Human cancer genomes harbor the mutational signature of tobacco-specific nitrosamines NNN and NNK.

Tobacco usage is linked to multiple cancer types and accounts for a quarter of all cancer-related deaths. Tobacco smoke contains various carcinogenic compounds, including polycyclic aromatic hydrocarbons (PAH), though the mutagenic potential of many tobacco-related chemicals remains largely unexplored. In particular, the highly carcinogenic tobacco-specific nitrosamines NNN and NNK form pre-mutagenic pyridyloxobutyl (POB) DNA adducts. In the study presented here, we identified genome-scale POB-induced mutational signatures in cell lines and rat tumors, while also investigating their role in human cancer. These signatures are characterized by T>N and C>T mutations forming from specific POB adducts damaging dT and dC residues. Analysis of 2,780 cancer genomes uncovered POB signatures in ∼180 tumors; from cancer types distinct from the ones linked to smoking-related signatures SBS4 and SBS92. This suggests that, unlike PAH compounds, the POB pathway may contribute uniquely to the mutational landscapes of certain hematological malignancies and cancers of the kidney, breast, prostate and pancreas.

Mutual interference between 3,6-dichlorinated carbazole and p,p'-dichlorodiphenyltrichloroethane in gas chromatography mass spectrometry analysis.

The widespread contamination of the environment by polyhalogenated carbazoles (PHCZs) has been increasingly observed during the past decade. Among numerous PHCZ congeners, 3,6-dichlorocarbazole (36-CCZ) is often among the most frequently detected at higher concentrations. Although the environmental level of the legacy pesticide p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) has been declining, it continues to be ubiquitously detected. These two compounds were found to interfere with each other during analyses using gas chromatography (GC) coupled with single- or triple-quadrupole low-resolution mass spectrometry (MS or MS/MS). The base peak in the mass spectra was that of m/z 235 for both compounds. In MS/MS with multiple reaction monitoring (MRM), the same transitions (235 → 200 and 235 → 165) were often used. Under the same GC operating conditions, the SH-I-5MS capillary column used in this work did not resolve the two compounds at baseline. Pre-treatment using cleanup column chromatography can fractionate the sample extract, with the two compounds separated in different fractions before instrumental analyses. Reversed-phase HPLC columns also work for resolving 36-CCZ and p,p'-DDT. Possible overlaps in GC retention and similarity in MS spectra might have caused data inaccuracy for 36-CCZ as well as p,p'-DDT in some studies published to date, and steps to avoid the interference should be taken into quality control protocols in future research and environmental monitoring.

Exposure to novel brominated and organophosphate flame retardants and associations with type 2 diabetes in East China: A case-control study.

The alternative flame retardants, novel brominated flame retardants (NBFRs) and organophosphate flame retardants (OPFRs) are ubiquitous in the environment and biota and may induce endocrine disruption effects. Associations between traditional endocrine-disrupting chemicals and type 2 diabetes have been extensively reported in epidemiological studies. However, the effects of NBFRs and OPFRs in humans have not been reported to date. This paper reports a case-control study of 344 participants aged 25-80 years from Shandong Province, East China, where potential associations between serum NBFR and OPFR concentrations and type 2 diabetes are assessed for the first time. After adjusting for covariates (i.e., age, sex, body mass index, smoking status, alcohol consumption, triglycerides, and total cholesterol), serum concentrations of pentabromotoluene, 2,3-dibromopropyl 2,4,6-tribromophenyl ether, tri-n-propyl phosphate, triphenyl phosphate, and tris (2-ethylhexyl) phosphate were significantly positively associated with type 2 diabetes. In the control group, decabromodiphenyl ethane and triphenyl phosphate were significantly positively associated with fasting plasma glucose, triglycerides, and high-density lipoprotein cholesterol. In the quantile g-computation model, significant positive mixture effect was found between the flame retardants mixtures and high-density lipoprotein cholesterol levels, and decabromodiphenyl ethane contributed the largest positive weights to the mixture effect. Overall, these findings suggest that exposure to NBFRs and OPFRs may promote type 2 diabetes.

Quantitation by Liquid Chromatography-Nanoelectrospray Ionization-High-Resolution Tandem Mass Spectrometry of Multiple DNA Adducts Related to Cigarette Smoking in Oral Cells in the Shanghai Cohort Study.

