Polychlorinated biphenyl (PCB) concentrations and breakpoint trends across the waters of the Great Lakes by isotope-dilution high-resolution mass spectroscopy.

Water samples were collected during each of the 2012-2019 Cooperative Science and Monitoring Initiative (CSMI) cruises aboard the U.S. EPA R/V Lake Guardian as part of the Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) lower food web contaminant assessment.

The unique distribution pattern of PFAS in landfill organics.

PFAS from degrading landfill waste partition into organic matter, leachate, and landfill gas. Driven by the limited understanding of PFAS distribution in landfill organics, we analyzed PFAS across various depths and seven spatially distinct locations within a municipal landfill. The measured PFAS concentrations in organics ranged from 6.

Short- and medium-chain chlorinated paraffins in surface sediment from Lake Ontario.

Concentrations of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) were analyzed and investigated in surficial sediment collected in 2018 from ten different nearshore sites in Lake Ontario and the St. Lawrence River influenced by inputs from varying urban and historical land uses. Sites were grouped into two categories of tributary and lake according to their location.

Correction to "Solvent-Free Nonthermal Destruction of PFAS Chemicals and PFAS in Sediment by Piezoelectric Ball Milling".

[This corrects the article DOI: 10.1021/acs.estlett.

PFAS occurrence and distribution in yard waste compost indicate potential volatile loss, downward migration, and transformation.

We discovered high concentrations of PFAS (18.53 ± 1.5 μg kg) in yard waste compost, a compost type widely acceptable to the public.

Solvent-Free Nonthermal Destruction of PFAS Chemicals and PFAS in Sediment by Piezoelectric Ball Milling.

Studies on the destruction of solid per- and polyfluoroalkyl substances (PFAS) chemicals and PFAS-laden solid wastes significantly lag behind the urgent social demand. There is a great need to develop novel treatment processes that can destroy nonaqueous PFAS at ambient temperatures and pressures. In this study, we develop a piezoelectric-material-assisted ball milling (PZM-BM) process built on the principle that ball collisions during milling can activate PZMs to generate ∼kV potentials for PFAS destruction in the absence of solvents.

Can blood proteome diversity among fish species help explain perfluoroalkyl acid trophodynamics in aquatic food webs?

Per- and polyfluoroalkyl substances (PFAS) are a diverse family of industrially significant synthetic chemicals infamous for extreme environmental persistence and global environmental distribution. Many PFAS are bioaccumulative and biologically active mainly due to their tendency to bind with various proteins. These protein interactions are important in determining the accumulation potential and tissue distribution of individual PFAS.

Suspect Screening and Nontargeted Analysis of Per- and Polyfluoroalkyl Substances in a Lake Ontario Food Web.

Per- and polyfluoroalkyl substances (PFAS) are globally distributed in the natural environment, and their persistent and bioaccumulative potential illicit public concern. The production of certain PFAS has been halted or controlled by regulation due to their adverse effect on the health of humans and wildlife. However, new PFAS are continuously developed as alternatives to legacy PFAS.

Bioaccumulation of perfluoroalkyl substances in the Lake Erie food web.

The bioaccumulation and biomagnification of perfluoroalkyl substances (PFAS) in the Lake Erie food web was investigated by analyzing surface water and biological samples including 10 taxa of fish species, 2 taxa of benthos and zooplankton. The carbon (δC) and nitrogen (δN) isotopic composition and fatty acids profiles of biological samples were used to evaluate the food web structure and assess the biomagnification of PFAS. Perfluorooctane sulfonate (PFOS) dominated the total PFAS (ΣPFAS) concentration (50-90% of ΣPFAS concentration), followed by C9-C11 perfluorinated carboxylic acids (PFCAs).

Is Mixtures' Additivity Supported by Empirical Data? A Case Study of Developmental Toxicity of PFOS and 6:2 FTS in Wildtype Zebrafish Embryos.

