@article {139, title = {Mechanisms of pH-Dependent Uptake of Ionizable Organic Chemicals by Fish from Oil Sands Process-Affected Water (OSPW).}, journal = {Environ Sci Technol}, volume = {54}, year = {2020}, month = {2020 Aug 04}, pages = {9547-9555}, abstract = {

Uptake and effects of ionizable organic chemicals (IOCs) that are weak acids in aqueous solution by fish can differ as a function of pH. While the pH-dependent behavior of select IOCs is well-understood, complex mixtures of IOCs, e.g., from oil sands process-affected water (OSPW), have not yet been studied systematically. Here, we established an in vitro screening method using the rainbow trout gill cell line, RTgill-W1, to investigate pH-dependent cytotoxicity and permeation of IOCs across cultured epithelia using ultra-high-performance liquid chromatography with high-resolution mass spectrometry (UPLC-HRMS). The assay was benchmarked using model chemicals and technical mixtures, and then used to characterize fractions and reconstituted extracts of field-collected OSPW. Significant pH-dependent cytotoxicity of individual IOCs, acidic fractions, and reconstituted extracts of OSPW was observed. In vitro data were in good agreement with data from a 96 h in vivo exposure experiment with juvenile rainbow trout. Permeation of some IOCs from OSPW was mediated by active transport, as revealed by studies in which inhibitors of these active transport mechanisms were applied. We conclude that the RTgill-W1 in vitro assay is useful for the screening of pH-dependent uptake of IOCs in fish, and has applications for in vitroin vivo extrapolation, and prioritization of chemicals in nontarget screenings.

}, issn = {1520-5851}, doi = {10.1021/acs.est.0c02522}, author = {Brinkmann, Markus and Alharbi, Hattan and Fuchylo, Ulyana and Wiseman, Steve and Morandi, Garrett and Peng, Hui and Giesy, John P and Jones, Paul D and Hecker, Markus} } @article {129, title = {Abundances and concentrations of brominated azo dyes detected in indoor dust.}, journal = {Environ Pollut}, volume = {252}, year = {2019}, month = {2019 Sep}, pages = {784-793}, abstract = {

Dust samples were collected from four indoor environments, including childcare facilities, houses, hair salons, and a research facility from the USA and were analyzed for brominated compounds using full scan liquid chromatography high-resolution mass spectrometry. A total of 240 brominated compounds were detected in these dust samples, and elemental formulas were predicted for 120 more abundant ions. In addition to commonly detected brominated flame retardants (BFRs), nitrogen-containing brominated azo dyes (BADs) were among the most frequently detected and abundant. Specifically, greater abundances of BADs were detected in indoor dusts from daycares and salons compared to houses and the research facility. Using authentic standards, a quantitative method was established for two BADs (DB373: Disperse Blue 373 and DV93: Disperse Violet 93) and 2-bromo-4,6-dinitroaniline, a commonly used precursor in azo dye production, in indoor dust. Generally, greater concentrations of DB373 (<=3850 ng/g) and DV93 (<=1190 ng/g) were observed in indoor dust from daycares highlighting children as a susceptible population to potential health risk from exposure to BADs. These data are important because, to date, targeted analysis of brominated compounds in indoor environments has focused mainly on BFRs and appears to underestimate the total amount of brominated compounds.

}, keywords = {Air Pollution, Indoor, Aniline Compounds, Azo Compounds, Child, Child Day Care Centers, Chromatography, Liquid, Dust, Flame Retardants, Halogenated Diphenyl Ethers, Humans, Hydrocarbons, Brominated, Nitrogen, Tandem Mass Spectrometry}, issn = {1873-6424}, doi = {10.1016/j.envpol.2019.05.153}, author = {Dhungana, Birendra and Peng, Hui and Kutarna, Steven and Umbuzeiro, Gisela and Shrestha, Sujan and Liu, Jing and Jones, Paul D and Subedi, Bikram and Giesy, John P and Cobb, George P} } @article {128, title = {Underlying mechanisms of reproductive toxicity caused by multigenerational exposure of 2, bromo-4, 6-dinitroaniline (BDNA) to Zebrafish (Danio rerio) at environmental relevant levels.}, journal = {Aquat Toxicol}, volume = {216}, year = {2019}, month = {2019 Nov}, pages = {105285}, abstract = {

2-bromo-4, 6-dinitroaniline (BDNA) is a mutagenic aromatic amine involved in the production and degradation of Disperse blue 79, one of the most extensively used brominated azo dyes. In our previous study, a multigenerational exposure of BDNA (0.5, 5, 50 and 500 μg/L) to zebrafish from F adult to F larvae including a recovery group in F larvae was conducted. The effects on apical points observed in individuals and the long-term effects predicted on population were all related to reproduction. In this study, we performed molecular analysis to elucidate the underlying mechanisms of the reproductive toxicity of BDNA. In F generation, measurement of vitellogenin and transcription levels of genes associated with hypothalamus-pituitary-gland (HPG) axis, estrogen receptor (ER) and androgen receptor (AR) were conducted. There was a decrease in VTG level in the blood of F female fish and transcription of genes related to ER was more affected than that of genes related to AR. These results were consistent with adverse effects that sexual differentiation was biased towards males and fecundity was impaired in a concentration-dependent manner in adults of F generation after 150 days exposure. In F generation, global gene transcriptions of F larvae were investigated. It was uncovered that processes related to apoptosis, development and DNA damage were strongly affected. Alterations to these biological pathways accounted for the irreversible parental influence on a significant decrease in hatchability and increase in abnormality of F larvae. All evidence suggested that the multigenerational exposure of BDNA posed lasting effects transmitted from parents to offspring that persisted after exposure ceased.

