Declining concentrations of chlorinated paraffins in endangered St. Lawrence Estuary belugas (Delphinapterus leucas): Response to regulations or a change in diet?

Very high levels of industrial contaminants in St. Lawrence Estuary (SLE) beluga whales represent one of the major threats to this population classified as endangered under the Species at Risk Act in Canada. Elevated concentrations of short-chained chlorinated paraffins (SCCPs) were recently reported in blubber of adult male SLE belugas.

Consumer behavior and exposure to parabens, bisphenols, triclosan, dichlorophenols, and benzophenone-3: Results from a crowdsourced biomonitoring study.

Nearly all Americans have detectable concentrations of endocrine disrupting chemicals from consumer products in their bodies, and expert panels recommend reducing exposures. To inform exposure reduction, we investigated whether consumers who are trying to avoid certain chemicals in consumer products have lower exposures than those who are not. We also aimed to make exposure biomonitoring more widely available.

Effect of Sample Storage on the Quantitative Determination of 29 PFAS: Observation of Analyte Interconversions during Storage.

In this study, we measured the effects of sample type and storage temperature on the stability of 29 per- and polyfluorinated alkyl substances (PFAS) in water. Spiked bottled water, surface water, and two types of effluent samples were stored in HDPE containers at +20, 4, and -20 °C over a period of up to 180 days. The analytes studied included C through C perfluorinated carboxylates (PFCAs); C through C and C perfluorinated sulfonates (PFSAs); 4:2, 6:2, and 8:2 fluorotelomer sulfonates (FTS); three perfluorooctane sulfonamides (PFOSA, N-MeFOSA, and N-EtFOSA); two perfluorooctane sulfonamide ethanols (N-MeFOSE and N-EtFOSE); and two perfluorooctane sulfonamide acetic acids (N-MeFOSAA and EtFOSAA).

Per- and polyfluoroalkyl substances in human serum and urine samples from a residentially exposed community.

Background: Per- and polyfluoroalkyl substances (PFAS) are considered chemicals of emerging concern, in part due to their environmental and biological persistence and the potential for widespread human exposure. In 2007, a PFAS manufacturer near Decatur, Alabama notified the United States Environmental Protection Agency (EPA) it had discharged PFAS into a wastewater treatment plant, resulting in environmental contamination and potential exposures to the local community.

Objectives: To characterize PFAS exposure over time, the Agency for Toxic Substances and Disease Registry (ATSDR) collected blood and urine samples from local residents.

Quantitative determination of hydroxy polycylic aromatic hydrocarbons as a biomarker of exposure to carcinogenic polycyclic aromatic hydrocarbons.

A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method was developed for quantitative analysis of hydroxy polycyclic aromatic hydrocarbons (OH-PAHs). Four hydroxy metabolites of known and suspected carcinogenic PAHs (benzo[a]pyrene (B[a]P), benz[a]anthracene (B[a]A), and chrysene (CRY)) were selected as suitable biomarkers of PAH exposure and associated risks to human health. The analytical method included enzymatic deconjugation, liquid - liquid extraction, followed by derivatization with methyl-N-(trimethylsilyl) trifluoroacetamide and instrumental analysis.

Quantitative determination of 13 organophosphorous flame retardants and plasticizers in a wastewater treatment system by high performance liquid chromatography tandem mass spectrometry.

A method for quantitative determination of 13 organophosphorous compounds (OPs) was developed and applied to influent, primary sludge, activated sludge, biosolids, primary effluent and final effluent from a wastewater treatment plant (WWTP). The method involved solvent extraction followed by solid phase clean-up and analysis by high performance liquid chromatography positive electrospray ionization-tandem mass spectrometry (HPLC(+ESI)MS/MS). Replicate spike/recovery experiments revealed the method to have good accuracy (70-132%) and precision (<19% RSD) in all matrices.

Pesticides in blood from spectacled caiman (Caiman crocodilus) downstream of banana plantations in Costa Rica.

Spectacled caiman (Caiman crocodilus) are fish-eating crocodilians that inhabit freshwater habitat in tropical regions of the Americas. To assess the exposure of caiman to pesticides from banana plantations, the authors collected whole blood samples (30 mL) from 14 adult caiman that were captured in the North Atlantic region of Costa Rica. Blood samples were analyzed for 70 legacy- and current-use pesticides and breakdown products using newly developed ultra-trace, high-resolution mass spectrometry (HRMS).

A novel derivatization-based liquid chromatography tandem mass spectrometry method for quantitative characterization of naphthenic acid isomer profiles in environmental waters.

A method for quantitative characterization of naphthenic acid (NA) isomer groups by carbon number and extent of cyclization was developed and validated with water samples from northern Alberta. Following solid phase extraction, NAs undergo derivatization with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) allowing detection by positive electrospray ionization tandem mass spectrometry (+ESI)-MS/MS. NA-EDC derivatives produce a common product ion by MS/MS, regardless of structure of the starting NA.

Biodegradation of N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE) and EtFOSE-based phosphate diester (SAmPAP diester) in marine sediments.