Per- and polyfluoroalkyl substances (PFASs) are a major priority for many federal and state regulatory agencies charged with monitoring levels of emerging contaminants in environmental media and setting health-protective benchmarks to guide risk assessments. While screening levels and toxicity reference values have been developed for numerous individual PFAS compounds, there remain important data gaps regarding the mode of action for toxicity of PFAS mixtures. The present study aims to contribute whole-mixture toxicity data and advance the methods for evaluating mixtures of two key components of aqueous film-forming foams: perfluorooctanesulfonic acid (PFOS), and 6:2 fluorotelomer sulfonic acid (6:2 FTS).

Bioaccumulation of polyfluoroalkyl substances in the Lake Huron aquatic food web.

Polyfluoroalkyl substances (PFAS) are a group of fluorinated organic chemicals that have been produced for industrial and commercial application since the 1950s. PFAS are highly persistent and ubiquitous in water, sediment, and biota. Toxic effects of PFAS on humans and the ecosystem have increased scientific and public concern.

Characterization of Halogenated Organic Compounds in Pelagic Sharks and Sea Turtles Using a Nontargeted Approach.

Halogenated organic compounds (HOCs) in marine species collected from the Atlantic Ocean [3 shortfin mako () and 1 porbeagle ()], and 12 sea turtles collected from the Pacific Ocean [3 loggerhead (), 3 green (), 3 olive ridley (), and 3 hawksbill ()] were analyzed with a nontargeted analytical method using two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry. Sharks and sea turtles had distinct HOC profiles. Halogenated methoxyphenols (halo-MeOPs) were the most abundant compound class identified in sea turtle livers, while polychlorinated biphenyls (PCBs) were the most abundant in shark livers.

Systematic Study on the Removal of Per- and Polyfluoroalkyl Substances from Contaminated Groundwater Using Metal-Organic Frameworks.

Harmful per- and polyfluoroalkyl substances (PFAS) are ubiquitously detected in aquatic environments, but their remediation remains challenging. Metal-organic frameworks (MOFs) have been recently identified as an advanced material class for the efficient removal of PFAS, but little is known about the fundamentals of the PFAS@MOF adsorption process. To address this knowledge gap, we evaluated the performance of 3 different MOFs for the removal of 8 PFAS classes from aqueous film-forming foam-impacted groundwater samples obtained from 11 U.

Trends (2005-2016) of perfluoroalkyl acids in top predator fish of the Laurentian Great Lakes.

This work presents the first assessment of temporal trends (2005-2016) for perfluoroalkyl acids (PFAAs) in top predator fish of the Laurentian Great Lakes except Lake Ontario, for which we provide a post-2008 update. Lake trout (Salvelinus namaycush) or walleye (Sander vitreus; Lake Erie only) collected annually from 2005 to 2016 were analyzed for 12 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkyl sulfonic acids (PFSAs) with carbon chain lengths between 4 and 16 (C4-C16). Individual analyte concentrations generally decreased in fish basin-wide between 2005 and 2016, including Lake Ontario lake trout previously found to lack declining PFAA concentrations up until 2008.

Nontargeted Discovery of Novel Contaminants in the Great Lakes Region: A Comparison of Fish Fillets and Fish Consumers.

Sport fish fillets and human sera (fish consumers) were collected in the Lake Superior and Lake Michigan basin and screened for novel contaminants using the isotopic profile deconvoluted chromatogram (IPDC) algorithm. The IPDC algorithm was extended beyond traditional Cl/Br filters to detect additional potential bioaccumulative and toxic (PBT) such as perfluoroalkyl substances (PFAS). The IPDC algorithm screened for approximately 13.

Nontargeted Screening of Halogenated Organic Compounds in Fish Fillet Tissues from the Great Lakes.

Fish have been used for decades as bioindicators for assessing toxic contaminants in the Great Lakes ecosystem. Routine environmental monitoring programs target predetermined compounds that do not reflect the complete exposure of chemicals to biota and do not provide the complete halogenated fingerprint of the biota. In the current work, a nontargeted screening method was developed using a two-dimensional gas chromatograph coupled to a high-resolution time-of-flight mass spectrometer and was applied to 149 edible fish fillets from different species in the Great Lakes to characterize a more robust set of halogenated organic compounds across species and among lakes.

Decadal Differences in Emerging Halogenated Contaminant Profiles in Great Lakes Top Predator Fish.

