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Urinary concentrations of phenols, parabens, and triclocarban have been extensively used as biomarkers of exposure. However, because these compounds are quickly metabolized and excreted in urine, characterizing participants' long-term average exposure from a few spot samples is challenging. To examine the variability of urinary concentrations of these compounds during pregnancy, we quantified four phenols, four parabens, and triclocarban in 357 first morning voids (FMVs) and 203 pooled samples collected during the second and third trimesters of 173 pregnancies. We computed intraclass correlation coefficients (ICCs) by the sample type (FMV and pool) across two trimesters and by the number of composite samples in pools, ranging from 2 to 4, within the same trimester. Among the three compounds detected in more than 50% of the samples, the ICCs across two trimesters were higher in pools (0.29-0.68) than in FMVs (0.17-0.52) and the highest ICC within the same trimester was observed when pooling either two or three composites. Methyl paraben and propyl paraben primarily exposed via cosmetic use had approximately 2-3 times higher ICCs than bisphenol A primarily exposed via diet. Our findings support that within-subject pooling of biospecimens can increase the reproducibility of pregnant women's exposure to these compounds and thus could potentially minimize exposure misclassification.

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 (p-hydroxybenzoic acid esters), bisphenols, benzophenone-type UV filters, triclosan, and triclocarban are used in a variety of consumer products, including baby teethers. Nevertheless, the exposure of infants to these chemicals through the use of teethers is still unknown. In this study, 59 teethers, encompassing three types, namely solid plastic, gel-filled, and water-filled (most labeled “bisphenol A-free”), were collected from the U.S. market and analyzed for 26 potential endocrine-disrupting chemicals (EDCs) from intact surfaces through migration/leaching tests performed with Milli-Q water and methanol. The total amount of the sum of six parent parabens (Σ6 Parabens) leached from teethers ranged from 2.0 to 1990 ng, whereas that of their four transformation products (Σ4 Parabens) ranged from 0.47 to 839 ng. The total amount of the sum of nine bisphenols (Σ9 bisphenols) and 5 benzophenones (Σ5 benzophenones) leached from teethers ranged from 1.93 to 213 ng and 0.59 to 297 ng, respectively. Tri...

Triclocarban (TCC) and triclosan (TCS), two of the most commonly used antimicrobial compounds, can be introduced into ecosystems by applying wastewater treatment plant biosolids to agricultural fields. Concentrations of TCC and TCS were measured in different trophic levels within a terrestrial food web encompassing land-applied biosolids, soil, earthworms (Lumbricus), deer mice (Peromyscus maniculatus), and eggs of European starlings (Sturnus vulgaris) and American kestrels (Falco sparverius) at an experimental site amended with biosolids for the previous 7 years. The samples from this site were compared to the same types of samples from a reference (biosolids-free) agricultural site. Inter-site comparisons showed that concentrations of both antimicrobials were higher on the experimental site in the soil, earthworms, mice (livers), and European starling eggs, but not American kestrel eggs, compared to the control site. Inter-species comparisons on the experimental site indicated significantly higher TCC concentrations in mice (TCC: 12.6-33.3 ng/g) and in starling eggs (TCC: 15.4-31.4 ng/g) than in kestrel eggs (TCC: 3.6 ng/g). Nesting success of kestrels only was significantly lower on the experimental site compared to the reference site due to nest abandonment. This study demonstrates that biosolids-derived TCC and TCS are present throughout the terrestrial food web, including secondary (e.g., starlings) and tertiary (i.e., kestrels) consumers, after repeated, long-term biosolids application.

Antibiotic resistance is increasingly widespread, largely due to human influence. Here, we explore the relationship between antibiotic resistance genes and the antimicrobial chemicals triclosan, triclocarban, and methyl-, ethyl-, propyl-, and butylparaben in the dust microbiome. Dust samples from a mixed-use athletic and educational facility were subjected to microbial and chemical analyses using a combination of 16S rRNA amplicon sequencing, shotgun metagenome sequencing, and liquid chromatography tandem mass spectrometry. The dust resistome was characterized by identifying antibiotic resistance genes annotated in the Comprehensive Antibiotic Resistance Database (CARD) from the metagenomes of each sample using the Short, Better Representative Extract Data set (ShortBRED). The three most highly abundant antibiotic resistance genes were tet(W), blaSRT-1, and erm(B). The complete dust resistome was then compared against the measured concentrations of antimicrobial chemicals, which for triclosan ranged from 0.5 to 1970 ng/g dust. We observed six significant positive associations between the concentration of an antimicrobial chemical and the relative abundance of an antibiotic resistance gene, including one between the ubiquitous antimicrobial triclosan and erm(X), a 23S rRNA methyltransferase implicated in resistance to several antibiotics. This study is the first to look for an association between antibiotic resistance genes and antimicrobial chemicals in dust.