We developed a liquid chromatography-nanoelectrospray ionization-high-resolution tandem mass spectrometry (LC-NSI-HRMS/MS) method for simultaneous quantitative analysis of 5 oral cell DNA adducts associated with cigarette smoking: (8R/S)-3-(2'-deoxyribos-1'-yl)-5,6,7,8-tetrahydro-8-hydroxypyrimido[1,2-a]purine-10(3H)-one (γ-OH-Acr-dGuo, 1) from acrolein; (6S,8S and 6R,8R)-3-(2'-deoxyribos-1'-yl)-5,6,7,8-tetrahydro-8-hydroxy-6-methylpyrimido[1,2-a]purine-10(3H)-one [(6S,8S)γ-OH-Cro-dGuo, 2; and (6R,8R)γ-OH-Cro-dGuo, 3] from crotonaldehyde; 1,N6-etheno-dAdo (4) from acrylonitrile, vinyl chloride, lipid peroxidation, and inflammation; and 8-oxo-dGuo (5) from oxidative damage. Oral cell DNA was isolated in the presence of glutathione to prevent artifact formation. Clear LC-NSI-HRMS/MS chromatograms were obtained allowing quantitation of each adduct using the appropriately labeled internal standards. The accuracy and precision of the method were validated, and the assay limit of quantitation was 5 fmol/µmol dGuo for adducts 1-4 and 20 fmol/µmol for adduct 5. The assay was applied to 80 buccal cell samples selected from those collected in the Shanghai Cohort Study: 40 from current smokers and 40 from never smokers. Significant differences were found in all adduct levels between smokers and nonsmokers. Levels of 8-oxo-dGuo (5) were at least 3000 times greater than those of the other adducts in both smokers and nonsmokers, and the difference between amounts of this adduct in smokers versus nonsmokers, while significant (P = 0.013), was not as great as the differences of the other DNA adducts between smokers and nonsmokers (P-values all less than 0.001). No significant relationship of adduct levels to risk of lung cancer incidence was found. This study provides a new LC-NSI-HRMS/MS methodology for the quantitation of diverse DNA adducts resulting from exposure to the α,ß-unsaturated aldehydes acrolein and crotonaldehyde, inflammation, and oxidative damage which are all associated with carcinogenesis. We anticipate application of this assay in ongoing studies of the molecular epidemiology of cancers of the lung and oral cavity related to cigarette smoking.

DNA damage in human oral cells induced by use of e-cigarettes.

The use of electronic cigarettes (e-cigarettes) has increased rapidly in the United States, especially among high school students. e-Cigarettes contain some recognized carcinogens and may induce DNA damage in oral cells. The aim of this review is to summarize studies reporting DNA adducts or other types of DNA damage in oral cells in vitro or in vivo upon exposure to e-cigarette vapor and to evaluate the possible connections between e-cigarette exposure and oral cancer. Three databases including PubMed, Scopus, and EMBASE and gray literature were searched for articles published up to April 24, 2022. After screening 321 articles, we extracted 27 for further investigation. Based on the inclusion criteria, 22 articles were eligible for this review. The in vitro studies demonstrate that e-cigarette liquid or vapor can induce DNA damage, oxidative stress, DNA double-stranded breaks, apoptosis, cytotoxicity, and genotoxicity in different types of oral cells. The clinical studies showed that e-cigarette users have significantly higher levels of N'-nitrosonornicotine, acrolein DNA adducts, metanuclear anomalies, gene regulation, and lactate dehydrogenase enzyme expression and significantly lower levels of apurinic/apyrimidinic sites than non-users. Comparison of micronuclei levels between e-cigarette users and non-users gave inconsistent results. e-Cigarettes are implicated in DNA damage to oral cells, but publications to date present limited evidence. Future studies with larger sample sizes are required to investigate the long-term consequences of e-cigarette use.

Occurrence and risk of iodinated X-ray contrast media in source and tap water from Jiangsu province, China.

