A validated approach for analysis of heterocyclic aromatic compounds in sediment samples.

The scientific literature is replete with analytical methods for the analysis of homocyclic aromatic compounds especially polycyclic aromatic hydrocarbons and their alkylated analogs. However, there is a paucity of methods for the analysis of nitrogen-, sulfur- and oxygen-containing polycyclic aromatic compounds (PACs). The lack of commercially available analytical standards, the presence of many structural derivatives and isomers and lack of certified reference materials all contribute to the inherent challenges in measuring these compounds. Gas chromatography coupled with a tandem mass spectrometer was used to develop two multiple reaction monitoring methods to detect and quantify fifty-three non-halogenated and halogenated hetero-polycyclic aromatic compounds (HPACs). Because of their greater polarity, strongly non-polar solvents typically employed to extract homocyclic PACs from sediment samples did not yield acceptable recoveries of our target analytes. By adding ethyl acetate to dichloromethane (50:50), recoveries of our target analytes using accelerated solvent extraction increased markedly. The performance characteristics of the validated method including accuracy [> than 67% for 46 (out of 53) analytes], inter- and intra-day precision [<30% for all analytes, (expressed as relative standard deviation)], limits of detection (0.1 to 2.3 ng/g) and quantitation (1.5 to 7.6 ng/g) imply that the method is fit for its intended purpose. A sediment sample from a known contaminated site in Canada was analyzed for both homo- and hetero-PACs. Measured concentrations of Σ27HPAC (7.3 µg/g, dry weight) were significantly smaller (p<0.05) than Σ16PAHs (80.9 µg/g, dry weight) and Σ30Alkylated-PAHs (14.2 µg/g, dry weight). These results suggest that the developed method is an effective and efficient approach for the targeted analysis of HPACs and their halogenated derivatives in sediment samples.

Gestational exposure to cannabidiol leads to glucose intolerance in 3-month-old male offspring.

Reports in North America suggest that up to 20% of young women (18-24 years) use cannabis during pregnancy. This is concerning given clinical studies indicate that maternal cannabis use is associated with fetal growth restriction and dysglycemia in the offspring. Preclinical studies demonstrated that prenatal exposure to Δ9-tetrahydrocannabinol, the main psychoactive component of cannabis, in rat dams led to female-specific deficits in ß-cell mass and glucose intolerance/insulin resistance. Yet to date, the contributions of cannabidiol (CBD), the primary nonpsychoactive compound in cannabis, remain elusive. This study aimed to define the effects of in utero cannabidiol (CBD) exposure on postnatal glucose regulation. Pregnant Wistar rat dams received daily intraperitoneal injections of either a vehicle solution or 3 mg/kg of CBD from gestational day (GD) 6 to parturition. CBD exposure did not lead to observable changes in maternal or neonatal outcomes; however, by 3 months of age male CBD-exposed offspring exhibited glucose intolerance despite no changes in pancreatic ß/α-cell mass. Transcriptomic analysis on the livers of these CBD-exposed males revealed altered gene expression of circadian rhythm clock machinery, which is linked to systemic glucose intolerance. Furthermore, alterations in hepatic developmental and metabolic processes were also observed, suggesting gestational CBD exposure has a long-lasting detrimental effect on liver health throughout life. Collectively, these results indicate that exposure to CBD alone in pregnancy may be detrimental to the metabolic health of the offspring later in life.

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.

Trihalomethanes in drinking water from three First Nation reserves in Manitoba, Canada.

Previous research indicates that the water distribution system used has a significant impact on the microbial quality of tap water sampled in First Nations reserves in Canada. This study tested tap water from homes in three First Nations reserves to compare the concentrations of four trihalomethanes and related water quality parameters between homes receiving piped water from a water treatment plant (WTP) versus homes equipped with cisterns that are filled by a water truck. Of all the samples collected across time from household taps, 75% of piped samples and 70% of cistern samples had TTHM concentrations exceeding Health Canada's maximum acceptable concentration (MAC) of 100 µg L-1 total trihalomethanes (TTHMs) in treated water. In all communities and across sampling times, trichloromethane (CHCl3) was the dominant trihalomethane (42-96%) followed by bromodichloromethane (CHBrCl2) (3-37%) and dibromochloromethane (CHClBr2) (1-18%). Tribromomethane (CHBr3) always accounted for < 5% of TTHMs. Within each of the three First Nations reserves, the water distribution system had no significant effect on TTHM concentration at the household level. Sampling month had a significant effect on TTHM concentration due to temporal changes in dissolved organic carbon of the source water. Results suggest that families in the studied First Nations reserves receive drinking water with high TTHM concentrations and that improvements to the water treatment plant might be the most effective way to minimize trihalomethane formation.