Biosolids contain a variety of pharmaceuticals and personal care products (PPCPs). Studies have observed the uptake of PPCPs into plants grown in biosolids-amended soils. This study examined the ability of Dynamic Plant Uptake (DPU) model and Biosolids-amended Soil Level IV (BASL4) model to predict the concentration of eight PPCPs in the tissue of plants grown in biosolids-amended soil under a number of exposure scenarios. Concentrations in edible tissue predicted by the models were compared to concentrations reported in the literature by calculating estimated human daily intake values for both sets of data and comparing them to an acceptable daily intake value. The equilibrium partitioning (EqP) portion of BASL4 overpredicted the concentrations of triclosan, triclocarban, and miconazole in root and shoot tissue by two to three orders of magnitude, while the dynamic carrot root (DCR) portion overpredicted by a single order of magnitude. DPU predicted concentrations of triclosan, triclocarban, miconazole, carbamazepine, and diphenhydramine in plant tissues that were within an order of magnitude of concentrations reported in the literature. The study also found that more empirical data are needed on the uptake of cimetidine, fluoxetine, and gemfibrozil, and other ionizable PPCPs, to confirm the utility of both models. All hazard quotient values calculated from literature data were below 1, with 95.7% of hazard quotient values being below 0.1, indicating that consumption of the chosen PPCPs in plant tissue poses de minimus risk to human health.

Removal of triclocarban (TCC) and triclosan (TCS) from wastewater is a function of adsorption, abiotic degradation, and microbial mineralization or transformation, reactions that are not currently controlled or optimized in the pollution control infrastructure of standard wastewater treatment. Here, we report on the levels of eight transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in raw and treated sewage sludge. Two sample sets were studied: samples collected once from 14 wastewater treatment plants (WWTPs) representing nine states, and multiple samples collected from one WWTP monitored for 12 months. Time-course analysis of significant mass fluxes (α = 0.01) indicate that transformation of TCC (dechlorination) and TCS (methylation) occurred during sewage conveyance and treatment. Strong linear correlations were found between TCC and the human metabolite 2′-hydroxy-TCC (r = 0.84), and between the TCC-dechlorination products dichlorocarbanilide (DCC) and monochlorocarbanilide (r = 0.99). Mass ratios of DCC-to-TCC and of methyl-triclosan (MeTCS)-to-TCS, serving as indicators of transformation activity, revealed that transformation was widespread under different treatment regimes across the WWTPs sampled, though the degree of transformation varied significantly among study sites (α = 0.01). The analysis of sludge sampled before and after different unit operation steps (i.e., anaerobic digestion, sludge heat treatment, and sludge drying) yielded insights into the extent and location of TCC and TCS transformation. Results showed anaerobic digestion to be important for MeTCS transformation (37–74%), whereas its contribution to partial TCC dechlorination was limited (0.4–2.1%). This longitudinal and nationwide survey is the first to report the occurrence of transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in sewage sludge.

Triclosan (TCS) and triclocarban (TCC) are antimicrobial agents formulated in a wide variety of consumer products (including soaps, toothpaste, medical devices, plastics, and fabrics) that are regulated by the U.S. Food and Drug Administration (FDA) and U.S. Environmental Protection Agency. In late 2014, the FDA will consider regulating the use of both chemicals, which are under scrutiny regarding lack of effectiveness, potential for endocrine disruption, and potential contribution to bacterial resistance to antibiotics. Here, we report on body burdens of TCS and TCC resulting from real-world exposures during pregnancy. Using liquid chromatography tandem mass spectrometry, we determined the concentrations of TCS, TCC, and its human metabolites (2'-hydroxy-TCC and 3'-hydroxy-TCC) as well as the manufacturing byproduct (3'-chloro-TCC) as total concentrations (Σ-) after conjugate hydrolysis in maternal urine and cord blood plasma from a cohort of 181 expecting mother/infant pairs in an urban multiethnic population from Brooklyn, NY recruited in 2007-09. TCS was detected in 100% of urine and 51% of cord blood samples after conjugate hydrolysis. The interquartile range (IQR) of detected TCS concentrations in urine was highly similar to the IQR reported previously for the age-matched population of the National Health and Nutrition Examination Survey (NHANES) from 2003 to 2004, but typically higher than the IQR reported previously for the general population (detection frequency = 74.6%). Urinary levels of TCC are reported here for the first time from real-world exposures during pregnancy, showing a median concentration of 0.21 μg/L. Urinary concentrations of TCC correlated well with its phase-I metabolite ∑-2'-hydroxy-TCC (r = 0.49) and the manufacturing byproduct ∑-3'-chloro-TCC C (r = 0.79), and ∑-2'-hydroxy-TCC correlated strongly with ∑-3'-hydroxy-TCC (r = 0.99). This human biomonitoring study presents the first body burden data for TCC from exposures occurring during pregnancy and provides additional data on composite exposure to TCS (i.e., from both consumer-product use and environmental sources) in the maternal-fetal unit for an urban population in the United States.

