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.

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.

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.

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.

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.

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.

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.

Spatial and Temporal Trends of Polyhalogenated Carbazoles in Sediments of Upper Great Lakes: Insights into Their Origin.

Polyhalogenated carbazoles (PHCZs) have been increasingly detected in the environment. Their similarities in chemical structure with legacy pollutants and their potential toxicity have caused increasing concern. In this work, 112 Ponar grab and 28 core sediment samples were collected from Lakes Michigan, Superior, and Huron, and a total of 26 PHCZs were analyzed along with unsubstituted carbazole using gas chromatography coupled with single- or triple-quadrupole mass spectrometry. Our results show that the total accumulation of PHCZs in the sediments of the upper Great Lakes is >3000 tonnes, orders of magnitude greater than those of polychlorinated biphenyls (PCBs) and decabromodiphenyl ether (BDE209). The 27 individual analytes differ in spatial distribution and temporal trend. Our results showed that PHCZs with substitution patterns of -Br2-5, -Cl1-2Br2-4, or having iodine, were more abundant in sediment of Lake Michigan deposited before 1900 than those deposited more recently, implying a natural origin. Some "emerging" PHCZs have been increasingly deposited into the sediment in recent decades, and deserve further environmental monitoring and research. Other PHCZs with low halogen substitution may form from in situ dehalogenation of PHCZs having more halogens. Anthropogenic sources of PHCZs may exist, particularly for the emerging and low molecular mass congeners.

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.

Identification of Marbon in the Indiana Harbor and Ship Canal.

Marbon is isomeric with Dechlorane Plus (DP). Both are produced by the Diels-Alder condensation of hexachlorocyclopentadiene with cyclic dienes, and both have elemental compositions of C18H12Cl12. Dechlorane Plus is commonly found in the environment throughout the world, but Marbon has, so far, only been detected at low levels in one sediment core collected near the mouth of the Niagara River in Lake Ontario. Here we report on the concentrations of Marbon and anti-DP in 59 water samples from five Lake Michigan tributaries [the Grand, Kalamazoo, St. Joseph, and Lower Fox Rivers, and the Indiana Harbor and Ship Canal (IHSC)], 10 surface sediment samples from the IHSC, and 2 surface sediment samples from the Chicago Sanitary and Ship Canal. Three Marbon diastereomers were detected in the water and sediment samples from the IHSC, which is far from the location of its previous detection in Lake Ontario. The sum of the concentrations of the three Marbons was greater in the water from the IHSC (N = 11, median =150 pg/L) compared to those in water from the other four tributaries (N = 11-13, medians =0.9-2.0 pg/L). Marbon concentrations in sediment samples from the IHSC were up to 450 ng/g dry weight. Anti-DP was also measured for comparison. Its concentrations were not significantly different among the water samples, but its sediment concentrations in the IHSC were significantly correlated with those of Marbon. The source of Marbon contamination in the IHSC is not clear.

Occurrence of Atrazine and Related Compounds in Sediments of Upper Great Lakes.

Surface grab and core sediment samples were collected from Lakes Michigan, Superior, and Huron from 2010 to 2012, and concentrations of herbicides atrazine, simazine, and alachlor, as well as desethylatrazine (DEA), were determined. Concentrations of atrazine in surface grabs ranged from 0.01 to 1.7 ng/g dry weight and are significantly higher in the southern basin of Lake Michigan (latitude <44°) than other parts of the three lakes. The highest concentration of alachlor was found in sediments of Saginaw Bay in Lake Huron. The inventory and net fluxes of these herbicides were found to decline exponentially from the south to the north. The concentration ratio of DEA to atrazine (DEA/ATZ) increased with latitude, suggesting degradation of atrazine to DEA during atmospheric transport. DEA/ATZ also increased with sediment depth in the sediment cores. Diffusion of deposited herbicides from the upper sediment into deeper sediments has occurred, on the basis of the observed patterns of concentrations in dated sediment cores. Concentrations of atrazine in pore water were estimated and were higher than those reported for the bulk waters, suggesting the occurrence of solid-phase deposition of atrazine through the water column and that contaminated sediments act as a source releasing atrazine to the overlying water.