}, keywords = {Aniline Compounds, Animals, DNA Damage, Environmental Exposure, Female, Larva, Male, Principal Component Analysis, Reproduction, Toxicity Tests, Transcription, Genetic, Transcriptome, Vitellogenins, Water Pollutants, Chemical, Zebrafish}, issn = {1879-1514}, doi = {10.1016/j.aquatox.2019.105285}, author = {Xie, Xianyi and Jin, Yaru and Ma, Zhiyuan and Tang, Song and Peng, Hui and Giesy, John P and Liu, Hongling} } @article {86, title = {Current and historical concentrations of poly and perfluorinated compounds in sediments of the northern Great Lakes - Superior, Huron, and Michigan.}, journal = {Environ Pollut}, volume = {236}, year = {2018}, month = {2018 May}, pages = {373-381}, abstract = {

Current and historical concentrations of 22 poly- and perfluorinated compounds (PFASs) in sediment collected from Lake Superior and northern Lake Michigan in 2011 and Lake Huron in 2012 are reported. The sampling was performed in two ways, Ponar grabs of surface sediments for current spatial distribution across the lake and dated cores for multi-decadal temporal trends. Mean concentrations of the sum of PFASs (∑PFASs) were 1.5, 4.6 and 3.1 ng g dry mas (dm) in surface sediments for Lakes Superior, Michigan and Huron, respectively. Of the five Laurentian Lakes, the watersheds of Superior and Huron are the less densely populated by humans, and concentrations observed were typically less and from more diffuse sources, due to lesser urbanization and industrialization. However, some regions of greater concentrations were observed and might indicate more local, point sources. In core samples concentrations ranged from 7 that include perfluoro-n-octane sulfonate (PFOS) bind more strongly to sediment, which resulted in more accurate analyses of temporal trends. Shorter-chain PFASs, such as perfluoro-n-butanoic acid which is the primary replacement for C8 PFASs that have been phased out, are more soluble and were identified in some core layers at depths corresponding to pre-production periods. Thus, analyses of temporal trends of these more soluble compounds in cores of sediments were less accurate. Total elemental fluorine (TF) and extractable organic fluorine (EOF) indicated that identified PFASs were not a significant fraction of fluorine containing compounds in sediment (\<0.01\% in EOF).

}, keywords = {Environmental Monitoring, Fluorocarbons, Geologic Sediments, Great Lakes Region, Lakes, Water Pollutants, Chemical}, issn = {1873-6424}, doi = {10.1016/j.envpol.2018.01.065}, author = {Codling, Garry and Hosseini, Soheil and Corcoran, Margaret B and Bonina, Solidea and Lin, Tian and Li, An and Sturchio, Neil C and Rockne, Karl J and Ji, Kyunghee and Peng, Hui and Giesy, John P} } @article {84, title = {Sono-chemical treatment of per- and poly-fluoroalkyl compounds in aqueous film-forming foams by use of a large-scale multi-transducer dual-frequency based acoustic reactor.}, journal = {Ultrason Sonochem}, volume = {45}, year = {2018}, month = {2018 Jul}, pages = {213-222}, abstract = {

Aqueous film-forming foams (AFFFs) contain a mixture of organic chemicals, including per- and poly-fluorinated, alkyl sulfonate substances (PFAS) (1-5\%, w/w). Some longer-chain PFAS can be toxic, moderately bioaccumulative and persistent in the environment. In the present work, decomposition of PFAS present in two commercially available AFFFs (ANSUL- and 3M-) was investigated using a sono-chemical reactor of volume 91 L. The reactor consists of 12 transducers with operating frequencies of 1 MHz or 500 kHz and total input power of 12 kW. Degradation of PFASs performed using various dilutions of AFFF revealed that release of F and SO ions was inversely proportional to initial pH of up to 4. Defluorination of ANSUL-AFFF resulted in an increase in the concentration of F released from 55.6 {\textpm} 0.3 {\textmu}M (500{\texttimes} dilution) to 58.6 {\textpm} 0.6 (25{\texttimes} dilution), while for 3M AFFF it increased from 19.9 {\textpm} 0.7 {\textmu}M (500{\texttimes} dilution) to 217.1 {\textpm} 2.4 {\textmu}M (25{\texttimes} dilution). Though amounts of F released were less for ANSUL-AFFF than for 3M-AFFF, there was a considerable increase in removal of TOC and release of SO present in ANSUL-AFFF. Approximately 90.5\% and 26.6\% reduction of perfluoroalkyl sulfonates (PFSA) and perfluoroalkyl carboxylates (PFCA) in 3M, respectively, and 38.4\% reduction of fluorotelomer sulfonates in ANSUL-AFFF were achieved in 13 h. Estimated costs of energy for the treatment of ANSUL-AFFF and 3M-AFFF at a 500{\texttimes} dilution were $0.015 {\textpm} 0.0001/L and $0.019 {\textpm} 0.0002/L, respectively.

