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Black carbon-amended bioretention systems are an increasingly popular strategy for the removal of organic contaminants, including poly- and perfluoroalkyl substances (PFASs) and other trace organic contaminants (TOrCs), from urban stormwater. Many PFASs preferentially accumulate at the air–water interface, but detention time requirements for stormwater bioretention systems typically result in full saturation of the bioretention systems, effectively removing their air–water interfaces. This study assessed the effect of bioretention system saturation on removal of PFASs, metals, and hydrophilic TOrCs. A field-aged mixture of 40% v/v sand, 30% v/v zeolite, and 30% v/v biochar was packed into columns which were operated with hydraulic controls to remain unsaturated or fully saturated throughout the duration of the experiment. Twenty-four storm events sized to a 95th percentile storm at a California, United States military site were simulated using synthetic stormwater fortified with aqueous film forming foam-derived PFASs, TOrCs, and metals to mimic real-world conditions. Unsaturated conditions outperformed saturated conditions for removal of all PFASs analyzed. A simulated inadvertent system perturbation (i.e.flooding event) in the unsaturated columns did not result in significantly greater mobilization of PFAS mass, suggesting that more sorption to the biochar occurred as a result of the transient retention of PFASs at the air–water interface reducing kinetic sorption limitations. Overall, maintaining unsaturated conditions in a biofilter may extend the sorptive filter lifetime for PFASs by up to 83%. The results have implications for bioretention system application and design for PFAS removal in contaminated catchment areas.

While foam fractionation (FF) process has emerged as a promising technology for removal of per- and polyfluoroalkyl substances (PFASs) from contaminated groundwater, management of the resulting foam concentrates with elevated concentrations of PFASs (e.g., >1 g/L) remains a challenge. Here, we applied hydrothermal alkaline treatment (HALT) to two foam concentrates derived from FF field demonstration projects that treated aqueous film-forming foam (AFFF)-impacted groundwater. Results showed >90% degradation and defluorination within 90 min of treatment (350 °C, 1 M NaOH) of all 62 PFASs (including cations, anions, and zwitterions) identified in foam concentrates. Observed rate constants for degradation of individual perfluoroalkyl sulfonates (PFSAs, CnF2n+1–SO3–), the most recalcitrant class of PFASs, in both foam concentrates were similar to values measured previously in other aqueous matrices, indicating that elevated initial PFAS concentrations (e.g., PFHxSinit= 0.55 g/L), dissolved organic carbon (DOC; up to 4.5 g/L), and salt levels (e.g., up to 325 mg/L chloride) do not significantly affect PFAS reaction kinetics. DOC was partially mineralized by treatment, but a fraction (∼15%) was recalcitrant. Spectroscopic characterization revealed molecular features of the HALT-recalcitrant DOC fraction, and nontarget high-resolution mass spectrometry tentatively identified 129 nonfluorinated HALT-recalcitrant molecules. Analysis of process energy requirements shows that treating PFAS-contaminated foam concentrates with HALT would add minimally (<5%) to the overall energy requirements of an integrated FF-HALT treatment train.

This study elucidates per- and polyfluoroalkyl substance (PFAS) fingerprints for specific PFAS source types. Ninety-two samples were collected from aqueous film-forming foam impacted groundwater (AFFF-GW), landfill leachate, biosolids leachate, municipal wastewater treatment plant effluent (WWTP), and wastewater effluent from the pulp and paper and power generation industries. High-resolution mass spectrometry operated with electrospray ionization in negative mode was used to quantify up to 50 target PFASs and screen and semi-quantify up to 2,266 suspect PFASs in each sample. Machine learning classifiers were used to identify PFASs that were diagnostic of each source type. Four C5–C7 perfluoroalkyl acids and one suspect PFAS (trihydrogen-substituted fluoroethernonanoic acid) were diagnostic of AFFF-GW. Two target PFASs (5:3 and 6:2 fluorotelomer carboxylic acids) and two suspect PFASs (4:2 fluorotelomer-thia-acetic acid and N-methylperfluoropropane sulfonamido acetic acid) were diagnostic of landfill leachate. Biosolids leachates were best classified along with landfill leachates and N-methyl and N-ethyl perfluorooctane sulfonamido acetic acid assisted in that classification. WWTP, pulp and paper, and power generation samples contained few target PFASs, but fipronil (a fluorinated insecticide) was diagnostic of WWTP samples. Our results provide PFAS fingerprints for known sources and identify target and suspect PFASs that can be used for source allocation.

Improved stormwater treatment is needed to prevent toxic and mobile contaminant transport into receiving waters and allow beneficial use of stormwater runoff. In particular, safe capture of stormwater runoff to augment drinking water supplies is contingent upon removing dissolved trace organic contaminants (TrOCs) not captured by conventional stormwater control measures. This study builds upon a prior laboratory-based column study investigating biochar and regenerated activated carbon (RAC) amendment for removing hydrophilic trace organic contaminants (HiTrOCs) and poly- and perfluoroalkyl substances (PFASs) from stormwater runoff. A robust contaminant transport model framework incorporating time-dependent flow and influent concentration is developed and validated to predict HiTrOC and PFAS transport in biochar- and RAC-amended stormwater filters. Specifically, parameters fit using a sorption-retarded intraparticle pore diffusion transport model were validated using data further along the depth of the column and compared to equilibrium batch isotherms. The transport model and fitted parameters were then used to estimate the lifetime of a hypothetical stormwater filter in Seal Beach, CA, to be 35 ± 6 years for biochar- and 51 ± 17 years for RAC-amended filters, under ideal conditions with no filter clogging. This work offers insights on the kinetics of HiTrOC and PFAS transport within biochar and RAC filters and on the impact of filter design on contaminant removal performance and longevity.

