validation. Accuracies for our analytes generally ranged from 70 - 120%, and intra and inter-day repeatability for most analytes were < 30%. Limits of detection/quantitation for the 75 target analytes were < 0.2/0.6 ng g-1. The level of contamination in our method blanks was significantly smaller in our stainless-steel tubes/lids relative to commercially available high-density plastic alternatives. Overall, our method meets our data quality objectives and results in a notable reduction in sample processing times relative to current approaches.

Polycyclic aromatic compound and trace metal element residues in Mytilus mussels at marine wildlife hotspots on the Pacific coast of Canada.

The Pacific coast of Canada has a rich marine fauna and a growing human population with increasing potential for pollution releases, but there is currently little overlap between marine wildlife hotspots and ongoing biomonitoring efforts for less bioaccumulative contaminants such as polycyclic aromatic compounds (PAC) and trace metals (metals). We surveyed PACs and metals at marine bird breeding colonies in coastal British Columbia in 2018 by analyzing chemical residues in the soft tissue of bivalve Mytilus sp. mussels collected from stations (n = 3) at seven sites. The concentration of sum PACs (∑43PAC) and high molecular weight (HMW) PACs were highest at the Second Narrows colony in Vancouver Harbour, a highly urbanized and industrialized port within the Salish Sea. For conservation areas, two Salish Sea and three Pacific Ocean coast colonies, PACs were generally lower. However, ∑43PAC, ∑HMWPAC, and several HMW congeners at the remote site of Triangle Island, a Marine National Wildlife Area, were not significantly different from Second Narrows. The dominant PAC sources at all sites are likely pyrogenic rather than petrogenic, as suggested by PAC profiles, proportion of parent PACs, and source-indicator congeners. For metals, site differences were found for seven out of eight priority metals, but principal component analysis indicated that site differences, such as high mercury and cadmium at offshore sites, are likely related to environmental and biological variables including salinity, condition index, water temperature, and shell length. Our survey across a broad coastal region shows that PAC and metal biomonitoring programs with mussels should include wildlife hotspots where the exposure of protected vertebrate species to pollutants with low bioaccumulation potential would be less obvious, and shows that collection of data on key covariates (e.g. lipid content, salinity) will be critical to tracking long-term trends and detecting pollution release events.

Decadal differences in polycyclic aromatic compound (PAC) concentrations in two seabird species in Arctic Canada.

Seabirds are exposed to a variety of environmental contaminants in the Arctic. While the persistence, bioaccumulation, and toxicity of some groups of contaminants have been well-studied in seabirds since the 1970s, there is less known about polycyclic aromatic compounds (PACs). With increased vessel traffic, and potential oil and gas development in the Arctic region, there is a need to understand existing PAC exposure in biota against which to compare potential effects of anticipated increases of PACs in the marine region. Thick-billed murres (Uria lomvia) and northern fulmars (Fulmarus glacialis) collected in the Baffin Bay - Davis Strait region during the International Polar Year (IPY; 2007-08), and during a recent Strategic Environmental Assessment (2018; SEA) were examined for hepatic PAC concentrations. We found that fulmars generally had higher concentrations of PACs than the murres, but murres and fulmars sampled in 2007/08 had higher concentrations of most groups of PACs compared to birds from 2018. The one exception to this pattern was that the sum of the alkylated congeners of the heterocyclic aromatic compounds containing a sulfur atom (dibenzothiophene; ΣAHET) was significantly higher in murres in the more recent sampling period (2018) as compared to 2007/08. ΣAHETs likely reflect recent exposure to more refined petroleum products associated with small boats, such as diesel, gasoline and motor oil. This work highlights the need for longitudinal studies on PAC concentrations in biota for us to gain a better understanding of how Arctic biota are exposed to this group of contaminants, and the potential deleterious effects associated with PACs.

Effects of diluted bitumen exposure on the survival, physiology, and behaviour of zebra finches (Taeniopygia guttata).