Legacy halogenated contaminants have been monitored in the Great Lakes for decades, but there are many additional unknown halogenated contaminants potentially affecting the Great Lakes ecosystem. To address this concern, lake trout () were collected in 2005/2006 and 2015/2016 from each lake and screened for previously unidentified compounds. The isotopic profile deconvoluted chromatogram algorithm was used to isolate unknown halogenated components using high-resolution mass spectrometry data files generated by an atmospheric pressure gas chromatography-quadrupole time-of-flight mass spectrometer operated in positive and negative modes.

Concentrations and Long-Term Temporal Trends of Hexabromocyclododecanes (HBCDD) in Lake Trout and Walleye from the Great Lakes.

Hexabromocyclododecane (HBCDD) is a hazardous, persistent, bioaccumlative brominated flame retardant. To investigate how its use has affected the Great Lakes, total HBCDD (∑HBCDD) concentrations and temporal trends in homogenized whole fish samples from the Great Lakes region (1978 to 2016) were determined. ∑HBCDD concentrations (ng/g ww) for each lake are Erie (0.

Automated Isotopic Profile Deconvolution for High Resolution Mass Spectrometric Data (APGC-QToF) from Biological Matrices.

An isotopic profile matching algorithm, the isotopic profile deconvoluted chromatogram (IPDC), was developed to screen for a wide variety of organic compounds in high-resolution mass spectrometry (HRMS) data acquired from instruments with resolution power as low as 22 000 fwhm. The algorithm initiates the screening process by generating a series of C/Br/Cl/S isotopic patterns consistent with the profiles of approximately 3 million molecular formulas for compounds with potentially persistent, bioaccumulative, and toxic (PBT) properties. To evaluate this algorithm, HRMS data were screened using these seed profiles to isolate relevant chlorinated and/or brominated compounds.

Breakdown Products from Perfluorinated Alkyl Substances (PFAS) Degradation in a Plasma-Based Water Treatment Process.

Byproducts produced when treating perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in water using a plasma treatment process intentionally operated to treat these compounds slowly to allow for byproduct accumulation were quantified. Several linear chain perfluoroalkyl carboxylic acids (PFCAs) (C4 to C7) were identified as byproducts of both PFOA and PFOS treatment. PFOA, perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS) were also found to be byproducts from PFOS degradation.

Comprehensive Analysis of the Great Lakes Top Predator Fish for Novel Halogenated Organic Contaminants by GC×GC-HR-ToF Mass Spectrometry.

The U.S. Environmental Protection Agency's Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) has traced the fate and transport of anthropogenic chemicals in the Great Lakes region for decades.

Differentiation of (Mixed) Halogenated Dibenzo-p-Dioxins by Negative Ion Atmospheric Pressure Chemical Ionization.

Brominated and mixed halogenated dibenzo-p-dioxins (PBDDs and PXDDs) may well be as toxic as 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2378-TCDD), a compound reputed as one of the most toxic chemicals known to exist. However, studies on the occurrence of PXDDs have been hampered by a lack of authentic standards as well as separation techniques capable of resolving the enormous number of potential isomers. Electron ionization (EI) mass spectrometry based methods are of limited value due to the lack of isomer specific fragmentation.

Evaluation of Firefighter Exposure to Wood Smoke during Training Exercises at Burn Houses.

Smoke from wood-fueled fires is one of the most common hazards encountered by firefighters worldwide. Wood smoke is complex in nature and contains numerous compounds, including methoxyphenols (MPs) and polycyclic aromatic hydrocarbons (PAHs), some of which are carcinogenic. Chronic exposure to wood smoke can lead to adverse health outcomes, including respiratory infections, impaired lung function, cardiac infarctions, and cancers.

Identification of the halogenated compounds resulting from the 1997 Plastimet Inc. fire in Hamilton, Ontario, using comprehensive two-dimensional gas chromatography and (ultra)high resolution mass spectrometry.

Between July 9-12, 1997, at least 400 tonnes of polyvinyl chloride (PVC) were consumed in a fire at the Plastimet Inc. plastics recycling facility in Hamilton, Ontario, Canada. This led to the release of contaminants, including highly toxic polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF).