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Nontargeted screening (NTS) of halogenated contaminants in biota is part of the routine monitoring of the Great Lakes ecosystem. NTS can give insight into new chemicals with possible persistent, bioaccumulative, and toxic (PBT) properties and help quantify known PBT's degradation and transformation products. The most common ionization technique for NTS is electron impact ionization (EI) due to the consistent and easily standardized fragmentation patterns. This research uses electron capture negative ionization (ECNI) as a complementary technique to broaden the range of halogenated contaminants detected in the Great Lakes. ECNI has higher sensitivity and selectivity to halogenated compounds compared to EI. GC × GC-HR-ToF MS with a multimode ion source (MMS) offers consecutive runs in EI and ECNI modes using the same chromatographic setup, facilitating retention time alignment. The exact mass measurements help in identifying compounds found only in ECNI. A total of 85 novel halogenated features were detected, 78% of which were detected only in ECNI. Only 9% of the features were detected in both modes, indicating that ECNI is a necessary complementary technique for NTS of halogenated features.

Water samples were collected during each of the 2012-2019 Cooperative Science and Monitoring Initiative (CSMI) cruises aboard the U.S. EPA R/V Lake Guardian as part of the Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) lower food web contaminant assessment. The CSMI rotates around each of the Great Lakes in a 5-year cycle providing top-to-bottom biological, chemical, and physical environmental assessments, including dissolved-phase surface water studies at two sample locations. Average polychlorinated biphenyl (∑PCB) concentrations across the Great Lakes was 268 pg/L with a station range of 72 pg/L (Keweenaw Point-Lake Superior) to 834 pg/L (Middle Bass Island-Lake Erie). The highest average Great Lakes concentration (pg/L-sample year) were measured in Lake Erie (645 pg/L-2014) and decreased in the order of Lake Huron (378 pg/L-2012) > Lake Erie (364 pg/L-2019) > Lake Ontario (300 pg/L-2013) > Lake Michigan (125 pg/L-2015) > Lake Huron (123 pg/L-2017) > Lake Superior (74 pg/L-2016). Lake Erie registered a 44 % reduction over the 2014-2019 period, attributed to sediment remediation in the late-1990's on the Detroit River, whereas Lake Huron exhibited a 67 % decrease over the 2012-2017 sample period. Our results indicate that dissolved-phase PCB water concentrations in Lake Ontario have significantly increased, rebounding from a low-point in the late-1990's likely due to the bioenergetic diversion of dissolved- and particulate-phase PCBs into the benthic food web by invasive zebra and quagga mussel colonization. Trend analyses uncovered breakpoints in the early 1990's documenting significantly slowing rates of PCB declines for both Lakes Superior and Michigan., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Concentrations of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) were analyzed and investigated in surficial sediment collected in 2018 from ten different nearshore sites in Lake Ontario and the St. Lawrence River influenced by inputs from varying urban and historical land uses. Sites were grouped into two categories of tributary and lake according to their location. Results show that tributary sites had higher concentrations of total chlorinated paraffin (CP) than lake sites. Humber Bay, a lake site, had the highest total CP concentration (55,000 ng/g TOC ) followed by Humber River, a tributary site (50,000 ng/g TOC ). The lowest concentrations were found in eastern Lake Ontario and Lake St. Francis in the St. Lawrence River (540 ng/g TOC ). Higher concentrations of chlorinated paraffins (CPs) were found where runoff and wastewater inputs from urban areas, current industrial activities, and population were the greatest. Levels of MCCPs were higher than SCCPs at all sites but one, Lake St. Francis. Among the SCCPs, C 13 and among the MCCPs C 14 were the dominant chain length alkanes, with C 14 being the highest among both groups. The SCCPs and MCCPs profiles suggest that they can be used to distinguish between sites impacted by local sources vs. sites impacted by short-/long-range transport of these chemicals., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Per- and polyfluoroalkyl substances (PFAS) are a diverse family of industrially significant synthetic chemicals infamous for extreme environmental persistence and global environmental distribution. Many PFAS are bioaccumulative and biologically active mainly due to their tendency to bind with various proteins. These protein interactions are important in determining the accumulation potential and tissue distribution of individual PFAS. Trophodynamics studies including aquatic food webs present inconsistent evidence for PFAS biomagnification. This study strives to identify whether the observed variability in PFAS bioaccumulation potential among species could correspond with interspecies protein composition differences. Specifically, this work compares the perfluorooctane sulfonate (PFOS) serum protein binding potential and the tissue distribution of ten perfluoroalkyl acids (PFAAs) detected in alewife (Alosa pseudoharengus), deepwater sculpin (Myoxocephalus thompsonii), and lake trout (Salvelinus namaycush) of the Lake Ontario aquatic piscivorous food web. These three fish sera and fetal bovine reference serum all had unique total serum protein concentrations. Serum protein-PFOS binding experiments showed divergent patterns between fetal bovine serum and fish sera, suggesting potentially two different PFOS binding mechanisms. To identify interspecies differences in PFAS-binding serum proteins, fish sera were pre-equilibrated with PFOS, fractionated by serial molecular weight cut-off filter fractionation, followed by liquid chromatography-tandem mass spectrometry analysis of the tryptic protein digests and the PFOS extracts of each fraction. This workflow identified similar serum proteins for all fish species. However, serum albumin was only identified in lake trout, suggesting apolipoproteins are likely the primary PFAA transporters in alewife and deepwater sculpin sera. PFAA tissue distribution analysis provided supporting evidence for interspecies variations in lipid transport and storage, which may also contribute to the varied PFAA accumulation in these species. Proteomics data are available via ProteomeXchange with identifier PXD039145., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The bioaccumulation and biomagnification of perfluoroalkyl substances (PFAS) in the Lake Erie food web was investigated by analyzing surface water and biological samples including 10 taxa of fish species, 2 taxa of benthos and zooplankton. The carbon (δ 13 C) and nitrogen (δ 15 N) isotopic composition and fatty acids profiles of biological samples were used to evaluate the food web structure and assess the biomagnification of PFAS. Perfluorooctane sulfonate (PFOS) dominated the total PFAS (ΣPFAS) concentration (50-90% of ΣPFAS concentration), followed by C9-C11 perfluorinated carboxylic acids (PFCAs). The highest PFOS concentrations (79 ± 4.8 ng/g, wet weight (wwt)) and ΣPFAS (88 ± 5.2 ng/g, wwt) were detected in yellow perch (Perca flavescens). The C8-C14 PFAS biomagnification factors (BMFs) between apex piscivorous fish and prey fish were found to be generally greater than 1, indicative of PFAS biomagnification, while biodilution (BMF<1) was observed between planktivorous fish and zooplankton. Trophic magnification factors (TMFs) of C8-C14 PFCA were not correlated with perfluoroalkyl chain length. The C4-C9 PFAS were detected in the surface water of Lake Erie, and PFBA was found to have the highest concentrations (2.1-2.8 ng/L) among all PFAS detected. The log of bioaccumulation factor (BAF) was found to generally increase with increasing log K ow for C6, 8, and 9 PFAS in all selected species from three tropic levels., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2022. Published by Elsevier Ltd.)