Diluted bitumen (dilbit) is an unconventional crude petroleum increasingly being extracted and transported to market by pipeline and tanker. Despite the transport of dilbit through terrestrial, aquatic, and coastal habitat important to diverse bird fauna, toxicity data are currently only available for fish and invertebrates. We used the zebra finch (Taeniopygia guttata) as a tractable, avian model system to investigate exposure effects of lightly weathered Cold Lake blend dilbit on survival, tissue residue, and a range of physiological and behavioural endpoints. Birds were exposed via oral gavage over 14-days with dosages of 0, 2, 4, 6, 8, 10, or 12 mL dilbit/kg bw/day. We identified an LD50 of 9.4 mL/kg/d dilbit, with complete mortality at 12 mL/kg/d. Mortality was associated with mass loss, external oiling, decreased pectoral and heart mass, and increased liver mass. Hepatic ethoxyresorufin-O-deethylase activity (EROD) was elevated in all dilbit-dosed birds compared with controls but there was limited evidence of sublethal effects of dilbit on physiological endpoints at doses < 10 mL/kg/d (hematocrit, hemoglobin, total antioxidants, and reactive oxygen metabolites). Dilbit exposure affected behavior, with more dilbit-treated birds foraging away from the feeder, more birds sleeping or idle at low dilbit doses, and fewer birds huddling together at high dilbit doses. Naphthalene, dibenzothiophene, and their alkylated congeners in particular (e.g. C2-napthalene and C2-dibenzothiophene) accumulated in the liver at greater concentrations in dilbit-treated birds compared to controls. Although directly comparable studies in the zebra finch are limited, our mortality data suggest that dilbit is more toxic than the well-studied MC252 conventional light crude oil with this exposure regime. A lack of overt sublethal effects at lower doses, but effects on body mass and composition, behaviour, high mortality, and elevated PAC residue at doses ≥ 10 mL/kg/d suggest a threshold effect.

Effects of Avian Eggshell Oiling With Diluted Bitumen Show Sublethal Embryonic Polycyclic Aromatic Compound Exposure.

Breeding birds that become oiled may contaminate the shells of their eggs, and studies of conventional crude oil suggest that even small quantities can be absorbed through the eggshell and cause embryotoxicity. Unconventional crude oils remain untested, so we evaluated whether a major Canadian oil sands product, diluted bitumen (dilbit), would be absorbed and cause toxicity when applied to eggshells of two species, domestic chicken (Gallus gallus domesticus) and double-crested cormorant (Nannopterum auritum). We artificially incubated eggs and applied lightly weathered dilbit (Cold Lake blend) to the eggshells (0.015-0.15 mg g-1 egg in chicken; 0.1-0.4 mg g-1 egg in cormorant) at various points during incubation before sampling prehatch embryos. Polycyclic aromatic compound (PAC) residue in cormorant embryos was elevated only at the highest dilbit application (0.4 mg g-1 egg) closest (day 16) to sampling on day 22. In contrast, cormorant liver cytochrome P450 1a4 (Cyp1a4) mRNA expression (quantitative polymerase chain reaction assay) was elevated only in embryos treated with the earliest and lowest dilbit application (0.1 mg g-1 egg on day 4). These results confirm that dilbit can cross through the eggshell and be absorbed by embryos, and they imply rapid biotransformation of PACs and a nonmonotonic Cyp1a4 response. Despite evidence of exposure in cormorant, we found no detectable effects on the frequency of survival, deformity, and gross lesions, nor did we find effects on physiological endpoints indicative of growth and cardiovascular function in either chicken or cormorant. In ovo dilbit exposure may be less toxic than well-studied conventional crude oils. The effects of an oil spill scenario involving dilbit to bird embryos might be subtle, and PACs may be rapidly metabolized. Environ Toxicol Chem 2022;41:159-174. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

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.

New approaches to reduce sample processing times for the determination of polycyclic aromatic compounds in environmental samples.

This study validates two approaches to streamlining the processing of sediment and biota for a suite of polycyclic aromatic compounds (PACs) with a wide range of chemical properties, including polycyclic aromatic hydrocarbons (PAHs) and alkyl-PAHs (APAHs), and a new class of environmental contaminants, halogenated PAHs (HPAHs). One method is based on one-step in situ extraction/cleanup using accelerated solvent extraction (ASE) in which a mixture of copper, deactivated alumina and silica gel were added directly to the ASE cell along with sample; the second technique is based on dispersive solid phase extraction (dSPE) using alumina/silica for cleanup of biota samples to augment conventional ASE extraction combined with gel permeation chromatography. Validation protocols were performed in accordance with the ISO/IEC 17025 guidelines, whereby method performance characteristics, i.e., accuracy, precision, linearity, limits of detection and ruggedness, were evaluated. Accuracies generally ranged from 70 to 120% for the in situ ASE method and 70-100% for the dSPE technique. Limits of detection/quantitation for the 45 target analytes for in situ ASE and dSPE methods were determined to be < 2.5/8 pg µL-1, and < 20/60 pg µL-1, respectively. Intra- and inter-day repeatability for both methods were < 25% except for 1 APAH which had an inter-day precision of 35% using the dSPE method. Neither method was affected by any of the purposeful changes attempted which implies that both methods are robust. Results of our validation studies showed excellent data quality for both methods in addition to achieving a reduction in sample processing times.