Microcontaminants in the water environment have received increasing attention due to their adverse effects on human health and wildlife. However, iodinated X-ray contrast media (ICM), a type of microcontaminants, have not yet been systematically documented in source and tap water. This study investigated ICM in water samples via a sampling activity from 25 drinking water sources and their corresponding 30 household taps in south-central Jiangsu Province, China. The total concentrations of ICM ranged from 14.2 to 138.5 ng/L in source water and 3.7 to 101.3 ng/L in tap water, respectively. The calculated average water treatment efficiency to remove ICM is 38.3% with large variation under different processes (ranging from 7.3% to 75.7%), which implied that ICM could not be effectively removed using current treatment technologies. By integrating other ICM into the predominant compound iohexol with relative potency factors, the health risks of total ICM through water consumption were assessed using the Monte Carlo simulation. The results concluded that the risk of ingesting ICM through tap water was not a major health concern for adults, teens, or children in the study area. Nevertheless, due to the lack of long-term toxicity data relevant for humans for ICM, this risk may be underestimated, which requires further research.

Increased acrolein-DNA adducts in buccal brushings of e-cigarette users.

DNA adducts are central in the mechanism of carcinogenesis by genotoxic agents. We compared levels of a DNA adduct of acrolein, a genotoxic carcinogen found in e-cigarette vapor, in oral cell DNA of e-cigarette users and non-users of any tobacco or nicotine product. e-Cigarette users and non-users visited our clinic once monthly for 6 months, and oral brushings and urine samples were collected. For this study, we analyzed oral cell DNA adducts from three monthly visits in e-cigarette users and non-users as confirmed by urinary cyanoethyl mercapturic acid and total nicotine equivalents. DNA was isolated from the oral brushings and analyzed by a validated liquid chromatography-nanoelectrospray ionization-high resolution tandem mass spectrometry method for the acrolein DNA adduct 8R/S-3-(2'-deoxyribos-1'-yl)-5,6,7,8-tetrahydro-8-hydroxypyrimido[1,2-a]purine-10-(3H)-one (γ-OH-Acr-dGuo). The median value of this DNA adduct in the e-cigarette users was 179 fmol/µmol dGuo (range 5.0 - 793 fmol/µmol dGuo) while that for non-users was 21.0 fmol/µmol dGuo (range 5.0 - 539 fmol/µmol dGuo), P = 0.001. These results demonstrate for the first time that e-cigarette users have elevated levels of a carcinogen-DNA adduct in their oral cells.

Liquid Chromatography-Nanoelectrospray Ionization-High-Resolution Tandem Mass Spectrometry Analysis of Apurinic/Apyrimidinic Sites in Oral Cell DNA of Cigarette Smokers, e-Cigarette Users, and Nonsmokers.

Cigarette smoking is an established risk factor for oral cancer. The health effects of e-cigarettes are still under investigation but may disturb oral cavity homeostasis and cause lung and cardiovascular diseases. Carcinogens and toxicants in tobacco products and e-cigarettes may damage DNA, resulting in the formation of apurinic/apyrimidinic (AP) sites and initiation of the carcinogenic process. In this study, we optimized a liquid chromatography-nanoelectrospray ionization-high-resolution tandem mass spectrometry method to analyze AP sites in buccal cell DNA of 35 nonsmokers, 30 smokers, and 30 e-cigarette users. AP sites in e-cigarette users (median 3.3 per 107 nts) were significantly lower than in smokers (median 5.7 per 107 nts) and nonsmokers (median 6.0 per 107 nts). AP sites in smokers were not significantly different from nonsmokers (p > 0.05). The e-cigarette vaporizing solvents propylene glycol and glycerin were tested and did not protect against AP site formation in in vitro control and carcinogen exposed rat liver homogenates. However, propylene glycol may inhibit bacteria in oral cells, resulting in reduced inflammation and related effects, and reduced AP site levels in e-cigarette user DNA. This is the first study to examine AP site formation in e-cigarette users and to evaluate AP sites in human oral cell DNA.

Mass Spectrometric Quantitation of Apurinic/Apyrimidinic Sites in Tissue DNA of Rats Exposed to Tobacco-Specific Nitrosamines and in Lung and Leukocyte DNA of Cigarette Smokers and Nonsmokers.

