Improving water quality in a hypereutrophic lake and tributary through agricultural nutrient mitigation: A Multi-year monitoring analysis.

Anthropogenic eutrophication remains a critical global issue, significantly impacting surface water quality. Numerous regions have implemented beneficial management practices to combat agricultural nonpoint pollution, often evaluating efficacy at the field scale, but not downstream. In this study, we conducted an extensive, 11-year (2010-2020), all-season, weekly monitoring program in a small, shallow, hypereutrophic lake and main tributary located in a cold climate, northern temperate zone, within a predominantly agricultural-forested mesoscale watershed. The monitoring took place before and after the implementation of field-scale agricultural nutrient mitigation measures in the catchment, allowing assessment of changes over time in the downstream tributary and lake. We analyzed long-term trends and temporal change points for nitrogen and phosphorus concentrations, aquatic trophic status, and nutrient stoichiometric ratios. The results revealed significant reductions in nitrogen and phosphorus concentrations, improved lake trophic status from hypereutrophic to eutrophic, and an increase in total nitrogen : total phosphorus ratios following the implementation of field-scale agricultural nutrient mitigation measures. Notably, both the lake and its main tributary exhibited significant temporal change points for these parameters. Our findings offer evidence of a relatively rapid, positive effect of the implementation of field-scale agricultural nutrient mitigation measures contributing to subsequent improvements in downstream water quality.

High Persistence of Novel Polyfluoroalkyl Betaines in Aerobic Soils.

Some contemporary aqueous film-forming foams (AFFFs) contain n:3 and n:1:2 fluorotelomer betaines (FTBs), which are often detected at sites impacted by AFFFs. As new chemical replacements, little is known about their environmental fate. For the first time, we investigated the biotransformation potential of 5:3 and 5:1:2 FTBs and a commercial AFFF that mainly contains n:3 and n:1:2 FTBs (n = 5, 7, 9, 11, and 13). Although some polyfluoroalkyl compounds are precursors to perfluoroalkyl acids, 5:3 and 5:1:2 FTBs exhibited high persistence, with no significant changes even after 120 days of incubation. While the degradation of 5:3 FTB into suspected products such as fluorotelomer acids or perfluoroalkyl carboxylic acids (PFCAs) could not be conclusively confirmed, we did identify a potential biotransformation product, 5:3 fluorotelomer methylamine. Similarly, 5:1:2 FTB did not break down or produce short-chain hydrogen-substituted polyfluoroalkyl acids (n:2 H-FTCA), hydrogen-substituted PFCA (2H-PFCA), or any other products. Incubating the AFFF in four soils with differing properties and microbial communities resulted in 0.023-0.25 mol % PFCAs by day 120. Most of the products are believed to be derived from n:2 fluorotelomers, minor components of the AFFF. Therefore, the findings of the study cannot be fully explained by the current understanding of structure-biodegradability relationships.

Per- and Polyfluoroalkyl Substances in Contaminated Soil and Groundwater at Airports: A Canadian Case Study.

The occurrence of 93 classes of per- and polyfluoroalkyl substances (PFASs) was investigated at aqueous film-forming foam (AFFF)-impacted sites of four Canadian airports. Surface/subsurface soil and groundwater samples were characterized using high-resolution mass spectrometry (HRMS) and an improved total oxidizable precursor (TOP) assay. PFAS profiles, loads, and spatial trends were highly site-specific, influenced by the AFFF use history, variations in sorption, transport, and in situ transformation potential of PFASs. All sites have been impacted by more than one AFFF chemistry, with the active firefighter training area exhibiting a greater PFAS variety and total PFAS burden than decommissioned sites. Zwitterionic and cationic compounds composed a large percentage (34.5-85.5%) of the total PFAS mass in most surface soil samples in the source zone but a relatively low percentage (<20%) in groundwater samples. Background soils surrounding the source zone contained predominantly unidentified precursors attributed to atmospheric deposition, while in AFFF-impacted soils, precursors originating from AFFFs can be largely captured by HRMS using available suspect lists. Horizontal transfer of PFASs in surface soils was limited, but vertical migration down the soil column occurred even in locations of low permeability. This study provides a critical data set to support developing new priority analyte lists and integrating TOP assay for comprehensive PFAS monitoring at AFFF-impacted sites.