Historical releases of aqueous film forming foam (AFFF) are significant sources of poly- and perfluoroalkyl substances (PFASs), including perfluoroalkyl acids (PFAAs) and their precursors, to the environment. While several studies have focused on microbial biotransformation of polyfluorinated precursors to PFAAs, the role of abiotic transformations at AFFF-impacted sites is less clear. Herein, we use photochemically generated hydroxyl radical to demonstrate that environmentally relevant concentrations of hydroxyl radical (•OH) can play a significant role in these transformations. High-resolution mass spectrometry (HRMS) was used to perform targeted analysis, suspect screening, and nontargeted analyses, which were used to identify the major products of AFFF-derived PFASs as perfluorocarboxylic acids, though several potentially semi-stable intermediates were also observed. Using competition kinetics in a UV/H2O2system, hydroxyl radical rate constants (kOH) for 24 AFFF-derived polyfluoroalkyl precursors were measured to be 0.28 to 3.4 × 109M–1s–1. Differences in kOHwere observed for compounds with differing headgroups and perfluoroalkyl chain lengths. Also, differences in kOHmeasured for the only relevant precursor standard available, n-[3-propyl]tridecafluorohexanesulphonamide (AmPr-FHxSA), as compared to AmPr-FHxSA present in AFFF suggest that intermolecular associations in the AFFF matrix may affect kOH. Considering environmentally relevant [•OH]ss, polyfluoroalkyl precursors are expected to exhibit half-lives of ∼8 days in sunlit surface waters and possibly as short as ∼2 h during oxygenation of Fe(II)-rich subsurface systems.

A remote sampling approach was developed at Eurofins for quantifying per- and polyfluoroalkyl substances (PFASs) in whole blood samples collected using volumetric absorptive microsamplers (VAMSs), which allow for self-collection of blood using a finger prick. This study compares PFAS exposure measured by self-collection of blood using VAMSs to the standard venous serum approach. Blood samples were collected from participants (n= 53) in a community with prior PFAS drinking water contamination using a venous blood draw as well as participant self-collection using VAMSs. Whole blood from the venous tubes was also loaded onto VAMSs to compare differences in capillary vs venous whole blood PFAS levels. Samples were quantified for PFASs using liquid chromatography tandem mass spectrometry and online solid-phase extraction. PFAS levels in serum were highly correlated with measurements in capillary VAMSs (r≥ 0.91 and p< 0.05). Serum PFAS levels were generally twofold higher than whole blood, reflecting expected differences in their composition. Of interest, FOSA was detected in whole blood (both venous and capillary VAMSs) but not in serum. Overall, these findings indicate that VAMSs are useful self-collection tools for assessing elevated human exposure to PFASs.

Advanced reduction processes (ARPs) that generate hydrated electrons (eaq–; e.g., UV-sulfite) have emerged as a promising remediation technology for recalcitrant water contaminants, including per- and polyfluoroalkyl substances (PFASs). The effectiveness of ARPs in different natural water matrices is determined, in large part, by the presence of non-target water constituents that act to quench eaq–or shield incoming UV photons from the applied photosensitizer. This study examined the pH-dependent quenching of eaq–by ubiquitous dissolved carbonate species (H2CO3*, HCO3–, and CO32–) and quantified the relative importance of carbonate species to other abundant quenching agents (e.g., H2O, H+, HSO3–, and O2(aq)) during ARP applications. Analysis of laser flash photolysis kinetic data in relation to pH-dependent carbonate acid–base speciation yields species-specific bimolecular rate constants for eaq–quenching by H2CO3*, HCO3–, and CO32–(kH2CO3*= 2.23 ± 0.42 × 109M–1s–1, kHCO3−= 2.18 ± 0.73 × 106M–1s–1, and kCO32−= 1.05 ± 0.61 × 105M–1s–1), with quenching dominated by H2CO3* (which includes both CO2(aq)and H2CO3) at moderately alkaline pH conditions despite it being the minor species. Attempts to apply previously reported rate constants for eaq–quenching by CO2(aq), measured in acidic solutions equilibrated with CO2(g), overpredict quenching observed in this study at higher pH conditions typical of ARP applications. Moreover, kinetic simulations reveal that pH-dependent trends reported for UV-sulfite ARPs that have often been attributed to eaq–quenching by varying [H+] can instead be ascribed to variable acid–base speciation of dissolved carbonate and the sulfite sensitizer.

Air–water interfacial retention of poly- and perfluoroalkyl substances (PFASs) is increasingly recognized as an important environmental process. Herein, column transport experiments were used to measure air–water interfacial partitioning values for several perfluoroalkyl ethers and for PFASs derived from aqueous film-forming foam, while batch experiments were used to determine equilibrium Kiadata for compounds exhibiting evidence of rate-limited partitioning. Experimental results suggest a Freundlich isotherm best describes PFAS air–water partitioning at environmentally relevant concentrations (101–106ng/L). A multiparameter regression analysis for Kiaprediction was performed for the 15 PFASs for which equilibrium Kiavalues were determined, assessing 246 possible combinations of 8 physicochemical and system properties. Quantitative structure–property relationships (QSPRs) based on three to four parameters provided predictions of high accuracy without model overparameterization. Two QSPRs (R2values of 0.92 and 0.83) were developed using an assumed average Freundlich nvalue of 0.65 and validated across a range of relevant concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and hexafluoropropylene oxide-dimer acid (i.e., GenX). A mass action model was further modified to account for the changing ionic strength on PFAS air–water interfacial sorption. The final result was two distinct QSPRs for estimating PFAS air–water interfacial partitioning across a range of aqueous concentrations and ionic strengths.

