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Perfluoroalkyl sulfonates (PFSAs), perfluoroalkyl carboxylates (PFCAs), and emerging alternatives and precursors of these compounds were determined in tissues of finless porpoise (Neophocaena asiaeorientalis sunameri) collected from East China Sea in 2009-2010 and 2018-2019. The median hepatic concentrations of emerging poly- and perfluoroalkyl substances (PFASs), including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA), 2,3,3,3-tetrafluoro-2-propanoate (HFPO-DA), and 4,8-dioxa-3H-perfluorononanoate (ADONA) were 16.2, 2.16, < LOQ (limit of quantification) and < LOQ ng/g ww (wet weight), respectively. The concentrations of legacy substances, perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA), were 86.9 and 1.95 ng/g ww, respectively. The liver concentrations of 6:2 Cl-PFESA, HFPO-DA, and perfluorohexanesulfonate (PFHxS) increased with time between 2009-2010 and 2018-2019. Further, concentrations of PFOA showed a declining trend in finless porpoise, whereas PFOS and its precursor (i.e., perfluorooctane sulfonamide [FOSA]) showed an increasing trend with time between 2009-2010 and 2018-2019. Analysis of PFASs in nine different tissues/organs of finless porpoise (i.e., liver, heart, intestine, spleen, kidney, stomach, lung, muscle, and skin) revealed a similar distribution pattern between 6:2 Cl-PFESA and PFOS; however, the tissue distribution patterns differed between HFPO-DA and PFOA. The concentrations of PFAS alternatives in kidney were similar or lower than the prototype compounds PFOS and PFOA (i.e., 8:2 Cl-PFESA < 6:2 Cl-PFESA ≈ PFOS; HFPO-DA < PFOA), implying slow renal excretion of PFAS alternatives as that of legacy PFASs. The estimates of body burdens of PFASs in porpoises suggested comparable accumulation of PFAS alternatives and legacy PFSAs and PFCAs. This study provides novel information on temporal trends and tissue distribution of emerging PFASs in marine mammals in China.

Neonicotinoids (NEOs) are insecticides that are widely used around the world. Following exposure, NEOs get metabolized in human bodies. The biomarkers to assess human NEO exposure are not well described because of the lack of information on the metabolites of NEOs (m-NEOs). In this study, five m-NEOs including N-desmethyl-acetamiprid (N-dm-ACE), 5-hydroxy-imidacloprid (5-OH-IMI), olefin-imidacloprid (Of-IMI), 1-methyl-3-(tetrahydro-3-furylmethyl) guanidine (DIN-G), and 1-methyl-3-(tetrahydro-3-furylmethyl) (DIN-U) were measured in 275 urine samples collected from 10 cities in China. All of the m-NEOs were frequently detected in urine samples with the median concentrations ranging from 0.42 (DIN-G) to 1.02 (5-OH-IMI) ng/mL. The urinary concentrations of N-dm-ACE and 5-OH-IMI measured in China were higher than those reported from Japan and the USA. In comparison to the parent NEO (i.e., acetamiprid, ACE; imidacloprid, IMI; and dinotefuran, DIN) concentrations reported in the same set of samples by our research group, the median ratios of m-NEO to the corresponding parent NEO (m-NEO/NEO) ranged from 4.95 (DIN-G/DIN) to 37.7 (N-dm-ACE/ACE), indicating that NEOs are mainly present as metabolites rather than the parent forms. Furthermore, the ratio of Σm-NEOs/ΣNEOs was significantly (p < 0.01) higher in females than in males, suggesting that NEOs are more readily metabolized in females or females are more highly exposed to m-NEOs. To our knowledge, this is the first study to measure Of-IMI, DIN-G, and DIN-U levels in urine samples from China. We recommend biomonitoring studies to include N-dm-ACE, 5-OH-IMI, and DIN-U (and DIN-G) for clear understanding of human exposure to ACE, IMI, and DIN, respectively.

Some artificial sweeteners (ASs) are used in pig feeds, although little is known on this regard. An investigation was conducted by determining seven common ASs in pig feed, manure, wastewater, compost, and soil from 16 pig farms in Tianjin, China. Saccharin (SAC) was predominant in feed (1.41-326 mg/kg) and manure samples (1.06-401 mg/kg). The annual mass loads of ASs in pig feeds were estimated at 5.69-119, 4.92-149, and 1.29-35 kg per 103 piglets, hogs, and sows, respectively. The annual emission of ASs via biowaste (i.e., manure) was estimated at 3.58-85.2, 0.04-26.2, and 0.08-9.97 kg per 103 capita for the three dominant ASs, i.e., SAC, neotame (NEO), and cyclamate (CYC). On a global scale, SAC was also widely detected at concentrations of 0.01-326 mg/kg in pig feed from China, Switzerland, Japan, Chile, and the United States, suggesting the worldwide use of ASs in pig feed. NEO and CYC were found in 41% and 30% of the feed samples, respectively, at concentrations of 0.05-70 mg/kg, whereas other ASs were barely found with rather lower concentrations. The annual mass loads of ASs consumed via pig feed consumption were estimated at 2400 tons worldwide. Thus, pig farming is an important source of ASs to the environment.