Investigations into the biodegradation potential of perfluorooctane sulfonate (PFOS)-precursor candidates have focused on low molecular weight substances (e.g., N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE)) in wastewater treatment plant sludge.

Bisphenol A is not detectable in media or selected contact materials used in IVF.

There is a lack of data regarding potential exposure of gametes to bisphenol A during IVF. Detectable concentrations of bisphenol A were not found in commonly used IVF plastic culture dishes, suction tubing or growth media under normal-use conditions.

Rapid characterization of perfluoralkyl carboxylate, sulfonate, and sulfonamide isomers by high-performance liquid chromatography-tandem mass spectrometry.

A rapid (<23 min) new HPLC-MS/MS method was developed for simultaneous characterization of 24 per- and polyfluoroalkyl compounds in landfill leachate. In addition to isomer-specific analysis of perfluorooctane sulfonate and perfluorooctanoate, branched from linear isomer separation was accomplished for C6 and C10 perfluoroalkyl sulfonates, C6, C7 and C9-C11 perfluoroalkyl carboxylates, perfluorooctane sulfonamide and, for the first time, 3 perfluorooctane sulfonamidoacetates. The method utilizes a fused-core pentafluorophenylpropyl (PFP) stationary phase and is approximately 4 times faster than previous comprehensive isomer-specific HPLC-MS/MS methods.

Observation of a novel PFOS-precursor, the perfluorooctane sulfonamido ethanol-based phosphate (SAmPAP) diester, in marine sediments.

The environmental occurrence of perfluorooctane sulfonate (PFOS) can arise from its direct use as well as from transformation of precursors ((N-alkyl substituted) perfluorooctane sulfonamides; FOSAMs). Perfluorooctane sulfonamidoethanol-based phosphate (SAmPAP) esters are among numerous potential PFOS-precursors which have not been previously detected in the environment and for which little is known about their stability. Based on their high production volume during the 1970s-2002 and widespread use in food contact paper and packaging, SAmPAP esters may be potentially significant sources of PFOS.

Pesticide multiresidues in waters of the Lower Fraser Valley, British Columbia, Canada. Part II. Groundwater.

In Part I of this work we presented pesticide levels in the surface waters of the Lower Fraser Valley (LFV) region of British Columbia, Canada. In Part II pesticide levels in the groundwater of the LFV are presented. During the period 2003 to 2005 a study was conducted to determine the occurrence and spatial distribution of 78 pesticides in the groundwater of the LFV.

Pesticide multiresidues in waters of the Lower Fraser Valley, British Columbia, Canada. Part I. Surface water.

In the period 2003 to 2005, a study was conducted to determine the occurrence, and spatial and temporal distribution of 78 pesticides in surface waters of the Lower Fraser Valley (LFV) region of British Columbia, Canada. A high resolution gas chromatography/electron impact high resolution mass spectrometry (HRGC/[EI]HRMS) method capable of detecting analytes at the subnanograms per liter level was developed for this study. Samples were collected and analyzed from three reference, five agricultural and two urban sites.

Partitioning of current-use and legacy pesticides in salmon habitat in British Columbia, Canada.

Current regulatory paradigms have favored a shift from persistent pesticides that amplify in aquatic food webs to pesticides with reduced persistence and bioaccumulative potential (low log K(OW)). Although these new generation pesticides preferentially partition away from food web-associated lipids, aquatic biota may nonetheless be exposed to them via other environmental compartments. To characterize pesticide patterns in coho salmon (Oncorhynchus kisutch) habitat, we studied two salmon-bearing watersheds (agricultural and urban) in British Columbia, Canada's Fraser River valley and one in a remote area of the province's central coast.

Acidic herbicides in surface waters of Lower Fraser Valley, British Columbia, Canada.

In the period 2003-2005 a study was conducted to determine the occurrence, spatial and temporal distribution of five acidic herbicides in the Lower Fraser Valley (LFV) region of British Columbia, Canada. A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method capable of detecting analytes at the sub ng/L level was developed for this study. Samples were collected and analyzed from two references, five agricultural, two urban and five agricultural and urban mixed sites.

Pyrethroids, pyrethrins, and piperonyl butoxide in sediments by high-resolution gas chromatography/high-resolution mass spectrometry.

A new method for determination of pyrethroids, pyrethrins, and piperonyl butoxide (PBO) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for aquatic sediments. The method detection limits for pyrethroids (15 compounds), pyrethrins, and PBO ranged from 0.16 to 1.

Quantitative determination of pyrethroids, pyrethrins, and piperonyl butoxide in surface water by high-resolution gas chromatography/high-resolution mass spectrometry.

A new method for determination of pyrethroids, pyrethrins, and piperonyl butoxide (PBO) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. The method is based on sampling 100 L of ambient surface water with a solid phase extraction (SPE) technique that uses both wound glass fiber filters for collecting the particulate-associated chemicals and XAD-2 resin for collecting the dissolved chemicals. The method detection limits of the analytes ranged from 0.

Isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry method for analysis of selected acidic herbicides in surface water.

In this work, an isotope dilution method for determination of selected acidic herbicides by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. Average percent recoveries of native analytes were observed to be between 70.8 and 93.