While several studies have focused on perfluoroalkyl acid (PFAA) leaching from soils, field studies evaluating the relationship between PFAA mass removal and porewater concentrations as the PFAA source becomes depleted are lacking. Herein, in situ water flushing was performed at a site historically impacted with AFFF to accelerate the leaching of PFAAs from unsaturated soils in a highly characterized field test cell. Porous cup suction lysimeters were used to assess the changes in PFAA porewater concentrations as a function of PFAA mass removal from the unsaturated soils, where flushing was intermittently paused to determine ambient PFAA porewater concentrations. Results showed that the fractional decreases in PFAA porewater concentrations during flushing exceeded the fractional decrease in PFAA mass removal from the soil. PFOS porewater concentrations decrease by 76% (with negligible rebound) compared to only a 7.4% decrease in overall PFOS mass removed from the unsaturated zone. Overall, the results observed herein suggest that, when considering soil impacts to groundwater, less stringent soil cleanup criteria than those that consider an equivalent relationship between mass removal and mass discharge may be appropriate. In addition, remedial approaches that remove only a modest fraction of the PFAA soil mass may be protective of underlying groundwater, particularly for perfluorinated sulfonates with at least six carbons.

Sites impacted by aqueous film-forming foam (AFFF) contain co-contaminants that can stimulate biotransformation of polyfluoroalkyl substances. Here, we compare how microbial enrichments from AFFF-impacted soil amended with diethyl glycol monobutyl ether (found in AFFF), aromatic hydrocarbons (present in co-released fuels), acetate, and methane (substrates used or formed during bioremediation) impact the aerobic biotransformation of an AFFF-derived six-carbon electrochemical fluorination (ECF) precursor N-dimethyl ammonio propyl perfluorohexane sulfonamide (AmPr-FHxSA). We found that methane- and acetate-oxidizing cultures resulted in the highest yields of identifiable products (38 and 30%, respectively), including perfluorohexane sulfonamide (FHxSA) and perfluorohexane sulfonic acid (PFHxS). Using these data, we propose and detail a transformation pathway. Additionally, we examined chemical oxidation products of AmPr-FHxSA and FHxSA to provide insights on remediation strategies for AmPr-FHxSA. We demonstrate mineralization of these compounds using the sulfate radical and test their transformation during the total oxidizable precursor (TOP) assay. While perfluorohexanoic acid accounted for over 95% of the products formed, we demonstrate here for the first time two ECF-based precursors, AmPr-FHxSA and FHxSA, that produce PFHxS during the TOP assay. These findings have implications for monitoring poly- and perfluoroalkyl substances during site remediation and application of the TOP assay at sites impacted by ECF-based precursors.

UV-sulfite has been shown to effectively degrade per- and polyfluoroalkyl substances (PFASs) in single-solute experiments. We recently reported treatment of 15 PFASs, including perfluoroalkyl sulfonic acids (PFSAs), perfluoroalkyl carboxylic acids (PFCAs), and fluorotelomer sulfonic acids (FTSs), detected in aqueous film-forming foam (AFFF) using high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Here, we extend the analysis within those original reaction solutions to include the wider set of PFASs in AFFF for which reactivity is largely unknown by applying recently established LC-QTOF-MS suspect screening and semiquantitative analysis protocols. Sixty-eight additional PFASs were detected (15 targeted + 68 suspect screening = 83 PFASs) with semiquantitative analysis, and their behavior was binned on the basis of (1) detection in untreated AFFF, (2) PFAS photogeneration, and (3) reactivity. These 68 structures account for an additional 20% of the total fluorine content in the AFFF (targeted + suspect screening = 57% of total fluorine content). Structure–reactivity trends were also revealed. During treatment, transformations of highly reactive structures containing sulfonamide (–SO2N–) and reduced sulfur groups (e.g., –S– and –SO–) adjacent to the perfluoroalkyl [F(CF2)n–] or fluorotelomer [F(CF2)n(CH2)2–] chain are likely sources of PFCA, PFSA, and FTS generation previously reported during the early stages of reactions. The results also show the character of headgroup moieties adjacent to the F(CF2)n–/F(CF2)n(CH2)2– chain (e.g., sulfur oxidation state, sulfonamide type, and carboxylic acids) and substitution along the F(CF2)n– chain (e.g., H–, ketone, and ether) together may determine chain length-dependent reactivity trends. The results highlight the importance of monitoring PFASs outside conventional targeted analytical methodologies.

•Toronto’s public transit introduced a 2019 equity policy to enhance bus services.•Our quantitative and spatial study evaluates the equity implications of this policy shift.•We moved from an aggregate neighbourhood-based to a disaggregated person-based approach.•Two-thirds of Toronto transit riders are equity-deserving, with 72% residing outside priority areas.•We recommend creating a dedicated equity tool with an individual-centric focus for service planning.

•Reducing car dependency for short trips is a foundation of the 15-, 20-, and x-Minute City.•We distinguish between 15-min access intensity and access sufficiency to different types of amenities.•Use spatially-filtered beta regression to predict car use by the access measures.•Highest levels of access sufficiency are associated with decreases in car use.•More dramatic car reductions associated with access intensity.

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs (C≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs (C≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship (R2= 0.6, p< 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

Hydrothermal alkaline treatment (HALT) can effectively degrade per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foam (AFFF). However, information is lacking regarding the treatment of PFASs in actual groundwater and soil from AFFF-impacted sites, especially for complex soil matrices. Given the lack of studies on direct soil treatment for PFAS destruction, we herein applied HALT to two groundwater samples and three soil samples from AFFF-impacted sites and characterized the destruction of PFASs using high-resolution mass spectrometry. Results showed that the 148 PFASs identified in all collected field samples, including 10 cationic, 98 anionic, and 40 zwitterionic PFASs, were mostly degraded to nondetectable levels within 90 min when treated with 5 M NaOH at 350 °C. The near-complete defluorination, as evidenced by fluoride release measurements, confirmed the complete destruction of PFASs. While many structures, including perfluoroalkyl carboxylic acids and polyfluorinated substances, were readily degraded, perfluoroalkyl sulfonates (PFSAs, CnF2n+1–SO3–), most notably with short chain lengths (n= 3–5), were more recalcitrant. Rates of PFSA destruction in groundwater samples were similar to those measured in laboratory water solutions, but reactions in soil were slow, presumably due to base-neutralizing properties of the soil. Further, the degradation of PFASs in groundwaters and soils was found to be a function of reaction temperature, NaOH concentration, and reaction time. These findings have important implications for the remediation of AFFF-impacted sites.