Per- and polyfluoroalkyl substances (PFAS) are globally distributed in the natural environment, and their persistent and bioaccumulative potential illicit public concern. The production of certain PFAS has been halted or controlled by regulation due to their adverse effect on the health of humans and wildlife. However, new PFAS are continuously developed as alternatives to legacy PFAS. Additionally, many precursors are unknown, and their metabolites have not been assessed. To better understand the PFAS profiles in the Lake Ontario (LO) aquatic food web, a quadrupole time-of-flight mass spectrometer (QToF) coupled to ultrahigh-performance liquid chromatography (UPLC) was used to generate high-resolution mass spectra (HRMS) from sample extracts. The HRMS data files were analyzed using an isotopic profile deconvoluted chromatogram (IPDC) algorithm to isolate PFAS profiles in aquatic organisms. Fourteen legacy PFAAs (C5-C14) and 15 known precursors were detected in the LO food web. In addition, over 400 unknown PFAS features that appear to biomagnify in the LO food web were found. Profundal benthic organisms, deepwater sculpin( Myoxocephalus thompsonii ), and Mysis were found to have more known precursors than other species in the food web, suggesting that there is a large reservoir of fluorinated substances in the benthic zone.

Polyfluoroalkyl substances (PFAS) are a group of fluorinated organic chemicals that have been produced for industrial and commercial application since the 1950s. PFAS are highly persistent and ubiquitous in water, sediment, and biota. Toxic effects of PFAS on humans and the ecosystem have increased scientific and public concern. To better understand the distribution of PFAS in the Laurentian Great Lakes, carbon ( 12 C and 13 C) and nitrogen ( 14 N and 15 N) stable isotope enrichment, fatty acid profiles, and PFAS were measured in the Lake Huron (LH) aquatic food web. The trophic level of the organisms was estimated using δ 15 N and found to be a determinant of PFAS biomagnification. The δ 13 C and fatty acid profiles were used to assess the carbon/energy flow pathway and predator-prey relationships, respectively. The δ 13 C, δ 15 N, and fatty acids were used to elucidate the trophodynamics and understand the PFAS trophic transfer in the LH aquatic food web. Perfluorooctanesulfonic acid (PFOS) was the dominant PFAS observed, followed by C9 - C11 perfluorinated carboxylic acids (PFCA). The highest PFOS concentrations (45 ± 11 ng/g, wet weight (wwt)) were detected in lake trout (Salvelinus namaycush), while the highest total PFCA concentrations (sum of C4 - C16 PFCAs) were detected in deepwater sculpin (Myoxocephalus thompsonii). With the exception of perfluorooctanoic acid (PFOA), C8-C14 PFAS biomagnification factors (BMFs) were found to be generally greater than 1, suggesting PFAS biomagnification from prey to predator. Trophic magnification factors (TMFs) of C8-C14 PFCA were found to be independent of compound hydrophobicity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Lake trout (Salvelinus namaycush) are a top-predator species in the Laurentian Great Lakes that are often used as bioindicators of chemical stressors in the ecosystem. Although many studies are done using these fish to determine concentrations of stressors like legacy persistent, bioaccumulative and toxic chemicals, there are currently no proteomic studies on the biological effects these stressors have on the ecosystem. This lack of proteomic studies on Great Lakes lake trout is because there is currently no complete, comprehensive protein database for this species. Here, we employed proteomics approaches to develop a lake trout protein database that could aid in future research on this fish, in particular exposomics and adductomics. The current study utilized heart tissue and blood from two lake trout. Our previous work using lake trout liver revealed 4194 potential protein hits in the NCBI databases and 3811 potential protein hits in the UniProtKB databases. In the current study, using the NCBI databases we identified 838 proteins for the heart and 580 proteins for the blood tissues in the biological replicate 1 (BR1) and 1180 potential protein hits for the heart and 561 potential protein hits for the blood in BR2. Similar results were obtained using the UniProtKB databases. This study builds on our previous work by continuing to build the first comprehensive lake trout protein database and provides insight into protein homology through evolutionary relationships. This data is available via the PRIDE partner repository with the dataset identifier PXD023970., (© 2021 Wiley-VCH GmbH.)

