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The effects of wetland wastewater treatment on estrogenic activity and estrogenic activity of water after tertiary treatment were evaluated usingin vivo(rainbow trout vitellogenin [VTG] expression) andin vitro(yeast estrogen screening) assays. Juvenile rainbow trout exposed to tertiary-treated wastewater from the Green Acres Treatment Plant in Orange County Water District had increased plasma VTG levels compared with control fish. When trout were exposed to wastewater-dominated water before it entered into Prado Wetland (Riverside County, CA), VTG concentrations were increased above those of controls and were not significantly different from fish exposed to water exiting the wetland. VTG E2-equivalent concentrations (EEQs) of the water samples from the Green Acres Plant were 16.92?±?16.49 ng/L. Activity of water entering Prado Wetland was 29.80?±?28.41 ng/L EEQ, and water exiting was 24.34?±?23.17 ng/L EEQ.In vitroassays estimated that estrogenic activity of water from the Green Acres Plant was<1 ng/L EEQ, whereas water entering and exiting Prado Wetland had yeast estrogen screening EEQs of 2.57 and<1 ng/L, respectively. Our results suggest that environmental estrogens that are not potent estrogen-receptor ligands exist in wastewaters from the Green Acres Plant as well as water entering and exiting Prado Wetland. Wetland treatment did not remove environmental estrogens in the water. Our results also suggest thatin vitroassays may underestimate estrogenic activity of sampled water. [ABSTRACT FROM AUTHOR]

As the occurrence of human diseases and conditions increase, questions continue to arise about their linkages to chemical exposure, especially for per-and polyfluoroalkyl substances (PFAS). Currently, many chemicals of concern have limited experimental information available for their use in analytical assessments. Here, we aim to increase this knowledge by providing the scientific community with multidimensional characteristics for 175 PFAS and their resulting 281 ion types. Using a platform coupling reversed-phase liquid chromatography (RPLC), electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), drift tube ion mobility spectrometry (IMS), and mass spectrometry (MS), the retention times, collision cross section (CCS) values, and m/z ratios were determined for all analytes and assembled into an openly available multidimensional dataset. This information will provide the scientific community with essential characteristics to expand analytical assessments of PFAS and augment machine learning training sets for discovering new PFAS., Competing Interests: Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

Fish and seafood are considered a major source of human dietary exposure to per- and polyfluoroalkyl substances (PFAS). In this study, we examined levels of 35 PFAS in fish samples of brown trout and mottled sculpin, which occupy different trophic positions, collected in 2014 from East Canyon Creek in Utah, USA. We observed 20 PFAS with ∑ 20 PFAS ranging from 0.46-63.9 ng/g and from

This study sought to develop a non-targeted workflow using high-resolution mass spectrometry (HRMS) to investigate previously unknown PFAS in consumer food packaging samples. Samples composed of various materials for different food types were subjected to methanolic extraction, controlled migration with food simulants and total oxidizable precursor (TOP) assay. The developed HRMS workflow utilized many signatures unique to PFAS compounds: negative mass defect, diagnostic breakdown structures, as well as retention time prediction. Potential PFAS features were identified in all packaging studied, regardless of food and material types. Five tentatively identified compounds were confirmed with analytical standards: 6:2 fluorotelomer phosphate diester (6:2 diPAP) and one of its intermediate breakdown products 2H-perfluoro-2-octenoic acid (6:2 FTUCA), perfluoropentadecanoic acid (PFPeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA). Longer perfluorocarboxylic acids including C 17 and C 19 to C 24 were also found present within a foil sample. Concentrations of 6:2 FTUCA ranged from 0.78 to 127 ng g -1 in methanolic extracts and up to 6 ng g -1 in food simulant after 240 h migration test. These results demonstrate the prevalence of both emerging and legacy PFAS in food packaging samples and highlight the usefulness of non-targeted tools to identify PFAS not included in targeted methods., 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 Ltd.)

Studies have reported health risks associated with seafood contamination, but few data exist on levels in commercially available seafood in the US. To better understand, the magnitude of foodborne exposure and identify vulnerable populations in the US, we measured concentrations of veterinary drugs, persistent organic pollutants (POPs) (polycyclic aromatic hydrocarbons [PAHs], polybrominated diphenyl ethers [PBDEs] and polychlorinated biphenyls [PCBs]), and legacy and current-use pesticides in 46 seafood samples purchased from retail outlets. Measured levels were used to estimate risk based on available maximum residue limits (MRLs) and toxic equivalence (TEQ) factors for analytes. Only seventeen of the 445 analytes were detected, at low substance frequencies. However, half of the samples tested positive for one or more analyte, with total concentrations ranging from below the limit of detection (LOD) to as high as 156 µg/kg wet weight. Based on the risk assessment for individual pesticides and veterinary drugs, the hazard quotients (HQ) were all <1, indicating no risk. However, for the sum of PCB126 and PCB167, two dioxin-like PCBs detected in our samples, the TEQ was nearly two orders of magnitude higher than the WHO limits in one catfish sample. Moreover, vulnerable groups with higher rates of consumption of specific fish types may face higher risks.

Seafood is a dominant source of human exposure to per- and polyfluoroalkyl substances (PFAS). Existing studies on foodborne PFAS exposure have focused on only a subset of these compounds. Here, we conducted a pilot study to screen 33 PFAS in 46 seafood samples from a cross-section of national and local stores in the US. Low levels of 8 PFAS were measured in 74% of the samples, predominated by PFHxS (59%). Total PFAS ranged between 0.12 and 20 ng/g; highest levels were measured in Estonia-sourced smelt. The highest median levels were of PFOA (0.84 ng/g) with elevated concentrations found in Chinese clams (2.4 ng/g), which exceeds the EU established maximum limits (MLs). Measured levels of PFHxS, PFOA, and PFNA also exceeded MLs in 24%, 7%, and 5% of the samples, respectively. For average consumption levels, exposures were below the EU established tolerable weekly intakes (TWIs). However, for more frequent consumption of flounder, catfish, and cod, exposures exceeded regulations, which warrants identifying vulnerable high seafood consuming populations. Accidental PFBS cross contamination from sample storage bags resulted in 100% detection in samples, highlighting the problem with post-purchase food handling practices such as storage and cooking that could also have a substantial impact on human exposure, potentially in larger amounts than the (sea)food itself., 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., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The purpose of this study was to investigate the presence and levels of per- and polyfluoroalkyl substances (PFAS) in food packaging originating from different geographic locations. Food packaging samples were extracted and analyzed by targeted analysis with liquid chromatography-mass spectrometry (LC-MS/MS) before and after a total oxidizable precursor (TOP) assay. Additionally, full-scan high resolution MS (HRMS) was used to screen for PFAS not included in the targeted list. Of the 88 food packaging samples, 84% had detectable levels of at least one PFAS prior to oxidation with a TOP assay, with 6:2 fluorotelomer phosphate diester (6:2 diPAP) found most frequently and at the highest levels (224 ng/g). Other frequently detected substances (in 15-17% of samples) were PFHxS, PFHpA and PFDA. Shorter chain perfluorinated carboxylic acids PFHpA (C7), PFPeA (C5) and PFHxS (C6) were present at levels up to 51.3, 24.1 and 18.2 ng/g, respectively. Average ∑PFAS levels were 28.3 ng/g and 381.9 ng/g before and after oxidation with the TOP assay. The 25 samples with highest frequency of detection and amounts of measured PFAS were selected for migration experiments with food simulants to better understand potential dietary exposure. PFHxS, PFHpA, PFHxA and 6:2 diPAP were measured in the food simulants of five samples at concentrations ranging from 0.04 to 12.2 ng/g and at increasing concentrations over the 10-day migration period. To estimate potential exposure to PFAS that had migrated from food packaging samples, weekly intake was calculated and ranged from 0.0006 ng/kg body weight/week for PFHxA exposure in tomato packaging to 1.1200 ng/kg body weight/week for PFHxS exposure in cake paper. These values were below the established EFSA maximum tolerable weekly intake (TWI) of 4.4 ng/kg body weight/week for the sum of PFOA, PFNA, PFHxS and PFOS., 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 Ltd.)