Targeted and Suspect Screening of Per- and Polyfluoroalkyl Substances in Cosmetics and Personal Care Products.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals reported in cosmetics and personal care products as ingredients, possible impurities in the raw material manufacturing process, or degradation products. The purpose of this study was to further delineate contributions of these varying PFAS sources to these products. Thirty-eight cosmetics and personal care products were selected and analyzed for polyfluoroalkyl phosphates (PAPs), perfluoroalkyl carboxylic acids (PFCAs), fluorotelomer sulfonic acids (FTSAs), and perfluoroalkyl sulfonic acids (PFSAs) using targeted liquid chromatography tandem mass spectrometry (LC-MS/MS). A subset of products was also subjected to suspect screening using LC-high resolution mass spectrometry (HRMS) for >200 compounds. Results of LC-MS/MS and LC-HRMS indicated a predominant and ubiquitous presence of PAPs (detection frequency 99.7%, mean and median ΣPAPs 1 080 000 and 299 ng/g). Total median PFCA and PFSA concentrations were 3 and 38 times lower, respectively. There were significant correlations (Spearman's correlation coefficients = 0.60-0.81, p < 0.05) between 6:2 PAPs and their biotransformation products. Low levels of other PFAS classes were detected, including those previously measured in wastewater and human blood (e.g., hydrido-PFCAs), and five compounds associated with aqueous film-forming foams. Overall, these data highlight that cosmetics and personal care products can contain a breadth of PFAS at extremely high levels, leading to human and environmental exposure.

Removal of Zwitterionic PFAS by MXenes: Comparisons with Anionic, Nonionic, and PFAS-Specific Resins.

Zwitterionic per- and polyfluoroalkyl substances are increasingly detected in aquatic environments. The magnitude of their concentration and increased frequency of detection worldwide raise questions on their presence in drinking water and associated health risk. Scientific knowledge on the identification of treatment technologies to effectively capture such zwitterionic PFAS from contaminated water sources remains largely unknown. In this study, we investigated the application of anionic organic scavenger ion exchange (IX) resins (A860), nonionic IX resins (XAD 4 and XAD 7), PFAS-specific resins (A694 and A592), and Ti3C2 MXenes (novel two-dimensional metal carbides) for the removal of select fluorotelomer zwitterionic PFAS from natural waters. The cumulative removal of zwitterionic PFAS at pH ∼ 7 follows the order: Ti3C2 MXenes > A694 > A592 > A860 > XAD 4 ∼ XAD 7. Ti3C2 MXenes were able to capture >75% of the total influent zwitterionic PFAS and the performance remained consistent in natural and synthetic water. Ti3C2 MXenes also exhibited efficient regeneration (>90% recovery) with 0.4 M Na2SO3 solution, while the regeneration efficacy of other IX resins generally remained below 20%. Treatment with ∼180 J/cm2 UV dosage in the 0.4 M Na2SO3 regenerant brine solution yielded >99.9% reduction in the zwitterionic PFAS concentration indicating that UV-sulfite systems exhibit promising potential for the treatment of zwitterionic PFAS concentrates.

Target and Nontarget Screening of PFAS in Biosolids, Composts, and Other Organic Waste Products for Land Application in France.

