Killer whales (
) are among the most highly polychlorinated biphenyl (PCB)-contaminated mammals in the world, raising concern about the health consequences of current PCB exposures. Using an ...individual-based model framework and globally available data on PCB concentrations in killer whale tissues, we show that PCB-mediated effects on reproduction and immune function threaten the long-term viability of >50% of the world's killer whale populations. PCB-mediated effects over the coming 100 years predicted that killer whale populations near industrialized regions, and those feeding at high trophic levels regardless of location, are at high risk of population collapse. Despite a near-global ban of PCBs more than 30 years ago, the world's killer whales illustrate the troubling persistence of this chemical class.
A comprehensive analytical approach for targeted and non-targeted discovery screening of per- and polyfluoroalkyl substances (PFAS) was developed and applied to model complex environmental biotic ...samples. Samples were extracted by formic acid-acetonitrile solution and cleaned up and fractionated by SPE (WAX). Target PFAS quantification was performed by ultra-high performance liquid chromatography interfaced with a triple quadrupole mass spectrometer (UPLC-QqQ-MS/MS). Non-targeted analysis (NTA) PFAS screening was performed with UPLC coupled with a quadrupole-Exactive orbitrap high resolution mass spectrometer (UPLC-Q-Exactive-HRMS). An iterative exclusion (IE) approach was applied to data acquisition for NTA suspect screening to increase the potential for unknown PFAS discovery with MS/MS. A complex workflow in Compound Discoverer was set up to automate data processing of the PFAS suspects search. New mass lists and MS/MS databases, which included a large number of PFAS, were set up and introduced into the search for high-throughput structure identification using HRMS techniques. The integrated targeted-NTA method successfully analyzed for legacy and alternative PFAS in model environmental biota samples, namely polar bear liver and bird egg samples. Targeted analysis provided unequivocal identification of well known/established PFAS (mainly perfluoroalkyl acids) with quantification at very low levels. The NTA suspect screening was able to determine a broader range of PFAS. The data analysis method offered high-confidence annotations for PFAS despite lacking available authentic standards. Overall, the analytical coverage of PFAS was greater and elucidated other PFAS present in these model apex predators.
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•Scotchgard™ fabric protector (pre- and post-2002) contain side-chain fluoropolymer surfactants (S1 and S2).•S1 and S2 concentrations were high in biosolids from Canadian wastewater ...treatment plants.•The concentration of 22 other PFASs were about 30 times lower than S1 and S2.•PFASs in biosolids would be underestimated without consideration of S1 and S2.
High concentrations of the main components in Scotchgard™ fabric protector products (pre-2002 and post-2002; side-chain fluorinated polymer surfactants, S1 and S2, respectively) were detected in biosolids samples from twenty pan-Canadian wastewater treatment plants (WWTPs). Based on mass spectrometric analysis, S1 and S2 can be named as side-chain perfluorooctane sulfonamide-urethane polymer and side-chain perfluorobutane sulfonamide-urethane polymer, respectively. S1 (with C8F17 side-chain) concentrations ranged from 1.08–105 ng/g d.w. and S2 (with C4F9 side-chain) concentrations ranged from 37.5–2051 ng/g d.w., which were much higher than that of other commonly monitored perfluoroalkyl substances (PFAS). S1 and S2 concentrations were significantly correlated (p < 0.001; r2 = 0.6142) indicating similar source origins. A negative linear correlation was observed (p < 0.05) between concentrations of S1 (or S2) with the volume of WWTP treated wastewater per day per person (m3/person/day). The total concentration of 22 other PFAS ranged from 4.93 to 92.6 ng/g d.w., and approximately thirty times lower than S1 and S2 concentrations. The calculated elemental fluorine concentrations of ƩFS1&S2 were generally much higher than the sum of the other PFAS. PFAS concentrations in biosolids are likely underestimated without consideration of S1 and S2.