}, issn = {1873-2828}, doi = {10.1016/j.ultsonch.2018.02.014}, author = {Gole, Vitthal L and Sierra-Alvarez, Reyes and Peng, Hui and Giesy, John P and Deymier, Pierre and Keswani, Manish} } @article {85, title = {Spatial and temporal trends in poly- and per-fluorinated compounds in the Laurentian Great Lakes Erie, Ontario and St. Clair.}, journal = {Environ Pollut}, volume = {237}, year = {2018}, month = {2018 Jun}, pages = {396-405}, abstract = {

The temporal and spatial trends in sediment of 22 poly- and perfluorinated (PFAS) compounds were investigated in the southern Great Lakes Erie and Ontario as well as Lake St. Clair. Surface concentrations measured by Ponar grab samples indicated a trend for greater concentrations near to urban sites. Mean concentrations ∑PFAS were 15.6, 18.2 and 19 ng g dm for Lakes St. Clair, Erie and Ontario, respectively. Perfluoro-n-butanoic acid (PFBA) and Perfluoro-n-hexanoic acid (PFHxA) were frequently determined in surface sediment and upper core samples indicating a shift in use patterns. Where PFBA was identified it was at relatively great concentrations typically \>10 ng g dm. However as PFBA and PFHxA are less likely to bind to sediment they may be indicative of pore water concentrations Sedimentation rates between Lake Erie and Lake Ontario differ greatly with greater rates observed in Lake Erie. In Lake Ontario, in general concentrations of PFAS observed in core samples closely follow the increase in use along with an observable change due to regulation implementation in the 1970s for water protection. However some of the more water soluble PFAS were observed in deeper core layers than the time of production could account for, indicating potential diffusion within the sediment. Given the greater sedimentation rates in Lake Erie, it was hoped to observe in greater resolution changes since the mid-1990s. However, though some decrease was observed at some locations the results are not clear. Many cores in Lake Erie had clearly observable gas voids, indicative of gas ebullition activity due to biogenic production, there were also observable mussel beds that could indicate mixing by bioturbation of core layers.

}, keywords = {Environmental Monitoring, Fluorocarbons, Great Lakes Region, Lakes, Ontario, Water Pollutants, Chemical, Water Pollution, Chemical}, issn = {1873-6424}, doi = {10.1016/j.envpol.2018.02.013}, author = {Codling, Garry and Sturchio, Neil C and Rockne, Karl J and Li, An and Peng, H and Tse, Timothy J and Jones, Paul D and Giesy, John P} } @article {92, title = {Hydroxylated 2-Ethylhexyl tetrabromobenzoate isomers in house dust and their agonistic potencies with several nuclear receptors.}, journal = {Environ Pollut}, volume = {227}, year = {2017}, month = {2017 Aug}, pages = {578-586}, abstract = {

In the current study, by combining ultra-high resolution (UHR) MS spectra, MS spectra, and derivatization, three hydroxylated isomers of 2-ethylhexyl tetrabromobenzoate (OH-TBB) were identified in Firemaster 550 and BZ-54 technical products. Also, a new LC-UHRMS method, using atmospheric pressure chemical ionization (APCI), was developed for simultaneous analysis of OH-TBB, TBB, hydroxylated bis(2-ethylhexyl)-tetrabromophthalate (OH-TBPH) and TBPH in 23 samples of dust collected from houses in Saskatoon, SK, Canada. OH-TBBs were detected in 91\% of samples, with a geometric mean concentration of 0.21\ ng/g, which was slightly less than those of OH-TBPH (0.35\ ng/g). TBB was detected in 100\% of samples of dust with a geometric mean concentration of 992\ ng/g. Significant (p\ \<\ 0.001) log-linear relationships between concentrations of OH-TBBs, TBB, or OH-TBPHs and TBPH in dust support the hypothesis of a common source of these compounds. OH-TBBs were found to be strong agonists of peroxisome proliferator-activated receptor gamma (PPARγ) and weaker agonists of the estrogen receptor (ER), but no agonistic potencies was observed with the androgen receptor (AR). Occurrence of OH-TBBs in technical products and house dust, together with their relatively strong PPARγ potencies, indicated their potential risk to health of humans.

}, keywords = {Air Pollution, Indoor, Bromobenzoates, Canada, Dust, Environmental Monitoring, Flame Retardants, Halogenated Diphenyl Ethers, Humans}, issn = {1873-6424}, doi = {10.1016/j.envpol.2017.04.094}, author = {Peng, Hui and Sun, Jianxian and Saunders, David M V and Codling, Garry and Wiseman, Steve and Jones, Paul D and Giesy, John P} } @article {93, title = {Identification of Chemicals that Cause Oxidative Stress in Oil Sands Process-Affected Water.}, journal = {Environ Sci Technol}, volume = {51}, year = {2017}, month = {2017 Aug 01}, pages = {8773-8781}, abstract = {

Oil sands process-affected water (OSPW) has been reported to cause oxidative stress in organisms, yet the causative agents remain unknown. In this study, a high-throughput in vitro Nrf2 reporter system was used, to determine chemicals in OSPW that cause oxidative stress. Five fractions, with increasing polarity, of the dissolved organic phase of OSPW were generated by use of solid phase extraction cartridges. The greatest response of Nrf2 was elicited by F2 (2.7 {\textpm} 0.1-fold), consistent with greater hydroperoxidation of lipids in embryos of Japanese medaka (Oryzias latipes) exposed to F2. Classic naphthenic acids were mainly eluted in F1, and should not be causative chemicals. When F2 was fractionated into 60 subfractions by use of HPLC, significant activation of Nrf2 was observed in three grouped fractions: F2.8 (1.30 {\textpm} 0.01-fold), F2.16 (1.34 {\textpm} 0.05-fold), and F2.25 (1.28 {\textpm} 0.15-fold). 54 compounds were predicted to be potential chemicals causing Nrf2 response, predominated by SO and O species. By use of high-resolution MS spectra, these SO and O species were identified as hydroxylated aldehydes. This study demonstrated that polyoxygenated chemicals, rather than classic NAs, were the major chemicals responsible for oxidative stress in the aqueous phase of OSPW.