Zwitterionic, cationic, and anionic per- and polyfluoroalkyl substances (PFAS) are increasingly reported in terrestrial and aquatic environments, but their inputs to agricultural lands are not fully understood. Here, we characterized PFAS in 47 organic waste products (OWP) applied in agricultural fields of France, including historical and recent materials. Overall, 160 PFAS from 42 classes were detected from target screening and homologue-based nontarget screening. Target PFAS were low in agriculture-derived wastes such as pig slurry, poultry manure, or dairy cattle manure (median ∑46PFAS: 0.66 µg/kg dry matter). Higher PFAS levels were reported in urban and industrial wastes, paper mill sludge, sewage sludge, or residual household waste composts (median ∑46PFAS: 220 µg/kg). Historical municipal biosolids and composts (1976-1998) were dominated by perfluorooctanesulfonate (PFOS), N-ethyl perfluorooctanesulfonamido acetic acid (EtFOSAA), and cationic and zwitterionic electrochemical fluorination precursors to PFOS. Contemporaneous urban OWP (2009-2017) were rather dominated by zwitterionic fluorotelomers, which represented on average 55% of ∑160PFAS (max: 97%). The fluorotelomer sulfonamidopropyl betaines (X:2 FTSA-PrB, median: 110 µg/kg, max: 1300 µg/kg) were the emerging class with the highest occurrence and prevalence in contemporary urban OWP. They were also detected as early as 1985. The study informs for the first time that urban sludges and composts can be a significant repository of zwitterionic and cationic PFAS.

Stability of Nitrogen-Containing Polyfluoroalkyl Substances in Aerobic Soils.

Zwitterionic per- and polyfluoroalkyl substances (PFASs) used in aqueous film-forming foams (AFFFs) could face diverse environmental fates once released at military bases, airports, fire-training areas, and accidental release sites. Here, we studied for the first time the transformation potential of four electrochemical fluorination (ECF)-based PFAS zwitterions (two carboxyl betaines and two tertiary amines) in aerobic soils. The two perfluoroalkyl sulfonamide derivatives were precursors to perfluorooctanesulfonate (PFOS), while the amide derivatives were precursors to perfluorooctane carboxylate (PFOA). These zwitterions and four other previously reported zwitterions or cations were compared for their transformation pathways and kinetics. Structural differences, especially the nitrogen head groups, largely influenced the persistence of these compounds in aerobic soils. The perfluoroalkyl sulfonamide-based compounds showed higher microbial stability than the corresponding perfluoroalkyl amide-based ones. Their stability in aerobic soils is ranked based on the magnitude of DT50 (time for 50% of substance to disappear): quaternary ammonium ≈ carboxyl betaine ≫ tertiary amine > amine oxide. The PFASs containing quaternary ammonium or betaine groups showed high stability in soils, with the longest DT50 likely to be years or decades, while those with tertiary amine or amine oxide groups showed DT50 of weeks or months. These eight ECF-based precursors provide insights into the degradation pathways and persistence in surface soils of other perfluoroalkyl cations and zwitterions present in AFFFs.

Bioaccumulation of Zwitterionic Polyfluoroalkyl Substances in Earthworms Exposed to Aqueous Film-Forming Foam Impacted Soils.

Critical knowledge gaps remain regarding the fate and effects of zwitterionic, cationic, and anionic perfluoroalkyl and polyfluoroalkyl substances (PFASs), including assessment of their bioaccumulation potential. Here, biota soil accumulation factors (BSAFs) were assessed in earthworms (Eisenia fetida) exposed to soil microcosms amended with zwitterionic fluorotelomers and anionic perfluoroalkyl acids. The 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB) bioaccumulated in earthworms [BSAF ∼ 2.5-5.4 (gdw,worm/gdw,soil)-1] but to a lesser extent than perfluorooctane sulfonate (PFOS: BSAF ∼ 21-29). The BSAF of perfluorocarboxylates increased from ∼2.0 for C4-C6 analogues to ∼92 for perfluorotridecanoate (C13). In earthworms exposed to Ansulite and Arctic Foam aqueous film-forming foams (AFFFs), the BSAF was related to perfluorinated chain length for n:3 fluorotelomer betaines (FtBs), n:1:2 FtB, and n:2 FTAB. Earthworms were also collected in situ from a fire-equipment testing site at a major Canadian airport. Summed PFAS concentrations were between 65 000 and 830 000 ng g-1 wet weight, possibly the highest burden recorded in terrestrial biota. Fluorotelomer sulfonates (6:2 FTS, 8:2 FTS, and 10:2 FTS) and FtB were particularly prevalent. Field worms also displayed elevated concentrations of n:3 acids (n = 3-11), but not those from laboratory microcosms exposed to fluorotelomer-based AFFFs. The findings provide an important confirmation to recent data suggesting that fluorotelomer compounds may accumulate in invertebrate species with limited metabolization.