Halogenated organic compounds (HOCs) in marine species collected from the Atlantic Ocean [3 shortfin mako ( Isurus oxyrinchus ) and 1 porbeagle ( Lamna nasus )], and 12 sea turtles collected from the Pacific Ocean [3 loggerhead ( Caretta caretta ), 3 green ( Chelonia mydas ), 3 olive ridley ( Lepidochelys olivacea ), and 3 hawksbill ( Eretmochelys imbricata )] were analyzed with a nontargeted analytical method using two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry. Sharks and sea turtles had distinct HOC profiles. Halogenated methoxyphenols (halo-MeOPs) were the most abundant compound class identified in sea turtle livers, while polychlorinated biphenyls (PCBs) were the most abundant in shark livers. In addition to legacy contaminants and halo-MeOPs, a total of 110 nontargeted/novel HOCs (NHOCs) were observed in the shark livers. Shortfin mako collected from the northern Gulf of Mexico contained the largest number (89) and most diverse structural classes of NHOCs. Among all NHOCs, a group of compounds with the elemental composition C 14 H 12- n Cl n ( n = 5-8) exhibited the highest concentrations, followed by chlorocarbazoles and tris(chlorophenyl) methanes (TCPMs). Using nontargeted workflows, a variety of known and unknown HOCs were observed, which demonstrate the need to develop more complete chemical profiles in the marine environment.

This work presents the first assessment of temporal trends (2005-2016) for perfluoroalkyl acids (PFAAs) in top predator fish of the Laurentian Great Lakes except Lake Ontario, for which we provide a post-2008 update. Lake trout (Salvelinus namaycush) or walleye (Sander vitreus; Lake Erie only) collected annually from 2005 to 2016 were analyzed for 12 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkyl sulfonic acids (PFSAs) with carbon chain lengths between 4 and 16 (C4-C16). Individual analyte concentrations generally decreased in fish basin-wide between 2005 and 2016, including Lake Ontario lake trout previously found to lack declining PFAA concentrations up until 2008. Declining fish PFAA burden reflects a positive response to the industrial phase-outs of these chemicals. Notable exceptions to this general decline included most analytes in lake trout collected from Lake Superior near Keweenaw Point and C6 and C8 PFSAs and C9 PFCAs in Lake Erie lake trout and walleye, which exhibited constant or increasing concentrations in recent years. Recent increases in Lake Superior shoreline development and mobilization from increased sediment resuspension and contamination from biosolids-amended agricultural soils in the Lake Erie watershed are plausible explanations for these cases. However, data scarcity prohibits confirmation of these suspected causes. The lingering lack of declining concentrations noted in this study together with the ongoing evolution of the fluorinated chemical industry emphasize the vigilance needed to better understand how past and future emissions will affect the Great Lakes and global ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Sport fish fillets and human sera (fish consumers) were collected in the Lake Superior and Lake Michigan basin and screened for novel contaminants using the isotopic profile deconvoluted chromatogram (IPDC) algorithm. The IPDC algorithm was extended beyond traditional Cl/Br filters to detect additional potential bioaccumulative and toxic (PBT) such as perfluoroalkyl substances (PFAS). The IPDC algorithm screened for approximately 13.5 million theoretical molecular formulas. Additional algorithm modules were developed to detect data independent MS/MS fragmentation products and a retention time index calculator using a series of 13 C-labeled perfluoroalkyl carboxylic acids ( 13 C-PFCAs). Ten potential compound classes were isolated including six untargeted PFAS, six homologue groups of polyfluorinated carboxylic acids, polyfluorinated telomer alcohols (PoFTOHs), two hydroxylated polychlorobiphenyls, pesticides, herbicides, antifungals, pharmaceuticals, artificial sweeteners, and personal care products with minimal postprocessing efforts. The algorithm isolated 48 ubiquitous PoFTOHs in both fish fillet and serum of fish consumers suggesting a region wide distribution of this class of compounds. The 3, 4, and 7 fluorine substituted PoFTOH were the most abundant congeners in both biological matrices.