}, keywords = {Animals, Carboxylic Acids, Oil and Gas Fields, Oryzias, Oxidative Stress, Water, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/acs.est.7b01987}, author = {Sun, Jianxian and Peng, Hui* and Alharbi, Hattan A and Jones, Paul D and Giesy, John P and Wiseman, Steve B} } @article {94, title = {Response to Comment on "Mutagenic Azo Dyes, Rather than Flame Retardants, are the Predominant Brominated Compounds in House Dust".}, journal = {Environ Sci Technol}, volume = {51}, year = {2017}, month = {2017 03 21}, pages = {3591-3592}, keywords = {Air Pollution, Indoor, Azo Compounds, Dust, Environmental Exposure, Flame Retardants, Halogenated Diphenyl Ethers, Hydrocarbons, Brominated, Mutagens}, issn = {1520-5851}, doi = {10.1021/acs.est.7b00675}, author = {Peng, Hui and Saunders, David M V and Jones, Paul D and Giesy, John P} } @article {100, title = {Combined Transcriptomic and Proteomic Approach to Identify Toxicity Pathways in Early Life Stages of Japanese Medaka (Oryzias latipes) Exposed to 1,2,5,6-Tetrabromocyclooctane (TBCO).}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 07 19}, pages = {7781-90}, abstract = {

Currently, the novel brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO) is considered a potential replacement for hexabromocyclododecane (HBCD). Therefore, use of TBCO could increase in the near future. To assess potential toxicological risks to aquatic organisms, embryos of Japanese medaka (Oryzias latipes) were exposed to 10, 100, or 1000 μg/L TBCO from 2 h postfertilization until 1 day post-hatch. TBCO accumulated in embryos in the order of 0.43-1.3 {\texttimes} 10(4)-fold, and the rate constant of accumulation was 1.7-1.8 per day. The number of days to hatch and the hatching success of embryos exposed to the medium and the greatest concentrations of TBCO were impaired. Responses of the transcriptome (RNA-seq) and proteome were characterized in embryos exposed to 100 μg/L TBCO because this was the least concentration of TBCO that caused an effect on hatching. Consistent with effects on hatching, proteins whose abundances were reduced by exposure to TBCO were enriched in embryo development and hatching pathways. Also, on the basis of the responses of transcriptome and proteome, it was predicted that TBCO might impair vision and contraction of cardiac muscle, respectively, and these effects were confirmed by targeted bioassays. This study provided a comprehensive understanding of effects of TBCO on medaka at early life stages and illustrated the power of "omics" to explain and predict phenotypic responses to chemicals.

}, keywords = {Animals, Oryzias, Proteomics, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/acs.est.6b01249}, author = {Sun, Jianxian and Tang, Song and Peng, Hui* and Saunders, David M V and Doering, Jon A and Hecker, Markus and Jones, Paul D and Giesy, John P and Wiseman, Steve} } @article {101, title = {High Conservation in Transcriptomic and Proteomic Response of White Sturgeon to Equipotent Concentrations of 2,3,7,8-TCDD, PCB 77, and Benzo[a]pyrene.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 05 03}, pages = {4826-35}, abstract = {

Adverse effects associated with exposure to dioxin-like compounds (DLCs) are mediated primarily through activation of the aryl hydrocarbon receptor (AHR). However, little is known about the cascades of events that link activation of the AHR to apical adverse effects. Therefore, this study used high-throughput, next-generation molecular tools to investigate similarities and differences in whole transcriptome and whole proteome responses to equipotent concentrations of three agonists of the AHR, 2,3,7,8-TCDD, PCB 77, and benzo[a]pyrene, in livers of a nonmodel fish, the white sturgeon (Acipenser transmontanus). A total of 926 and 658 unique transcripts were up- and down-regulated, respectively, by one or more of the three chemicals. Of the transcripts shared by responses to all three chemicals, 85\% of up-regulated transcripts and 75\% of down-regulated transcripts had the same magnitude of response. A total of 290 and 110 unique proteins were up- and down-regulated, respectively, by one or more of the three chemicals. Of the proteins shared by responses to all three chemicals, 70\% of up-regulated proteins and 48\% of down-regulated proteins had the same magnitude of response. Among treatments there was 68\% similarity between the global transcriptome and global proteome. Pathway analysis revealed that perturbed physiological processes were indistinguishable between equipotent concentrations of the three chemicals. The results of this study contribute toward more completely describing adverse outcome pathways associated with activation of the AHR.

}, keywords = {Animals, Benzo(a)pyrene, Dioxins, Fishes, Polychlorinated Dibenzodioxins, Proteomics}, issn = {1520-5851}, doi = {10.1021/acs.est.6b00490}, author = {Doering, Jon A and Tang, Song and Peng, Hui and Eisner, Bryanna K and Sun, Jianxian and Giesy, John P and Wiseman, Steve and Hecker, Markus} } @article {95, title = {Mutagenic Azo Dyes, Rather Than Flame Retardants, Are the Predominant Brominated Compounds in House Dust.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 12 06}, pages = {12669-12677}, abstract = {

Characterization of toxicological profiles by use of traditional targeted strategies might underestimate the risk of environmental mixtures. Unbiased identification of prioritized compounds provides a promising strategy for meeting regulatory needs. In this study, untargeted screening of brominated compounds in house dust was conducted using a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) approach, which used data-independent acquisition (DIA) and a chemometric strategy to detect peaks and align precursor ions. A total of 1008 brominated compound peaks were identified in 23 house dust samples. Precursor ions and formulas were identified for 738 (73\%) of the brominated compounds. A correlation matrix was used to cluster brominated compounds; three large groups were found for the 140 high-abundance brominated compounds, and only 24 (17\%) of these compounds were previously known flame retardants. The predominant class of unknown brominated compounds was predicted to consist of nitrogen-containing compounds. Following further validation by authentic standards, these compounds (56\%) were determined to be novel brominated azo dyes. The mutagenicity of one major component was investigated, and mutagenicity was observed at environmentally relevant concentrations. Results of this study demonstrated the existence of numerous unknown brominated compounds in house dust, with mutagenic azo dyes unexpectedly being identified as the predominant compounds.