Land application accounts for ∼50% of wastewater solid disposal in the United States. Still, little is known regarding the ecological impacts of nonregulated contaminants found in biosolids. Because of the myriad of contaminants, there is a need for a rapid, high-throughput method to evaluate their ecotoxicity. Herein, we developed a novel assay that measures denitrification inhibition in a model denitrifier, Paracoccus denitrificans Pd1222. Two common (triclosan and triclocarban) and four emerging (2,4,5 trichlorophenol, 2-benzyl-4-chlorophenol, 2-chloro-4-phenylphenol, and bis(5-chloro-2-hydroxyphenyl)methane) antimicrobial agents found in biosolids were analyzed. Overall, the assay was reproducible and measured impacts on denitrification over 3 orders of magnitude exposure. The lowest observable adverse effect concentrations (LOAECs) were 1.04 μM for triclosan, 3.17 μM for triclocarban, 0.372 μM for bis-(5-chloro-2-hydroxyphenyl)methane, 4.89 μM for 2-chloro-4-phenyl phenol, 45.7 μM for 2-benzyl-4-chor...

We developed a multiresidue method for the target and suspect screening of more than 180 pharmaceuticals personal care products pesticides biocides additives corrosion inhibitors musk fragrances UV light stabilizers and industrial chemicals in sediments. Sediment samples were freeze dried extracted by pressurized liquid extraction and cleaned up by liquid liquid partitioning. The quantification and identification of target compounds with a broad range of physicochemical properties (log Kow 0 12) was carried out by liquid chromatography followed by electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) coupled to high resolution Orbitrap mass spectrometry (HRMS/MS). The overall method average recoveries and precision are 103 and 9 (RSD) respectively. The method detection limits range from 0.010 to 4 ng/gdw while limits of quantification range from 0.030 to 14 ng/gdw. The use of APPI as an alternative ionization source helped to distinguish two isomeric musk fragrances by means of different ionization behavior. The method was demonstrated on sediment cores from Lake Greifensee located in northeastern Switzerland. The results show that biocides musk fragrances and other personal care products were the most frequently detected compounds with concentrations ranging from pg/gdw to ng/g dw whereas none of the targeted pharmaceuticals were found. The concentrations of many urban contaminants originating from wastewater correlate with the highest phosphorus input into the lake as a proxy for treatment efficiency. HRMS enabled a retrospective analysis of the full scan data acquisition allowing the detection of suspected compounds like quaternary ammonium surfactants the biocide triclocarban and the tentative identification of further compounds without reference standards among others transformation products of triclosan and triclocarban. © 2012 American Chemical Society.

Persistent environmental contaminants may enter agricultural fields via the application of sewage sludge, by irrigation with treated municipal wastewater or by manuring. It has been shown that such contaminants can be incorporated into crop plants. The metabolism of the bacteriostatic agents triclocarban, triclosan, and its transformation product methyl triclosan was investigated after their uptake into carrot cell cultures. A fast metabolization of triclosan was observed and eight so far unknown phase II metabolites, conjugates with saccharides, disaccharides, malonic acid, and sulfate, were identified by liquid chromatography-mass spectrometry. Triclocarban and methyl triclosan lack a phenolic group and remained unaltered in the cell cultures. Phase I metabolization was not observed for any of the compounds. All eight triclosan conjugates identified in the cell cultures were also detected in extracts of intact carrot plants cultivated on triclosan contaminated soils. Their total amount in the plants was assessed to exceed the amount of the triclosan itself by a factor of 5. This study shows that a disregard of conjugates in studies on plant uptake of environmental contaminants may severely underestimates the extent of uptake into plants and, eventually, the potential human exposure to contaminants via food of plant origin.

