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Hexabromocyclododecane (HBCD) is a brominated flame retardant (BFR) labeled by the Stockholm Convention as a persistent organic pollutant (POP) and exists primarily as three stereoisomers, i.e. α-, β-, and γ. One of the major routes of human exposure to HBCD is dust found in homes, offices, and cars and dust may be the most important route of HBCD exposure in young children. A study was conducted to determine the oral bioavailability of HBCD from household dust in rats over a 21-d feeding period relative to HBCD bioavailability from a corn oil matrix. Twenty-four hours after the last exposure, rats were sacrificed, and various tissues were collected. HBCD diastereomers were detected in adipose, blood, and liver of both dose groups, suggesting HBCD is bioavailable from both oil and dust. β-HBCD concentrations were below the limit of detection in all tissues, but α-HBCD was detected in the brain of oil-dose rats and in adipose and liver of both dose groups. γ-HBCD was the dominant diastereomer in adipose, blood, and liver samples regardless of dosing matrix. Except for γ-HBCD in muscle of the oil-dosed group, muscle did not contain measurable HBCDs. Adipose tissue accumulated HBCD to a greater extent than muscle or liver, having bioaccumulation factors greater than 1., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Inc.)

Abstract: Perfluorooctanoic acid (PFOA) is used as a surfactant in consumer and industrial products and is frequently found in biosolids from wastewater treatment plants. When present in biosolids applied to croplands, PFOA can contaminate feed and fodder used by livestock, but the extent of PFOA transfer from soil to plants is not well characterized. A single dose of radiocarbon (14C)-tagged PFOA was applied to unplanted soil or soil containing growing alfalfa. PFOA transport through unplanted soil and uptake by alfalfa was monitored over a 10-week study period. Radiocarbon was initially measured in roots, stems, and leaves 7 days after [14C]-PFOA application to soil. PFOA accumulation was greatest in leaves during the 10-week sampling. By week 10, PFOA migration through unplanted soil had reached a depth of 22.8 ± 2.5 cm. In contrast, PFOA migrated to 7.5 ± 2.5 cm in soil containing alfalfa plants. The greatest predictor of PFOA concentration in alfalfa leaves was PFOA concentration in the top 5 cm of soil; PFOA concentrations at lower depths were not correlated with alfalfa PFOA concentrations. PFOA transport through soil may be slowed by the presence of forage; however, PFOA accumulation in edible portions of forage plants may increase food animal exposure to PFOA residues., (Published 2022 by the International Association for Food Protection. Not subject to U.S. Copyright.)

Abstract: Perfluorooctanoic acid (PFOA) is a perfluorinated alkyl substance used as a surfactant in a wide variety of industrial and consumer products. Over the past decade, concern has increased over the presence of PFOA in biosolids from wastewater treatment plants used as fertilizer on agricultural lands because of the potential for PFOA to enter the food chain. In this study, the uptake of 14C-PFOA from soil by alfalfa and 14C-PFOA bioavailability from consumption of this alfalfa was evaluated in Sprague-Dawley rats. Alfalfa leaves accumulated 14C-PFOA up to 4 to 5 μg/g of dry leaf, approximately 10 times higher than accumulation in the stem. Alfalfa was ground for feeding to 15 female Sprague-Dawley rats (175 to 200 g). Animals within metabolism cages were fed 10 g of feed (6 g of alfalfa plus 4 g of ground rat chow) twice daily for 14 days (equivalent to 50 μg of 14C-PFOA per kg per day). At the end of the feeding period, three rats were euthanized for sample collection on each of withdrawal days 0, 3, 7, 11, and 14. During the feeding and withdrawal phases, urine and feces were collected daily. At necropsy, blood, liver, kidney, adipose, muscle, skin, brain, heart, adrenal glands, spleen, lungs, and thymus were removed and assayed for 14C-PFOA by combustion and liquid scintillation counting. Rats had eliminated 72.8% ± 3.4% of the total dose via urine at 14 days, but urinary radioactivity fell below the level of detection by day 3 of the withdrawal period. Fecal elimination was 6.5% ± 1.2% of the dose and fell below the level of detection by day 2 of the withdrawal period. The rapid and high elimination via urine indicates that a majority of the dose was absorbed. The uptake of 14C-PFOA into alfalfa was low from soil with a high organic concentration; however, 14C-PFOA was highly bioavailable from the alfalfa when used as a feed component for rats. This study provides data for regulators investigating 14C-PFOA bioavailability and disposition in animals or animal products exposed to contaminated feed., (Published 2021 by the International Association for Food Protection. Not subject to U.S. Copyright.)

Polybrominated dibenzo-p-dioxins (PBDDs) and mixed bromo/chloro dibenzo-p-dioxins (PXDDs) are persistent organic pollutants that can possess the same toxicity as their fully chlorinated analogs (PCDDs) and have been identified in the same matrices. Herein a general synthetic methodology is described to produce multiple congeners of PBDDs and PXDDs with varying degrees of halogenation and substitution patterns for use as analytical and/or internal standards, and for absorption, disposition, metabolism, and excretion (ADME) studies. The syntheses of PBDDs and PXDDs were accomplished by condensing a common precursor, 4,5-dibromo catechol, with variable precursors, i.e., polychlorinated 1-chloro-2-nitrobenzenes or polybrominated 1-fluoro-2-nitrobenzenes, to introduce a desired number of halogens and specific substitution patterns. Initial attempts to synthesize PBDDs and PXDDs were performed in potassium carbonate with DMSO at 145-150 °C. PXDDs syntheses resulted in formation of the desired products at >90% purity but attempts at higher brominated PBDDs syntheses resulted in dehalogenated by-products. To preclude by-product formation, additional syntheses for some PBDDs were conducted by refluxing the precursors in acetonitrile, which resulted in pure products at higher yield. Six PXDDs ranging from four to six halogens were synthesized (20-84% yield), of which three contained the halogen substitution pattern of 2,3,7,8. Five PBDDs ranging from four to six bromines were produced in 23-83% yield, three of which were toxic. Using the initial DMSO method, [ 14 C]-1,3,7,8-tetrabromodibenzo-p-dioxin (0.26 μCi/μmol; 11% overall yield) was synthesized from commercially available [ 14 C]-phenol to allow an ADME study to be conducted., (Published by Elsevier Ltd.)

Although livestock manure, such as from swine (Sus scrofa domestica), have high capacity to introduce endocrine-disrupting free estrogens into the environment, the frequency of estrogen detections from reconnaissance studies suggest that these compounds are ubiquitous in the environment, perhaps resulting from historic manure inputs (e.g. cattle grazing residues, undocumented historic manure applications) or uncontrolled natural sources. Compared to free estrogens, conjugates of estrogens are innocuous but have greater mobility in the environment. Estrogen conjugates can also hydrolyze to re-form the potent free estrogens. The objective of this study was to identify the transport of free and conjugated estrogens to subsurface tile drains and groundwater beneath fields treated with swine manure slurry. Three field treatments were established, two receiving swine lagoon manure slurry and one with none. Manure slurry was injected into soils at a shallow depth (∼8 cm) and water samples from tile drains and shallow wells were sampled periodically for three years. Glucuronide and sulfate conjugates of 17β-estradiol (E2) and estrone (E1) were the only estrogen compounds detected in the tile drains (total detects = 31; 5% detection frequency; conc. range = 3.9-23.1 ng L -1 ), indicating the important role conjugates played in the mobility of estrogens. Free estrogens and estrogen conjugates were more frequently detected in the wells compared to the tile drains (total detects = 70; 11% detection frequency; conc. range = 4.0-1.6 × 10 3  ng L -1 ). No correlations were found between estrogen compound detections and dissolved or colloidal organic carbon (OC) fractions or other water quality parameters. Estrogenic compounds were detected beneath both manure treated and non-treated plots; furthermore, the total potential estrogenic equivalents (i.e. estrogenicity of hydrolyzed conjugates + free estrogens) were similar between treated and non-treated plots., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The distribution of 12 environmental contaminants or metabolites with diverse polarities (2,2',4,4',5-pentabromodiphenyl ether; bisphenol A; estrone; glyphosate; β-hexabromocyclododecane; imidacloprid; 2,3',4,4',5-pentachlorobiphenyl; 3'-methylsulfone 2,2',4,5,5'-pentachlorobiphenyl; 1,2,7,8-tetrachlorodibenzo- p -dioxin; 2-hydroxy-1,3,7,8-tetrachlorodibenzo- p -dioxin; tetrabromobisphenol A; and triclocarban) among skim milk, fat, curd, whey, whey retentate, and whey permeate was characterized. Analysis of these compounds along with 15 drugs previously studied provided a robust linear model predicting the distribution between skim and fat and the chemical's lipophilicity (log P , r 2 = 0.71; log D , r 2 = 0.79). Similarly, distribution between curd and whey was correlated with lipophilicity (log P , r 2 = 0.63; log D , r 2 = 0.73). Phenolic compounds had less predictable distribution patterns based on their lipophilicities. Within the whey fraction, chemicals with greater lipophilicity are associated with whey proteins more than hydrophilic chemicals. The resultant model could help predict the potential distribution of chemical contaminants among milk products in cow milk, if present., Competing Interests: The authors declare no competing financial interest.