Fish have been used for decades as bioindicators for assessing toxic contaminants in the Great Lakes ecosystem. Routine environmental monitoring programs target predetermined compounds that do not reflect the complete exposure of chemicals to biota and do not provide the complete halogenated fingerprint of the biota. In the current work, a nontargeted screening method was developed using a two-dimensional gas chromatograph coupled to a high-resolution time-of-flight mass spectrometer and was applied to 149 edible fish fillets from different species in the Great Lakes to characterize a more robust set of halogenated organic compounds across species and among lakes. Lake Ontario had the largest number of novel halogenated organic compounds (NHOCs). Seven NHOCs were observed in species from all lakes, indicating that this regional signature was not species-dependent. Hierarchical cluster analysis showed identical NHOC profiles between bottom dwelling and pelagic species. The NHOCs were grouped into seven clusters with similar structures and potentially similar environmental behaviors. Seven of the 29 NHOCs likely containing methoxy or ethoxy groups on a benzene or benzene-methanol backbone were clustered into one group with similar retention times. Five NHOCs were clustered with legacy contaminants that likely have similar structures or are their degradation products.

Legacy halogenated contaminants have been monitored in the Great Lakes for decades, but there are many additional unknown halogenated contaminants potentially affecting the Great Lakes ecosystem. To address this concern, lake trout ( Salvelinus namaycush ) were collected in 2005/2006 and 2015/2016 from each lake and screened for previously unidentified compounds. The isotopic profile deconvoluted chromatogram algorithm was used to isolate unknown halogenated components using high-resolution mass spectrometry data files generated by an atmospheric pressure gas chromatography-quadrupole time-of-flight mass spectrometer operated in positive and negative modes. The temporal and spatial differences in the newly detected features were used to isolate new potential contaminants. Decadal differences in the unknown halogenated compounds (or features) were compared with the total polychlorinated biphenyl concentration trends. Greater than 2000 unknown halogenated features were detected. As expected, Lake Superior contained the lowest number of unknown halogenated features, whereas Lake Ontario contained the highest. Unknown features tended to have fewer Cl and/or Br atoms compared to traditional legacy contaminant features typically monitored. Diverse patterns of unknown halogenated compounds between lakes suggested that there continues to be unidentified sources of halogenated contaminants in the Great Lakes missed by current monitoring programs.

Hexabromocyclododecane (HBCDD) is a hazardous, persistent, bioaccumlative brominated flame retardant. To investigate how its use has affected the Great Lakes, total HBCDD (∑HBCDD) concentrations and temporal trends in homogenized whole fish samples from the Great Lakes region (1978 to 2016) were determined. ∑HBCDD concentrations (ng/g ww) for each lake are Erie (0.49-2.60), Ontario (3.12-8.90), Michigan (3.91-9.01), Superior (5.69-13.1), and Huron (5.57-13.7). Early years (1978 to 1992) showed no significant trend. However, recent trends (2004 to 2016) suggest concentrations are increasing in Lakes Erie and Ontario, decreasing in Lakes Superior and Michigan, and not changing in Lake Huron. Decreasing trends for Lakes Superior and Michigan are likely the result of decreased usage of the compound globally, regionally, and locally. For the other lakes, increasing or zero trends are consistent with food web changes due to invasive species and climate change, which has caused more intense storms and less ice cover leading to increased sediment resuspension.

An isotopic profile matching algorithm, the isotopic profile deconvoluted chromatogram (IPDC), was developed to screen for a wide variety of organic compounds in high-resolution mass spectrometry (HRMS) data acquired from instruments with resolution power as low as 22 000 fwhm. The algorithm initiates the screening process by generating a series of C/Br/Cl/S isotopic patterns consistent with the profiles of approximately 3 million molecular formulas for compounds with potentially persistent, bioaccumulative, and toxic (PBT) properties. To evaluate this algorithm, HRMS data were screened using these seed profiles to isolate relevant chlorinated and/or brominated compounds. Data reduction techniques included mass defect filtering and retention time prediction from estimated boiling points predicted using molecular formulas and reasonable elemental conformations. A machine learning classifier was also developed using spectrometric and chromatographic variables to minimize false positives. A scoring system was developed to rank candidate molecular formulas for an isotopic feature. The IPDC algorithm was applied to a Lake Michigan lake trout extract analyzed by atmospheric pressure gas chromatography-quadrupole time-of-flight (APGC-QToF) mass spectrometry in positive and negative modes. The IPDC algorithm detected isotopic features associated with legacy contaminants and a series of unknown halogenated features. The IPDC algorithm resolved 313 and 855 halogenated features in positive and negative modes, respectively, in Lake Michigan lake trout.