Phthalates have been associated with reproductive toxicity and precocious puberty in females, but the occurrence of these toxicants in feminine hygiene products is rarely reported. In this study, eight phthalates were determined in 120 feminine hygiene products (56 feminine care products and 64 sanitary napkins) collected from China. Phthalates were found in 86% and 98% of feminine care products and sanitary napkins, respectively, with the total concentrations varying between not detectable and 813 μg/g (median: 0.26 μg/g) and 0.25 and 8.76 μg/g (1.43 μg/g), respectively. Diethyl phthalate, dibutyl phthalate, and bis(2-ethylhexyl)phthalate were the major compounds, accounting for60% of the total concentrations. The plastic materials used on the top and bottom layers and the hot melt adhesive used during the manufacturing process are the potential sources of phthalates in sanitary napkins. The range of daily exposure doses of phthalates in women from the use of feminine care products and sanitary napkins was0.001-0.156 μg/kg-bw/day and0.001-0.731 μg/kg-bw/day, respectively. Sanitary napkins contributed to 8.2% of the total exposure, and the levels of exposure to several phthalates from sanitary napkins were much higher than those reported from indoor dust ingestion but were lower than those of dietary intakes. Our study confirmed a new source of women's exposure to phthalates, sanitary napkins.

Polar bear (Ursus maritimus) populations accumulate dioxins and related compounds (DRCs) at levels that are of health concern. The toxicities of DRCs are primarily mediated via aryl hydrocarbon rec...

Human exposure to microplastics has been a topic of interest, but measurements of exposure are limited. Pet animals are sentinels of human exposure, as they share a common living environment with humans. In this study, 58 pet (cat and dog) foods and 78 pet feces samples were collected from Albany, NY, USA, for the analysis of polyethylene terephthalate (PET) and polycarbonate (PC) by alkali-assisted thermal depolymerization and liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) methods. PET was detected at concentrations in the range of

Melamine received public and regulatory attention in 2008 following a scandal that involved the adulteration of milk and infant formula in China that affected tens of thousands of infants. Little is known about human exposure and the food chain transfer of melamine and its derivatives. In this study, melamine, cyanuric acid, ammeline, and ammelide were analyzed in 100 human milk samples collected from the United States during the period of 2009-2012. ∑Melamine (sum of melamine and its three derivatives) was found in breast milk at concentrations that ranged from 0.176 to 10.0 ng/mL (median: 1.40 ng/mL). Cyanuric acid was the major derivative, accounting for 73% of the total concentrations, followed by melamine (21%). No remarkable associations were noted between melamine and cyanuric acid concentrations and maternal/infant characteristics. The cumulative daily intakes of melamine (16.9-30.6 ng/kg bw/day) and cyanuric acid (88.8-161 ng/kg bw/day) were calculated for breast-fed infants and were found to be 1-2 orders of magnitude below the current tolerable daily intake. This is the first study to report the distribution of melamine and its derivatives in breast milk from the United States.

Parabens have been of global concern due to their endocrine disrupting properties. However, few studies have reported tissue-specific distribution of parabens in wildlife. In this study, we measured parabens and their metabolites in organs and tissues (blubber, muscle, melon, stomach, kidney, liver, gonad, brain, uterus, and umbilical cord, total n = 94) of common dolphins (Delphinus capensis) and finless porpoises (Neophocaena asiaeorientalis), to investigate tissue-specific accumulation and body burden. Among the target compounds, methyl paraben (MeP) and para-hydroxybenzoic acid (4-HB) were detected in all organs. Compared to common dolphins, finless porpoises had significantly higher concentrations of MeP and 4-HB due to their near-shore habitat. Higher concentrations of MeP and 4-HB were found in the kidney, liver, and stomach than in other organs, indicating selective accumulation of parabens in certain organs. Significant correlations between MeP and 4-HB in liver/kidney suggested metabolic transformation of the former to the latter. Detection of parabens in brains, umbilical cords, and uteri suggests that these chemicals cross biological barriers such as the blood-brain and placental barriers. The body burdens of total parabens were in the ranges of 13000-90600 mu g and 19800-81500 mu g for common dolphins and finless porpoises, respectively.