}, keywords = {Azo Compounds, Dust, Flame Retardants, Halogenated Diphenyl Ethers, Hydrocarbons, Brominated, Mutagens}, issn = {1520-5851}, doi = {10.1021/acs.est.6b03954}, author = {Peng, Hui and Saunders, David M V and Sun, Jianxian and Jones, Paul D and Wong, Chris K C and Liu, Hongling and Giesy, John P} } @article {99, title = {Peroxisome Proliferator-Activated Receptor γ is a Sensitive Target for Oil Sands Process-Affected Water: Effects on Adipogenesis and Identification of Ligands.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 07 19}, pages = {7816-24}, abstract = {

Identification of toxic components of complex mixtures is a challenge. Here, oil sands process-affected water (OSPW) was used as a case study to identify those toxic components with a known protein target. Organic chemicals in OSPW exhibited dose-dependent activation of peroxisome proliferator-activated receptor γ (PPARγ) at concentrations less than those currently in the environment (0.025{\texttimes} equivalent of full-strength OSPW), by use of a luciferase reporter gene assay. Activation of PPARγ-mediated adipogenesis by OSPW was confirmed in 3T3L1 preadipocytes, as evidenced by accumulation of lipids and up-regulation of AP2, LPL, and PPARγ gene expression after exposure to polar fractions of OSPW. Unexpectedly, the nonpolar fractions of OSPW inhibited differentiation of preadipocytes via activation of the Wnt signaling pathway. Organic chemicals in OSPW that were ligands of PPARγ were identified by use of a pull-down system combined with untargeted chemical analysis (PUCA), with a recombinant PPARγ protein. Thirty ligands of PPARγ were identified by use of the PUCA assay. High resolution MS(1) and MS(2) spectra were combined to predict the formulas or structures of a subset of ligands, and polyoxygenated or heteroatomic chemicals, especially hydroxylated carboxylic/sulfonic acids, were the major ligands of PPARγ.

}, keywords = {Adipogenesis, Ligands, Oil and Gas Fields, PPAR gamma, Water}, issn = {1520-5851}, doi = {10.1021/acs.est.6b01890}, author = {Peng, Hui and Sun, Jianxian and Alharbi, Hattan A and Jones, Paul D and Giesy, John P and Wiseman, Steve} } @article {96, title = {Sonochemical degradation of perfluorinated chemicals in aqueous film-forming foams.}, journal = {J Hazard Mater}, volume = {317}, year = {2016}, month = {2016 Nov 05}, pages = {275-283}, abstract = {

Aqueous film-forming foams (AFFFs) are complex mixtures containing 1-5\% w/w fluorocarbons (FCs). Here, we have investigated degradation of two commercial AFFF formulations, 3M and Ansul, using sound field at 500kHz and 1MHz, with varying initial concentrations ranging from 200 to 930{\texttimes} dilution. The foams were readily degraded by 1MHz, with percentage of defluorination ranging from 11.1{\textpm}1.4\% (200{\texttimes} dilution of 3M) to 47.1{\textpm}5.8\% (500{\texttimes} dilution of Ansul). Removal of total organic carbon (TOC) ranged from 16.0{\textpm}1.4\% (200{\texttimes} dilution Ansul) to 39.0{\textpm}7.2\% (500{\texttimes} dilution Ansul). Degradation of AFFF was affected by sound frequency with rates of defluorination 10-fold greater when the frequency was 1MHz than when it was 500kHz. Mineralization of TOC was 1.5- to 3.0-fold greater under 1MHz than 500kHz. Rate of fluoride release was 60\% greater for the greatest initial concentration of FC in Ansul compared to the least initial concentration. While the rate of mineralization of AFFF was directly proportional to the initial concentration of Ansul, that was not the case for 3M, where the rates of mineralization were approximately the same for all three initial concentrations. Results of the study demonstrate that sonolysis is a promising technology to effectively treat AFFFs.

}, issn = {1873-3336}, doi = {10.1016/j.jhazmat.2016.05.078}, author = {Rodriguez-Freire, Lucia and Abad-Fern{\'a}ndez, Nerea and Sierra-Alvarez, Reyes and Hoppe-Jones, Christiane and Peng, Hui and Giesy, John P and Snyder, Shane and Keswani, Manish} } @article {103, title = {Untargeted Screening and Distribution of Organo-Bromine Compounds in Sediments of Lake Michigan.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 Jan 05}, pages = {321-30}, abstract = {