Antimicrobial coatings are designed to inhibit the growth of pathogens and have been used to reduce foodborne illness bacteria on food processing equipment. Novel N-halamine based antimicrobial coatings are highly advantageous due to their unique properties and low cost, and are being investigated for applications in food safety, health care, water and air disinfection, etc. In this study, we evaluated the chemical safety of a novel N-halamine antimicrobial polymer coating (Halofilm) for use on food processing equipment. Migration tests were performed on stainless steel tiles prepared with four different treatment groups: negative control, positive control, Halofilm coating without chlorination, and Halofilm coating with chlorination. An LC-MS/MS method was developed and validated for four formulation components: polyethylenimine (PEI), Trizma ® base, hydantoin acrylamide (HA) and dopamine methacrylamide (DMA), followed by stability and recovery tests. Migration tests were conducted at 40 °C with three food simulants (10, 50 and 95% ethanol/water) to mimic various food properties, and aliquots of migration extracts were analyzed at 2, 8, 72, 240 and 720 h. In general, measured concentration levels were consistent among simulant types for the four tested chemicals. Chlorinated tiles had non-detects for three analytes (PEI, HA and DMA), and less than 0.05 mg/kg of HA migration over 30 days. A chlorination step could possibly change the measured mass ( m/z ) hence leading to non-detects in targeted LC-MS/MS. In non-chlorinated tiles, all four compounds were detected during the migration test. This suggests that addition of the chlorination step may have a stabilizing effect on the polymer. Additionally, full scan high resolution mass spectrometry (HRMS) analysis was employed to screen for migration of other extractable and leachable (E&L) chemicals, which led to the identification of eight common E&L chemicals. To our knowledge, this is the first report evaluating chemical migration from an N-halamine antimicrobial polymer coating product.

Instances of food contamination with per- and polyfluoroalkyl substances (PFAS) continue to occur globally, but sample preparation and analytical methods are quite limited and often monitor for a small percentage of known PFAS. This study aimed to evaluate, validate, and compare performance of two instruments with the recently developed "quick, easy, cheap, effective, rugged, safe, efficient, and robust" (QuEChERSER) sample preparation mega-method - a method developed to monitor chemicals over a broad range of physicochemical properties. Initial evaluation of the QuEChERSER mega-method for determination of PFAS in food demonstrated recoveries, matrix interferences, and co-extractive removal comparable to (or better than) US Food and Drug Administration (FDA) and USDA Food Safety and Inspection Service (FSIS) methods. Subsequent validation of QuEChERSER in beef, catfish, chicken, pork, liquid eggs, and powdered eggs on a high-resolution mass spectrometer achieved acceptable recoveries (70-120%) and precision (RSDs ≤20%) for all 33 target analytes at the 1 and 5 ng g -1 levels and 67-88% of analytes at the 0.1 ng g -1 level, depending on the matrix. Additional validation was performed by tandem mass spectrometry on a triple quadrupole instrument. This approach provided no non-detects and better recoveries at the 0.1 ng g -1 level than the HRMS method but exhibited more variability at 1 and 5 ng g -1 spiking levels. Analysis of NIST SRMs 1946 and 1947 gave accuracies of 70-117%. These results demonstrate the capability of combining PFAS analysis with a mega-method previously validated for 350 analytes, while collecting non-target data for future retrospective analysis of emerging alternatives with a high-resolution mass spectrometry method., 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., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Potential contamination of food with chemicals migrating from food packaging is an important, yet under-investigated area of food safety. In this study, we examined chemicals migrating from common paper-based food packaging: pizza boxes and pizza box liners, butcher paper and liquid egg containers. Migration tests were conducted with a food simulant for 10 days, and migrated chemicals were identified with liquid chromatography (LC) - high resolution mass spectrometry (HRMS) with mass error < 3 ppm. HRMS identification was based on spectra and/or structure matching against commercial databases (MzCloud, ChemSpider, and Extractable and Leachable high resolution accurate mass (HRAM) database). Following HRMS identification, orthogonal LC retention information was utilized to further refine the data and reduce false positive findings. A model for calculating retention times (t R ) based on octanol-water partition coefficient (log K ow ) values was evaluated and applied for HRMS data refining. Using this approach, 153 migrated chemicals were identified, of which five were further confirmed with reference analytical standards. Additionally, amounts of bisphenol A and bisphenol S, the chemicals of toxicological concerns, were measured at the levels below the established regulatory limits for migration, indicating no/low risk to consumer's health. This study demonstrated the utility of LC-HRMS for confident identification of food packaging migrants., 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 B.V.)

Analysis of chemical residues in foods is a big challenge for developing countries due to lack of financial and professional resources needed to meet international quality standards for trade. However, the implementation of simple multiclass, multi-residue methods in monitoring programs can provide significant benefits to save cost, time, and labor. The aim of this project was to investigate the "quick, easy, cheap, effective, rugged, safe, efficient, and robust" (QuEChERSER) mega-method for the fatty muscle matrices of goat and lamb. To achieve wide analytical scope covering pesticides, environmental contaminants, and veterinary drugs, extracts were analyzed by both ultrahigh-performance liquid and low-pressure gas chromatography (UHPLC and LPGC) coupled with tandem mass spectrometry (MS/MS). The QuEChERSER mega-method was validated in ovine (goat) and caprine (lamb) muscles at four different spiking levels with 10 replicates per level for a total of 330 analytes and metabolites, consisting of 225 pesticides, 89 veterinary drugs, and 16 polychlorinated biphenyls (PCBs). In the case of LPGC-MS/MS (preceded by automated "instrument-top sample preparation"), 92% and 82% of the analytes met the data quality objectives of 70-120% recovery and <20% RSD for goat and lamb, respectively. For UHPLC-MS/MS, 95% and 92% of the analytes met the acceptable validation criteria in goat and lamb, respectively. Thus, the QuEChERSER mega-method has been demonstrated to be a useful streamlined approach to more efficiently replace multiple methods currently used to cover the same analytical scope.

