Bioavailability of non-aromatic brominated flame retardants in rats from dust and oil vehicles.

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.

Perfluorooctanoic Acid Transport in Soil and Absorption and Distribution in Alfalfa (Medicago sativa).

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.

Absorption, distribution, metabolism, and excretion of three [C]PBDE congeners in laying hens and transfer to eggs.

Polybrominated diphenyl ethers (PBDEs) levels in environmental matrices have generally declined following their phaseout as flame retardants. The objective of this study was to determine the absorption, distribution, metabolism, and excretion of three persistent PBDEs in laying hens and their transfer into eggs. Laying hens (n = 4 per congener) received a single oral dose of BDE-99, -153, or -209 and eggs and excreta were collected daily for 7 days, then tissues were collected and analysed.

Perfluorooctanoic Acid Uptake by Alfalfa (Medicago sativa) and Bioavailability in Sprague-Dawley Rats.

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.

Free and conjugated estrogens detections in drainage tiles and wells beneath fields receiving swine manure slurry.

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.

Facile synthesis of bromo- and mixed bromo/chloro dibenzo-p-dioxins and [C]-labeled 1,3,7,8-tetrabromodibenzo-p-dioxin.

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.

Distribution of Chemical Residues among Fat, Skim, Curd, Whey, and Protein Fractions in Fortified, Pasteurized Milk.

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--dioxin; 2-hydroxy-1,3,7,8-tetrachlorodibenzo--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 , = 0.71; log , = 0.

Atmospheric Solid Analysis Probe and Modified Desorption Electrospray Ionization Mass Spectrometry for Rapid Screening and Semi-Quantification of Zilpaterol in Urine and Tissues of Sheep.

Ambient ionization mass spectrometric methods including desorption electrospray ionization (DESI) and atmospheric solid analysis probe (ASAP) have great potential for applications requiring real-time screening of target molecules in complex matrixes. Such techniques can also rapidly produce repeatable semiquantitative data, with minimal sample preparation, relative to liquid chromatography-mass spectrometry (LC-MS). In this study, a commercial ASAP probe was used to conduct both ASAP-MS and modified DESI (MDESI) MS analyses.

Facile synthesis of high specific activity 4-[1- C]butyl-1,2-diphenylpyrazolidine-3,5-dione (phenylbutazone) using nucleophilic substitution.

Metabolism, environmental fate, and low concentration food residue studies would be facilitated by the use of radiolabeled test articles that can be readily quantified within complex matrices. However, radiochemical approaches for such studies require high specific activities to allow analytical detection of correspondingly low masses of test article. The synthesis of high specific activity (>50 μCi/μmol) [ C]-radiolabeled phenylbutazone presents a challenge using existing methodology, mainly due to the low solvent volumes required and vigorous refluxing needed to close the pyrazolidinedione ring.

Distribution of Spiked Drugs between Milk Fat, Skim Milk, Whey, Curd, and Milk Protein Fractions: Expansion of Partitioning Models.

The distributions of eight drugs (acetaminophen, acetylsalicylic acid/salicylic acid, ciprofloxacin, clarithromycin, flunixin, phenylbutazone, praziquantel, and thiamphenicol) were determined in milk products (skim milk, milk fat, curd, whey, and whey protein) and used to expand a previous model (from 7 drugs to 15 drugs) for predicting drug distribution. Phenylbutazone and praziquantel were found to distribute with the lipid and curd phases (≥50%). Flunixin distribution was lower but similar in direction (12% in milk fat, 39% in curd).

Halogenated 17β-Estradiol Surrogates: Synthesis, Estrogenic Activity, and Initial Investigations of Fate in Soil/Water Systems.

17β-Estradiol (E2), a natural, endocrine-disrupting, steroid hormone, is excreted by all vertebrates and can enter the environment from domestic animal and wildlife wastes. Multiple field studies using livestock manures as E2 sources suggest significant background concentrations of E2 (e.g.

Polybrominated diphenyl ethers (PBDEs) in US meat and poultry: 2012-13 levels, trends and estimated consumer exposures.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants whose use has contaminated foods and caused subsequent human exposures. To address the issue of possible human exposure, samples from a 2012-13 US meat and poultry (beef, pork, chicken, turkey) study were analysed for seven PBDEs. The mean summed concentrations of the seven BDE congeners (ΣPBDE) from beef, pork, chicken and turkey were 0.

Distribution of Animal Drugs among Curd, Whey, and Milk Protein Fractions in Spiked Skim Milk and Whey.

It is important to understand the partitioning of drugs in processed milk and milk products, when drugs are present in raw milk, in order to estimate the potential consumer exposure. Radioisotopically labeled erythromycin, ivermectin, ketoprofen, oxytetracycline, penicillin G, sulfadimethoxine, and thiabendazole were used to evaluate the distribution of animal drugs among rennet curd, whey, and protein fractions from skim cow milk. Our previous work reported the distribution of these same drugs between skim and fat fractions of milk.

Fate and transport of the β-adrenergic agonist ractopamine hydrochloride in soil-water systems.

The feed additive ractopamine hydrochloride was fortified at four concentrations into batch vials containing soils that differed in both biological activity and organic matter (OM). Sampling of the liquid layer for 14days demonstrated that ractopamine rapidly dissipated from the liquid layer. Less than 20% of the fortified dose remained in the liquid layer after 4hr, and recoveries of dosed ractopamine ranged from 8 to 18% in the liquid layer at 336hr.