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.

Alkylation of Benz[a]anthracene Affects Toxicity to Early-Life Stage Zebrafish and In Vitro Aryl Hydrocarbon Receptor 2 Transactivation in a Position-Dependent Manner.

Polycyclic aromatic hydrocarbons (PAHs) are structurally diverse organic chemicals that can have adverse effects on the health of fishes through activation of aryl hydrocarbon receptor 2 (AhR2). They are ubiquitous in the environment, but alkyl PAHs are more abundant in some environmental matrices. However, relatively little is known regarding the effects of alkylation on the toxicity of PAHs to fishes in vivo and how this relates to potency for activation of AhR2 in vitro. Therefore, the objectives of the present study were to determine the toxicity of benz[a]anthracene and three alkylated homologs representing various alkylation positions to early life stages of zebrafish (Danio rerio) and to assess the potency of each for activation of the zebrafish AhR2 in a standardized in vitro AhR transactivation assay. Exposure of embryos to each of the PAHs caused a dose-dependent increase in mortality and malformations characteristic of AhR2 activation. Each alkyl homolog had in vivo toxicities and in vitro AhR2 activation potencies different from those of the parent PAH in a position-dependent manner. However, there was no statistically significant linear relationship between responses measured in these assays. The results suggest a need for further investigation into the effect of alkylation on the toxicity of PAHs to fishes and greater consideration of the contribution of alkylated homologs in ecological risk assessments. Environ Toxicol Chem 2022;41:1993-2002. © 2022 SETAC.

An Emerging Cross-Species Marker for Organismal Health: Tryptophan-Kynurenine Pathway.

Tryptophan (TRP) is an essential dietary amino acid that, unless otherwise committed to protein synthesis, undergoes metabolism via the Tryptophan-Kynurenine (TRP-KYN) pathway in vertebrate organisms. TRP and its metabolites have key roles in diverse physiological processes including cell growth and maintenance, immunity, disease states and the coordination of adaptive responses to environmental and dietary cues. Changes in TRP metabolism can alter the availability of TRP for protein and serotonin biosynthesis as well as alter levels of the immune-active KYN pathway metabolites. There is now considerable evidence which has shown that the TRP-KYN pathway can be influenced by various stressors including glucocorticoids (marker of chronic stress), infection, inflammation and oxidative stress, and environmental toxicants. While there is little known regarding the role of TRP metabolism following exposure to environmental contaminants, there is evidence of linkages between chemically induced metabolic perturbations and altered TRP enzymes and KYN metabolites. Moreover, the TRP-KYN pathway is conserved across vertebrate species and can be influenced by exposure to xenobiotics, therefore, understanding how this pathway is regulated may have broader implications for environmental and wildlife toxicology. The goal of this narrative review is to (1) identify key pathways affecting Trp-Kyn metabolism in vertebrates and (2) highlight consequences of altered tryptophan metabolism in mammals, birds, amphibians, and fish. We discuss current literature available across species, highlight gaps in the current state of knowledge, and further postulate that the kynurenine to tryptophan ratio can be used as a novel biomarker for assessing organismal and, more broadly, ecosystem health.

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.

Kynurenine to tryptophan ratio as a biomarker of acute stress in fish.

The aim of this study was to determine the kynurenine (KYN) to tryptophan (TRP) ratio (KTR) in fish tissue to assess its usefulness as a biomarker of acute stress. Laboratory held rainbow trout (Oncorhynchus mykiss) were subjected to an acute stressor and KYN, TRP and cortisol were measured in liver and brain tissues at 4- and 48-h post-stress. The analytical method used to determine our analytes was based on lyophilization, and liquid-solid extraction followed by isotope dilution high-performance liquid chromatography positive ion electrospray tandem mass spectrometry. The [KYN]/[TRP] ratio (KTR) was greater in fish liver and brain in the 48-h post-stress exposure group (n = 8) relative to controls (n = 8, p < 0.05); a similar increase was not observed in fish in the 4-h post-stress exposure group. Hepatic and brain cortisol levels were also elevated in fish from both stress-induced groups relative to their respective controls implying that cortisol responded more quickly to the stressful stimulus than KYN and TRP. Our results suggest that the KTR is a promising acute stress diagnostic biomarker in fish. Efforts are ongoing to assess whether the KTR can be used as a biomarker for chronic stress in fish exposed to aquatic contaminants and other environmental stressors and if similar assessments can be made on tissues collected via non-lethal approaches.

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.

Polycyclic aromatic compounds in the Canadian Environment: Aquatic and terrestrial environments.

Polycyclic aromatic compounds (PACs) are ubiquitous across environmental media in Canada, including surface water, soil, sediment and snowpack. Information is presented according to pan-Canadian sources, and key geographical areas including the Great Lakes, the Alberta Oil Sands Region (AOSR) and the Canadian Arctic. Significant PAC releases result from exploitation of fossil fuels containing naturally-derived PACs, with anthropogenic sources related to production, upgrading and transport which also release alkylated PACs. Continued expansion of the oil and gas industry indicates contamination by PACs may increase. Monitoring networks should be expanded, and include petrogenic PACs in their analytical schema, particularly near fuel transportation routes. National-scale roll-ups of emission budgets may not expose important details for localized areas, and on local scales emissions can be substantial without significantly contributing to total Canadian emissions. Burning organic matter produces mainly parent or pyrogenic PACs, with forest fires and coal combustion to produce iron and steel being major sources of pyrogenic PACs in Canada. Another major source is the use of carbon electrodes at aluminum smelters in British Columbia and Quebec. Temporal trends in PAC levels across the Great Lakes basin have remained relatively consistent over the past four decades. Management actions to reduce PAC loadings have been countered by increased urbanization, vehicular emissions and areas of impervious surfaces. Major cities within the Great Lakes watershed act as diffuse sources of PACs, and result in coronas of contamination emanating from urban centres, highlighting the need for non-point source controls to reduce loadings.

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.

Application of a fugacity model to estimate emissions and environmental fate of ship stack PAHs in Shanghai, China.

The understandings of environmental activities and regional inventory of ship stack PAHs are very limited in Shanghai due, in part, to the lack of source-segregated analysis. To address this, measured PAHs in organic film on ship surfaces were employed to reconstruct concentrations in various compartments through a fugacity model to investigate the level, transport, fate and annual emission of ship stack PAHs in Shanghai. The results revealed that ship stack PAHs results in 11.2-181 ng L-1 and 71.0-1710 ng g-1 in water and sediment of Shanghai, respectively. After being released into air, ship stack PAHs mainly concentrated in organic films and sediments while sunk in water and sediment. Crucial mass transfer pathways include deposition of airborne and sediment PAHs. The mass loss of ship stack PAHs was primarily through air advection, followed by degradation in sediment. The ship emissions (53.7 tons annually) accounted for approximate one tenth of the regional total in Shanghai (in 2017). Additionally, shipping was estimated to release 127 tons of PAHs annually into the Shanghai section of Yangtze River. Our results suggest our fugacity-based approach can be used to estimate the regional emissions and inventory of ship stack PAHs in the surrounding environment.

Polycyclic aromatic hydrocarbon contamination along roads based on levels on vehicle window films.

Vehicular emissions are known to be major contributors of airborne polycyclic aromatic hydrocarbons (PAHs) in cities. In order to assess the long-term contamination of PAHs along roads, we collected organic films from vehicle windows (26 private cars and 4 buses, in Shanghai, China) and used mathematical models to convert the film-bound PAH concentrations to the airborne PAH concentrations. The field measurements of airborne PAHs revealed that the partitioning and Level III fugacity model was suitable to estimate the airborne concentrations of high and low volatile PAHs (expect for naphthalene), respectively. The total airborne PAH concentrations along roads in Shanghai ranged from 0.83 to 3.37 µg m-3 and the incremental lifetime cancer risks (ILCRtotal) by exposure to PAHs along roads were greater than the USEPA lower guideline of 10-6, indicating non-negligible carcinogenic risks to drivers and passengers, especially via ingestion processes. This study provided a practicable method to investigate long-term air contamination of PAHs in vehicles and along roads based on film-bound PAH on vehicle windows. In addition, it was also possible to investigate the health risk in vehicles as a result of exposure to PAHs. Comparisons of PAHs between roads and shipping lanes also facilitated the delineation of vehicular and shipping PAH inventories. A capsule that summarizes the main finding of the work: Investigating film-bound PAH on vehicle windows is a practicable pathway to investigate the long-term contamination of PAHs in vehicles and along roads. This method can not only simplify the sampling processes, but the model calculations. The results also enabled investigations into ILCR in vehicles and specified source apportionment of traffic PAHs.