Li et al explore liquid crystal monomers (LCMs), as a new generation of persistent bioaccumulative and toxic (PBT) compounds. They note the chemicals in the growing array of smart devises that are ...comprised of LCMs, which transform between liquid and solid phases as a function of temperature in these liquid crystal displays (LCDs). With the huge number of LCD devices produced, many such devices end up being discarded and at best end up in e-waste sites, which raises the spectre of eventually being released and entering into the natural environment. LCMs generally have a diphenyl backbone structure and where phenyl ring hydrogen atoms are replaced by various functional groups, that is, cyano, fluorine, chlorine, or bromine.
Arctic contaminant research in the marine environment has focused on organohalogen compounds and mercury mainly because they are bioaccumulative, persistent and toxic. This review summarizes and ...discusses the patterns and trends of persistent organic pollutants (POPs) and mercury in ringed seals (Pusa hispida) and polar bears (Ursus maritimus) in the Eastern Canadian Arctic relative to the rest of the Canadian Arctic. The review provides explanations for these trends and looks at the implications of climate-related changes on contaminants in these marine mammals in a region that has been reviewed little. Presently, the highest levels of total mercury (THg) and the legacy pesticide HCH in ringed seals and polar bears are found in the Western Canadian Arctic relative to other locations. Whereas, highest levels of some legacy contaminants, including ∑PCBs, PCB 153, ∑DDTs, p,p′-DDE, ∑CHLs, ClBz are found in the east (i.e., Ungava Bay and Labrador) and in the Beaufort Sea relative to other locations. The highest levels of recent contaminants, including PBDEs and PFOS are found at lower latitudes. Feeding ecology (e.g., feeding at a higher trophic position) is shaping the elevated levels of THg and some legacy contaminants in the west compared to the east. Spatial and temporal trends for POPs and THg are underpinned by historical loadings of surface ocean reservoirs including the Western Arctic Ocean and the North Atlantic Ocean. Trends set up by the distribution of water masses across the Canadian Arctic Archipelago are then acted upon locally by on-going atmospheric deposition, which is the dominant contributor for more recent contaminants. Warming and continued decline in sea ice are likely to result in further shifts in food web structure, which are likely to increase contaminant burdens in marine mammals. Monitoring of seawater and a range of trophic levels would provide a better basis to inform communities about contaminants in traditionally harvested foods, allow us to understand the causes of contaminant trends in marine ecosystems, and to track environmental response to source controls instituted under international conventions.
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•Mercury and legacy HCH in marine mammals are highest in the Western Arctic.•Most legacy POPs in marine mammals are highest in the East and the Beaufort Sea.•More recent POPs are highest in seals and polar bears at lower latitudes.•Food web structure is shaping spatial trends of mercury and some legacy POPs.•Water is driving legacy POPs whereas atmospheric deposition is driving recent POPs.
Histones are the major proteinaceous components of chromatin in eukaryotic cells and an important part of the epigenome. The broad-spectrum herbicide atrazine ...(2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine) and its metabolites are known to form protein adducts, but the formation of atrazine–histone adducts has not been studied. In this study, a bottom-up proteomics analysis method was optimized and applied to identify histone adduction by atrazine in vitro
.
Whole histones of calf thymus or human histone H3.3 were incubated with atrazine. After solvent-based protein precipitation, the protein was digested by trypsin/Glu-C and the resulting peptides were analyzed by high-resolution mass spectrometry using an ultra-high-performance liquid chromatograph interfaced with a quadrupole Exactive-Orbitrap mass spectrometer. The resulting tryptic/Glu-C peptide of DTNLCAIHAK from calf thymus histone H3.1 or human histone H3.3 was identified with an accurate mass shift of +179.117 Da in atrazine incubated samples. It is deduced that a chemical group with an elemental composition of C
8
H
13
N
5
(179.1171 Da) from atrazine adducted with calf thymus histone H3.1 or human histone H3.3. It was confirmed by MS/MS analysis that the adduction position was at its cysteine 110 residue. Time- and concentration-dependent assays also confirmed the non-enzymatic covalent modification of histone H3.3 by atrazine in vitro. Thus, the potential exists that atrazine adduction may lead to the alteration of histones that subsequently disturbs their normal function.