Occurrence and Distribution of Per- and Polyfluoroalkyl Substances in Tianjin, China: The Contribution of Emerging and Unknown Analogues.

Tianjin, located in Bohai Bay, China, constitutes a relevant study area to investigate emerging per- and polyfluoroalkyl substances (PFASs) due to its high population density, clustering of chemical and aircraft industries, as well as international airports, harbors, and oil rigs. In this study, 53 anionic, zwitterionic, and cationic PFASs were monitored in river surface water, groundwater, seawater, and sediments in this area (overall n = 226). 6:2 chlorinated polyfluorinated ether sulfonic acid (Cl-PFESA), perfluorooctanoic acid, and perfluorooctane sulfonic acid were generally the predominant PFASs. 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB) was also widespread (occurrence >86%), with the highest concentration (1300 ng/L) detected at contamination hot spots impacted by wastewater effluents. The aqueous film-forming foam (AFFF)-related PFASs with sulfonamide betaine, amine oxide, amine, or quaternary ammonium moieties are also reported for the first time in river water and seawater samples. Fifteen classes of infrequently reported PFASs, including n:2 FTABs and n:2 fluorotelomer sulfonamide amines, hydrogen-substituted PFESA homologues, and p-perfluorous nonenoxybenzenesulfonate (OBS), were also identified in the water and sediment samples using suspect screening. Field-derived sediment-water distribution coefficients (Kd) of these emerging PFASs are provided for the first time, confirming that cationic and zwitterionic PFASs tend to be strongly associated with sediments.

Precipitation effects on parasite, indicator bacteria, and wastewater micropollutant loads from a water resource recovery facility influent and effluent.

The variability of fecal microorganisms and wastewater micropollutants (WWMPs) loads in relation to influent flow rates was evaluated for a water resource recovery facility (WRRF) in support of a vulnerability assessment of a drinking water source. Incomplete treatment and bypass discharges often occur following intense precipitation events that represent conditions that deviate from normal operation. Parasites, fecal indicator bacteria, and WWMPs concentrations and flow rate were measured at the WRRF influent and effluent during dry and wet weather periods. Influent concentrations were measured to characterize potential bypass concentrations that occur during wet weather. Maximum influent Giardia and C. perfringens loads and maximum effluent Escherichia coli and C. perfringens loads were observed during wet weather. Influent median loads of Cryptosporidium and Giardia were 6.8 log oocysts/day and 7.9 log cysts/day per 1,000 people. Effluent median loads were 3.9 log oocysts/day and 6.3 log cysts/day per 1,000 people. High loads of microbial contaminants can occur during WRRF bypasses following wet weather and increase with increasing flow rates; thus, short-term infrequent events such as bypasses should be considered in vulnerability assessments of drinking water sources in addition to the increased effluent loads during normal operation following wet weather.

Adequate Reducing Conditions Enable Conjugation of Oxidized Peptides to Polymers by One-Pot Thiol Click Chemistry.