Triclosan (TCS) and triclocarban (TCC) are widely used broad spectrum bactericides that are common pollutants of waterways and soils. Methyl triclosan (mTCS) is the predominant bacterial TCS metabolite. Previous studies have shown that TCS disrupts thyroid hormone (TH) action; however, the effects of mTCS or TCC are not known. The present study uses the cultured frog tadpole tail fin biopsy (C-fin) assay and the TH-responsive rat pituitary GH3 cell line to assess the effects of these three chemicals (1-1000 nM) on TH signaling and cellular stress within 48 h. mRNA abundance of TH receptor β, Rana larval keratin type I (TH-response), heat shock protein 30, and catalase (stress-response) was measured using quantitative real-time polymerase chain reaction in the C-fin assay. The TH-responsive gene transcripts encoding growth hormone, deiodinase I, and prolactin were measured in GH3 cells with the heat shock protein 70 transcript acting as a cellular stress indicator. We found alteration of stress indicators at a wide range of concentrations of TCS, mTCS, and TCC in both test systems. mTCS and TCC affected TH-responsive gene transcripts at the highest concentration in mammalian cells, whereas a modest effect included lower concentrations in the C-fin assay. In contrast, TCS did not affect TH-responsive transcripts. These results identify nontarget biological effects of these bacteriocides on amphibian and mammalian cells and suggest the TH-disrupting effects observed for TCS could be mediated through its metabolite.

Hourly samples of tertiary wastewater effluent were analyzed for 30 pharmaceuticals, personal care products, estrogenic steroids, and alkylphenols in order to better understand the rate at which these compounds enter the environment. Several distinct patterns of daily cycling were observed, and were characterized as three separate categories. The concentrations of compounds such as trimethoprim, sulfamethoxazole, naproxen, estrone, and triclosan varied greatly during a daily cycle, with relative standard deviations exceeding 100% of their daily mean. Less extreme daily cycles were seen for other compounds such as azithromycin, atenolol, tert-octylphenol, iopromide and gemfibrozil. Peak concentrations for most compounds occurred in the early evening (5-8 pm). However, some compounds including carbamazepine, primidone, fluoxetine, and triclocarban exhibited little or no variability.

Triclocarban, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)urea, is a polychlorinated phenyl urea pesticide, marketed under the trademark TCC and used primarily as an antibacterial additive in personal care products. Despite its extensive use over several decades, environmental occurrence data on TCC are scarce. This is due in part to a lack of analytical techniques offering the desired sensitivity, selectivity, affordability, and ease of use. This need is addressed here by introducing a liquid chromatography electrospray ionization mass spectrometry (LC/ESI/MS) method allowing for the determination of TCC concentrations in aquatic environments at the ng/L level. TCC was concentrated from aqueous samples by solid-phase extraction, separated from interferences on a C18 column by either isocratic or gradient elution, and detected and identified in negative ESI mode by selectively monitoring the (M - H)- base peak (m/z 313) and its 37Cl-containing isotopes (m/z 315, 317) that served as reference ions. Particulates contained in aquatic samples were extracted and analyzed separately. Accurate quantification was achieved using stable isotopes of TCC and triclosan as internal standards. Addition of 10 mM acetic acid to the mobile phase yielded acetic acid adducts ([M - H + 60]-) that were successfully exploited to boost method sensitivity and selectivity, especially when analyzing challenging environmental matrixes. Method detection limits were matrix dependent, ranging from 3 to 50 ng/L. In 36 grab samples obtained from the Greater Baltimore area, TCC was detected in river water and wastewater at concentrations of up to 5600 and 6750 ng/L, respectively. Raw and finished drinking water did not contain detectable quantities of the pesticide (

Triclosan is used as an antimicrobial agent in a wide range of medical and consumer care products. To investigate the occurrence and fate of triclosan in the aquatic environment, analytical methods for the quantification of triclosan in surface water and wastewater, sludge, and sediment were developed. Furthermore, the fate of triclosan in a wastewater treatment plant (biological degradation, 79%; sorption to sludge, 15%; input into the receiving surface water, 6%) was measured during a field study. Despite the high overall removal rate, the concentration in the wastewater effluents were in the range of 42-213 ng/L leading to concentrations of 11-98 ng/L in the receiving rivers. Moreover, a high removal rate of 0.03 d(-1) for triclosan in the epilimnion of the lake Greifensee was observed. This is due to photochemical degradation. The measured vertical concentration profile of triclosan in a lake sediment core of lake Greifensee reflects its increased use over 30 years. As the measured concentrations in surface waters are in the range of the predicted no effect concentration of 50 ng/L, more measurements and a detailed investigation of the degradation processes are needed.