Results of a study of teamwork and managerial attitudes in companies leading in innovations show that the factors contributing to this lead is enthusiasm and confidence about the innovation, persistence and involvement of right mix of people. For the purpose, data was collected from the team and managerial sample at various intervals.

It has been hypothesized that type 1 diabetes is initiated by neonatal physiological pancreatic β-cell death, indicating that the early stages of this autoimmune response may reflect a dysregulated response to immune 'danger' signals. One potential danger signal is ATP, high concentrations of which stimulate the purinergic receptor P2[X.sub.7] on hematopoietic cells. We compared the sensitivity of lymphocytes from model type 1 diabetic (NOD) and control (C57BL/10) mite to activation of this pathway. Stimulation of the P2[X.sub.7] receptor of NOD mice resulted in more pronounced shedding of the lymphocyte homing receptor CD62L and in increased programmed cell death. Levels of major histocompatibility complex class I molecules, which have previously been reported to be poorly expressed on NOD lymphocytes, were initially normal, but the molecules were shed preferentially from NOD cells after P2[X.sub.7] receptor stimulation. Thus, although NOD lymphocytes have been considered resistant to programmed cell death, they are highly sensitive to that stimulated through the P2[X.sub.7] receptor. Because NOD mice express a low activation threshold allele of the P2[X.sub.7] receptor and the P2[X.sub.7] gene maps to a locus associated with disease, P2[X.sub.7] is a good candidate susceptibility gene for NOD diabetes., The concept that the immune system has evolved not to simply discriminate self from nonself, but also to respond to signals perceived as dangerous (1), is now widely accepted. These [...]

Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF2-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil–water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF2≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Low-impact, green infrastructure systems such as biofilters, particularly when amended with biochar, can help address chemical pollution conveyed viastormwater that is increasingly posing a threat to aquatic ecosystems and groundwater quality. Although removal of organic contaminants including pesticides by biochar-amended systems has been studied, the role of a biofouling layer on contaminant removal, biotransformation, and filter lifetime remains poorly understood. This study evaluated the removal of the pesticides atrazine, imidacloprid, and clothianidin in biologically active biochar-amended columns through complete exhaustion of contaminant removal capacity. The resultant data indicate that biological processes accounted for 20–36% of overall removal in the biochar-amended sand columns. In addition, a combined target and suspect screening approach using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) was employed to evaluate the potential transformation of these three pesticides and release of the transformation products (TPs). All TPs detected in the effluent remained below 2.5% of their respective parent influent concentrations for the duration of the experiment. Furthermore, at a biochar application rate of 0.5 wt%, the presence of an active biofilm prolonged the filter lifetime by 1.8–2.3 times compared to a fouled but inactive filter, where removal was presumably dominated by adsorption only. Scenario modelling estimates showed that biochar-amended biofilters could last at least 17 years before exceeding aquatic life threshold values at biochar-application rates as low as 1 wt% (5 vol%) in a representative case study. Results of this study provide novel insight on pesticide TP formation in biochar-amended biofilters and estimation of filter lifetimes.

The claim that career and non-career women have different responses to part-time work as opposed to a career due to different motivations and work-contexts is argued. However, such work have lower work-to-family interference, and better time management ability for women in both kinds of positions, while career women report less depression and higher life satisfaction.

Per- and polyfluoroalkyl substances (PFASs) are highly mobile in the saturated subsurface, yet aqueous film-forming foam (AFFF)-impacted source zones appear to be long lasting PFAS reservoirs. This study examined the release of over one hundred anionic and zwitterionic PFASs from two AFFF-impacted surface soils under saturated conditions with packed soil columns. Perfluoroalkyl acids (PFAAs) were released more rapidly than their polyfluorinated precursors, while anionic PFASs that were present in partially uncharged states were released more slowly than PFASs that were present entirely as anions, as were zwitterionic PFASs with terminal cationic functional groups when compared with analogous zwitterions with only anionic terminal groups. Nonideal transport was observed in both per- and polyfluorinated classes, as soil column effluent concentrations of slowly released PFASs increased by up to 107-fold with sustained artificial groundwater flow. A flow-interruption experiment suggested the influence of rate-limited desorption on diverse PFAS classes, including PFAAs with as few as four perfluorinated carbons. These results suggest that during infiltration the slow, rate-limited desorption of anionic and zwitterionic PFAA precursors may result in these compounds comprising an increasingly large fraction of the remaining PFASs in AFFF-impacted surface soils.

Recently new heights have been achieved in both the prominence of systems integrators and the expenditures on integration. The increased expenditures and attention have not been matched with increased understanding […]

One of managers' best sources of information for improving Information Systems departments is user complaints. This article discusses user complaints as valuable feedback to help Information Systems departments deliver effective […]

Interviews were conducted with parents employed in the public service sector to determine how they cope with work and family responsibilities. The results showed that most employed parents experience average stress levels and cope primarily by setting priorities and by dividing chores within the family. Employed parents stressed the need for employer support and understanding of family-related demands. In addition, employers should provide more flexible work arrangements as well as facilities and subsidies for child care., This article presents data from an interview study conducted with parents employed in the federal public service in the National Capital Region. In recent years, there have been dramatic shifts [...]

The effects of gender, parental status and job type on the ability to balance work and family life were evaluated. Variables were examined based on organizational and individual outcomes such as job commitment, job satisfaction, work conflict, time management, life satisfaction and perceived stress. The results showed that although workplace demographics have undergone considerable changes, organizational policies have not. Most employers are still insensitive to family concerns. Some recommendations on how to better manage employees in public sector organizations are presented., As in most transition periods, changing behaviours often outpace social and organizational structures. Such is the case for today's working parents. In the past 20 years there have been substantial [...]

A survey was conducted to determine the number of hours devoted to work-related activities by Canadian public and private sector employees. The results showed that the average Canadian white-collar employee works approximately 45 hours a week at the office. In addition, several additional hours are spent on job-related activities at home and on non-work days. Since reducing time spent working is usually not a feasible option, employers should consider adopting more flexible work-time and work-location policies to prevent the development of stress-related medical problems., Time spent at work offers an important and concrete measure of one dimension of employment that affects individuals and their families. Time at work is the cornerstone around which the [...]

The traditional 5-day, 40-hour work week schedule is one of the primary reasons for the eroding family life of both public and private sector employees. The introduction of more flexible work schedules and work locations can be an efficient, cost-effective way to balance work and family concerns. In addition, more liberal work arrangements are very effective inducements for the retention of top-level personnel. Since contented employees perform their functions better, it is good business to assist employees in balancing their work and family life.

The effect of work-induced stress on family relationships has taken a significant turn with the increasing number of career mothers. A shift in female involvement from home to work and a change in male interests from work to home can induce work-family conflicts. These conflicts result in higher health risks, less effective performance both at home and in the workplace and an overall dissatisfaction with situations. Since the nature of work is a major stress factor, it is suggested that employers look into ways of reducing stress, using both human cognizance and technological developments.

The source tracking of per- and polyfluoroalkyl substances (PFASs) is a new and increasingly necessary subfield within environmental forensics. We define PFAS source tracking as the accurate characterization and differentiation of multiple sources contributing to PFAS contamination in the environment. PFAS source tracking should employ analytical measurements, multivariate analyses, and an understanding of PFAS fate and transport within the framework of a conceptual site model. Converging lines of evidence used to differentiate PFAS sources include: identification of PFASs strongly associated with unique sources; the ratios of PFAS homologues, classes, and isomers at a contaminated site; and a site’s hydrogeochemical conditions. As the field of PFAS source tracking progresses, the development of new PFAS analytical standards and the wider availability of high-resolution mass spectral data will enhance currently available analytical capabilities. In addition, multivariate computational tools, including unsupervised (i.e., exploratory) and supervised (i.e., predictive) machine learning techniques, may lead to novel insights that define a targeted list of PFASs that will be useful for environmental PFAS source tracking. In this Perspective, we identify the current tools available and principal developments necessary to enable greater confidence in environmental source tracking to identify and apportion PFAS sources.

The long-term leaching of polyfluoroalkyl substances (PFAS) within the vadose zone of an AFFF application site for which the depth to groundwater is approximately 100 m was investigated by characterizing the vertical distribution of PFAS in a high spatial resolution. The great majority (99%) of PFAS mass resides in the upper 3 m of the vadose zone. The depths to which each PFAS migrated, quantified by moment analysis, is an inverse function of molar volume, demonstrating chromatographic separation. The PFAS were operationally categorized into three chain-length groups based on the three general patterns of retention observed. The longest-chain (>∼335 cm3/mol molar volume) PFAS remained within the uppermost section of the core, exhibiting minimal leaching. Conversely, the shortest-chain (<∼220 cm3/mol) PFAS accumulated at the bottom of the interval, which coincides with the onset of a calcic horizon. PFAS with intermediate-chain lengths were distributed along the length of the core, exhibiting differential magnitudes of leaching. The minimal or differential leaching observed for the longest- and intermediate-chain-length PFAS, respectively, demonstrates that retention processes significantly impacted migration. The accumulation of shorter-chain PFAS at the bottom of the core is hypothesized to result from limited deep infiltration and potential-enhanced retention associated with the calcic horizon.

Per- and polyfluoroalkyl substances (PFASs) from aqueous film forming foams (AFFFs) can hinder bioremediation of co-contaminants such as trichloroethene (TCE) and benzene, toluene, ethylbenzene, and xylene (BTEX). Anaerobic dechlorination can require bioaugmentation of Dehalococcoides, and for BTEX, oxygen is often sparged to stimulate in situ aerobic biodegradation. We tested PFAS inhibition to TCE and BTEX bioremediation by exposing an anaerobic TCE-dechlorinating coculture, an aerobic BTEX-degrading enrichment culture, and an anaerobic toluene-degrading enrichment culture to n-dimethyl perfluorohexane sulfonamido amine (AmPr-FHxSA), perfluorohexane sulfonamide (FHxSA), perfluorohexanesulfonic acid (PFHxS), or nonfluorinated surfactant sodium dodecyl sulfate (SDS). The anaerobic TCE-dechlorinating coculture was resistant to individual PFAS exposures but was inhibited by >1000× diluted AFFF. FHxSA and AmPr-FHxSA inhibited the aerobic BTEX-degrading enrichment. The anaerobic toluene-degrading enrichment was not inhibited by AFFF or individual PFASs. Increases in amino acids in the anaerobic TCE-dechlorinating coculture compared to the control indicated stress response, whereas the BTEX culture exhibited lower concentrations of all amino acids upon exposure to most surfactants (both fluorinated and nonfluorinated) compared to the control. These data suggest the main mechanisms of microbial toxicity are related to interactions with cell membrane synthesis as well as protein stress signaling.