Thiol(-click) chemistry has been extensively investigated to conjugate (bio)molecules to polymers. Handling of cysteine-containing molecules may however be cumbersome, especially in the case of fast-oxidizing coiled-coil-forming peptides. In the present study, we investigated the practicality of a one-pot process to concomitantly reduce and conjugate an oxidized peptide to a polymer. Three thiol-based conjugation chemistries (vinyl sulfone (VS), maleimide, and pyridyldithiol) were assayed along with three reducing agents (tris(2-carboxyethyl)phosphine (TCEP), dithiothreitol, and ß-mercaptoethanol). Seven out of the nine possible combinations significantly enhanced the conjugation yield, provided that an adequate concentration of reductant was used. Among them, the coincubation of an oxidized peptide with TCEP and a VS-modified polymer displayed the highest level of conjugation. Our results also provide insights into two topics that currently lack consensus: TCEP is stable in 10 mM phosphate buffered saline and it reacts with thiol-alkylating agents at submillimolar concentrations, and thus should be carefully used in order to avoid interference with thiol-based conjugation reactions.

Evaluation of on-line concentration coupled to liquid chromatography tandem mass spectrometry for the quantification of neonicotinoids and fipronil in surface water and tap water.

A study was initiated to investigate a fast and reliable method for the determination of selected systemic insecticides in water matrixes and to evaluate potential sources of bias in their analysis. Acetamiprid, clothianidin, desnitro-imidacloprid, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam were amenable to analysis via on-line sample enrichment hyphenated to ultra-high-performance liquid chromatography tandem mass spectrometry. The selection of on-line solid-phase extraction parameters was dictated by a multicriterion desirability approach. A 2-mL on-line injection volume with a 1500 µL min-1 loading flow rate met the objectives sought in terms of chromatographic requirements, extraction efficiency, sensitivity, and precision. A total analysis time of 8 min per sample was obtained with method limits of detection in the range of 0.1-5 ng L-1 for the scope of targeted analytes. Automation at the sample concentration step yielded intraday and interday precisions in the range of 1-23 and 2-26%, respectively. Factors that could affect the whole method accuracy were further evaluated in matrix-specific experiments. The impact of the initial filtration step on analyte recovery was evaluated in ultra-pure water, tap water, and surface water. Out of the nine membranes tested, glass fiber filters and polyester filters appeared as the most appropriate materials. Sample storage stability was also investigated across the three matrix types; the targeted analytes displayed suitable stability during 28 days at either 4 °C or - 20 °C, with little deviations (± 10%) with respect to the initial T0 concentration. Method applicability was demonstrated in a range of tap water and surface water samples from the province of Québec, Canada. Results from the present survey indicated a predominance of thiamethoxam (< 0.5-10 and 3-61 ng L-1 in tap water and river water, respectively), clothianidin (< 0.5-6 and 2-88 ng L-1 in tap water and river water, respectively), and imidacloprid (< 0.1-1 and 0.8-38 ng L-1 in tap water and river water, respectively) among the targeted analytes. Graphical abstract ᅟ Development of solid-phase extraction coupled on-line to UHPLC-MS/MS for the rapid screening of systemic insecticides in water.

Assessment of the Influence of Soil Characteristics and Hydrocarbon Fuel Cocontamination on the Solvent Extraction of Perfluoroalkyl and Polyfluoroalkyl Substances.

Sites impacted by the use of aqueous film-forming foams (AFFFs) present elevated concentrations of perfluoroalkyl and polyfluoroalkyl substances (PFAS). The characterization of the PFAS contamination at such sites may be greatly complicated by the presence of hydrocarbon cocontaminants and by the large variety of PFAS potentially present in AFFFs. In order to further a more comprehensive characterization of AFFF-contaminated soils, the solvent extraction of PFAS from soil was studied under different conditions. Specifically, the impact of soil properties (textural class, organic matter content) and the presence of hydrocarbon contamination (supplemented in the form of either diesel or crude oil) on PFAS recovery performance was evaluated for two extraction methods [methanol/sodium hydroxide (MeOH/NaOH) and methanol/ammonium hydroxide (MeOH/NH4OH)]. While both methods performed satisfactorily for perfluoroalkyl acids and fluorotelomer sulfonates, the extraction of newly identified surfactants with functionalities such as betaine and quaternary ammonium was improved with the MeOH/NaOH based method. The main factors that were found to influence the extraction efficiency were the soil properties; a high organic matter or clay content was observed to negatively affect the recovery of the newly identified compounds. While the MeOH/NaOH solvent yielded more efficient recovery rates overall, it also entailed the disadvantage of presenting higher detection limits and substantial matrix effects at the instrumental analysis stage, requiring matrix-matched calibration curves. The results discussed herein bear important implications for a more comprehensive and reliable environmental monitoring of PFAS components at AFFF-impacted sites.