Polyhalogenated carbazoles in sediments of Lake Michigan: a new discovery.

Previously unknown halogenated compounds were detected during the analysis of halogenated flame retardants in two sediment cores collected from Lake Michigan. Gas chromatography coupled with high- or low-resolution mass spectrometry (MS) was used to determine the chemical structures for a total of 15 novel polyhalogenated carbazoles (PHCs) with the general molecular formula C12H9-x-y-zNClxBryIz. On the basis of the mass spectra generated by electron impact (EI) and electron capture negative ionization (ECNI) MS, eight PHCs were tentatively identified as polybrominated carbazoles, while the others were mixed halogenated carbazoles containing, in addition to bromine, either chlorine or iodine or both. Patterns of halogen substitution of PHCs included Br2 to Br5, ClBr2, ClBr3, ClBr4, ClBr3I, Br4I, and Br3I2. 3,6-Dibromocarbazole and 1,3,6,8-tetrabromocarbazole were also found among the PHCs. Profiles of the concentration versus depth of sediment at the two sites showed various patterns among polybrominated carbazoles. The abundance of mixed halogenated carbazoles peaked at depths of 12-16 cm, remained at relatively constant levels in deeper sediment, but declined markedly in more recently deposited sediments. This is the first study discovering the seven mixed halogenated carbazoles in the environment. Detailed methods for their detection and identification are provided.

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.

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.

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.

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.

Emerging brominated flame retardants in the sediment of the Great Lakes.

The concentrations of 13 currently used brominated flame retardants (BFRs) were analyzed in 16 sediment cores collected from the North American Great Lakes. Among them, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromocyclododecane (HBCD), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), and hexachlorocyclopentadienyl dibromocyclooctane (HCDBCO) were more frequently detected than others. In general, these emerging BFRs have much lower concentrations than polybromodiphenyl ethers (PBDEs) and dechloranes. Inventories of the five BFRs named above, given on a logarithm basis, were found to decrease linearly with the increasing latitude of the sampling locations, but with weaker statistics than those previously reported for the dechloranes. Logarithm of surface fluxes, on the other hand, was found to be a better parameter in correlating with the longitude. With regard to time trends, the exponential increases in concentrations of these BFRs, particularly DBDPE and BTBPE, in recent years are particularly disturbing. The sediment concentration of DBDPE doubles every 3-5 years in Lake Michigan, and approximately every 7 years in Lake Ontario. The corresponding doubling times for BTBPE are about 5 and 7 years in Lakes Ontario and Michigan, respectively, although declines or leveling off were observed in the top sediment layers in Lake Ontario. In contrast to PCBs, PBDEs, and most dechloranes, the correlations between the surface concentration of emerging BFRs and the latitude or longitude of the sampling sites were not strengthened by normalization of the concentration based on the organic matter content of the sediment.

Historically and currently used Dechloranes in the sediments of the Great Lakes.

Dechlorane (mirex), Dechlorane Plus (DP), Dechlorane 602 (Dec602), Dechlorane 603 (Dec603), Dechlorane 604 (Dec604), and Chlordecone (Kepone) were analyzed in 16 sediment cores collected in 2007 from the Great Lakes of North America. Results show that Lake Ontario sediments have accumulated mirex, DP, Dec602 and Dec604 in amounts 1 to 2 orders of magnitude higher than other Great Lakes. The chemical inventory decreases log-linearly with increasing latitude (N) and longitude (W) of the sampling locations, but Lake Ontario sites are outliers in the regression against latitude. The regression analyses suggest differences among the analytes with regard to source impact and long-range transport behavior. Temporal trends of input differ among lakes. Most sites in Lake Superior are still receiving increasing fluxes of DP and Dec602, while these have been declining in Lake Ontario from the peak around 1990. The relative abundance of the two DP isomers, represented by f(syn), increases with increasing distance from the potential discharge source in Niagara Falls, NY, suggesting the anti-DP isomer is more vulnerable to degradation during long-range atmospheric transport. Kepone was not detected in the sediments of Lakes Ontario, Erie, and Michigan.