Previously unreported natural and synthetic organo-bromine compounds (NSOBCs) have been found to contribute more than 99\% of total organic bromine (TOB) in environmental matrices. We recently developed a novel untargeted method (data-independent precursor isolation and characteristic fragment, DIPIC-Frag) and identified \~{}2000 NSOBCs in two sediments from Lake Michigan. In this study, this method was used to investigate the distributions of these NSOBCs in 23 surficial samples and 24 segments of a sediment core from Lake Michigan. NSOBCs were detected in all 23 surficial samples and exhibited 10- to 100-fold variations in peak abundance among locations. The pattern of distributions of NSOBCs was correlated with depth of the water column (r(2) = 0.61, p \< 0.001). Hierarchical cluster analysis showed that sediments in close proximity exhibited similar profiles of NSOBCs. Distributions of NSOBCs in 24 segments of a sediment core dated from 1766 to 2008 were investigated, and samples from similar depths exhibited similar profiles of NSOBCs. NSOBCs were grouped into four clusters (soft-cluster analysis) with different temporal trends of abundances. 515 and 768 of the NSOBCs were grouped into cluster 1 and cluster 3 with increasing temporal trends, especially since 1950, indicating that abundances of these compounds might have been affected by human activities.

}, keywords = {Bromine Compounds, Environmental Monitoring, Geologic Sediments, Halogenated Diphenyl Ethers, Hydrocarbons, Brominated, Lakes, Michigan, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/acs.est.5b04709}, author = {Peng, Hui and Chen, Chunli and Cantin, Jenna and Saunders, David M V and Sun, Jianxian and Tang, Song and Codling, Garry and Hecker, Markus and Wiseman, Steve and Jones, Paul D and Li, An and Rockne, Karl J and Sturchio, Neil C and Giesy, John P} } @article {98, title = {Untargeted Screening and Distribution of Organo-Iodine Compounds in Sediments from Lake Michigan and the Arctic Ocean.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 09 20}, pages = {10097-105}, abstract = {

The majority of halogenated organic compounds present in the environment remain unidentified. To address this data gap, we recently developed an untargeted method (data-independent precursor isolation and characteristic fragment; DIPIC-Frag) for identification of unknown organo-bromine compounds. In this study, the method was adapted to enable untargeted screening of natural and synthetic organo-iodine compounds (NSOICs) in sediments. A total of 4,238 NSOIC peaks were detected in sediments from Lake Michigan. Precursor ions and formulas were determined for 2,991 (71\%) of the NSOIC peaks. These compounds exhibited variations in abundances (\<10(3) to \~{}10(7)), m/z values (206.9304-996.9474), retention times (1.0-29.7 min), and number of iodine atoms (1-4). Hierarchical cluster analysis showed that sediments in closer proximity exhibited similar profiles of NSOICs. NSOICs were screened in 10 samples of sediment from the Arctic Ocean to compare the profiles of NSOICs between freshwater and marine sediments. A total of 3,168 NSOIC peaks were detected, and profiles of NSOICs in marine sediments were clearly distinct from Lake Michigan. The coexistence of brominated and iodinated analogues indicated that some NSOICs are of natural origin. Different ratios of abundances of iodinated compounds to brominated analogues were observed and proposed as a marker to distinguish sources of NSOICs.

}, keywords = {Geologic Sediments, Iodine Compounds, Lakes, Michigan, Oceans and Seas, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/acs.est.6b03221}, author = {Peng, Hui and Chen, Chunli and Cantin, Jenna and Saunders, David M V and Sun, Jianxian and Tang, Song and Codling, Garry and Hecker, Markus and Wiseman, Steve and Jones, Paul D and Li, An and Rockne, Karl J and Sturchio, Neil C and Cai, Minghong and Giesy, John P} } @article {107, title = {Detection, identification, and quantification of hydroxylated bis(2-ethylhexyl)-tetrabromophthalate isomers in house dust.}, journal = {Environ Sci Technol}, volume = {49}, year = {2015}, month = {2015 Mar 03}, pages = {2999-3006}, abstract = {

Ultra-High Resolution LC/mass spectrometry (LC-UHRMS; Thermo Fisher Q-Exactive) was used to identify two novel isomers of hydroxylated bis(2-ethylhexyl)-tetrabromophthalate (OH-TBPH) which were unexpectedly observed in a commercial standard of TBPH. By combining ultra-high resolution (UHR) mass spectra (MS(1)), mass errors to theoretical [TBPH-Br+O](-) were 2.1 and 1.0 ppm for the two isomers, UHR-MS(2) spectra and NMR analysis; the structures of the two compounds were identified as hydroxylated TBPH with a hydroxyl group on the aromatic ring. Relatively great proportions of the two isomers of OH-TBPH were detected in two technical products, Firemaster 550 (FM-550; 0.1\% and 6.2\%, respectively) and Firemaster BZ 54 (BZ-54; 0.1\% and 7.9\%), compared to a commercial standard (0.4\% and 0.9\%). To simultaneously analyze OH-TBPH isomers and TBPH in samples of dust, a method based on LC-UHRMS was developed to quantify the two compounds, using negative and positive ion modes, respectively. The instrumental limit of detection for TBPH was 0.01 μg/L, which was 200-300 times better than traditional methods (2.5 μg/L) based on gas chromatography-mass spectrometry. The analytical method combined with a Florisil cleanup was successfully applied to analyze TBPH and OH-TBPH in 23 indoor dust samples from Saskatoon, Saskatchewan, Canada. Two OH-TBPH isomers, OH-TBPH1 and OH-TBPH2, were detected in 52\% and 91\% of dust samples, respectively. Concentrations of OH-TBPH2 (0.35 {\textpm} 1.0 ng/g) were 10-fold greater than those of OH-TBPH1 (0.04 {\textpm} 0.88 ng/g) in dust, which was similar to profiles in FM-550 and BZ-54. TBPH was also detected in 100\% of dust samples with a mean concentration of 733 {\textpm} 0.87 ng/g. A significant (p \< 0.001) log-linear relationship was observed between TBPH and OH-TBPH isomers, further supporting the hypothesis of a common source of emission. Relatively small proportions of OH-TBPH isomers were detected in dust (0.01\% {\textpm} 0.67 OH-TBPH1 and 0.1\% {\textpm} 0.60 OH-TBPH2), which were significantly less than those in technical products (p \< 0.001). This result indicated different environmental behaviors of OH-TBPH and TBPH. Detection of isomers of OH-TBPH is important, since compounds with phenolic groups have often shown relatively greater toxicities than nonhydroxylated analogues. Further study is warranted to clarify the environmental behaviors and potential toxicities of OH-TBPH isomers.