Environmental Occurrence of Perfluoroalkyl Acids and Novel Fluorotelomer Surfactants in the Freshwater Fish Catostomus commersonii and Sediments Following Firefighting Foam Deployment at the Lac-Mégantic Railway Accident.

On July 6th 2013, an unmanned train laden with almost 8 million liters of crude oil careened off the rails downtown Lac-Mégantic (Québec, Canada). In the aftermath of the derailment accident, the emergency response entailed the deployment of 33 000 L of aqueous film forming foam (AFFF) concentrate that contained proprietary fluorosurfactants. The present study examines the environmental occurrence of perfluoroalkyl acids (PFAAs) and newly identified per and polyfluoroalkyl substances (PFASs) in the benthic fish white sucker (Catostomus commersonii) and sediments from Lake Mégantic and Chaudière River. In sediments, PFAAs displayed relatively low concentrations (∑PFAAs = 0.06-0.5 ng g-1 dw) while the sum of fluorotelomer-based PFASs was in the range < LOD-6.2 ng g-1 dw. Notably, fluorotelomer sulfonamide betaines (8:2-FTAB and 10:2-FTAB), fluorotelomer betaines (9:3-FTB, 11:3-FTB and 9:1:2 FTB) and 6:2 fluorotelomer sulfonate (6:2-FTSA) were ubiquitously identified in the sediment samples surveyed. Levels of PFAAs remained moderate in fish muscle (e.g. , PFOS: 0.28-2.1 ng g-1 wet-weight), with little or no differences when comparing 2013 or 2014 fish samples with 2011 archived samples. In contrast, n:2-FTSAs emerged in the immediate weeks or months that followed the accident, as did several betaine-based PFASs (8:2-FTAB, 10:2-FTAB, 9:3-FTB, 11:3-FTB, 7:1:2 FTB and 9:1:2 FTB), observed for the first time in situ. Fluorotelomer thioether amido sulfonate (10:2-FTSAS) and fluorotelomer sulfoxide amido sulfonate (10:2-FTSAS-sulfoxide) were also occasionally reported after the AFFF spill. With time, levels of betaine-based PFASs gradually decreased in fish, possibly indicating attenuation by biodegradation of the fluorine-free moiety, supported by the observation of likely metabolites such as n:3-fluorotelomer carboxylates and n:2-fluorotelomer sulfonamides.

Novel Fluoroalkylated Surfactants in Soils Following Firefighting Foam Deployment During the Lac-Mégantic Railway Accident.