Metabolic activation of the carcinogenic tobacco-specific nitrosamines 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and N'-nitrosonornicotine (NNN) results in formation of reactive electrophiles that modify DNA to produce a variety of products including methyl, 4-(3-pyridyl)-4-oxobutyl (POB)-, and 4-(3-pyridyl)-4-hydroxybutyl adducts. Among these are adducts such as 7-POB-deoxyguanosine (N7POBdG) which can lead to apurinic/apyrimidinic (AP) sites by facile hydrolysis of the base-deoxyribonucleoside bond. In this study, we used a recently developed highly sensitive mass spectrometric method to quantitate AP sites by derivatization with O-(pyridin-3-yl-methyl)hydroxylamine (PMOA) (detection limit, 2 AP sites per 108 nucleotides). AP sites were quantified in DNA isolated from tissues of rats treated with NNN and NNK and from human lung tissue and leukocytes of cigarette smokers and nonsmokers. Rats treated with 5 or 21 mg/kg bw NNK for 4 days by s.c. injection had 2-6 and 2-17 times more AP sites than controls in liver and lung DNA (p < 0.05). Increases in AP sites were also found in liver DNA of rats exposed for 10 and 30 weeks (p < 0.05) but not for 50 and 70 weeks to 5 ppm of NNK in their drinking water. Levels of N7POBG were significantly correlated with AP sites in rats treated with NNK. In rats treated with 14 ppm (S)-NNN in their drinking water for 10 weeks, increased AP site formation compared to controls was observed in oral and nasal respiratory mucosa DNA (p < 0.05). No significant increase in AP sites was found in human lung and leukocyte DNA of cigarette smokers compared to nonsmokers, although AP sites in leukocyte DNA were significantly correlated with urinary levels of the NNK metabolite 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL). This is the first study to use mass spectrometry based methods to examine AP site formation by carcinogenic tobacco-specific nitrosamines in laboratory animals and to evaluate AP sites in DNA of smokers and nonsmokers.

Halogenated flame retardants in sediments from the Upper Laurentian Great Lakes: Implications to long-range transport and evidence of long-term transformation.

Most hydrophobic halogenated flame retardants (HFRs) are highly accumulative and persistent in aquatic sediments. The objective of this study was to reveal spatial distributions, temporal trends, and transformation of selected legacy and emerging HFRs in sediments of Lakes Superior, Michigan, and Huron. We collected Ponar grab samples at 112 locations and sediment cores at 28 sites in the three lakes, and measured concentrations of 19 brominated FRs and 12 chlorinated FRs. Based on grab samples, concentrations were higher at southeastern and sites near Sleeping Bear Dunes of Lake Michigan, and Saginaw Bay and the North Channel of Lake Huron. The annual loadings of polybrominated diphenyl either (PBDEs) and Dechlorane Plus (DPs) to sediment have leveled off or been declining since 2000, while loadings of DBDPE and Dec604 have increased since the 1960s in most cores. The concentration ratio of BB101 to BB153 increased with sediment depth, suggesting the occurrence of in situ debromination of BB153. The ratio of dechlorinated anti-Cl11DP over anti-DP increases with the increasing latitude of sampling locations, suggesting the occurrence of dechlorination of anti-DP to anti-Cl11DP during transport. This ratio also increases with increasing sediment age in most cores, implying in situ dechlorination over time.

Sedimentary records of polychlorinated biphenyls in the East China Marginal Seas and Great Lakes: Significance of recent rise of emissions in China and environmental implications.

Polychlorinated biphenyls (PCBs) in dated sediment cores from the East China Marginal Seas (ECMSs) and the chronology of the net fluxes to sediments were analyzed. The accumulation of 27 PCBs (ΣPCBs) in the ECMS sediments is about 5-26 ng cm-2, with the net depositional fluxes of ΣPCBs 10 times lower than those observed in the Great Lakes during the 1960s-1970s. Exponential increases in PCB deposition to the ECMS sediments since the 1990s were observed, which closely follows the fast growth of PCB emissions from industrial thermal processes and e-waste related sources in China. Recent PCB fluxes to the study sites in the ECMSs and the Great Lakes are comparable; the former surged forward with a rising tendency, while the latter showed continued decline after the late 1970s. Due to the different PCB application histories and sources between the two regions, the ECMS sediments may remain as a net sink for land-derived PCBs, while sediments in the Great Lake may have been acting as a secondary source releasing PCBs to water. A higher proportion of trichlorobiphenyls in the ECMS sediments than the Great Lakes was indicated, which may imply the net transport of atmospheric PCBs from China.