Graphical abstract
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•Fifty-one studies on E/BFR metabolism have been mostly on PBDE, HBCDD and TBBPA.•More E/BFR studies on metabolism shown in e.g. fish, birds, rodents and mammals.•The metabolism and ...toxicokinetics are critically understudied for 30 E/NBFRs.•Species-specific differences in metabolic capacity of BFRs exists across species.•In vitro metabolism studies often lack, e.g. active controls, ignore enzyme activity.
Over the past few decades, production trends of the flame retardant (FR) industry, and specifically for brominated FRs (BFRs), is for the replacement of banned and regulated compounds with more highly brominated, higher molecular weight compounds including oligomeric and polymeric compounds. Chemical, biological, and environmental stability of BFRs has received some attention over the years but knowledge is currently lacking in the transformation potential and metabolism of replacement emerging or novel BFRs (E/NBFRs). For articles published since 2015, a systematic search strategy reviewed the existing literature on the direct (e.g., in vitro or in vivo) non-human BFR metabolism in fauna (animals). Of the 51 papers reviewed, and of the 75 known environmental BFRs, PBDEs were by far the most widely studied, followed by HBCDDs and TBBPA. Experimental protocols between studies showed large disparities in exposure or incubation times, age, sex, depuration periods, and of the absence of active controls used in in vitro experiments. Species selection emphasized non-standard test animals and/or field-collected animals making comparisons difficult. For in vitro studies, confounding variables were generally not taken into consideration (e.g., season and time of day of collection, pollution point-sources or human settlements). As of 2021 there remains essentially no information on the fate and metabolic pathways or kinetics for 30 of the 75 environmentally relevant E/BFRs. Regardless, there are clear species-specific and BFR-specific differences in metabolism and metabolite formation (e.g. BDE congeners and HBCDD isomers). Future in vitro and in vivo metabolism/biotransformation research on E/NBFRs is required to better understand their bioaccumulation and fate in exposed organisms. Also, studies should be conducted on well characterized lab (e.g., laboratory rodents, zebrafish) and commonly collected wildlife species used as captive models (crucian carp, Japanese quail, zebra finches and polar bears).
Liquid crystal monomers (LCMs) are used widely in liquid crystal displays (LCDs), which are dramatically changing the world due to the provision of convenient communication. However, there are ...essentially no published reports on the fate and/or effects of LCMs in the environment. Of 362 currently produced LCMs, 87 were identified as persistent and bioaccumulative (P&B) chemicals, which indicated that these chemicals would exhibit resistance to degradation and exhibit mobility after entering the environment. Following exposure to mixtures of LCM collected from 6 LCD devices, significant modulation of 5 genes, CYP1A4, PDK4, FGF19, LBFABP, and THRSP, was observed in vitro. Modulation of expressions of mRNAs coding for these genes has frequently been reported for toxic (T) persistent organic pollutants (POPs). In LCM mixtures, 33 individual LCMs were identified by use of mass spectrometry and screened for in 53 samples of dust from indoor environments. LCMs were detectable in 47% of analyzed samples, and 17 of the 33 LCMs were detectable in at least 1 sample of dust. Based on chemical properties, including P&B&T of LCMs and their ubiquitous detection in dust samples, the initial screening information suggests a need for studies to determine status and trends in concentrations of LCMs in various environmental matrices as well as tissues of humans and wildlife. There is also a need for more comprehensive in vivo studies to determine toxic effects and potencies of LCMs during chronic, sublethal exposures.