Some components of plastic food packaging can migrate into food, and whereas migration studies of known components are required and relatively straightforward, identification of nonintentionally added substances (NIAS; unknowns) is challenging yet imperative to better characterizing food safety. To this aim, migration was investigated across 24 unique plastic food packaging products including plastic wrap, storage bags, vacuum bags, and meat trays. Gas and liquid chromatography separation systems coupled with Orbitrap mass analyzers were used for comprehensive nontargeted screening of migrants. Tentative identifications of features were assigned by searching commercial databases (e.g., NIST, MZCloud, ChemSpider, Extractables and Leachables) and filtering results based on mass accuracy, retention time indices, and mass spectral patterns. Several migrants showed elevated levels in specific food packaging types, particularly meat trays and plastic wrap, and varying degrees of migration over the 10 days. Eleven putative migrants are listed as substances of potential concern or priority hazardous substances. Additionally, migration amounts of an Irgafos 168 degradation product determined by semiquantitation exceeded proposed theoretical maximum migration values.

Diverse food safety programmes around the world are designed to help ensure production of safe food. To meet this need, the development and implementation of more efficient and effective analytical methods to monitor residues (pesticides and veterinary drugs) and contaminants in food is important. In this study, we report the validation results for a simple high-throughput mega-method for residual analysis of 213 pesticides and veterinary drugs, including 15 metabolites, plus 12 environmental contaminants (polychlorinated biphenyls) in tilapia muscle for implementation in routine laboratory analyses. The generic sample preparation method and analytical approach are known as QuEChERSER (more than QuEChERS). A small portion of the initial extract (204 µL) is taken for analysis by ultrahigh-performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS) covering 145 analytes, and the remaining extract undergoes a salting out step followed by an automated robotic instrument top sample preparation (ITSP) cleanup, also known as micro-solid-phase extraction (µSPE), plus fast low-pressure gas chromatography LPGC-MS/MS for 134 analytes (66 pesticides are targeted in both UHPLC-MS/MS and LPGC-MS/MS). The mega-method was validated in spiked tilapia samples at 5, 10, 15, and 20 ng/g with 10 replicates per level over two days (n = 80 overall), and 70-140% recoveries with RSDs ≤20% were achieved for 92% of the analytes in LC and 82% in GC. No significant matrix effects were observed for the analytes in LPGC-MS/MS, and only 5% of the analytes exceeded ±20% matrix effect in UHPLC-MS/MS. Analysis of standard reference materials (NIST SRMs 1946 and 1947) for contaminants in freeze-dried fish showed acceptable results, further demonstrating that the QuEChERSER mega-method can be implemented to expand analytical scope and increase laboratory efficiency compared to the QuEChERS method.

Contamination of food with chemicals migrating from food contact materials (FCMs) is an important area of food safety. This study was aimed to investigate migration of chemicals from plastic FCMs used for microwave and conventional oven heating. Migration tests were conducted for samples of microwave trays, microwave oven bags, and oven bags. GC- and LC-Orbitrap mass spectrometry (MS) was used for non-targeted screening and identification of chemicals with mass error <5 ppm. A non-targeted identification approach was validated with isotopically labeled chemicals to establish acceptable criteria for identification of migrated compounds. A total of 74 migrated compounds were tentatively identified: 24 chemicals by GC-Orbitrap MS with electron ionization (EI), plus 35 and 19 by LC-Orbitrap MS electrospray ionization (ESI) with positive and negative polarities, respectively. Four migrated chemicals were identified by more than one instrumental analysis. Both intentionally added substances (IAS), i.e. additives used in the production of polymeric materials and plastics, and non-intentionally added substances (NIAS), i.e. derivatives and degradation/oxidation products of IAS, were identified among the migrated chemicals. The levels of 25 migrated chemicals were significantly different (p < 0.05) between microwave treatments and conventional oven treatments, where 20 migrants had higher levels for microwave compared with 5 for conventional oven treatments. For several identified chemicals, no previous reports on their migration from FCMs were found., 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., (Copyright © 2021. Published by Elsevier B.V.)

The aim of this study was to identify chemicals migrating from paper-based food packaging materials by GC-Orbitrap mass spectrometry (MS). Migration tests were conducted with samples of butcher paper, liquid egg containers, pizza boxes and pizza box liners. A new approach for an automated data processing of GC-Orbitrap EI data was developed and evaluated with Compound Discoverer™ software. A total of 35 migrated chemicals were putatively identified. They represented natural compounds, fatty acid ethyl esters, FDA substances added to food and Indirect Additives in Food Contact Substances, common phthalates, alkanes, siloxanes, ketones, and chemicals used as additives in packaging. Additionally, some unexpected compounds suspected to be degradation products of additives were identified. Levels of 23 identified chemicals significantly (p < 0.05) changed over the 10-day migration test. For two identified migrants, dibutyl phthalate and benzophenone, calculated specific migration limits (SMLs) were below the established regulatory levels. The information on the identity of chemicals migrating from food packaging materials is important to inform regulatory agencies and to develop risk management strategies., (Published by Elsevier B.V.)

The goal of this study was to develop and validate a new method for simultaneous determination of 106 veterinary drugs and 227 pesticides and their metabolites plus 16 polychlorinated biphenyls (PCBs) at and below their regulatory levels established for catfish muscle in the European Union and U.S.A. To do this, two different QuEChERS-based methods for veterinary drugs and pesticides and PCBs were modified and merged into a single mega-method dubbed "QuEChERSER" (more than QuEChERS), which is presented here for the first time. The mega-method was validated in catfish at four different spiking levels with 10 replicates per level. Sample extraction of 2 g test portions was made with 10 mL of 4:1 (v/v) acetonitrile/water, and then an aliquot was taken for ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis of 106 veterinary drugs and 125 pesticides, including metabolites. The remaining extract after salting out was subjected to automated mini-solid-phase extraction cleanup (Instrument Top Sample Preparation) for immediate injection in low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS). The cleanup was conducted in parallel with the 10 min LPGC-MS/MS analysis for 167 PCBs, pesticides, and metabolites, which was conducted in parallel with the 10 min UHPLC-MS/MS analysis for 231 analytes to increase sample throughput (49 analytes were included in both techniques). In MS/MS, three ion transitions were monitored for nearly all targeted analytes to provide unambiguous identification as well as quantification. Satisfactory recoveries (70-120%) and relative standard deviations of ≤20% were achieved for 98 (92%) of the veterinary drugs and their metabolites and for 222 (91%) of pesticides, metabolites, and PCBs, demonstrating that the developed method is applicable for the analysis of these contaminants in fish as part of regulatory monitoring programs and other purposes.

In this work, a new mega-method of sample preparation called "QuEChERSER" (more than QuEChERS) is being presented for the first time. Fast, efficient, and cost-effective analysis of chemical contaminants in meat is useful for international trade, domestic monitoring, risk assessment, and other purposes. The goal of this study was to develop and validate a simple high-throughput mega-method for residual analysis of 161 pesticides, 63 veterinary drugs, 24 metabolites, and 14 legacy environmental contaminants (polychlorinated biphenyls) in bovine muscle for implementation in routine laboratory analyses. Sample preparation of 2 g test portions entailed QuEChERS-based extraction with 10 mL of 4:1 (v/v) acetonitrile/water, and then 204 μL was taken, diluted, and ultracentrifuged prior to analysis of veterinary drugs and pesticides by ultra-high-performance liquid chromatography-tandem mass spectrometry. The remaining extract was salted out with 4:1 (w/w) anhydrous MgSO 4 /NaCl, and 1 mL was transferred to an autosampler vial for automated mini-cartridge solid-phase extraction (Instrument Top Sample Preparation) cleanup with immediate injection using fast low-pressure gas chromatography-tandem mass spectrometry analysis. The automated cleanup and both instruments were all operated in parallel in 13-15 min cycle times per sample. Method validation according to United States Department of Agriculture requirements demonstrated that 221 (85%) of the 259 analytes gave average recovery between 70 and 120% and interday relative standard deviation of ≤25%. Analysis of a certified reference material for veterinary drugs in freeze-dried bovine muscle was also very accurate, further demonstrating that the QuEChERSER mega-method can be implemented to save time, labor, and resources compared to current practices to use multiple methods to cover the same analytical scope.