1H NMR based metabolomic profiling of early life stage zebrafish (Danio rerio) exposed to a water-soluble fraction of weathered sediment-bound diluted bitumen.

Spills of diluted bitumen (dilbit) from pipelines pose a risk to the health of aquatic organisms, including fish, and with expected increases in production and transportation of dilbit, these risks could increase. To date, the majority of studies have investigated effects of fresh dilbit on aquatic organisms, but little is known about effects of weathered sediment-bound dilbit, including mechanisms of toxicity. The goal of this study was to use 1H NMR based metabolomics to identify altered metabolites and pathways in early life-stages of zebrafish (Danio rerio) exposed to a sediment derived water-soluble fraction of dilbit (SDWSF) to better understand mechanisms of adverse effects. Zebrafish embryos exposed to the SDWSF until 120 h post-fertilization exhibited increased prevalence of pericardial edema, yolk sac edema, and swim bladder malformations that are typical of exposure to fresh dilbit. Concentrations of nine metabolites (alanine, glutamine, lysine, threonine, tyrosine, betaine, taurine, inosine, and glycerol) were significantly altered in embryos exposed to SDWSF. Pathway topology analysis revealed four potentially impacted pathways: 1) phenylalanine, tyrosine, and tryptophan biosynthesis, 2) taurine and hypotaurine metabolism, 3) alanine, aspartate, and glutamate metabolism, and 4) glycine, serine, and threonine metabolism. Altered metabolites were linked to several biological process, that when perturbed could be key events in mechanisms of developmental effects observed in embryos. Future studies should further investigate the role of perturbations to these metabolites and pathways to determine the specific role they might play in adverse effects of exposure to dilbit.

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.

A review of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane in the environment and assessment of its persistence, bioaccumulation and toxicity.

Following the ban of many historically-used flame retardants (FRs), numerous replacement chemicals have been produced and used in products, with some being identified as environmental contaminants. One of these replacement flame retardants is 1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane (DBE-DBCH; formerly abbreviated as TBECH), which to date has not been identified for risk assessment and potential regulation. DBE-DBCH technical mixtures consist largely of α- and ß-diastereomers with trace amounts of γ- and δ-DBE-DBCH. The α- and ß-isomers are known contaminants in various environmental media. While current global use and production volumes of DBE-DBCH are unknown, recent studies identified that DBE-DBCH concentrations were among the highest of the measured bromine-based FRs in indoor and urban air in Europe. Yet our mass balance fugacity model and modeling of the physical-chemical properties of DBE-DBCH estimated only 1% partitioning to air with a half-life of 2.2 d atmospherically. In contrast, our modeling characterized DBE-DBCH adsorbing strongly to suspended particulates in the water column (~12%), settling onto sediment (2.5%) with minimal volatilization, but with most partitioning and adsorbing strongly to soil (~85%) with negligible volatilization and slow biodegradation. Our modeling further predicted that organisms would be exposed to DBE-DBCH through partitioning from the dissolved aquatic phase, soil, and by diet, and given its estimated logKow (5.24) and a half-life of 1.7 d in fish, DBE-DBCH is expected to bioaccumulate into lipophilic tissues. Low concentrations of DBE-DBCH are commonly measured in biota and humans, possibly because evidence suggests rapid metabolism. Yet toxicological effects are evident at low exposure concentrations: DBE-DBCH is a proven endocrine disruptor of sex and thyroid hormone pathways, with in vivo toxic effects on reproductive, metabolic, and other endpoints. The objectives of this review are to identify the current state of knowledge concerning DBE-DBCH through an evaluation of its persistence, potential for bioaccumulation, and characterization of its toxicity, while identifying areas for future research.

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.