}, keywords = {Chromatography, Liquid, Dust, Flame Retardants, Limit of Detection, Mass Spectrometry, Phthalic Acids}, issn = {1520-5851}, doi = {10.1021/es505743d}, author = {Peng, Hui and Saunders, David M V and Sun, Jianxian and Codling, Garry and Wiseman, Steve and Jones, Paul D and Giesy, John P} } @article {105, title = {Untargeted Identification of Organo-Bromine Compounds in Lake Sediments by Ultrahigh-Resolution Mass Spectrometry with the Data-Independent Precursor Isolation and Characteristic Fragment Method.}, journal = {Anal Chem}, volume = {87}, year = {2015}, month = {2015 Oct 20}, pages = {10237-46}, abstract = {

While previous studies have found that unknown natural and synthetic organo-bromine compounds (NSOBCs) contributed more than 99\% of the total organic bromine (Br) in the environment, there was no efficient method for untargeted screening to identify NSOBCs in environmental matrixes. A novel untargeted method for identifying NSOBCs, based on ultrahigh-resolution mass spectrometry (UHRMS) with the Q Exactive instrument was developed. This method included a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) procedure to identify NSOBCs. A total of 180 successive 5-m/z-wide windows were used to isolate precursor ions. This resulted in a sufficient dynamic range and specificity to identify peaks of Br fragment ions for analysis. A total of 2520 peaks of NSOBC compounds containing Br were observed in sediments from Lake Michigan, United States. A new chemometric strategy which combined chromatographic profiles, isotopic peaks, precursor isolation window information, and intensities was used to identify precursor ions and chemical formulas for detecting NSOBCs. Precursor ions for 2163 of the 2520 NSOBCs peaks (86\%) were identified, and chemical formulas for 2071 NSOBCs peaks (82\%) were determined. After exclusion of isotopic peaks, 1593 unique NSOBCs were identified and chemical formulas derived for each. Most of the compounds identified had not been reported previously and had intensities which were 100- to 1000-fold greater than the congeners of polybrominated diphenyl ethers (PBDEs). In extracts of sediments, these compounds exhibited variations in intensities (\<10(3) to \~{}10(8)), m/z values (170.9438-997.5217), retention times on a C18 column (1.0-29.3 min), and the number of Br atoms (1-8). Generally, compounds with greater m/z values had longer retention times and greater numbers of Br atoms. Three compounds were used in a proof-of-concept experiment to demonstrate that structures of some of the screened NSOBCs could be further predicted by combining searching of database libraries and high-resolution MS(2) spectra.

}, keywords = {Databases, Chemical, Geologic Sediments, Hydrocarbons, Brominated, Lakes, Mass Spectrometry}, issn = {1520-6882}, doi = {10.1021/acs.analchem.5b01435}, author = {Peng, Hui and Chen, Chunli and Saunders, David M V and Sun, Jianxian and Tang, Song and Codling, Garry and Hecker, Markus and Wiseman, Steve and Jones, Paul D and Li, An and Rockne, Karl J and Giesy, John P} } @article {112, title = {Isomer-specific accumulation of perfluorooctanesulfonate from (N-ethyl perfluorooctanesulfonamido)ethanol-based phosphate diester in Japanese Medaka (Oryzias latipes).}, journal = {Environ Sci Technol}, volume = {48}, year = {2014}, month = {2014 Jan 21}, pages = {1058-66}, abstract = {

While (N-ethyl perfluorooctanesulfonamido)ethanol (FOSE) -based phosphate diester (diSPAP) has been proposed as a candidate precursor of perfluorooctanesulfonate (PFOS), its potential biotransformation to PFOS has not been verified. Metabolism of diSPAP was investigated in Japanese medaka ( Oryzias latipes ) after exposure in water for 10 days, followed by 10 days of depuration. Branched isomers of diSPAP (B-diSPAP) were preferentially enriched in medaka exposed to diSPAP, with the proportion of branched isomers (BF) ranging from 0.56 to 0.80, which was significantly greater than that in the water to which the medaka were exposed (0.36) (p \< 0.001). This enrichment was due primarily to preferential uptake of B-diSPAP. PFOS together with perfluorooctanesulfonamide (PFOSA), N-ethyl perfluorooctanesulfonamide (NEtFOSA), 2-(perfluorooctanesulfonamido)acetic acid (FOSAA), NEtFOSAA, FOSE, and NEtFOSE were detected in medaka exposed to diSPAP, which indicated the potential for biotransformation of diSPAP to PFOS via multiple intermediates. Due to preferential metabolism of branched isomers, FOSAA and PFOSA exhibited greater BF values (\>0.5) than those of NEtFOSA, NEtFOSAA, and NEtFOSE (\<0.2). Such preferential metabolism of branched isomers along the primary pathway of metabolism and preferential accumulation of B-diSPAP led to enrichment of branched PFOS (B-PFOS) in medaka. Enrichment of B-PFOS was greater for 3-, 4-, and 5-perfluoromethyl PFOS (P3MPFOS, P4MPFOS, and P5MPFOS), for which values of BF were 0.58 {\textpm} 0.07, 0.62 {\textpm} 0.06, and 0.61 {\textpm} 0.05 (day 6), respectively; these values are 5.8-, 7.8-, and 6.4-fold greater than those of technical PFOS. This work provides evidence on the isomer-specific accumulation of PFOS from diSPAP and will be helpful to track indirect sources of PFOS in the future.