To identify abiotic processes that govern the fate of a sulfate conjugated estrogen, 17β-estradiol-17-sulfate (E2-17S), soil batch experiments were conducted to investigate the dissipation, sorption, and degradation of radiolabeled E2-17S under sterilized conditions. The aqueous dissipation half-lives (DT50) for E2-17S ranged from 2.5 to 9.3h for the topsoil of high organic carbon (OC) content (1.29%), but E2-17S remained at ∼80% of applied dose in the low OC (0.26%) subsoil by 14 d. The non-linear sorption isotherms indicated limited sorption of E2-17S, and the concentration-dependent log KOC values were 2.20 and 2.45 for the topsoil and subsoil, respectively. Additionally, two types of hydroxyl E2-17S (OH-E2-17S and diOH-E2-17S) were found as major metabolites in the aqueous phase, which represented 9-25% and 6-7% of applied dose for the topsoil and subsoil at 14 d, respectively. Free estrogens, 17β-estradiol (E2) and estrone (E1), were detected from the sorbed phase of the soil-water systems., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Animal manure is the primary source of exogenous free estrogens in the environment, which are known endocrine-disrupting chemicals to disorder the reproduction system of organisms. Conjugated estrogens can act as precursors to free estrogens, which may increase the total estrogenicity in the environment. In this study, a comprehensive model was used to simultaneously simulate the coupled sorption and transformation of a sulfate estrogen conjugate, 17β-estradiol-17-sulfate (E2-17S), in various soil-water systems (non-sterile/sterile; topsoil/subsoil). The simulated processes included multiple transformation pathways (i.e. hydroxylation, hydrolysis, and oxidation) and mass transfer between the aqueous, reversibly sorbed, and irreversibly sorbed phases of all soils for E2-17S and its metabolites. The conceptual model was conceived based on a series of linear sorption and first-order transformation expressions. The model was inversely solved using finite difference to estimate process parameters. A global optimization method was applied for the inverse analysis along with variable model restrictions to estimate 36 parameters. The model provided a satisfactory simultaneous fit (R(2)adj=0.93 and d=0.87) of all the experimental data and reliable parameter estimates. This modeling study improved the understanding on fate and transport of estrogen conjugates under various soil-water conditions., (Copyright © 2014 Elsevier B.V. All rights reserved.)