Lake trout are used as bioindicators for toxics exposure in the Great Lakes ecosystem. Here the first lake trout (Salvelinus namaycush) liver proteomics study is performed and searched against specific databases: (NCBI and UniProtKB) Salvelinus, Salmonidae, Actinopterygii, and Oncorhynchus mykiss, and the more distant relative, Danio rerio. In the biological replicate 1 (BR1), technical replicate 1 (TR1), (BR1TR1), a large number of lake trout liver proteins are not in the Salvelinus protein database, suggesting that lake trout liver proteins have homology to some proteins from the Salmonidae family and Actinopterygii class, and to Oncorhynchus mykiss and Danio rerio, two more highly studied fish. In the NCBI search, 4194 proteins are identified: 3069 proteins in Actinopterygii, 1617 in Salmonidae, 68 in Salvelinus, 568 in Oncorhynchus mykiss, and 946 in Danio rerio protein databases. Similar results are observed in the UniProtKB searches of BR1RT1, as well as in a technical replicate (BR1TR2), and then in a second biological replicate experiment, with two technical replicates (BR2TR1 and BR2TR2). This study opens the possibility of identifying evolutionary relationships (i.e., adaptive mutations) between various groups (i.e., zebrafish, rainbow trout, Salmonidae, Salvelinus and lake trout) through evolutionary proteomics. Data are available via the PRIDE Q2 (PXD011924)., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polybrominated diphenyl ethers (PBDEs) were widely used as fire retardants and have been detected throughout the Great Lakes (GL) ecosystem. The concentration trends (after fish age normalization) of PBDEs in top predator fish (lake trout and walleye) of the GLs were determined from 1979 to 2016, which includes most of the period when PBDEs were manufactured and used in this region. The fish samples were collected by two national (U.S. and Canada) long-term monitoring and surveillance programs. Trends in total concentrations (age-normalized) of the five major PBDE congeners (BDE-47, 99, 100, 153, and 154) found in fish across all five lakes have varied over time. Significant increases were observed from 1990 to 2000 (16.3% per year). Rapidly decreasing concentrations (-19.5% per year) were found from 2000 to 2007. Since 2007, the decreasing trend has become smaller (less than -5.5% per year) and relatively unchanged from 2011 to 2015. BDE-47, the congener with the highest concentrations in lake trout, has decreased continuously (ranging from -6.7% to -16.2% per year) in all lakes except Lake Erie. This decrease can be associated with the voluntary and regulatory phase out of production and/or usage of PBDEs since 2000. However, it has been offset by recent (since 2007) increasing trends of the other four higher brominated BDE congeners, especially BDE-100 and 154. Production and usage of commercial penta- and octa- BDE mixtures containing primarily the five major PBDE congeners was discontinued in 2004 in the U.S.A. and 2008 in Canada. These results indicate increasing fish uptake and bioaccumulation of higher brominated BDE congeners may be related to the transformation of BDE-209 to lower brominated BDE compounds in the GL environment or food web. Considering the abundance of BDE-209 in existing products and sediment in GL region, the duration of the unchanging total PBDE concentration trend in GL fish could be longer than expected.

Following the phase-out of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCDD) flame retardants (FRs) from North American markets, the use of alternative FRs has increased. In this study the occurrence and spatiotemporal distributions of 18 dechlorane analogues (collectively referred to as DECs) and 20 alternative brominated FRs (referred to as ABFRs, i.e., brominated FRs other than PBDEs and HBCDD) were investigated in top predator fish megacomposites (i.e., a composite of all 50 fish) collected yearly from each of the Great Lakes from 2004 to 2016. Frequently detected substances include dechlorane 602, 603, 604 Component B, anti- and syn-dechlorane plus, and chlordene plus, as well as several brominated benzene FRs (i.e., hexabromobenzene, pentabromotoluene, and tetrabromo- o-chlorotoluene). Concentrations of ΣDECs and ΣABFRs ranged from 0.33-31.9 ng/g lipid weight (lw) (0.01-8.3 ng/g wet weight or ww) and 0.91-54.7 ng/g lw (0.09-7.1 ng/g ww), respectively. Flame retardant contamination exhibited chemical-specific spatial variations across the five lakes. Concentrations of ΣABFRs in Lake Erie fish were generally lower than those from other lakes. By contrast, fish ΣDEC concentrations were highest in Lake Ontario and the composition of dechlorane analogues differed significantly between Lake Ontario and the other lakes, indicating likely point-source influences. Temporal analyses revealed declining trends of ΣDECs and ΣABFRs in most lakes except Lake Erie, with age corrected trend slopes of -13.5% to -8.8% and -20.1% to -7.0% per year, respectively.

Contaminant monitoring programs have been tasked with understanding the fate and transport of toxic chemicals in the environment. Mass spectrometry based methods have traditionally been developed to maximize sensitivity and accuracy of a select set of target compounds. As mass spectrometry methods have advanced, so has the breadth of questions proposed by environmental chemists. Incorporating these methods in chemical monitoring programs provides large data sets to explore the effects of complex mixtures on environmental systems.

Proteomics is a mass spectrometry-based discipline that aims to analyze proteomes and their functions. Many proteomic studies require well-developed protein databases for reference. However, most proteomes are not well-annotated, aside from model organisms. Techniques like six-frame translation, ab initio gene prediction, and EST databases can aid in maximizing the amount of proteins identified in proteomics experiments, however, each of these has its downfalls. Proteogenomics is a term used to describe the union of proteomics, genomics and transcriptomics to assist in the identification of peptides which would help build better annotated proteome databases. Here, current proteomic and proteogenomic methods will be reviewed, and an example of a comparative proteomics method using lake trout liver samples will be described.