Co-exposures to trace elements and polycyclic aromatic compounds (PACs) impacts North American river otter (Lontra canadensis) baculum.

Environmental loadings of polycyclic aromatic compounds (PACs) and trace elements are increasing in areas with marked oil and gas extraction, such as in the Athabasca oil sands region, Alberta, Canada. Some of these chemicals are recognized as potent endocrine disrupting compounds (EDCs). The impacts of co-exposure to PACs and metals on free-ranging wildlife is of considerable concern. River otters (Lontra canadensis) are sentinel species of aquatic ecosystem health. The baculum (penile bone) is an important part of the reproductive system in otters that ensures successful copulation. Although baculum health is critical to male reproductive success and is sensitive to exposure to EDCs, there is no information available regarding the impact of PAC and metal exposures on measures of baculum health. River otter baculum and livers were dissected from carcasses obtained from the fur trade. Trace element and PAC analyses were carried out in liver with matching baculums subjected to dimensional analysis, bone mineral density (BMD) and mechanical loading testing. Trace elements and select PACs exhibited both protective and deleterious effects on baculum bone health metrics. Alkylated four ring PACs were negatively associated with baculum bone material properties (ex: C4-Chrysene and C4-pyrene). The same compounds have been shown to exhibit strong anti-androgenic activities. Few comparable studies exist related to contamination and adverse effects of PACs in wild terrestrial mammals. Baculum health metrics may be an important tool to include in biomonitoring studies as to date, there are limited means to assess male reproductive performance in wildlife biomonitoring programs.

Validated quantitative cannabis profiling for Canadian regulatory compliance - Cannabinoids, aflatoxins, and terpenes.

In response to the Canadian federal government's Cannabis Tracking and Licensing System compliance standards, a quantitative method was created for cannabis analysis, and validated using Eurachem V.2 (2014) guidelines. Cannabinol, cannabidiol, cannabigerol, cannabichromene, cannabidiolic acid, cannabigerolic acid, Δ-9-tetrahydrocannabinol, and Δ-9-tetrahydrocannabinolic acid A were all analysed by scheduled multiple reaction monitoring (MRM) via LC-MS/MS and isotope dilution. In addition, aflatoxins B1, B2, G1, and G2 were also analysed by scheduled MRM via LC-MS/MS and matrix matched calibration curves in order to achieve the reporting limits (≤2 µg kg-1) set out by the European Pharmacopoeia. The LODs/LOQs were 0.50/1.7, 2.0/6.7, 0.59/2.0, and 0.53/1.8 µg kg-1, for B1, B2, G1, and G2 respectively. Thirty one terpenes were analysed by selected reaction monitoring via GC-MS/MS and isotope dilution using ß-myrcene-d6 as a surrogate. All quantitative analyses can be accomplished using less than 1 g of material, with minimal solvent and consumable use, on low resolution instruments in less than 30 min of instrument time. Of important note is this method's power of selectivity, working ranges, and lack of need for extraction consumables such as SPE or QuEChERS, thereby minimising analytical costs and time.

Identification of halogenated polycyclic aromatic hydrocarbons in biological samples from Alberta Oil-Sands Region.

Halogenated polycyclic aromatic hydrocarbons (HPAHs) were identified in biological samples from the Alberta Oil-Sands Region (AOSR) using gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC-HRTOF-MS) at a resolving power of 25,000. Knowledge of the electron ionization (EI) fragmentation behavior of individual HPAH isomers, achieved by injecting authentic standards in full-scan MS mode, was paramount in identifying a suite of HPAHs in samples from the AOSR. Confirmation of compounds in biological samples was based on the measured mass accuracy (±3 ppm) of 2 characteristic ions prominent in the EI mass spectra of each compound. Numerous compounds were detected in the high resolution total ion chromatogram in liver extracts of 4 biological species from the AOSR: river otter (Lontra Canadensis), northern pike (Esox lucius), lake whitefish (Coregonus clupeaformis) and snails (Gastropod sp.) many of which remain unidentified. Careful examination of the high-resolution accurate mass data suggests that dichloro-anthracene/phenanthrene, bromo-anthracene/phenanthrene and dibromo-fluorene were present in the biological samples. Lipid corrected concentrations of dichloro-PAHs were estimated to be 16.3 ±â€¯11.4 (n = 4) and 5.5 (n = 1) ng/g in lake whitefish and river otter, respectively. Concentrations of mono-bromo-PAHs were an order of magnitude greater in snails (170.5 ng/g) than in northern pike (12.5 ng/g) while concentrations of dibromo-PAHs were 4 times greater in snails than in northern pike. The detection of these compounds in biota implies that these compounds are bioaccumulative. The liver-based biomagnification factor of the dichloro-PAH congener in the river otter/lake whitefish feeding relationship is much smaller than 1 implying that this compound does not biomagnify.