Melamine and its derivatives (i.e., ammeline, ammelide, and cyanuric acid) are extensively used in household products, such as furniture, dinnerware, and food utensils. Nevertheless, limited information is available on human exposures, other than dietary sources, to melamine and its derivatives. In this study, the occurrence of melamine and its derivatives was determined, for the first time, in 341 samples of indoor dust, collected from 12 countries. All of the dust samples contained target analytes, with global median concentrations of 1800, 1100, 48, and 45 ng/g for melamine, cyanuric acid, ammelide, and ammeline, respectively. The total concentrations of melamine and its derivatives varied among countries in the following decreasing order: United States (median: 17 000 ng/g)Japan (8400)China (8000)South Korea (7300)Saudi Arabia (4400)Romania (4300)Greece (3400)Kuwait (2400)Vietnam (2300)Colombia (1300)Pakistan (820)India (430). Correlation analysis indicated the existence of multiple and varied sources for melamine and cyanuric acid. Estimated daily intakes of melamine via indoor dust ingestion were at least 2 orders of magnitude below the current tolerable daily intake.

In the 2000s, nail polish manufacturers started promoting “3-Free” products, phasing out three widely publicized toxic chemicals: toluene, formaldehyde, and dibutyl phthalate (DnBP). However, DnBP was sometimes replaced by another endocrine-disrupting plasticizer, triphenyl phosphate (TPHP). Many new “n-Free” labels have since appeared, without any standardization on which n chemicals are excluded. This study aimed to compare measured plasticizer content against nail polish labels. First, we summarized definitions of labels. Then, we measured 12 phthalate and 10 organophosphate plasticizers in 40 nail polishes from 12 brands selected for popularity and label variety. We found labels ranging from 3- to 13-Free; 10-Free was the most inconsistently defined (six definitions). Our samples contained TPHP and bis(2-ethylhexyl) phthalate (DEHP) at up to 7940 and 331 μg/g, respectively. The 5- to 13-Free samples had lower TPHP levels than unlabeled or 3-Free samples (median

Pantyhose, a skin-tight item of clothing made of synthetic fibers and worn by women in many countries, is a source of exposure to several endocrine-disrupting chemicals. Little is known regarding the occurrence of and dermal exposure to chemicals present in pantyhose. In this study, concentrations and profiles of 23 endocrine-disrupting chemicals, including bisphenols, benzophenones, chlorophenols, parabens, and triclocarban (TCC), were determined in 74 pantyhose samples collected from 6 countries. Pantyhose samples were analyzed by two extraction methods: complete dissolution and ultrasonic extraction. Dissolution of the fabric in 1,1,1,3,3,3-hexafluoro-2-propanol/chloroform yielded concentrations of several target chemicals that were up to 286 times higher than in the ultrasonic extraction. Bisphenol S (BPS) and bisphenol A (BPA) were found in 100% and 96% of the samples at median concentrations of 1430 and 14.3 ng/g, respectively. Several brands of pantyhose contained BPS, bisphenol F (BPF), benzophenone-1 (BP-1), ethyl-paraben (EtP), and TCC at concentrations of milligrams per gram. Benzophenone-3 (BP-3), 4-hydroxy benzoic acid (4-HB), and methyl- (MeP) and propyl-parabens (PrP) were found in ≥85% of the samples at median concentrations on the order of several tens to hundreds of nanograms per gram of fabric. Pantyhose made in Japan and China with 21-50% Spandex contained the highest concentrations of BPS (2.2 mg/g), BP-1 (2.4 mg/g), and EtP (88 μg/g). Calculated dermal exposure doses to BPS, BP-1, and EtP by women via pantyhose were as high as 45 900, 50 600, and 1800 picograms per kilogram of body weight per day, respectively.

Parabens are used as preservatives in many consumer products, and human exposure to these chemicals has been a public concern. In this study, mollusks ( n = 186), collected from the Chinese Bohai Sea during 2006-2015, were analyzed for six parabens and their five metabolites. The total concentration of parabens was in the range of 2.66-299 ng/g dw (geometric mean: 24.1). Methyl paraben and 4-hydroxybenzoic acid were the predominant parent and metabolic parabens, respectively found in mollusks. Mollusk species, Mactra veneriformis, Mytilus edulis, and Cyclina sinensis contained elevated concentrations of both parent and metabolic parabens. A gradual increase in paraben concentrations was found in mollusks collected between 2006 and 2012. Principal component analysis suggested the existence of a common source for these chemicals in mollusks. Consumption of mollusks can contribute to human exposures and we estimated daily intakes of parabens through the consumption of mollusks. This is the first study to report temporal trends and accumulation of parabens and their metabolites in a variety of invertebrate species from coastal marine environments.