In the present study we examined spatial and seasonal trends in the levels of a wide suite of semi-volatile organic compounds (SVOCs) in brown trout (Salmo trutta) and mottled sculpin (Cottus bairdii) in East Canyon Creek, Utah, USA, an effluent-dominated stream during summer months. Fish samples were collected from four sampling sites, including one reference site upstream, and three sites at incremental distances downstream of the effluent discharge over multiple seasons. The samples were analyzed for 218 lipophilic contaminants, including pesticides and their metabolites, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and polybrominated diphenyl ethers (PBDEs) and other flame retardants. Some PAHs, pesticides and their metabolites, PCBs, PBDEs and other flame retardants were measured in mottled sculpin (11 analytes) and brown trout (17 analytes). Hexachlorobenzene (HCB), p,p'-DDE, BDE-47 and triphenyl phosphate (TPHP) were the most frequently detected contaminants in mottled sculpin and brown trout, while BDE-47 and p,p'-DDE were measured at the highest concentrations, reaching up to 73 and 19 ng/g wet weight, respectively. Our results indicated that snowmelt did not alter accumulation of the examined lipophilic contaminants, and no consistent seasonal differences were observed in their accumulation. A spatial pattern was observed for PBDE congeners, where lowest levels were measured in fish tissues from a reference site, and highest concentrations were measured in fish collected downstream of the effluent discharge, indicating that municipal effluent discharge contributes to the elevated PBDE levels in fish residing in this effluent-dominated stream. We further calculated screening level consumption risks following United States Environmental Protection Agency (EPA) methods, and identified the importance of considering discharge gradients in effluent-dominated systems during bioaccumulation assessments., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Published by Elsevier B.V.)

A fast, fit-for-purpose, high-throughput method was developed and validated for the analysis of 302 targeted contaminants in catfish muscle. Targeted contaminants included pesticides and metabolites with US regulatory levels, plus other lipophilic pesticides and environmental contaminants: PAHs, PCBs, PBDEs and other flame retardants. The sample preparation was based on QuEChERS extraction. The extract was split and analyzed by UHPLC-MS/MS for 128 analytes after filtering and by low pressure (LP) GC-MS/MS for 219 analytes after an automated robotic micro-SPE cleanup. The method was validated at four spiking levels (5, 10, 20 and 40 ng/g) with 10 replicates per level, and satisfactory recoveries (70-120%) and RSDs (≤20%) were achieved for 80% of the analytes. The method was further validated with NIST SRMs 1946 and 1947 and applied for the analysis of 22 market fish samples. Six pesticides and one PAH were found in the market fish samples, all below US regulatory levels., 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 Ltd.)

Coregonid fishes are among the most successful groups in the subarctic, boreal, and subalpine fresh waters of the northern hemisphere. Limnetic-benthic sympatric species-pairs from two different evolutionary lineages, the North American lake whitefish ( Coregonus clupeaformis species complex), and the European whitefish ( Coregonus lavaretus species complex), are becoming the subject of close attention to explore the role of natural selection during the ecological speciation. Baikal endemic coregonids, limnetic omul ( Coregonus migratorius ), and benthic lacustrine whitefish ( Coregonus baicalensis ) are the only representatives of another unique lineage that has not left the lake since the divergence from the two above. Due to Pleistocene oscillations sympatric limnetic-benthic divergence has been replicated here many times within the same water body over a long geological period in contrast to both Europe and America where sympatric species-pairs are the results of post-glacial secondary-contacts between glacial isolates during the Late Pleistocene on the territory of each continent. Mitochondrial genomes encode genes that are essential for respiration and metabolism. Data on complete mitogenomes of Baikal endemic coregonids provided here will complement ongoing investigations on energy metabolism as the main biological function involved in the divergence between limnetic and benthic whitefish., Competing Interests: The authors report no conflict of interest. The authors alone are responsible for the content and writing of the article., (© 2020 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.)

Organophosphate esters (OPEs) are chemicals extensively used as plasticizers and flame retardants in commercial and consumer products. In this study, we developed and validated a method for the analysis of 13 common OPEs in meat (chicken, pork, and beef) and fish (catfish and salmon) to study their occurrence in those foods in the United States. The method was based on QuEChERS extraction with acetonitrile and automated robotic cleanup of the extracts, followed by low pressure gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis for 8 of the OPEs and ultrahigh-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis for 13 OPEs, including 8 overlapping OPEs. The developed method was validated in the muscle tissues at four spiking levels (5, 10, 20, and 40 ng/g). The background levels in the laboratory environment and materials presented a challenge for accurate quantification at low ng/g levels. UHPLC-Q-Orbitrap MS analysis was utilized to pinpoint the source of their contamination. OPEs were found in the water used in the liquid chromatography (LC) mobile phase, and flow injection analysis with organic mobile phase was suggested as an alternative to avoid OPEs contamination in LC-MS/MS analysis. The validated method was applied to the analysis of 68 real-world meat and fish samples from the U.S. markets by three instrumental methods. Tris(2-chloro-isopropyl) phosphate (TCPP), tri- n -butyl phosphate (TnBP), and triphenyl phosphate (TPP) were found in meat, and TCPP and TPP were measured in fish samples. The sum of median OPE concentrations (averaged for the three instrumental methods) measured in the meat and fish samples were 6.2 and 8.7 ng/g wet weight, respectively. No regulations on the maximum residue levels of OPEs permitted in food were found for the U.S. or other countries.

A high throughput method for simultaneous determination of 200 pesticides and 65 environmental contaminants: polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and other flame retardants, was developed and validated in cattle, swine and poultry muscle tissues. The method was based on sample preparation with QuEChERS extraction followed by an automated robotic sample cleanup with solid phase extraction (SPE) mini-columns using Instrument Top Sample Preparation (ITSP). The automated robotic ITSP was integrated with instrumental analysis (low pressure (LP)GC-MS/MS) to conduct sample cleanup and analysis in parallel. Another aliquot of the initial QuEChERS extract was subjected to UHPLC-MS/MS analysis, and 53 overlapping pesticides were analyzed by both LPGC- and UHPLC-MS/MS (10 min each). Fit-for-purpose LOQs<5 ng/g were achieved for ≥90% of the analytes. The method was validated in cattle, swine and chicken muscles at three spiking levels at and below the US regulatory levels of concern, and satisfactory recoveries (70-120%) and RSDs ≤ 20% were demonstrated for 219 analytes. Matrix effects were within ±20% for 78-97% of LC- and GC-amenable analytes. The validated method was successfully applied for the analysis of real-world incurred meat and poultry samples, further demonstrating its applicability to real-world samples, and potential for implementation in routine monitoring of contaminants., (Published by Elsevier B.V.)