Distribution of Animal Drugs between Skim Milk and Milk Fat Fractions in Spiked Whole Milk: Understanding the Potential Impact on Commercial Milk Products.

Seven animal drugs [penicillin G (PENG), sulfadimethoxine (SDMX), oxytetracycline (OTET), erythromycin (ERY), ketoprofen (KETO), thiabendazole (THIA), and ivermectin (IVR)] were used to evaluate the drug distribution between milk fat and skim milk fractions of cow milk. More than 90% of the radioactivity was distributed into the skim milk fraction for ERY, KETO, OTET, PENG, and SDMX, approximately 80% for THIA, and 13% for IVR. The distribution of drug between milk fat and skim milk fractions was significantly correlated to the drug's lipophilicity (partition coefficient, log P, or distribution coefficient, log D, which includes ionization).

Comparative Metabolism Studies of Hexabromocyclododecane (HBCD) Diastereomers in Male Rats Following a Single Oral Dose.

Male Sprague-Dawley rats were dosed orally with 3 mg/kg of one of three hexabromocyclododecane (HBCD) diastereomers. Each diastereomer was well absorbed (73-83%), and distributed preferentially to lipophilic tissues. Feces were the major route of excretion; cumulatively accounting for 42% of dose for α-HBCD, 59% for ß-HBCD, and 53% for γ-HBCD.

Fate of 17β-estradiol in anaerobic lagoon digesters.

The fate of [C]17β-estradiol ([C]E2) was monitored for 42 d in triplicate 10-L anaerobic digesters. Total radioactive residues decreased rapidly in the liquid layer of the digesters and reached a steady-state value of 22 to 26% of the initial dose after 5 d. High-performance liquid chromatography and liquid chromatography-tandem mass spectrometry analyses of the liquid layer of the anaerobic digesters indicated a rapid degradation of E2 to estrone (E1), which readily adsorbed to the sludge layer subsequent to its formation.

Modeling coupled sorption and transformation of 17β-estradiol-17-sulfate in soil-water systems.

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).

Potential bioactivity and association of 17β-estradiol with the dissolved and colloidal fractions of manure and soil.

The dissolved (DF) and colloidal fractions (CF) of soil and manure play an important role in the environmental fate and transport of steroidal estrogens. The first objective of this study was to quantify the association of 17β-estradiol (E2) with the DF and CF isolated from (i) liquid swine manure (LSM), (ii) a soil:water mixture (soil), and (iii) a LSM:soil:water mixture (Soil+LSM). The appropriate CF and DF size fractions of the Soil, Soil+LSM, and LSM media were obtained by first filtering through a 0.

Sorption and degradation of 17β-estradiol-17-sulfate in sterilized soil-water systems.

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.

Dissipation and transformation of 17β-estradiol-17-sulfate in soil-water systems.

In the environment, estrogen conjugates can be precursors to the endocrine-disrupting free estrogens, 17β-estradiol (E2) and estrone (E1). Compared to other estrogen conjugates, 17β-estradiol-17-sulfate (E2-17S) is detected at relatively high concentrations and frequencies in animal manure and surface runoff from fields receiving manure. To elucidate the lifecycle of manure-borne estrogens and their conjugates in the environment, the fate of radiolabelled E2-17S in agricultural soils was investigated using laboratory batch studies with soils of different organic carbon (OC) content (1.

Radioassay-Based Approach to Investigate Fate and Transformation of Conjugated and Free Estrogens in an Agricultural Soil.

Estrogens, a potent group of endocrine disruptors toward aquatic species, are primarily excreted as conjugates from humans and animals. Radioassay-based approaches with detailed speciation have been frequently conducted for environmental-fate studies for pesticides; however, such techniques have not been exploited for reproductive hormones, and especially for hormone conjugates. This article describes a simple, robust, and high-mass-recovery approach to investigate the fate and transformation of a prototype estrogen conjugate, that is, 17β-estradiol-3-glucuronide (E2-3G), and its metabolites (free estrogens) in a laboratory soil and water matrix without the need for enzymatic cleavage and/or fluorescent derivatization.

Novel and distinct metabolites identified following a single oral dose of α- or γ-hexabromocyclododecane in mice.

The metabolism of α- and γ-hexabromocyclododecane (HBCD) was investigated in adult C57BL/6 female mice. α- or γ-[(14)C]HBCD (3 mg/kg bw) was orally administered with subsequent urine and feces collection for 4 consecutive days; a separate group of mice was dosed and sacrificed 3 h postexposure to investigate tissue metabolite levels. Extractable and nonextractable HBCD metabolites were quantitated in liver, blood, fat, brain, bile, urine, and feces and characterized by LC/MS (ESI-).

Fate and transformation of an estrogen conjugate and its metabolites in agricultural soils.

In the environment, conjugated estrogens are nontoxic but may hydrolyze to their potent unconjugated, 'free' forms. Compared to free estrogens, conjugated estrogens would be more mobile in the environment because of their higher water solubility. To identify the fate of a conjugated estrogen in natural agricultural soils, batch experiments were conducted with a (14)C labeled prototype conjugate, 17β-estradiol-3-glucuronide (E2-3G).

Dissipation of 17β-estradiol in composted poultry litter.

The excreted estrogen rate of all livestock in the United States is estimated at 134 kg d. The influence of manure treatment on the fate of estrogens is critical in deciding the recycling of over 300 million dry tons of livestock produced annually. The effects of two common manure management practices, heated composting and ambient temperature decomposition, on the fate of 17β-estradiol in poultry litter were determined.