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.

Absorption of polycyclic aromatic hydrocarbons by a highly absorptive polymeric medium.

The efficacy of a lightly cross-linked polymeric bead to absorb polycyclic aromatic hydrocarbons (PAHs) from the surface of fresh- and salt-water in a simulated oil-spill scenario was assessed in this study. A layer of PAHs at the water surface was created by first preparing the PAHs in hexane and then carefully spiking this mixture onto the surface of water. Beads were then applied to the surface of the organic phase and the amount of hydrocarbons absorbed by the beads was examined at prescribed time intervals and at different temperatures. Absorption of PAHs into the beads was exhaustive with ∼86 ±â€¯4% being selectively removed from the organic phase by 120 s. First order reaction rates best described the uptake kinetics and absorption rates ranged from 0.0085 (naphthalene) to 0.0325 s-1 (dibenzo[a,h]anthracene). Absorption of PAHs into the beads was driven by molecular volume (A3). Uptake rates increased markedly for PAHs with molecular volumes between 130 A3 and 190 A3. Beyond this molecular volume there was no apparent change in the rate of uptake. This study shows that these polymeric beads have a high affinity for PAHs and can be used under various environmental conditions with negligible difference in absorptive efficacy.

Enumeration of the constitutional isomers of environmentally relevant substituted polycyclic aromatic compounds.

Polycyclic aromatic compounds (PACs) are a diverse group of environmentally relevant compounds which can be persistent, bioaccumulative and toxic. The cyclic backbone of PACs can be substituted with halogens or hydrocarbon chains. The amount and positions of these substituents influence their toxicity. For many classes of PACs, substitution creates mixtures containing large numbers of isomers. For example, 209 theoretical isomers of chlorinated biphenyls are possible. Many other classes of environmentally relevant PACs exist where the number of theoretical isomers are unknown. Here, a mathematical approach using molecular symmetry and the binomial coefficient is presented that determines the number of theoretical isomers of PACs. The approach was validated on PACs with known isomer numbers and then applied to PACs with unknown isomer numbers. When the approach was applied to alkylated polycyclic aromatic hydrocarbons, the possible theoretical isomers ranged from 2 for C1 naphthalene up to 19 502 for C6 dibenzo(ah)anthracene. Heterocyclic PACs had similar numbers ranging from 4 isomers for C1 dibenzothiophene to 13 938 for C6 dibenzo[a,i]carbazole. The work presented will aide analytical chemists and ecotoxicologists in their efforts to develop methods to measure these compounds, and in attempting to assess the toxicity and environmental fate of individual isomers.

Validation of a simultaneous method for determining polycyclic aromatic compounds and alkylated isomers in biota.

RATIONALE: There is a need for a validated method to improve detection limits and simultaneously quantify polycyclic aromatic compounds (PACs, both parent and alkylated homologues) in biota by gas chromatography/tandem mass spectrometry because of their environmental significance. The validation of the method was performed in accordance to the Eurachem Guide to Quality in Analytical Chemistry. METHODS: Gas chromatography coupled with a triple quadrupole mass spectrometer used in multiple reaction monitoring (MRM) mode was used for detection and quantification. Retention time windows and selective MRM ion transitions were optimized for a suite of PACs. The developed method was validated by comparing our measurements made on a reference material of freeze-dried mussel tissue (Mytilus edulis) with the certified values. RESULTS: Linearity was observed between 10-1000 pg/µL (PAHs) and 2-500 pg/µL (alkyl-PACs including S-based PACs). The overall mean (±SD) for the limits of detection of 43 PACs studied were 0.305 ± 0.276 and 2.69 ± 1.10 ng/g, respectively. For the 14 certified target analytes, the percent relative error ranged from 1.3 to 33%. With the exception of benzo(a)pyrene, the between-day and within-day repeatability for all target analytes was lower than 15% RSD. CONCLUSIONS: This is the first report of a fully validated method to simultaneously quantify PACs in biota performed in an ISO accredited laboratory.