Structural isomeric pesticides are used in agriculture and may be challenging to differentiate for accurate identification in pesticide monitoring programs. Due to structural similarity, isomeric pesticides are difficult to separate chromatographically, and thus, their accurate identification may rely solely on mass spectrometric analysis (MS). In this study, we challenged the ability of high-resolution quadrupole-orbitrap (Q-Orbitrap) mass spectrometry to produce and evaluate the tandem mass spectrometry (MS/MS) product ions for the selected five pairs of isomeric pesticides from different classes: Pebulate and vernolate, methiocarb and ethiofencarb, uniconazole and cyproconazole, sebuthylazine and terbuthylazine, and orbencarb and thiobencarb. The use of Q-Orbitrap instrument with a mass error <3 ppm allowed proposed elucidation of the product ion structures with consideration of the ion formulae, data interpretation, and literature searches. Product ions unique to pebulate, vernolate, methiocarb, ethiofencarb, and uniconazole were observed. Elucidation of the observed MS/MS product ion structures was conducted, and the fragmentation pathways were proposed. This information is valuable to increase selectivity in MS/MS analysis and differentiate isomeric pesticides, and thereby reduce the rates of false positives in pesticide monitoring programs.

In routine monitoring of foods, reduction of analyzed test portion size generally leads to higher sample throughput, less labor, and lower costs of monitoring, but to meet analytical needs, the test portions still need to accurately represent the original bulk samples. With the intent to determine minimal fit-for-purpose sample size, analyses were conducted for up to 93 incurred and added pesticide residues in 10 common fruits and vegetables processed using different sample comminution equipment. The commodities studied consisted of apple, banana, broccoli, celery, grape, green bean, peach, potato, orange, and squash. A Blixer® was used to chop the bulk samples at room temperature, and test portions of 15, 10, 5, 2, and 1 g were taken for analysis (n = 4 each). Additionally, 40 g subsamples (after freezing) were further comminuted using a cryomill device with liquid nitrogen, and test portions of 5, 2, and 1 g were analyzed (n = 4 each). Both low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS) and ultrahigh-performance liquid chromatography (UHPLC)-MS/MS were used for analysis. An empirical approach was followed to isolate and estimate the measurement uncertainty contribution of each step in the overall method by adding quality control spikes prior to each step. Addition of an internal standard during extraction normalized the sample preparation step to 0% error contribution, and coefficients of variation (CVs) were 6-7% for the analytical steps (LC and GC) and 6-9% for the sample processing techniques. In practice, overall CVs averaged 9-11% among the different analytes, commodities, batches, test portion weights, and analytical and sample processing methods. On average, CVs increased up to 4% and bias 8-12% when using 1-2 g test portions vs. 10-15 g. Graphical abstract Efficient quality control approach to include sample processing.

Aquaculture, which is growing 3-5 times faster than terrestrial agriculture, will play an important role to meet future global food production needs. However, over 80% of global sewage production is returned to the environment untreated or poorly treated. In developing nations, these nontraditional waters of diverse quality are being recycled for aquaculture, yet chemical residues are differentially studied. Here, we examined pharmaceuticals, pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and flame retardants in marine bivalves using isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) and low-pressure gas chromatography-tandem mass spectrometry (LP GC-MS/MS). Green-lipped mussels from the field and oysters from aquaculture net pens, which are harvested as food products, were collected adjacent to point source municipal wastewater and landfill leachate effluent discharges, respectively, in Hong Kong, the fourth most densely populated country in the world. Multiple classes of pharmaceutical, pesticides, PAHs, and phosphorus-based flame retardants were detected at low μg/kg levels. Acceptable servings per week indicated minimal risk for a number of chemicals; however, such calculations could not be performed for other contaminants of emerging concern. Future efforts are needed to better understand contaminant influences on marine bivalve populations and aquaculture product safety, particularly in rapidly urbanizing regions of developing countries with limited wastewater infrastructure.

In this study, analytical results were compared when using different approaches to bulk food sample comminution, consisting of a vertical chopper (Blixer) at room temperature and dry ice cryogenic conditions, followed by further subsample processing (20 g) using liquid nitrogen cryogenic conditions (cryomill). Analysis of the 43 targeted spiked and incurred contaminants in a food mixture consisting of equal parts orange, apple, kale, salmon, and croaker involved quick, easy, cheap, effective, rugged, and safe (QuEChERS) with automated mini-column solid-phase extraction (known as ITSP) cleanup, followed by low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS). Different ambient Blixer test portion sizes of 20, 10, 5, 2, and 1 g were assessed, and for cryogenic Blixer conditions, a 0.5 g test portion was also tested. In the case of the cryomill, test portions were 2, 1, and 0.5 g and all subsamples in all cases entailed five replicates. Determined concentrations and precisions (CV) of the analytes were compared to assess possible differences in systematic and random forms of error. A quality control spike was made before each step in the procedures to isolate that individual step in the uncertainty measurements using the error propagation sum of squares approach. Results indicated that the uncertainty of the sample preparation and LPGC-MS/MS analysis steps were 2-7 and 11% CV, respectively, while uncertainties of sample processing ranged from 6% CV for the cryomill to 12% CV for the ambient Blixer conditions. The common use of internal standards reduced overall method uncertainty from 12-15 to 7-10% CV. For the analytes, matrix, conditions, and tools used in this study, the minimal test sample weight that gave satisfactory recoveries and precision was found to be 1 g in all cases.

In this study, a multi-residue analytical method using quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and dispersive solid-phase extraction (d-SPE) cleanup, followed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), was investigated for rapid determination of 60 pesticide residues in whole crayfish and crayfish meat. The final method used 10 mL of acetonitrile for extraction, 3 g of NaCl for partitioning, and 50 mg of primary secondary amine for d-SPE cleanup. The method was validated at three spiking levels (10, 50, and 100 ng/g) using triphenyl phosphate as an internal standard and both gradient and isocratic HPLC elution. Under gradient conditions, satisfactory recoveries (70-120%) and relative standard deviations of ≤20% were achieved for 83 and 88% of pesticides in whole crayfish and crayfish meat, respectively. Matrix effects were estimated using both gradient and isocratic HPLC elution. To our knowledge, this is the first study involving multi-residue analysis of HPLC-amenable pesticides in crayfish and mantis shrimp. The final method was successfully applied for analysis of 11 crayfish and mantis shrimp samples from markets in China, and propamocarb (