The derailment of an unmanned train carrying crude oil and subsequent fire in the town of Lac-Mégantic, Quebec, led to the use of 33 000 L of aqueous film forming foam (AFFF) concentrate. While it is known that per- and polyfluoroalkyl substances (PFASs) contained in AFFFs pose a potential environmental and health risk, critical knowledge gaps remain as regards to their environmental fate after release. The accident in Lac-Mégantic provided valuable information regarding the identity and concentration of PFASs present in the soil after the AFFF deployment, as well as their possible transformation over time. The current study analyzed four sets of samples from Lac-Mégantic: soil collected days after the accident from a heavily impacted area, soil sampled two years later from the treatment biopiles, soil collected two years after the accident from downtown Lac-Mégantic, and nonimpacted soil from a nearby area. A total of 33 PFASs were quantified in the soils. The highest observed concentrations correspond to those of 6:2 fluorotelomer sulfonamidoalkyl betaine, 6:2 and 8:2 fluorotelomer sulfonates, and short chain perfluorocarboxylic acids. The soils collected in Lac-Mégantic two years after the accident show a total PFAS concentration that is ∼50 times lower than soils collected in 2013, while the proportion of perfluoroalkyl acids in those samples shows an increase. Qualitative analysis revealed the presence in soil of 55 additional PFASs that had been previously identified in AFFF formulations. The present study highlights the need to perform detailed analysis of AFFF impacted sites, instead of focusing solely on perfluoroalkyl acids.

Generation of Perfluoroalkyl Acids from Aerobic Biotransformation of Quaternary Ammonium Polyfluoroalkyl Surfactants.

The aerobic biotransformation over 180 days of two cationic quaternary ammonium compounds (QACs) with perfluoroalkyl chains was determined in soil microcosms, and biotransformation pathways were proposed. This is the first time that polyfluoroalkyl cationic surfactants used in aqueous film-forming foam (AFFF) formulations were studied for their environmental fate. The biotransformation of perfluorooctaneamido quaternary ammonium salt (PFOAAmS) was characterized by a DT50 value (time necessary to consume half of the initial mass) of 142 days and significant generation of perfluoroalkyl carboxylic acid (PFOA) at a yield of 30 mol % by day 180. The biotransformation of perfluorooctane sulfonamide quaternary ammonium salt (PFOSAmS) was very slow with unobservable change of the spiked mass; yet the generation of perfluorooctanesulfonate (PFOS) at a yield of 0.3 mol % confirmed the biotransformation of PFOSAmS. Three novel biotransformation intermediates were identified for PFOAAmS and three products including perfluorooctane sulfonamide (FOSA) for PFOSAmS through high-resolution mass spectrometry (MS) analysis and t-MS(2) fragmentation. The significantly slower PFOSAmS biotransformation is hypothesized to be due to its stronger sorption to soil owing to a longer perfluoroalkyl chain and a bulkier sulfonyl group, when compared to PFOAAmS. This study has demonstrated that despite overall high stability of QACs and their biocide nature, the ones with perfluoroalkyl chains can be substantially biotransformed into perfluoroalkyl acids in aerobic soil.

Phytoremediation of groundwater contaminated with pesticides using short-rotation willow crops: A case study of an apple orchard.

The occurrence of pesticides in groundwater represents an important health issue, notably for population whose drinking water supply source is located in agricultural areas. However, few solutions have been considered with regard to this issue. We tested the efficacy of a vegetal filtering system made of shrub willows planted at a high density (16,000 plants ha(-1)) to filter or degrade pesticides found in the groundwater flowing out of an apple orchard. Ethylene urea (EU), ethylene thiourea (ETU), tetrahydrophthalimide (THPI), atrazine, and desethylatrazine were monitored in the soil solution in willow and control plots over one growing season. ETU and atrazine concentrations were lower in the willow plots relative to the control plots, whereas desethylatrazine concentration was higher in the willow plots. No significant difference was detected for EU and THPI. Furthermore, pesticide concentrations displayed complex temporal patterns. These results suggest that willow filter systems can filter or degrade pesticides, notably ETU and atrazine, and could be used for phytoremediation purposes. Yet, this potential remains to be quantified with further studies using experimental settings allowing more estimation in time and space.

On the threshold conditions for electron beam damage of asbestos amosite fibers in the transmission electron microscope (TEM).