The occurrence and profiles of 14 triester organophosphate flame retardants (OPFRs) and plasticizers were investigated in surface water, tap water, rainwater, and seawater collected from New York State. In total, 150 samples collected from rivers ( n = 35), lakes ( n = 39), tap water ( n = 58), precipitation/rainwater ( n = 15), and seawater ( n = 3) were analyzed for 14 organophosphate esters (OPEs). An additional nine Hudson River water samples were collected periodically to delineate seasonal trends in OPE levels. The total concentrations of OPEs were found at part-per-trillion ranges, with average concentrations that ranged from 0.01 ng/L for tripropyl phosphate (TPP) in river water to 689 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in lake water. Tris(1-chloro-2-propyl)phosphate (TCIPP) was the most abundant compound among the investigated OPEs in all types of water. The concentrations of OPEs in river-, lake-, and rainwater were similar but3 times higher than those found in tap water. Chlorinated alkyl OPFRs accounted for a major proportion of total concentrations. TCIPP, TBOEP, and triethyl phosphate (TEP) were found in90% of the samples analyzed. Wet deposition fluxes for 14 OPFRs were estimated, on the basis of the concentrations measured in rainwater in Albany, New York, and the values were between 440 and 5250 ng/m

Benzothiazole and its derivatives (BTs) are high production volume chemicals that have been used for several decades in a large number of industrial and consumer products, including vulcanization accelerators, corrosion inhibitors, fungicides, herbicides, algicides, and ultraviolet (UV) light stabilizers. Several benzothiazole derivatives are used commercially, and widespread use of these chemicals has led to ubiquitous occurrence in diverse environmental compartments. BTs have been reported to be dermal sensitizers, respiratory tract irritants, endocrine disruptors, carcinogens, and genotoxicants. This article reviews occurrence and fate of a select group of BTs in the environment, as well as human exposure and toxicity. BTs have frequently been found in various environmental matrices at concentrations ranging from sub-ng/L (surface water) to several tens of μg/g (indoor dust). The use of BTs in a number of consumer products, especially in rubber products, has resulted in widespread human exposure. BTs undergo chemical, biological, and photolytic degradation in the environment, creating several transformation products. Of these, 2-thiocyanomethylthio-benzothiazole (2-SCNMeS-BTH) has been shown to be the most toxic. Epidemiological studies have shown excess risks of cancers, including bladder cancer, lung cancer, and leukemia, among rubber factory workers, particularly those exposed to 2-mercapto-benzothiazole (2-SH-BTH). Human exposure to BTs continues to be a concern.

The exposure of pets, such as dogs and cats, to a wide range of chemicals present in the indoor environment and the concomitant increase in noninfectious diseases in these companion animals are a concern. Nevertheless, little is known about the sources and pathways of exposure to chemicals in pets. In this study, we determined the concentrations of parabens in commercially available cat and dog foods as well as in urine samples from these pets collected from the Albany area of the state of New York in the United States. Parabens, especially methyl paraben (MeP), and their metabolites were found in all pet food and urine samples. The mean concentrations of total parabens (i.e., sum of parabens and their metabolites) in dog ( n = 23) and cat ( n = 35) food were 1350 and 1550 ng/g fresh wt, respectively. Dry food contained higher concentrations of parabens and their metabolites than did wet food, and cat food contained higher concentrations of target chemicals than did dog food. The mean concentrations of total parabens found in dog ( n = 30) and cat ( n = 30) urine were 7230 and 1040 ng/mL, respectively. In both pet food and urine, MeP (among parabens) and 4-hydroxy benzoic acid (4-HB) (among metabolites) were the dominant compounds. The metabolites of parabens accounted for ∼99% (∼99.1% in food and ∼98.9% in urine) of the total concentrations in both food and urine. The profiles of parabens and their metabolites in the urine of dogs and cats varied. In addition to diet, other sources of paraben exposures were found for dogs, whereas, for cats, the majority of exposures was identified as related to diet.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental contaminants, but the sources of these chemicals in the environment are not well-known. In this study, we developed a kinetic model describing the chlorination of PAHs to elucidate the mechanism of formation of ClPAHs during the combustion of organic waste containing chlorinated compounds and/or chlorine in an incinerator. Pyrene (Pyr) and polyvinyl chloride (PVC) were selected as a model PAH and a model organic substrate, respectively. All combustion experiments were carried out using a model furnace operated under similar experimental conditions. Combustion of PVC in the model furnace produced 1-ClPyr, 1,3-Cl2Pyr, 1,6-Cl2Pyr, 1,8-Cl2Pyr, 1,3,6-Cl3Pyr, and 1,3,6,8-Cl4Pyr. The developed model supported the experimental data on the sequential chlorination of pyrene. The rate constants for the formation of mono- to trichlorinated pyrenes were over 30 times of those for the formation of tetra- and penta-chlorinated p...