Though long recognized as synthetic precursors to other poly- and perfluoroalkyl substances (PFASs), most poly- and perfluoroalkyl sulfonyl halides (PASXs) cannot be directly measured and have generally received minimal attention. Inspired by the redox reaction between sulfonyl halide groups and p-toluenethiol in organic chemistry, we developed a novel nontarget analysis strategy for PASXs by intergrating derivatization and specific fragment-based liquid chromatography-high resolution mass spectrometry screening for m/z82.961 [SO2F–] and m/z95.934 [S2O2–]. By using this strategy, we discovered 11 PASXs, namely, perfluoroalkyl sulfonyl fluorides (5), polyfluoroalkyl sulfonyl fluorides (2), unsaturated perfluoroalkyl sulfonyl fluoride (1), and perfluoroalkyl sulfonyl chlorides (3) in soil samples collected from an abandoned fluorochemical manufacturing park. These average ∑PASXs concentrations were 1120 μg kg–1(range: 9.7–9860 μg kg–1), which were very likely to be the key intermediates and undesired byproducts of electrochemical fluorination processes. Spatial variation in the mass ratio of ∑PASXs to ∑PFSAs (range: 0.7–795%) also indicates their different transportation pathways. More importantly, the decline of PASXs and increase of perfluoroalkyl sulfonates (when compared to a prior study at this site) suggest the continued hydrolysis of PASXs and the relatively fast environmental transformation rates in the abandoned fluorochemical park soils. Overall, these findings demonstrated the utility of a novel nontarget analysis strategy, which may change most PASXs from inferred precursors to measured intermediates and further could be adapted for structures, distribution, and transformation studies of PFASXs in other matrices.

Monitoring contamination from per- and polyfluoroalkyl substances (PFASs) in water systems impacted by aqueous film-forming foams (AFFFs) typically addresses a few known PFAS groups. Given the diversity of PFASs present in AFFFs, current analytical approaches do not comprehensively address the range of PFASs present in these systems. A suspect-screening and nontarget analysis (NTA) approach was developed and applied to identify novel PFASs in groundwater samples contaminated from historic AFFF use. A total of 88 PFASs were identified in both passive samplers and grab samples, and these were dominated by sulfonate derivatives and sulfonamide-derived precursors. Several ultrashort-chain (USC) PFASs (≤C3) were detected, 11 reported for the first time in Australian groundwater. Several transformation products were identified, including perfluoroalkane sulfonamides (FASAs) and perfluoroalkane sulfinates (PFASis). Two new PFASs were reported (((perfluorohexyl)sulfonyl)sulfamic acid; m/z477.9068 and (E)-1,1,2,2,3,3,4,5,6,7,8,8,8-tridecafluorooct-6-ene-1-sulfonic acid; m/z424.9482). This study highlights that several PFASs are overlooked using standard target analysis, and therefore, the potential risk from all PFASs present is likely to be underestimated.

The characteristics and techniques of champions, people who promote new ideas, were investigated by conducting in-depth interviews with 25 middle managers from Canadian organizations who had been involved with successful information technology innovations. The factors contributing to the success of champions included self confidence, persistence, high energy, the ability to motivate, many years of work experience, and work experience in many geographic regions. The techniques used by the champions included the rational process of obtaining top management's support of an idea before gaining the support of others, the participative process of gaining the support of employees before obtaining the approval of top management, and the renegade process of implementing ideas without obtaining organizational approval., Champions of Change: Identifying, Understanding, and Supporting Champions of Technological Innovations Top executives who support champions of innovation can help keep the organization competitive and creative. There is no shortage [...]

The widespread use of aqueous film-forming foam (AFFF) for firefighting activities (e.g., fire training to extinguish fuel-based fires at aircraft facilities) has led to extensive groundwater and soil contamination by per- and polyfluoroalkyl substances (PFASs) that are highly recalcitrant to destruction using conventional treatment technologies. This study reports on the hydrothermal alkaline treatment of diverse PFASs present in AFFFs. Quantitative and semiquantitative high-resolution mass spectrometry analyses of PFASs demonstrate a rapid degradation of all 109 PFASs identified in two AFFFs (sulfonate- and fluorotelomer-based formulations) in water amended with an alkali (e.g., 1–5 M NaOH) at near-critical temperature and pressure (350 °C, 16.5 MPa). This includes per- and polyfluoroalkyl acids and a range of acid precursors. Most PFASs were degraded to nondetectable levels within 15 min, and the most recalcitrant perfluoroalkyl sulfonates were degraded within 30 min when treated with 5 M NaOH. 19F NMR spectroscopic analysis and fluoride ion analysis confirm the near-complete defluorination of PFASs in both dilute and concentrated AFFF mixtures, and no stable volatile organofluorine species were detected in reactor headspace gases by the gas chromatography–mass spectrometry analysis. These findings indicate a significant potential for application of hydrothermal treatment technologies to manage PFAS waste streams, including on-site treatment of unused AFFF chemical stockpiles, investigation-derived wastes, and concentrated source zone materials.

Per and polyfluoroalkyl substances (PFASs) are an important class of organic pollutants. Many diverse PFASs are used in commerce and most are not amenable to conventional targeted chemical analysis due to lack of reference standards. Therefore, methods for elucidating the chemical structure of previously unreported or unexpected PFASs in the environment rely extensively on high-resolution mass spectrometry (HRMS). High-throughput structure identification by HRMS is hindered by a lack of PFAS molecular databases and tandem mass spectral libraries. Here, we report a new approach for generating an environmentally relevant PFAS molecular database constructed from curated structure lists and biotic/abiotic in silicopredicted transformation products. Further, we have generated a predicted tandem mass spectral library using computational mass spectrometry tools. Results demonstrate the utility of the generated database and approach for identifying PFASs in HRMS-enabled suspect- and nontarget screening studies.

Soil and groundwater from an aqueous film-forming foam (AFFF)-impacted site were sampled at high resolution (n= 105 for soil, n= 58 for groundwater) and analyzed for an extensive list of anionic, zwitterionic, and cationic poly- and perfluoroalkyl substances (PFASs). Spatial trends for perfluoroalkyl acids and many precursors enabled a better understanding of PFAS composition, transport, and transformation. All PFASs without analytical standards were semi-quantified. Summed PFAS and individual PFAS concentrations were often higher at depth than near the surface in soil and groundwater. Zwitterionic and cationic compounds composed a majority of the total PFAS mass (up to 97%) in firefighter training area (FTA) soil. Composition of PFAS class, chain length, and structural isomers changed with depth and distance from the FTA, suggesting in situ transformation and differential transport. The percentage of branched perfluorooctane sulfonate increased with depth, consistent with differential isomeric transport. However, linear perfluorooctanoic acid (PFOA) was enriched, suggesting fluorotelomer precursor transformation to linear PFOA. Perfluorohexane sulfonamide, a potential transformation product of sulfonamide-based PFASs, was present at high concentrations (maximum 448 ng/g in soil, 3.4 mg/L in groundwater). Precursor compounds may create long-term sources of perfluoroalkyl acids, although many pathways remain unknown; precursor analysis is critical for PFAS fate and transport understanding.