Asbestos amosite fibers were investigated to evaluate the damage caused by a transmission electron microscope (TEM) electron beam. Since elemental x-ray intensity ratios obtained by energy dispersive x-ray spectroscopy (EDS) are commonly used for asbestos identification, the impact of beam damage on these ratios was evaluated. It was determined that the magnesium/silicon ratio best represented the damage caused to the fiber. Various tests showed that most fibers have a current density threshold above which the chemical composition of the fiber is modified. The value of this threshold current density varied depending on the fiber, regardless of fiber diameter, and in some cases could not be determined. The existence of a threshold electron dose was also demonstrated. This value was dependent on the current density used and can be increased by providing a recovery period between exposures to the electron beam. This study also established that the electron beam current is directly related to the damage rate above a current density of 165 A/cm2. The large number of different results obtained suggest, that in order to ensure that the amosite fibers are not damaged, analysis should be conducted below a current density of 100 A/cm2.

Development of a suspect and non-target screening approach to detect veterinary antibiotic residues in a complex biological matrix using liquid chromatography/high-resolution mass spectrometry.

RATIONALE: Swine manure can contain a wide range of veterinary antibiotics, which could enter the environment via manure spreading on agricultural fields. A suspect and non-target screening method was applied to swine manure samples to attempt to identify veterinary antibiotics and pharmaceutical compounds for a future targeted analysis method. METHODS: A combination of suspect and non-target screening method was developed to identify various veterinary antibiotic families using liquid chromatography coupled with high-resolution mass spectrometry (LC/HRMS). The sample preparation was based on the physicochemical parameters of antibiotics for the wide scope extraction of polar compounds prior to LC/HRMS analysis. The amount of data produced was processed by applying restrictive thresholds and filters to significantly reduce the number of compounds found and eliminate matrix components. RESULTS: The suspect and non-target screening was applied on swine manure samples and revealed the presence of seven common veterinary antibiotics and some of their relative metabolites, including tetracyclines, ß-lactams, sulfonamides and lincosamides. However, one steroid and one analgesic were also identified. The occurrence of the identified compounds was validated by comparing their retention times, isotopic abundance patterns and fragmentation patterns with certified standards. CONCLUSIONS: This identification method could be very useful as an initial step to screen for and identify emerging contaminants such as veterinary antibiotics and pharmaceuticals in environmental and biological matrices prior to quantification.

Determination of BMAA and three alkaloid cyanotoxins in lake water using dansyl chloride derivatization and high-resolution mass spectrometry.

A new analytical method was developed for the detection of alkaloid cyanotoxins in harmful algal blooms. The detection of the nonproteinogenic amino acid ß-N-methylamino-L-alanine (BMAA) and two of its conformation isomers, 2,4-diaminobutyric acid (DAB) and N-(2-aminoethyl) glycine (AEG), as well as three alkaloid cyanotoxins, anatoxin-a (ANA-a), cylindrospermopsin (CYN), and saxitoxin (STX), is presented. The use of a chemical derivatization with dansyl chloride (DNS) allows easier separation with reversed phase liquid chromatography. Detection with high-resolution mass spectrometry (HRMS) with the Q-Exactive enables high selectivity with specific fragmentation as well as exact mass detection, reducing considerably the possibilities of isobaric interferences. Previous to analysis, a solid phase extraction (SPE) step is used for purification and preconcentration. After DNS derivatization, samples are submitted to ultra high-performance liquid chromatography coupled with heated electrospray ionisation and the Q-Exactive mass spectrometer (UHPLC-HESI-HRMS). With an internal calibration using isotopically-labeled DAB-D3, the method was validated with good linearity (R (2) > 0.998), and method limits of detection and quantification (MLD and MLQ) for target compounds ranged from 0.007 to 0.01 µg L(-1) and from 0.02 to 0.04 µg L(-1), respectively. Accuracy and within-day/between-days variation coefficients were below 15%. SPE recovery values ranged between 86 and 103%, and matrix effects recovery values ranged between 75 and 96%. The developed analytical method was successfully validated with 12 different lakes samples, and concentrations were found ranging between 0.009 and 0.3 µg L(-1) except for STX which was not found in any sample.