Polyhalogenated carbazoles (PHCZs) were recently discovered in Great Lakes sediment and other aquatic systems. However, knowledge about their bioaccumulation and potential risks to fish and wildlife remains very limited. The present study investigated PHCZs in Great Lakes lake trout ( Salvelinus namaycush) and walleye ( Sander vitreus; Lake Erie only) composites collected between 2004 and 2016. Median concentrations of ∑PHCZs by lake ranged from 54.7 to 154 ng/g lipid weight or lw (6.8-28.0 ng/g wet weight). Dominant congeners included 3,6-dichlorocarbazole, 1,3,6-tribromocarbazole, and 1,3,6,8-tetrachlorocarbazole. The highest ∑PHCZs concentrations were found in Lakes Michigan and Ontario fish, followed by Lake Huron, whereas Lakes Erie and Superior fish contained the lowest concentrations. Congener profiles of PHCZs also exhibited spatial variations. After age normalization to minimize fish age influence on bioaccumulation rates, fish ∑PHCZs' concentrations declined significantly over time in all lakes except Lake Erie, with slopes ranging from -10.24% to -3.85% per year. The median toxic equivalent (TEQ) of PHCZs due to their dioxin-like activity was determined to range from 8.7 to 25.7 pg/g lw in Great Lakes fish. This study provides the first insight into the bioaccumulation and spatiotemporal trends of PHCZs in Great Lakes and suggests the need for further research on this group of chemicals.

The U.S. Environmental Protection Agency's Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) has traced the fate and transport of anthropogenic chemicals in the Great Lakes region for decades. Isolating and identifying halogenated species in fish is a major challenge due to the complexity of the biological matrix. A nontargeted screening methodology was developed and applied to lake trout using a 2-dimensional gas chromatograph coupled to a high resolution time-of-flight mass spectrometer (GC×GC-HR-ToF MS). Halogenated chemicals were identified using a combination of authentic standards and library spectral matching, with molecular formula estimations provided by exact mass spectral interpretation. In addition to the halogenated chemicals currently being targeted by the GLFMSP, more than 60 nontargeted halogenated species were identified. Most appear to be metabolites or breakdown products of larger halogenated organics. The most abundant compound class was halomethoxyphenols accounting for more than 60% of the total concentration of halogenated compounds in top predator fish from all five Great Lakes illustrating the need and utility of nontargeted halogenated screening of aquatic systems using this platform.

Our research reports polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (CP-PCBs) concentrations and age-corrected trends for lake trout and walleye in the Great Lakes over the 2004-2014 period. We determined that age-contaminant corrections are required to accurately report contaminant trends due to significant lake trout age structure changes. The age-trend model (ATM) described here uses a lake-specific age-contaminant regression to mitigate the effect of a fluctuating lake trout age structure to directly improve the log-linear regression model. ATM results indicate that half-life (t 1/2 ) and percent decreases for PCDD/Fs, CP-PCBs, and toxic equivalence (TEQ) (average -56 to 70%) were fairly uniform and consistent across the Great Lakes over the 2004-2014 period. The vast majority of TEQ associated with all Great Lakes lake trout and walleye samples is due to the nonortho CP-PCBs (average = 79%) as compared with PCDD/Fs (average = 21%). On average, CP-PCB&#95;126 individually accounted for over 95% of the total CP-PCB TEQ. A retrospective analysis (1977-2014) of 2378-TCDF and 2378-TCDD raw concentrations in Lake Ontario lake trout revealed decreases of 94% and 96%, respectively. Tissue residue guidelines for wildlife protection based on lake trout and walleye total TEQ were uniformly exceeded in all the Great Lakes.

A versatile screening algorithm capable of efficiently searching liquid chromatographic/mass spectrometric data for unknown compounds has been developed using a combination of open source and generic computing software packages. The script was used to search for select novel polyfluorinated contaminants in Great Lakes fish. However, the framework is applicable whenever full-scan, high-resolution mass spectral and chromatographic data are collected. Target compound classes are defined and a matrix of candidates is generated that includes mass spectral profiles and likely fragmentation pathways. The initial calibration was performed using a standard solution of known linear perfluoroalkyl acids. Once validated, Lake Michigan trout data files were analyzed for polyfluoroalkyl acids using the algorithm referencing 3570 possible compounds including C4-C10 perfluoro- and polyfluoroalkyl, polyfluorochloroalkyl acids and sulfonates, and potential ether forms. The results suggest the presence of 30 polyfluorinated chemical formulas which have not been previously reported in the literature. The identified candidates included mono- to hexafluoroalkyl carboxylic acids, mono- and trifluoroalkyl carboxylic acid ethers, and novel polyfluoroalkyl sulfonates. Candidate species identified in lake trout were qualified using theoretical isotopic profile matching, characteristic fragmentation patterns based on known linear perfluoroalkyl acid (PFAA) fragmentation, and retention time reproducibility among replicate extractions and injections. In addition, the relative retention times of multiple species within a compound class were compared based on theoretical octanol-water partition coefficients.