Photochemical degradation of polyhalogenated carbazoles in hexane by sunlight.

Polyhalogenated carbazoles (PHCZs) are a class of halogenated dibenzopyrrole, which have been increasingly detected in the environment and found to be bioaccumulative and potentially toxic. However, their environmental transformation potential is largely unknown. In this study, UV absorption spectra of carbazole (CZ) and 10 PHCZs were obtained with wavelength range 290-400 nm, and three peaks were identified in most cases with the highest occurring around 300 nm. Hexane solutions of CZ, 10 individual PHCZs, and a sediment extract containing nine other PHCZs were separately irradiated under natural sunlight in order to investigate their photodegradation kinetics and pathways. The pseudo-first-order reaction rate constants (k) of these PHCZs varied from 0.183 h-1 to 2.394 h-1, and increased exponentially with increasing numbers of chlorines and bromines in PHCZ molecules. Contribution to ln k from each bromine atom is more than doubling of that from each chlorine atom. Stepwise reduction debromination was confirmed to be one of the photodegradation mechanisms for both brominated and mixed halogenated (containing both bromine and chlorine) carbazoles. Only sporadic dechlorinated products were found during the photolysis of chlorinated carbazoles. By adopting a simplified kinetic approach, we estimated that dehalogenation contributed approximately 20% to 51% of the total loss of the parent PHCZs.

Tri(2,4-di- t-butylphenyl) Phosphate: A Previously Unrecognized, Abundant, Ubiquitous Pollutant in the Built and Natural Environment.

Using high-resolution mass spectrometry, we identified tri(2,4-di- t-butylphenyl) phosphate (TDTBPP) in e-waste dust. This is a previously unsuspected pollutant that had not been reported before in the environment. To assess its abundance in the environment, we measured its concentration in e-waste dust, house dust, sediment from the Chicago Ship and Sanitary Canal, Indiana Harbor water filters, and filters from high-volume air samplers deployed in Chicago, IL. To provide a context for interpreting these quantitative results, we also measured the concentrations of triphenyl phosphate (TPhP), a structurally similar compound, in these samples. Median concentrations of TDTBPP and TPhP were 14 400 and 41 500 ng/g, respectively, in e-waste dust and 4900 and 2100 ng/g, respectively, in house dust. TDTBPP was detected in sediment, water, and air with median concentrations of 527 ng/g, 3700 pg/L, and 149 pg/m3, respectively. TDTBPP concentrations were generally higher or comparable to those of TPhP in all media analyzed, except for the e-waste dust. Exposure from dust ingestion and dermal absorption in the e-waste recycling facility and in homes was calculated. TDTBPP exposure was 571 ng/kg bw/day in the e-waste recycling facility (pro-rated for an 8-h shift), and 536 ng/kg bw and 7550 ng/kg bw/day for adults and toddlers, respectively, in residential environments.

Accumulation of flame retardants in paired eggs and plasma of bald eagles.

In this study, we measured the concentrations of 58 flame retardants (and related compounds) in bald eagle (Haliaeetus leucocephalus) egg and plasma samples from the Michigan. These analytes include polybrominated diphenyl ethers (PBDEs), novel flame retardants (nFRs), Dechlorane-related compounds (Decs), and organophosphate esters (OPEs). A total of 24 paired eaglet plasma and egg samples were collected from inland (IN, N = 13) and the Great Lakes (GL, N = 11) breeding areas from 2000 to 2012. PBDEs were the most abundant chemical group with a geometric mean of 181 ng/g wet weight (ww) in egg and 5.31 ng/g ww in plasma. Decs were barely found in plasma samples, but they were frequently found in eggs (geometric mean 23.5 ng/g ww). OPE levels were comparable to those of PBDEs in the plasma but lower than those of PBDEs in eggs. Dec and PBDE concentrations were significantly higher in GL than in IN (p < 0.05). The ratio of egg to plasma concentrations (lipid normalized) varied with chemicals and correlated with the chemical's octanol-water partition coefficient. The lipid normalized bald eagle egg and plasma concentrations from Lake Superior and Huron were one to three orders of magnitude higher than concentrations measured in composite lake trout (Salvelinus namaycush) from the same lake, implying that they biomagnify in the environment.