17β-estradiol (E2) is a natural estrogenic hormone found in animal manure and urine, which may cause endocrine disruption in sensitive organisms. 17β-Estradiol has been widely detected in the environment, and animal agriculture may be an important source. The objectives of this study were to investigate the potential sources and/or spatial and temporal characteristics contributing to detections of E2 at the farm-scale. Soil cores, segmented into 0.15m increments, were taken down to the water table from four locations (three potential E2 sources and one control) at or around a swine (Sus scrofa domesticus) farm on five different dates between 2006 and 2007. Estradiol was quantified in the soil-water extracts using liquid chromatography-with tandem mass spectrometry (LC/MS/MS) analysis. Estradiol detections were widespread and found in 128 out of 345 extractions (37%). Concentrations ranged from 0 to 1910 ng L⁻¹ (porewater equivalents). A location that received field application of manure had significantly lower E2 concentrations compared to other locations. Also, the spring 2007 E2 concentrations were significantly higher than all other sample dates, perhaps related to climatic and hydrological events. Results suggested E2 was not directly related to manure sources, but was widespread in this environment. Where E2 was detected, highest concentrations favored the upper profile, while the greatest frequency of detections was in the lower profile and near the water table. Detections of E2 were associated with high organic mater contents in the upper profile and high sand contents in the lower profile. The study suggests that E2 is widespread in some soil environments, raising questions as to the source and mechanisms that facilitate its transport and mobility., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The hormone 17beta-estradiol (E2) can cause endocrine disruption in sensitive species at part per trillion concentrations. The persistence and transport pathways of manure-borne E2 in agricultural soils were determined by comparing its occurrence with the transfer of water and the transport of non-sorbing fluorobenzoic acid (FBA) tracers. This comparison was done using capillary wick lysimeters installed 0.61m beneath three corn (Zea mays L.) plots that receive swine (Sus scrofa domesticus) manure from various sources. An additional control plot was included that received no manure. Soil water transfer was modeled to compare actual versus predicted percolation. On average, lysimeters collected 61% of the expected percolation and 8% of the FBA. There were frequent E2 detections, where there were an average of 8 detections for the 11 sample events. The average detection was 21ngL(-1) and its range was 1-245ngL(-1). 17beta-Estradiol was detected before manure was applied and also in the control plot lysimeters. Furthermore, the average mass recovery of E2 in all the lysimeters was >50%, which was greater than the FBA tracer recovery. Results indicated that tracer was transported with precipitated water infiltrating into the soil surface and percolating down through the soil profile. There was substantial evidence for antecedent E2, which was persistent and mobile. The persistence and mobility of the E2 may result from its associations with colloids, such as dissolved organic matter. Furthermore, this antecedent E2 appeared to overwhelm any observable effect of manure management on E2 fate and transport.

Steroidal hormones are constantly released into the environment by man-made and natural sources. The goal of this study was to examine the persistence and fate of 17beta-estradiol and testosterone, the two primary natural sex hormones. Incubation experiments were conducted under aerobic and anaerobic conditions using [4-(14)C]-radiolabeled 17beta-estradiol and testosterone. The results indicated that 6% of 17beta-estradiol and 63% of testosterone could be mineralized to (14)CO(2) in native soils under aerobic conditions. In native soils under anaerobic conditions, 2% of testosterone and no 17beta-estradiol was methanogenized to (14)CH(4). Essentially, no mineralization of either testosterone or 17beta-estradiol to (14)CO(2) occurred in autoclaved soils under aerobic or anaerobic condition. Results also indicated that 17beta-estradiol could be transformed to an unidentified polar compound through abiotic chemical processes; however, 17beta-estradiol was only oxidized to estrone via biological processes. The TLC results also indicated that testosterone was degraded, not by physical-chemical processes but by biological processes. Results also indicated that the assumed risks of estrogenic hormones in the environment might be over-estimated due to the soil's humic substances, which can immobilize majority of estrogenic hormones, and thereby reduce their bioavailability and toxicity.