The in vitro biotransformation and kinetics of six organophosphate triester (OPE) flame retardants were investigated in herring gulls (Larus argentatus) from the Great Lakes using a hepatic ...microsomal metabolism assay. Administration of each individual OPE (tri-n-butyl phosphate (TNBP), tris(2-butoxyethyl) phosphate (TBOEP), triphenyl phosphate (TPHP), triethyl phosphate (TEP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP)) to the in vitro assay (concentration range 0.01 to 10μM) resulted in rapid depletion with the exception of TEP. Following the Michaelis-Menten enzyme kinetics model, a preliminary 2-minute incubation period was used to estimate the Vmax (±SE) values (i.e., the maximal rate of reaction for a saturated enzyme system), which ranged from 5.0±0.4 (TPHP) to 29±18pmol/min/mg protein (TBOEP), as well as the KM (±SE) values (i.e., the OPE concentration corresponding to one half of the Vmax), which ranged from 9.8±1 (TPHP) to 189±135nM (TBOEP). Biotransformation assays over a 100-minute incubation period revealed that TNBP was metabolized most rapidly (with a depletion rate of 73±4pmol/min/mg protein), followed by TBOEP (53±8pmol/min/mg), TCIPP (27±1pmol/min/mg), TPHP (22±2pmol/min/mg) and TDCIPP (8±1pmol/min/mg). In vitro biotransformation of OP triesters was clearly structure-dependent where non-halogenated alkyl OP triesters were metabolized more rapidly than halogenated alkyl triesters. Halogenated OP triesters were transformed to their respective diesters more efficiently relative to non-halogenated OP triesters. To our knowledge, this is the first study to investigate OP triester metabolism and OP diester formation in an avian or wildlife model system, which is important to understand the fate and biological activity of OPEs in an exposed organism.
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•The metabolism and kinetics of 6 OPEs were examined in herring gull liver microsomes.•The metabolism of OPEs was rapid, with the exception of TEP (no metabolism observed).•Relative metabolism rates (pmol/min/mg protein): TNBP>TBOEP>TPHP>TDCIPP>TCIPP.•OPE metabolite (i.e., OP diesters) formation was shown for all 5 OP triesters.•Structure-dependent metabolism rates and OP diester formation were observed.
► A quantitative method was developed for organophosphate flame retardants (OPFRs). ► For avian eggs, 12 (non)halogenated OPFRs were determined by LC–ESI(+)-MS/MS. ► Method limits of quantification ...(MLOQs) ranged from 0.06 to 0.20
ng/g wet weight. ► Mean percent matrix effects of 89–106% were encountered for all the OPFRs. ► The method is novel and sensitive for a suite of environmentally relevant OPFRs.
Numerous triester organophosphate flame retardants (OPFRs) have been used for several decades and continue to be used in a variety of commercial products. We developed a sensitive quantitative method for the analysis of, seven non-halogenated, three chlorinated and two brominated OPFRs of known or possible environmental relevance in herring gull eggs. This method is based on a simple two-step sample extraction followed by liquid chromatography–electrospray ionization(+)-tandem mass spectrometry. Instrumental detection limits and method limits of quantification (MLOQs) among the 12 OPFRs ranged from 0.01 to 0.12
ng/mL and 0.06 to 0.20
ng/g, respectively. The mean OPFR recovery efficiencies of replicate analyses (
n
=
6) were very quantitative and ranged from 89% to 104%, with the two brominated OPFRs being somewhat lower but reproducible, i.e., 67% and 72%, respectively. Essentially negligible matrix effects were indicated by a standard addition approach that revealed mean percent signal recoveries (
n
=
5 replicates) of 89–106% for most OPFRs. In the analysis of
n
=
13 herring gull eggs from the Channel-Shelter Island colony (Lake Huron), tris(2-chloroisopropyl) phosphate (<MLOQ – 4.1
ng/g wet weight, ww), tris(2-chloroethyl) phosphate (<MLOQ – 0.6
ng/g ww) and tris(2-butoxyethyl) phosphate (<MLOQ – 2.2
ng/g ww) were detected and/or quantified.
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