Alternative Flame Retardant, 2,4,6-Tris(2,4,6-tribromophenoxy)-1,3,5-triazine, in an E-waste Recycling Facility and House Dust in North America.

A high molecular weight compound, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ), was detected during the analysis of brominated flame retardants in dust samples collected from an electrical and electronic waste (e-waste) recycling facility in Ontario, Canada. Gas chromatography coupled with both high-resolution and low-resolution mass spectrometry (MS) was used to determine TTBP-TAZ's chemical structure and concentrations. To date, TTBP-TAZ has only been detected in plastic casings of electrical and electronic equipment and house dust from The Netherlands. Here we report on the concentrations of TTBP-TAZ in selected samples from North America: e-waste dust ( n = 7) and air ( n = 4), residential dust ( n = 30), and selected outdoor air ( n = 146), precipitation ( n = 19), sediment ( n = 11) and water ( n = 2) samples from the Great Lakes environment. TTBP-TAZ was detected in all the e-waste dust and air samples, and in 70% of residential dust samples. The median concentrations of TTBP-TAZ in these three types of samples were 5540 ng/g, 5.75 ng/m3 and 6.76 ng/g, respectively. The flame retardants 2,4,6-tribromophenol, tris(2,3-dibromopropyl) isocyanurate, and 3,3',5,5'-tetrabromobisphenol A bis(2,3-dibromopropyl) ether, BDE-47 and BDE-209 were also measured for comparison. None of these other flame retardants concentrations was significantly correlated with those of TTBP-TAZ in any of the sample types suggesting different sources. TTBP-TAZ was not detected in any of the outdoor environmental samples, which may relate to its application history and physicochemical properties. This is the first report of TTBP-TAZ in North America.

Updated Polychlorinated Biphenyl Mass Budget for Lake Michigan.

This study revisits and updates the Lake Michigan Mass Balance Project (LMMBP) for polychlorinated biphenyls (PCBs) that was conducted in 1994-1995. This work uses recent concentrations of PCBs in tributary and open lake water, air, and sediment to calculate an updated mass budget. Five of the 11 LMMBP tributaries were revisited in 2015. In these five tributaries, the geometric mean concentrations of ∑PCBs (sum of 85 congeners) ranged from 1.52 to 22.4 ng L-1. The highest concentrations of PCBs were generally found in the Lower Fox River and in the Indiana Harbor and Ship Canal. The input flows of ∑PCBs from wet deposition, dry deposition, tributary loading, and air to water exchange, and the output flows due to sediment burial, volatilization from water to air, and transport to Lake Huron and through the Chicago Diversion were calculated, as well as flows related to the internal processes of settling, resuspension, and sediment-water diffusion. The net transfer of ∑PCBs is 1240 ± 531 kg yr-1 out of the lake. This net transfer is 46% lower than that estimated in 1994-1995. PCB concentrations in most matrices in the lake are decreasing, which drove the decline of all the individual input and output flows. Atmospheric deposition has become negligible, while volatilization from the water surface is still a major route of loss, releasing PCBs from the lake into the air. Large masses of PCBs remain in the water column and surface sediments and are likely to contribute to the future efflux of PCBs from the lake to the air.

Assessing bioaccessibility and bioavailability of chlorinated organophosphorus flame retardants in sediments.

The distribution of chlorinated organophosphate flame retardants (OPFRs) in sediments has been well documented, but the study about their bioavailability remains lacking. This study investigated the applicability of solid phase microextraction (SPME) fiber and Tenax extraction to predict the bioavailability of two chlorinated OPFRs: tri(2-chloroisopropyl) phosphate and tri(1,3-dichloro-2-isopropyl) phosphate, in sediments. Our results showed that both SPME fiber and Tenax extracted concentrations correlated significantly with the measured concentrations in the aquatic worm (Lumbriculus variegatus). We also measured the Tenax extracted concentrations at 6 and 24 h, and a strong linear relationship between these two time durations was found. In addition, the 6-h Tenax extracted concentrations also significantly correlated with the SPME fiber extracted concentrations, and the Tenax extracted concentrations were much higher than the SPME fiber extracted concentrations. These results demonstrate the efficiency of SPME and Tenax extraction methods to predict the bioavailability of chlorinated OPFRs in sediments, and it was found that the Tenax extraction is more promising than the SPME extraction.