The aim of this study was to assess the soil–water partitioning behavior of a wider range of per- and polyfluoroalkyl substances (PFASs) onto soils covering diverse soil properties. The PFASs studied include perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs), fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides (FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids (GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil–water partitioning coefficients (log Kdvalues) of the PFASs ranged from less than zero to approximately three, were chain-length-dependent, and were significantly linearly related to molecular weight (MW) for PFASs with MW > 350 g/mol (R2= 0.94, p< 0.0001). Across all soils, the Kdvalues of all short-chain PFASs (≤5 −CF2– moieties) were similar and varied less (<0.5 log units) compared to long-chain PFASs (>0.5 to 1.5  log units) and zwitterions AmPr- and TAmPr-FHxSA (∼1.5 to 2 log units). Multiple soil properties described sorption of PFASs better than any single property. The effects of soil properties on sorption were different for anionic, nonionic, and zwitterionic PFASs. Solution pH could change both PFAS speciation and soil chemistry affecting surface complexation and electrostatic processes. The Kdvalues of all PFASs increased when solution pH decreased from approximately eight to three. Short-chain PFASs were less sensitive to solution pH than long-chain PFASs. The results indicate the complex interactions of PFASs with soil surfaces and the need to consider both PFAS type and soil properties to describe mobility in the environment.

Transport of poly- and perfluoroalkyl substances (PFAS) at aqueous film-forming foam (AFFF)-impacted sites is limited by various processes that can retain PFAS mass within the source area. This study used concentration data obtained via a high-resolution sampling and analytical protocol to estimate the PFAS mass distribution in source and downgradient areas of a former firefighter training area. The total PFAS mass present at the site was approximately 222 kg, with 106 kg as perfluoroalkyl acids (PFAAs) and 116 kg as polyfluorinated precursors. Zwitterionic and cationic PFAS represented 83% of the total precursor mass and were found primarily in the source and up/side-gradient areas (75%), likely due to preferential hydrophobic partitioning, electrostatic interactions, and diffusion into lower-permeability soils. Based on the release history and the high percentage of total PFAS mass represented by precursors (primarily electrochemical fluorination-derived compounds), the estimated conversion rate of precursors to PFAAs was less than 2% annually. Eighty-two percent of the total PFAS mass was encountered in lower-permeability soils, which limited the potential for advection and transformation. This contributed to a 99% decrease in the mass discharge rate at the far-downgradient plume (0.048 kg/yr compared to the near-source area (3.6 kg/yr)). The results provide field-scale evidence of the importance of these PFAS retention processes at sites where AFFF has been released.

Irrigation water or soil contaminated with per- and polyfluoroalkyl substances (PFASs) raises concerns among regulators tasked with protecting human health from potential PFAS-contaminated food crops, with several studies identifying crop uptake as an important exposure pathway. We estimated daily dietary exposure intake of individual PFASs in vegetables for children and adults using Monte Carlo simulation in a tiered stochastic modeling approach: exposures were the highest for young children (1–2 years > adults > 3–5 years > 6–11 years > 12–19 years). Using the lowest available human health toxicity reference values (RfDs) and no additional exposure, estimated fifth percentile risk-based threshold concentrations in irrigation water were 38 ng/L (median 180 ng/L) for perfluorooctanoate (PFOA) and 140 ng/L (median 850 ng/L) for perfluorooctane sulfonate (PFOS). Thus, consumption of vegetables irrigated with PFAS-impacted water that meets the current 70 ng/L of PFOA and PFOS U.S. Environmental Protection Agency’s lifetime health advisory for drinking water may or may not be protective of vegetable exposures to these contaminants. Hazard analyses using real-world PFAS-contaminated groundwater data for a hypothetical farm showed estimated exposures to most PFASs exceeding available or derived RfDs, indicating water-to-crop transfer is an important exposure pathway for communities with PFAS-impacted irrigation water.

Ultraviolet photochemical reaction of sulfite (SO32–) photosensitizer generates strongly reducing hydrated electrons (eaq–; NHE = −2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize eaq–reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via eaq–reactions with precursor structures in AFFF. These results indicate that while UV-sulfite treatment can be effective for treating PFOS and PFOA to meet health advisory levels, remediation of the wider range of PFASs in AFFF will prove more challenging.

Per- and polyfluoroalkyl substances (PFASs) are widespread in the blood of the general human population, and their bioaccumulation is of considerable scientific and regulatory interest. PFAS exposure resulting from aqueous film-forming foam (AFFF) ingestion is poorly understood due to the complexity of AFFF mixtures and the presence of polyfluorinated substances that may undergo metabolic transformation. C57BL/6 mice were dosed with an AFFF primarily containing electrochemically fluorinated PFASs for 10 days, followed by a 6 day depuration. Urine was collected throughout the study and serum was collected post-depuration. Samples were analyzed via high-resolution mass spectrometry. Relative to the dosing solution, C6 and C7 perfluoroalkyl sulfonates (PFSAs) were enriched in dosed mouse serum, suggesting in vivo transformation of sulfonamide precursors. Some substituted C8 PFSAs [keto-perfluorooctane sulfonate (PFOS), hydrogen-PFOS, and unsaturated PFOS] appeared to be more bioaccumulative than linear PFOS, or were formed in vivo from unidentified precursors. A series of seven peaks in dosed mouse serum was tentatively identified as sulfonimide dimers that were either a minor component of the AFFF or were formed via metabolism of other AFFF components. This work highlights the importance of sulfonamide precursors in contributing to bioaccumulation of AFFF-associated PFSAs and identifies several classes of potentially bioaccumulative novel PFASs that warrant further investigation.