A novel carbon/zirconia-based material, Supel TM QuE Verde, was evaluated in a filter-vial dispersive solid-phase extraction cleanup of pork, salmon, kale, and avocado extracts for the residual analysis of 65 pesticides and 52 environmental contaminants (flame retardants, polychlorinated biphenyls, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons) using low-pressure gas chromatography with tandem mass spectrometry. An amount of 180 mg sorbent per 0.6 mL extract in filter-vial dispersive solid-phase extraction cleanup was found the optimum in terms of achieving satisfactory removal of co-extractives and recoveries of analytes, especially for structurally planar compounds. For analytes partially retained by Verde, normalization to an internal standard resulted in 62-107% recoveries. Addition of Verde to primary secondary amine and C 18 in cleanup resulted in 38% more removal of gas-chromatography-amenable co-extractives in avocado, 30% in kale, 39% in salmon, and 50% in pork. The removal efficiency of co-extracted chlorophyll was 93% for kale and 64% for avocado based on ultraviolet-visible absorbance. The developed method was validated at three spiking levels (10, 25, and 100 ng/g), and 70-120% recoveries with ≤20% relative standard deviation were achieved for 96 (83%) out of 117 analytes in pork, 79 (69%) in salmon, 71 (62%) in kale, and 75 (65%) in avocado., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A multiresidue analytical method using a modification of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) sample preparation approach combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis was established and validated for the rapid determination of 69 pesticides at different levels (1-100 ng/g) in wheat and rice straws. In the quantitative analysis, the recoveries ranged from 70 to 120%, and consistent RSDs ≤ 20% were achieved for most of the target analytes (53 pesticides in wheat straw and 58 in rice straw). Almost all of the analytes achieved good linearity with R(2) > 0.98, and the limit of validation levels (LVLs) for diverse pesticides ranged from 1 to 10 ng/g. Different extraction and cleanup conditions were evaluated in both types of straw, leading to different options. The use of 0.1% formic acid or not in extraction with acetonitrile yielded similar final outcomes, but led to the use of a different sorbent in dispersive solid-phase extraction. Both options are efficient and useful for the multiresidue analysis of targeted pesticides in wheat and rice straw samples.

This study demonstrates the application of a novel lipid removal product to the residue analysis of 65 pesticides and 52 environmental contaminants in kale, pork, salmon, and avocado by fast, low pressure gas chromatography - tandem mass spectrometry (LPGC-MS/MS). Sample preparation involves QuEChERS extraction followed by use of EMR-Lipid ("enhanced matrix removal of lipids") and an additional salting out step for cleanup. The optimal amount of EMR-Lipid was determined to be 500mg for 2.5mL extracts for most of the analytes. The co-extractive removal efficiency by the EMR-Lipid cleanup step was 83-98% for fatty samples and 79% for kale, including 76% removal of chlorophyll. Matrix effects were typically less than ±20%, in part because analyte protectants were used in the LPGC-MS/MS analysis. The recoveries of polycyclic aromatic hydrocarbons and diverse pesticides were mostly 70-120%, whereas recoveries of nonpolar polybrominated diphenyl ethers and polychlorinated biphenyls were mostly lower than 70% through the cleanup procedure. With the use of internal standards, method validation results showed that 76-85 of the 117 analytes achieved satisfactory results (recoveries of 70-120% and RSD≤20%) in pork, avocado, and kale, while 53 analytes had satisfactory results in salmon. Detection limits were 5-10ng/g for all but a few analytes. EMR-Lipid is a new sample preparation tool that serves as another useful option for cleanup in multiresidue analysis, particularly of fatty foods., (Published by Elsevier B.V.)

This study demonstrated the application of an automated high-throughput mini-cartridge solid-phase extraction (mini-SPE) cleanup for the rapid low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS) analysis of pesticides and environmental contaminants in QuEChERS extracts of foods. Cleanup efficiencies and breakthrough volumes using different mini-SPE sorbents were compared using avocado, salmon, pork loin, and kale as representative matrices. Optimum extract load volume was 300 µL for the 45 mg mini-cartridges containing 20/12/12/1 (w/w/w/w) anh. MgSO 4 /PSA (primary secondary amine)/C 18 /CarbonX sorbents used in the final method. In method validation to demonstrate high-throughput capabilities and performance results, 230 spiked extracts of 10 different foods (apple, kiwi, carrot, kale, orange, black olive, wheat grain, dried basil, pork, and salmon) underwent automated mini-SPE cleanup and analysis over the course of 5 days. In all, 325 analyses for 54 pesticides and 43 environmental contaminants (3 analyzed together) were conducted using the 10 min LPGC-MS/MS method without changing the liner or retuning the instrument. Merely, 1 mg equivalent sample injected achieved <5 ng g -1 limits of quantification. With the use of internal standards, method validation results showed that 91 of the 94 analytes including pairs achieved satisfactory results (70-120 % recovery and RSD ≤ 25 %) in the 10 tested food matrices ( n  = 160). Matrix effects were typically less than ±20 %, mainly due to the use of analyte protectants, and minimal human review of software data processing was needed due to summation function integration of analyte peaks. This study demonstrated that the automated mini-SPE + LPGC-MS/MS method yielded accurate results in rugged, high-throughput operations with minimal labor and data review.

Organic ultraviolet filters (UV-F) are increasingly being used in personal care products to protect skin and other products from the damaging effects of UV radiation. In this study, marine water was collected monthly for approximately one year from six coastal South Carolina, USA sites and analyzed for the occurrence of seven organic chemicals used as UV filters (avobenzone, dioxybenzone, octocrylene, octinoxate, oxybenzone, padimate-o and sulisobenzone). The results were used to examine the relationship between beach use and the distribution of UV-F compounds along coastal South Carolina, USA. Five of the seven target analytes were detected in seawater along coastal South Carolina during this study. Dioxybenzone and sulisobenzone were not detected. The highest concentrations measured were >3700 ng octocrylene/L and ~2200 ng oxybenzone/L and beach use was greatest at this site; a local beach front park. Patterns in concentrations were assessed based on season and a measure of beach use., (Published by Elsevier Ltd.)

Nitrites are added as a preservative to a variety of cured meats, including bacon, to kill bacteria, extend shelf life, and improve quality. During cooking, nitrites in the meat can be converted to carcinogenic nitrosamines (NAs), the formation of which is mitigated by the addition of antioxidants. In the past, the U.S. Department of Agriculture (USDA) Food Safety and Inspection Service (FSIS) monitored NAs in pan-fried bacon, but FSIS terminated monitoring of NAs in the 1990s due to the very low levels found. FSIS recently chose to conduct a risk assessment of NAs in cooked bacon to determine if current levels warrant routine monitoring of NAs again. To meet FSIS needs, we developed, validated, and implemented a new method of sample preparation and analysis to test cooked bacon for five NAs of most concern, which consist of N-nitroso-dimethylamine, -diethylamine, -dibutylamine, -piperidine, and -pyrrolidine. Sample preparation was based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) approach and analysis by gas chromatography-tandem mass spectrometry. Ruggedness was improved markedly in the analysis of the complex fatty extracts by backflushing the guard column, injection liner, and half of the analytical column after every injection. Validation results were acceptable with recoveries of 70-120% and <20% RSDs for the five NAs, with a reporting limit of 0.1 ng/g. NA concentrations in 48 samples were all <15 ng/g, with most <1 ng/g and many <0.1 ng/g. Also, microwave cooking of bacon gave slightly lower concentrations overall compared to pan-frying.