Polybrominated diphenyl ethers (PBDE) are common flame retardants used in polyurethane foam, high impact polystyrene, and textiles which appear to be increasing in the environment and biota. Two PBDE congeners that are particularly prominent in environmental samples are 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and 2,2',4,4',5-pentabromodiphenyl ether (BDE-99). These two congeners are major components in penta-BDE formulations which constitute a minor percentage of the commercial PBDE market. In order to determine the bioavailability and bioconcentration potential of these PBDEs, we have conducted a feeding experiment in rats, dosing with low amounts of a commercial penta-BDE mixture for 21 days to mimic an environmental exposure. The carcasses, livers, and feces from control and dosed rats were quantitated for PBDEs by a high resolution GC-MS isotope dilution method. Between 25% and 50% of each of the dosed congeners was retained in the rats with the liver being a minor depot (<1% of the dose). Fecal excretion accounted for 4-12% of the dosed congeners. A large percent of the dose (40-60%) was not recovered indicating that metabolic transformations may have occurred in the rats. Hydroxylated metabolites were qualitatively identified in the feces and carcass by GC-MS. The relative congener distribution in each tissue was nearly identical to the congener distribution of the commercial mixture. Conclusions from the study suggest that the tetra- to hexa-BDEs present in commercial penta-BDE formulations are largely bioavailable, that bioavailability in the rat is not dependent on the degree of bromination, and that metabolism may occur to a large extent during a chronic exposure.

Atrazine (ATR) significantly inhibited phosphodiesterase (PDE) in crude homogenates of swine heart, brain, and lung, but not liver or kidney tissues. Except for heart, PDE activities in the cytosolic fraction of the tissue homogenates were not affected by ATR. The inhibition of the PDE activity in the cytosol from heart homogenate was not significantly different between ATR and a non-specific PDE inhibitor, 3-isobutyl-1-methylxanthine (IBMX). Dixon plots of the crude tissue homogenates showed that heart and brain were inhibited via two different mechanisms (competitive or mixed inhibition, and noncompetitive inhibition, respectively), suggesting that ATR may be a semi-specific PDE inhibitor. Furthermore, in crude tissue homogenates, ATR did not inhibit PDE as effectively as IBMX suggesting that there are ATR-susceptible and ATR-nonsusceptible forms of PDE. Association constants for ATR were 55 microM for heart and 310 microM for brain. The stability of the activity of PDE was affected by freezing, requiring the use of only freshly prepared tissue homogenates.

A single oral dose of [14C] 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) was administered to conventional and bile-duct cannulated male Sprague-Dawley rats. Tissue disposition, excretion and metabolism was determined. BTBPE is a low-volume brominated flame retardant used in resins or plastics, and toxicity data in peer-reviewed journals is extremely limited. BTBPE was fairly insoluble in lipophilic solutions, which made dose preparation difficult. The great majority of 14C (>94%) was excreted in the feces of both groups of rats at 72 h, and tissue retention was minimal. Lipophilic tissues contained the highest concentrations of BTBPE, e.g. thymus, adipose tissue, adrenals, lung, and skin. Metabolites were excreted in the urine, bile and feces, but at a very low level. Fecal metabolites were characterized as monohydroxylated, monohydroxylated with debromination, dihydroxylated/debrominated on a single aromatic ring, monohydroxylated on each aromatic ring with accompanying debromination, and cleavage on either side of the ether linkage to yield tribromophenol and tribromophenoxyethanol. Despite a limited quantity of stable metabolites extractable in the feces, non-extractable 14C levels were relatively high (39% of the 0-24 h fecal 14C), which suggested that BTBPE could be metabolically activated in the rat and covalently bound to fecal proteins and/or lipids. It was concluded that limited absorption and metabolism of BTBPE would occur by ingestion in mammals.

A tissue distribution, excretion, and metabolism study was conducted using a relatively non-toxic dioxin congener, i.e., 1,2,7,8-tetrachlorodibenzo-p-dioxin (1278-TCDD), to gain a better understanding of mammalian metabolism of dioxins. Conventional, bile duct cannulated, and germ free male rats were administered mg/kg quantities as a single oral dose. Elimination of 1278-TCDD was largely complete by 72 h. Distribution of [14C]1278-TCDD was low in all tissues examined. Metabolites were identified in urine, bile, and feces by negative ion FAB-MS and 1H-NMR, or GC/MS. The major fecal metabolite was a NIH-shifted hydroxylated TCDD. The bile contained a glucuronide conjugate of this hydroxy TCDD, and a diglucuronide conjugate of a dihydroxy-triCDD. The major metabolites in urine were glucuronide and sulfate conjugates of 4,5-dichlorocatechol.