Poly- and perfluoroalkyl substances (PFASs) derived from aqueous film-forming foam (AFFF) are increasingly recognized as groundwater contaminants, though the composition and distribution of AFFF-derived PFASs associated with soils and subsurface sediments remain largely unknown. This is particularly true for zwitterionic and cationic PFASs, which may be incompletely extracted from subsurface solids by analytical methods developed for anionic PFASs. Therefore, a method involving sequential basic and acidic methanol extractions was developed and evaluated for recovery of anionic, cationic, and zwitterionic PFASs from field-collected, AFFF-impacted soils. The method was validated by spike-recovery experiments with equilibrated soil-water-AFFF and analytical standards. To determine the relative importance of PFASs lacking commercially available analytical standards, their concentrations were estimated by a novel semiquantitation approach. Total PFAS concentrations determined by semiquantitation were compared with concentrations determined by the total oxidizable precursor assay. Finally, the described method was applied to two soil cores from former fire-training areas in which cations and zwitterions were found to contribute up to 97% of the total PFAS mass. This result demonstrates the need for extraction and analysis methods, such as the ones presented here, that are capable of quantifying cationic and zwitterionic PFASs in AFFF-impacted source zone soils.

Bench-scale experiments were performed to evaluate the electrochemical oxidation, viadirect anodic oxidation and indirect oxidation from salt-derived species, of diluted aqueous film forming foam (AFFF) in brine solutions to mimic anion exchange resin regenerant solutions that are loaded with poly- and perfluoroalkyl substances (PFASs). Results showed that initial transformations of the polyfluorinated compounds, which accounted for approximately 45% of the organic fluorine in the initial mixtures, occurred primarily viaan indirect oxidation pathway that targeted the non-fluorinated head groups. Depending on the brine solution, this indirect oxidation likely occurred viahydroxyl radical production or salt-derived oxidants (e.g., SO4−derived from anodic oxidation of sulfate). However, perfluoroalkyl acid (PFAA) transformation and the overall rate of defluorination were controlled viaa combination of direct and indirect electron transfer. Chloride levels (>0.2% by weight) and the presence of 100 mM of the radical scavenger tert-butyl alcohol substantially reduced pseudo first order defluorination rate constants by up to 80%. Evaluation of fluorine mass balances (viafluoride generation and PFAS levels) suggested that up to approximately 41% (based on a fluorine mass balance) electrochemically transformed intermediate products were not identified under some conditions. Thus, evaluating electrochemical treatment effectiveness solely on the disappearance of PFAAs and other suspect analytes described in current analytical libraries could substantially underestimate the PFAS mass remaining in AFFF-impacted waters.

Stormwater biofilters are being implemented widely in urban environments to provide green space, alleviate flooding, and improve stormwater quality. However, biofilters with conventional media (sand, soil, and/or mulch or compost) do not reliably remove contaminants from stormwater. Research suggests addition of biochar to the biofilter media can improve the pollutant removal capacity of biofilters. In the current work, we present a systematic review of laboratory and mesocosm studies of biochar-augmented biofilters and an assessment of watershed-scale implementation of biofilters on local water quality. A full text review of 84 papers was conducted; of these, data were extracted from the 14 that met our inclusion criteria. log10removal of microbial pollutants and trace organic contaminants (TOrCs) by biochar-augmented media is generally greater than those of the controls containing just sand, soil, and/or compost. log10removal of nitrogen, phosphorous, total organic carbon, and total suspended solids in biochar-augmented biofilters is not clearly higher than those of control experiments. A supplemental analysis of four studies reporting longer-term breakthrough data revealed that TOrC removal effectiveness varies substantially among high temperature wood-based biochars, and that operational lifetimes of full-scale systems constrained by TOrC sorption capacity could range from five months to over seven years depending on the selected biochar. At the watershed-scale, biochar-augmented biofilters can provide enhanced treatment of runoff, resulting in the need for fewer treatment units or a smaller volume of watershed runoff treated to meet water quality criteria compared to their conventional counterparts. While their installation can reduce the load of pollutants to receiving waters, achieving concentration-based water quality targets may prove difficult even when pollutant removal capacity is high. This work highlights the importance of a systems approach to studying how biofilter installation affects water quality within a watershed. We identify several topical areas where further research is needed, especially as installation of biofilters and other stormwater control measures gain popularity in highly urbanized watersheds.

Aqueous film-forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per- and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though hydrocarbon surfactants are more abundant (5–10% w/w) than PFASs (0.9–1.5% w/w) in AFFFs. Eight commercial AFFFs manufactured between 1988 and 2012 and 10 AFFF-contaminated groundwaters collected from near source zones of fire-fighter training areas were analyzed for suspect hydrocarbon surfactants by liquid chromatography quadrupole time-of-flight mass spectrometry. A suspect list and a homologous series detection computational tool, enviMass, were combined to screen for hydrocarbon surfactants. Nine classes of hydrocarbon surfactants were detected in AFFFs including octylphenol polyethoxylates, linear alcohol ethoxylates, ethoxylated cocoamines, alkyl ether sulfates, alkyl amido dipropionates, linear alkyl benzenesulfonates, alkyl sulfates, and polyethylene glycols. Of those, six were also found in groundwater along with diethanolamines and alkyl amido betaines, which were not found in the eight archived AFFFs. This indicates that although aerobically biodegradable, hydrocarbon surfactants likely persist in groundwater due to anaerobic aquifer conditions. To the best of our knowledge, this is the first screening for hydrocarbon surfactants in AFFFs and in AFFF-contaminated groundwater.