The concept of low pressure (LP) vacuum outlet gas chromatography (GC) was introduced more than 50 years ago, but it was not until the 2000s that its theoretical applicability to fast analysis of GC-amenable chemicals was realized. In practice, LPGC is implemented by placing the outlet of a short, wide (typically 10-15 m, 0.53 mm inner diameter) analytical column under vacuum conditions, which speeds the separation by reducing viscosity of the carrier gas, thereby leading to a higher optimal flow rate for the most separation efficiency. To keep the inlet at normal operating pressures, the analytical column is commonly coupled to a short, narrow uncoated restriction capillary that also acts as a guard column. The faster separations in LPGC usually result in worse separation efficiency relative to conventional GC, but selective detection usually overcomes this drawback. Mass spectrometry (MS) provides highly selective and sensitive universal detection, and nearly all GC-MS instruments provide vacuum outlet conditions for implementation of LPGC-MS(/MS) without need for adaptations. In addition to higher sample throughput, LPGC provides other benefits, including lower detection limits, less chance of analyte degradation, reduced peak tailing, increased sample loadability, and more ruggedness without overly narrow peaks that would necessitate excessively fast data acquisition rates. This critical review summarizes recent developments in the application of LPGC with MS and other detectors in the analysis of pesticides, environmental contaminants, explosives, phytosterols, and other semi-volatile compounds., (Published by Elsevier B.V.)

Sample processing is often ignored during analytical method development and validation, but accurate results for real samples depend on all aspects of the analytical process. Also, validation is often conducted using only spiked samples, but extraction yields may be lower in incurred samples. In this study, different variables in extraction for incurred pesticides and environmental contaminants in fish were investigated. Among 207 analytes screened using low-pressure gas chromatography-tandem mass spectrometry, consisting of 150 pesticides, 15 polycyclic aromatic hydrocarbons (PAHs), 14 polychlorinated biphenyls (PCBs), 6 polybrominated diphenyl ethers (PBDEs), and 22 other flame retardants (FRs), 35 (16 pesticides, 9 PCBs, 5 PBDEs, and 5 PAHs) were identified for quantification in samples of salmon, croaker, and NIST Standard Reference Material 1947 (Lake Michigan Fish Tissue). Extraction efficiencies using different extraction devices (blending, vortexing, and vibrating) versus time, sample size, and sample/solvent ratio were determined. In comparison to blending results, use of a pulsed-vortexer for 1 min with 1/1 (g/mL) sample/acetonitrile ratio was generally sufficient to extract the incurred contaminants in the homogenized fish tissues. Conversely, extraction with a prototype vibration shaker often took 60 min to achieve 100% extraction efficiency. A main conclusion from this study is that accurate results for real samples can be obtained using batch extraction with a pulsed-vortexer in a simple and efficient method that achieves high sample throughput.

A simple, fast, and cost-effective sample preparation method, previously developed and validated for the analysis of organic contaminants in fish using low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS), was evaluated for the analysis of polybrominated diphenyl ethers (PBDEs) and dichlorodiphenyltrichloroethane (DDT) pesticides using enzyme-linked immunosorbent assay (ELISA). The sample preparation technique was based on the quick, easy, cheap, rugged, effective, and safe (QuEChERS) approach with filter-vial dispersive solid phase extraction (d-SPE). Incurred PBDEs and DDTs were analyzed in three types of fish with 3-10% lipid content: Pacific croaker, salmon, and National Institute of Standards and Technology (NIST) Standard Reference Material 1947 (Lake Michigan fish tissue). LPGC-MS/MS and ELISA results were in agreement: 108-111 and 65-82% accuracy ELISA versus LPGC-MS/MS results for PBDEs and DDTs, respectively. Similar detection limits were achieved for ELISA and LPGC-MS/MS. Matrix effects (MEs) were significant (e.g., -60%) for PBDE measurement in ELISA, but not a factor in the case of DDT pesticides. This study demonstrated that the sample preparation method can be adopted for semiquantitative screening analysis of fish samples by commercial kits for PBDEs and DDTs.

Bifenthrin is a widely used synthetic pyrethroid insecticide that is often applied to crops, turf, and residential structures for the control of insects. Like other insecticides, bifenthrin has the potential to contaminate bodies of water that are adjacent to the application site via spray drift and runoff during storm events. The objective of this study was to examine the lethal and sublethal effects of bifenthrin on grass shrimp, Palaemonetes pugio, and sheepshead minnow, Cyprinodon variegatus in a 28 d mesocosm experiment under estuarine conditions. Endpoints included mortality and growth and the oxidative stress biomarkers of lipid peroxidation, glutathione, and catalase. In the mesocosm experiment, 24 h and 96 h caged shrimp LC50s were 0.061 and 0.051 μg L(-1), respectively. The uncaged grass shrimp 28 d LC50 was 0.062 μg L(-1). Fifty percent mortality was not reached in the uncaged sheepshead minnow. Bifenthrin did not have a significant effect on the growth of the shrimp, but there was an increasing impact on fish growth. However, it is uncertain as to whether this pattern is a direct effect of the chemical or if it is due to increased food availability resulting from mortality in prey species. The oxidative stress assays were largely inconclusive. Bifenthrin was eliminated rapidly from the water column and readily partitioned to sediments. The LC50s for adult and larval P. pugio were below published Estimated Environmental Concentration (EEC) values and were within the range of bifenthrin concentrations that have been measured in rivers, channels, and creeks., (Published by Elsevier Ltd.)

Pyrethroid insecticides are widely used on agricultural crops, as well as for nurseries, golf courses, urban structural and landscaping sites, residential home and garden pest control, and mosquito abatement. Evaluation of sensitive marine and estuarine species is essential for the development of toxicity testing and risk-assessment protocols. Two estuarine crustacean species, Americamysis bahia (mysids) and Palaemonetes pugio (grass shrimp), were tested with the commonly used pyrethroid compounds, lambda-cyhalothrin, permethrin, cypermethrin, deltamethrin, and phenothrin. Sensitivities of adult and larval grass shrimp and 7-day-old mysids were compared using standard 96-h LC50 bioassay protocols. Adult and larval grass shrimp were more sensitive than the mysids to all the pyrethroids tested. Larval grass shrimp were approximately 18-fold more sensitive to lambda-cyhalothrin than the mysids. Larval grass shrimp were similar in sensitivity to adult grass shrimp for cypermethrin, deltamethrin, and phenothrin, but larvae were approximately twice as sensitive to lambda-cyhalothrin and permethrin as adult shrimp. Acute toxicity to estuarine crustaceans occurred at low nanogram per liter concentrations of some pyrethroids, illustrating the need for careful regulation of the use of pyrethroid compounds in the coastal zone., (Copyright © 2013 Wiley Periodicals, Inc., a Wiley company.)

A new method of sample preparation was developed and is reported for the first time. The approach combines in-vial filtration with dispersive solid-phase extraction (d-SPE) in a fast and convenient cleanup of QuEChERS (quick, easy, cheap, effective, rugged, and safe) extracts. The method was applied to simultaneous analysis of 42 diverse pesticides and 17 environmental contaminants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), and flame retardants, in shrimp as the sample matrix. Final extracts were analyzed by both low-pressure gas chromatography - triple quadrupole tandem mass spectrometry (LPGC-MS/MS), and high-performance liquid chromatography - triple quadrupole tandem mass spectrometry (HPLC-MS/MS) to provide a wide scope of analysis for targeted analytes. During method development, several different commercial sorbents for d-SPE were investigated and compared with respect to analyte recoveries. The method was validated at 10, 50, and 100 ng g(-1) spiking levels (10-fold lower for PCBs), and the results for nearly all analytes were between 70 and 115% recoveries with ≤17% relative standard deviations. The method was shown to be simple, fast, and effective for multi-application analysis of chemical residues in the representative food and environmental marker matrix., (Copyright © 2014. Published by Elsevier B.V.)