}, keywords = {Alkanesulfonic Acids, Animals, Biotransformation, Chromatography, High Pressure Liquid, Environmental Monitoring, Esters, Fluorocarbons, Gas Chromatography-Mass Spectrometry, Half-Life, Hydrocarbons, Fluorinated, Isomerism, Kinetics, Metabolic Networks and Pathways, Organophosphorus Compounds, Oryzias, Phosphates, Reference Standards, Sulfonamides}, issn = {1520-5851}, doi = {10.1021/es404867w}, author = {Peng, Hui and Zhang, Shiyi and Sun, Jianxian and Zhang, Zhong and Giesy, John P and Hu, Jianying} } @article {119, title = {Tissue distribution and maternal transfer of poly- and perfluorinated compounds in Chinese sturgeon (Acipenser sinensis): implications for reproductive risk.}, journal = {Environ Sci Technol}, volume = {44}, year = {2010}, month = {2010 Mar 01}, pages = {1868-74}, abstract = {

It is critical to investigate the tissue distribution and maternal transfer of poly- and perfluorinated compounds (PFCs) in wild fish for assessing potential effects on ecosystems. Concentrations of 23 PFCs in nine organs and egg were measured in 16 17- to 25-year-old female Chinese sturgeon (Acipenser sinensis, an anadromous fish), that died during propagation. Three polyfluorinated amides were detected in stomach, intestine, and gills and 7:3 FTCA was specifically accumulated in liver. The greatest total concentration of PFCs in egg was 35.1 +/- 10.4 ng/g ww and was predominated by perfluorooctane sulfonate (PFOS) and perfluorotridecanoate acid (PFTriDA). The longer-chain C(11)-C(14) and C(16) perfluorinated carboxylates were more accumulated in Chinese sturgeon than PFOS, partly due to the increasing trends of PFCAs with fish age. Maternal transfer ratios of PFCs expressed as ratios of concentrations in the egg to those in the liver ranged from 0.79 (perfluorooctanoate) to 5.5 (PFTriDA), depending on their carbon chain lengths or protein-water coefficients. The PFOS equivalent of PFC mixtures, calculated by multiplying the relative potency factor of each PFC to PFOS by the corresponding concentration, ranged from 90.6 to 262 ng/g. The hazard quotient was 0.20, implying potential reproductive effects of PFCs on Chinese sturgeon.

}, keywords = {Alkanesulfonic Acids, Animals, Female, Fertility, Fertilization in Vitro, Fishes, Fluorocarbons, Organ Specificity, Reproduction, Risk Factors, Tissue Distribution}, issn = {0013-936X}, doi = {10.1021/es903248d}, author = {Peng, Hui and Wei, Qiwei and Wan, Yi and Giesy, John P and Li, Luoxin and Hu, Jianying} } @article {120, title = {Malformations of the endangered Chinese sturgeon, Acipenser sinensis, and its causal agent.}, journal = {Proc Natl Acad Sci U S A}, volume = {106}, year = {2009}, month = {2009 Jun 09}, pages = {9339-44}, abstract = {

The anadromous Chinese sturgeon (Acipenser sinensis) is endangered and listed among the first class of protected animals in China. The possible causes for the decline of this species are the effects of synthetic chemicals, and loss of critical habitat. Chinese sturgeon in the Yangtze River have accumulated triphenyltin (TPT) to 31-128 ng/g wet weigh (ww) in liver, which is greater than the concentrations of tributyltin (\<1.0 ng/g ww). Maternal transfer of TPT has resulted in concentrations of 25.5 +/- 13.0 ng/g ww in eggs of wild Chinese sturgeon, which poses a significant risk to the larvae naturally fertilized or hatched in the Yangtze River. The incidence of deformities in fry was 7.5\%, with 1.2\% of individuals exhibiting ocular abnormal development, and 6.3\% exhibited skeletal/morphological deformations. The incidences of both ocular and skeletal/morphological deformations were directly proportional to the TPT concentration in the eggs of both the Chinese sturgeon and the Siberian sturgeon (Acipenser baerii) in controlled laboratory studies. The rates of deformities in the controlled studies were consistent with the rates caused at the similar concentrations in eggs collected from the field. Thus, TPT is the causal agent to induce the malformation of larvae of Chinese sturgeon. The incidence of deformed larvae of Chinese sturgeon is an indicator of overall population-level effects of TPT on Chinese sturgeon, because TPT at environmentally relevant concentrations can result in significantly decrease both quality and quantity of eggs and spawning frequency of fish.

}, keywords = {Animals, China, Fishes, Organotin Compounds, Trialkyltin Compounds, Water Pollutants, Chemical}, issn = {1091-6490}, doi = {10.1073/pnas.0809434106}, author = {Hu, Jianying and Zhang, Zhaobin and Wei, Qiwei and Zhen, Huajun and Zhao, Yanbin and Peng, Hui and Wan, Yi and Giesy, John P and Li, Luoxin and Zhang, Bo} }