Current-Use Flame Retardants in the Water of Lake Michigan Tributaries.

In this study, we measured the concentrations of 65 flame retardants in water samples from five Lake Michigan tributaries. These flame retardants included organophosphate esters (OPEs), brominated flame retardants (BFRs), and Dechlorane-related compounds. A total of 59 samples, including both the particulate and the dissolved phases, were collected from the Grand, Kalamazoo, Saint Joseph, and Lower Fox rivers and from the Indiana Harbor and Ship Canal (IHSC) in 2015. OPEs were the most abundant among the targeted compounds with geometric mean concentrations ranging from 20 to 54 ng/L; OPE concentrations were comparable among the five tributaries. BFR concentrations were about 1 ng/L, and the most-abundant compounds were bis(2-ethylhexyl) tetrabromophthalate, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate, and decabromodiphenyl ether. The highest BFR concentrations were measured in either the IHSC or the Saint Joseph River. The dechlorane-related compounds were detected at low concentrations (<1 pg/L). The fraction of target compounds in the particulate phase relative to the dissolved phase varied by chemical and tended to increase with their octanol-water partition coefficient. The chemical loading from all the five tributaries into Lake Michigan were <10 kg/year for the BFRs and about 500 kg/year for the OPEs.

Organophosphate Esters in Sediment of the Great Lakes.

This is the first study on organophosphate ester (OPEs) flame retardants and plasticizers in the sediment of the Great Lakes. Concentrations of 14 OPEs were measured in three sediment cores and 88 Ponar surface grabs collected from Lakes Ontario, Michigan, and Superior of North America. The sum of these OPEs (Σ14OPEs) in Ponar grabs averaged 2.2, 4.7, and 16.6 ng g-1 dw in Lakes Superior, Michigan, and Ontario, respectively. Multiple linear regression analyses demonstrated statistically significant associations between logarithm concentrations of Σ14OPEs as well as selected congeners in surface grab samples and sediment organic carbon content as well as a newly developed urban distance factor. Temporal trends observed in dated sediment cores from Lake Michigan demonstrated that the recent increase in depositional flux to sediment is dominated by chlorinated OPEs, particularly tris(2-chloroisopropyl) phosphate (TCPP), which has a doubling time of about 20 years. Downward diffusion within sediment may have caused vertical fractionation of OPEs over time. Two relatively hydrophilic OPEs including TCPP had much higher concentrations in sediment than estimated based on equilibria between water and sediment organic carbon. Approximately a quarter (17 tonnes) of the estimated total OPE burden (63 tonnes) in Lake Michigan resides in sediment, which may act as a secondary source releasing OPEs to the water column for years to come.

Bioaccumulation of Dechloranes, organophosphate esters, and other flame retardants in Great Lakes fish.

We measured the concentrations of 60 flame retardants (and related compounds) in fish samples collected in the Great Lakes basin. These analytes include dechlorane-related compounds (Decs), organophosphate esters (OPEs), and brominated flame retardants (BFRs). Composite lake trout (Salvelinus namaycush) or walleye (Sander vitreus, from Lake Erie) samples were collected (N=3 for each lake) in 2010 from each of the five Great Lakes (a total of 15 samples). Among the dechlorane-related compounds, Dechlorane, Dechlorane Plus, Dechlorane-602, Dechlorane-603, and Dechlorane-604 (with zero to three bromines and with four chlorines) were detected in >73% of the fish samples. The concentrations of some of these dechlorane-related compounds were 3-10 times higher in Lake Ontario trout than in fish from the other four lakes. Tris(1-chloroisopropyl) phosphate, tri-n-butylphosphate, tris(2-chloroethyl)phosphate, and triphenyl phosphate were found in >50% of the fish samples. Polybrominated diphenyl ethers (PBDEs) were the most abundant of the flame retardants in fish, with a mean concentration of 250ng/g lipid. Our findings suggest that the Decs and BFRs with 3-6 bromines are more bioaccumulative in the fish than the OPEs and high molecular weight BFRs.