A novel electrical discharge plasma reactor configuration with and without iron ions was evaluated for the degradation of 0.02 mM Bisphenol A (BPA). The pseudo-first-order reaction rate constant calculated for the plasma treatment of BPA with a stainless steel electrode in the presence of dissolved ferrous ion (Fe(2+)) salts (termed plasma/Fenton treatment) was higher than in the plasma treatment in the absence of iron salts. At the optimal ferrous ion concentration, longer plasma treatment times resulted in higher BPA degradation rates, likely due to increased hydroxyl (OH) radical concentration formed through the decomposition of H2O2. Replacing the stainless steel with a carbon steel grounded electrode resulted in the release of iron ions from the carbon steel thereby increasing the rate of BPA removal and eliminating the need for iron salts. After the plasma/Fenton treatment, >97% of the residual iron salts were removed by coagulation/flocculation/sedimentation. Byproduct identification coupled with density functional theory (DFT) calculations confirmed that OH radical attack on BPA's hydroxyl group is the primary pathway for byproduct formation., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Current directions in autism spectrum disorder (ASD) research may require moving beyond genetic analysis alone, based on the complexity of the disorder, heterogeneity and convergence of genetic alterations at the cellular/functional level. Mass spectrometry (MS) has been increasingly used to study CNS disorders, including ASDs. Proteomic research using MS is directed at understanding endogenous protein changes that occur in ASD. This review focuses on how MS has been used to study ASDs, with particular focus on proteomic analysis. Other neurodevelopmental disorders have been investigated using MS, including fragile X syndrome (FXS) and Smith-Lemli-Opitz Syndrome (SLOS), genetic syndromes highly associated with ASD comorbidity., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant's hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.

A new method for measuring perfluoroalkyl contaminants (PFCs) in biological matrices has been developed. An ultra-high pressure liquid chromatograph equipped with a quadrupole time-of-flight mass spectrometer (UPLC-QToF) was optimized using a continuous precursor/product ion monitoring mode. Unlike traditional targeted studies that isolate precursor/product ion pairs, the current method alternates between two ionization energy channels to continuously capture standard electrospray ionization (low energy) and collision induced dissociation (high energy) spectra. The result is the indiscriminant acquisition of paired low and high energy spectra for all constituents eluting from the chromatographic system. This technique was evaluated for the routine analysis of perfluoroalkyl species. Using this technique, linear perfluoroalkyl carboxylic acids (C4 to C14) and perfluoroalkyl sulfonates (C4, C6, C8 and C10) exhibited a linear range spanning over three orders of magnitude and were detectable at levels less than 1 pg on column with a root mean squared signal to noise ratio of 5 to 20. Lake trout (Salvelinus namaycush) and National Institutes of Standards and Technology Standard Reference Material 1946 were used to evaluate matrix effects and the accuracy of this method when applied to a whole fish extract. The current method was also evaluated as a diagnostic tool to identify unknown PFCs using experimental fragmentation patterns, mass defect filtering and Kendrick plots.

Temporal trend analysis of the latest Great Lake Fish Monitoring and Surveillance Program (GLFMSP) data showed statistically significant decreases in persistent bioaccumulative and toxic (PBT) contaminant (polychlorinated biphenyls (PCBs), dichloro-diphenyl-trichlorethane and its metabolites (DDTs), dieldrin, cis-chlordane, oxychlordane, cis-nonachlor) concentrations in Lakes Huron, Ontario, and Michigan lake trout over the period of 1999 to 2009. In contrast, for most contaminants, no statistically significant concentration trends were found in top predator fish in Lakes Superior and Erie during the same period. For Lakes Huron, Ontario, and Michigan 5.0 ± 2.6% average annual concentration decreases were found for PCBs, DDTs, dieldrin, and other organochlorine pesticides (OCs) decreased at a faster rate, ranging from 10 ± 4.3% to 20 ± 7.1% per year. For these three lakes, with the exception of PCBs, these current decreases are greater than were shown by an earlier trend analysis that estimated an annual contaminant decrease of about 2-5% for the period of 1980 to 2003. For Lakes Superior and Erie, the finding of no statistically significant trend is in agreement with previously reported results for these lakes., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Lake trout and walleye composites were collected between 2004 and 2009 as part of the Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) and analyzed for polybrominated diphenyl ethers (PBDEs). Yearly mean total PBDE concentrations (sum of congeners BDE-47, BDE-99, BDE-100, BDE-153, BDE-154) ranged from 44-192, 28-113, 50-107, 37-111, and 11-22 ng/g wet wt. for Lakes Michigan, Huron, Ontario, and Superior lake trout, and Lake Erie walleye, respectively. A 1980-2009 temporal record of PBDE concentrations in the Great Lakes' top predator fish (lake trout and walleye) was assembled by integrating previous GLFMSP data (1980-2003) with current results (2004-2009). Temporal profiles show obvious breakpoints between periods of PBDE accumulation and decline in trout for Lakes Huron, Michigan and Ontario with a significant (p < 0.0001 and r = 0.55, 0.72, and 0.51, respectively) decrease in concentration after 2000-2001. A similar transition was observed in Lake Superior for the nearshore site accompanied by a less significant decreasing trend (p = 0.016, r = 0.33), suggesting concentrations are declining very slowly or have leveled off. In contrast, Lake Erie walleye concentrations began leveling off in the late 1990s and no statistically significant trend (increasing or decreasing) has been observed in recent years. A decrease in the BDE-47/BDE-153 ratio was also recently observed, suggesting a transition to more highly brominated PBDEs is occurring in Great Lakes trout. This study provides region-wide evidence that PBDE concentrations are generally declining in Great Lakes trout, although there are clear exceptions to this trend. Results from this study reflect the positive impact of the 2004 PentaBDE ban on macro-scale aquatic freshwater ecosystems.