A simple and fast method for the analysis of a wide range of polyphenolic compounds in juice, tea, and coffee samples was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method was based on a simple sample preparation "dilute and shoot" approach, and LC-MS/MS quantification using genistein-d4 as an internal standard. The performance of six different syringeless filter devices was tested for sample preparation. The method was evaluated for recoveries of polyphenols at three spiking levels in juice, tea, and coffee samples. The recoveries of the majority of polyphenols were satisfactory (70-120%), but some varied significantly (20-138%) depending on the matrix. NIST Standard Reference Materials (SRM) 3257 Catechin Calibration Solutions and 3255 Camellia sinensis (Green Tea) Extract with certified concentrations of catechin and epicatechin were used for method validation. The measurement accuracy in two SRMs was 71-113%. The method was successfully applied to the analysis of liquid samples of grape juice, green tea, and coffee., (Published by Elsevier Ltd.)

A multiresidue method for the analysis of 143 pesticide residues in fish was developed and evaluated using fast, low-pressure gas chromatography/triple-quadrupole tandem mass spectrometry (LP-GC/MS-MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) cleanup with zirconium-based sorbent. The developed method was evaluated at four spiking levels (1, 5, 50, and 100 ng/g) and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974b and 1947 for selected pesticides with certified concentrations. Acceptable recoveries (70-120%) and standard deviations below 20% were achieved for the majority of pesticides from fortified samples. The measured values for both SRMs agreed with certified values (71-115% accuracy, 4-14% relative standard deviations) for all pesticides, except for p,p-DDD + o,p-DDT (45%) and heptachlor (133%) in SRM 1974b and except for mirex (58%) and trans-chlordane (136%) in SRM 1947. The developed method is fast, simple, and inexpensive with detection limits of 0.5-5 ng/g. Residues of dimethoate, hexachlorobenzene, BHC, lindane, nonachlor, chlorpyrifos, trifluralin, p,p-DDE, p,p-DDD, o,p-DDD, o,p-DDT, p,p-DDD, and chlordane were measured in catfish samples from the market.

Compositional changes of powder dietary supplements made from mushrooms exposed to different levels of UV-B irradiation were evaluated for the bioactive naturally occurring mushroom antioxidant, ergothioneine; other natural polyphenolic compounds, e.g., flavonoids, lignans, etc.; and selected phytosterols. Four types of mushroom powder consisting of white, brown (Agaricus bisporus), oyster (Pleurotus ostreatus), and shiitake (Lentinula edodes) mushrooms from three different treatment groups (control, low and high UV-B exposures) were evaluated. Ergothioneine concentrations found in mushroom powders were 0.4-10.4 mg/g dry weight (dw) and were not appreciably affected by UV-B radiation. No individual polyphenols were detected above 0.1 μg/g. Phytosterols ergosterol (2.4-6.2 mg/g dw) and campesterol (14-43 μg/g dw) were measured in mushroom powder samples. Ergosterol concentrations decreased significantly with the increased level of UV-B treatment for all mushroom powder types, except for white. These results provide some new information on effects of UV-B radiation on these important natural bioactive compounds in mushrooms.

Irgarol 1051 is a common antifouling biocide and is highly toxic to non-target plant species at low ng/L concentrations. We measured up to 254 ng/L Irgarol in water and up to 9 ng/g dry weight Irgarol in sediments from Southern California recreational marinas. Irgarol's metabolite, M1, concentrations were up to 62 ng/L in water and 5 ng/g dry weight in sediments. Another antifouling biocide, diuron, reached up to 68 ng/L in water and 4 ng/g dry weight in sediments. The maximum Irgarol concentrations in water were greater than the Irgarol concentration recommended as the plant toxicity benchmark (136 ng/L), suggesting that Irgarol concentrations may be high enough to cause changes in phytoplankton communities in the sampled marinas. Irgarol concentrations measured in sediments were greater than calculated Environmental Risk Limits (ERLs) for Irgarol in sediments (1.4 ng/g). Antifouling pesticide accumulation in sediments may present a potential undetermined risk for benthic organisms., (Published by Elsevier Ltd.)

A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated using fast low pressure gas chromatography triple quadrupole tandem mass spectrometry (LP-GC/MS-MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) clean-up with zirconium-based sorbent prior to LP-GC/MS-MS analysis. The developed method was evaluated at 4 spiking levels and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974B and 1947. Sample preparation for a batch of 10 homogenized samples took about 1h/analyst, and LP-GC/MS-MS analysis provided fast separation of multiple analytes within 9min achieving high throughput. With the use of isotopically labeled internal standards, recoveries of all but one analyte were between 70 and 120% with relative standard deviations less than 20% (n=5). The measured values for both SRMs agreed with certified/reference values (72-119% accuracy) for the majority of analytes. The detection limits were 0.1-0.5ng g(-1) for PCBs, 0.5-10ng g(-1) for PBDEs, 0.5-5ng g(-1) for select pesticides and PAHs and 1-10ng g(-1) for flame retardants. The developed method was successfully applied for analysis of catfish samples from the market., (Published by Elsevier B.V.)

This study assessed seasonal and regional trends of pharmaceuticals and personal care products (PPCPs) detected in monthly samples from two local wastewater treatment plants (WWTPs) in Charleston, South Carolina, USA, over the period of one year. Surface water of Charleston Harbor was also analyzed to examine environmental distribution in an estuarine ecosystem. Of the 19 compounds examined, 11 were quantified in wastewater influent, 9 in effluent, and 7 in surface water. Aqueous concentrations of many PPCPs were reduced by >86% in wastewater effluent compared with influent, though some compounds showed low removal and greater effluent concentrations compared with influent (e.g. estrone and fluoxetine). Differences in effluent concentrations and estimated removal between facilities were likely related to variations in the facilities' operating procedures. Surface water concentrations were generally reduced by >90% for those chemicals found in effluent. Additionally, there were seasonal trends that indicate reduced degradation in colder months in wastewater and surface water. To our knowledge, this is the first study examining PPCPs in the South Atlantic Bight., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Phenothrin is a synthetic pyrethroid used as a contact insecticide in mosquito control programs. This study compared the toxicity of phenothrin to adult, larval and embryonic grass shrimp (Palaemonetes pugio) and examined oxidative stress responses in adult and larval grass shrimp. The adult 24-h LC50 was 0.341 μg/L (95 % confidence intervals 0.282-0.412) and the 96-h LC50 was 0.161 μg/L (95 % CI 0.128-0.203 μg/L). The larval 24-h LC50 was 0.50 μg/L (95 % CI 0.441-0.568) and the 96-h LC50 was 0.154 μg/L (95 % CI 0.139-0.170 μg/L). In the presence of sediment, the 24-h LC50 was 6.30 μg/L (95 % CI 5.00-7.44 μg/L) for adults and 0.771 μg/L (95 % CI 0.630-0.944) for larvae. The sublethal biomarkers glutathione and lipid peroxidase (LPx) were examined after 96-h phenothrin exposure at five concentrations, and there were no statistically significant differences in these levels in adults or larvae compared to controls. There was a significant downward trend in larval LPx levels. This research confirms that phenothrin is highly toxic to grass shrimp and suggests that both adult and larval grass shrimp are appropriate life stages for risk assessments.