Mercury (Hg) contamination is widespread in the Laurentian Great Lakes region and is a serious environmental concern. In anaerobic environments such as lake sediments, mercury is transformed into methylmercury (MeHg) and can biomagnify up the food chain to toxic concentrations. The Great Lakes Fish Monitoring Program (GLFMP), administered by the US EPA Great Lakes National Program Office (GLNPO), aims to monitor temporal trends of mercury in the five Great Lakes using top predator fish as biomonitors. Total Hg (THg) concentrations were measured in Great Lake fish collected between 1999 and 2009. Single factor ANOVA determined that average fish THg concentrations over this time period in the five lakes were significantly different from one another in the order of Superior > Huron > Michigan > Ontario > Erie. By fitting the data to three different models (linear, quadratic, and two-segment piecewise), it was determined that Hg concentrations in top predator fish (lake trout, or walleye in Lake Erie) are currently increasing in Lake Erie and the Apostle Island sampling site in Lake Superior. Significant decreasing trends are evident in Lakes Michigan, Ontario, and the Rockport sampling site in Lake Huron, although all of the lakes exhibit elevated concentrations in fish compared to historic concentrations. As new Hg emission controls are implemented in the US, continued monitoring of Hg in Great Lakes fish will be needed to determine if they influence the current concentrations and trends.

Chlorinated camphenes, toxaphene, are persistent organic pollutants of concern in the Great Lakes since elevated concentrations are found in various media throughout the system. While concentrations have decreased since their peak values in the 1970s and 80s, recent measurements have shown that the rate of this decline in Lake Superior has decreased significantly. This modeling study focused on toxaphene cycling in the Great Lakes and was performed primarily to determine if elevated water and fish concentrations in Lake Superior can be explained by physical differences among the lakes. Specifically, the coastal zone model for persistent organic pollutants (CoZMo-POP), a fugacity-based multimedia fate model, was used to calculate toxaphene concentrations in the atmosphere, water, soil, sediment, and biota. The performance of the model was evaluated by comparing calculated and reported concentrations in these compartments. In general, simulated and observed concentrations agree within one order of magnitude. Both model results and observed values indicate that toxaphene concentrations have declined in water and biota since the 1980s primarily as the result of decreased atmospheric deposition rates. Overall the model results suggest that the CoZMo-POP2 model does a reasonable job in simulating toxaphene variations in the Great Lakes basin. The results suggest that the recent findings of higher toxaphene concentrations in Lake Superior can be explained by differences in the physical properties of the lake (primarily large volume, large residence time and cold temperatures) compared to the lower lakes and increased recent inputs are not needed to explain the measured values., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Toxaphene is considered to be a problematic organochlorine pollutant because of its bioaccumulation potential and persistence in aquatic environments. In this study, whole lake trout and walleye composites were used to evaluate two analytical techniques for total toxaphene and selected congener analysis. The efficacy of using gas chromatography electron ionization tandem mass spectrometry (GC-EI/MS/MS) and electron capture negative ionization mass spectrometry (GC-ECNI-MS) were compared. Although the sensitivity using GC-ECNI-MS was approximately five times greater than GC-EI/MS/MS, the latter provided more consistent inter-Parlar relative response factors (RRF). When using technical calibration mixtures, these results suggest a more accurate total toxaphene measurement was obtained using the GC-EI/MS/MS method. Total toxaphene concentrations in lake trout composites from both methods were highly correlated (R(2) = 0.985) with the MS/MS concentrations approximately half of those determined by ECNI, suggesting systematic high bias in toxaphene concentrations when measured using GC-ECNI.

Water, sediments, and aquatic biota were sampled in a tidal river-marsh on the Potomac River near Washington, DC (USA) to assess baseline concentrations of polychlorinated biphenyls (PCBs) and bioaccumulation in finish species. The mean sediment total-PCB concentration in the wetland was 50 ng/g dry weight, and mean concentrations in biota ranged from 150 ng/g to 450 ng/g wet weight. The highest PCB concentrations were observed in channel catfish. The median biota-sediment accumulation factor (BSAF) estimated in all finfish species for total-PCBs was 2.9. However, some of the individual and co-eluting PCB congeners had median BSAFs that were substantially greater (e.g., congener numbers 42, 74, 182/187/128, and 171) or lower (e.g., congener numbers 18/15, 45, 185, and 208) than the total-PCB average. Apparent bioaccumulation factors (biota/water PCB concentration ratios) for PCB congeners showed a parabolic relation with n-octanol/water partition coefficients, confirming some previous investigations. There was no clear trend between apparent bioaccumulation factors and trophic level. Organic-carbon-normalized sediment distribution constants (sediment/water PCB concentration ratios) were linearly related to the apparent bioaccumulation factors for all the finfish species investigated.