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1.
Environ Sci Technol ; 2024 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-39271478

RESUMO

Granular activated carbon (GAC) adsorption is frequently used to remove recalcitrant organic micropollutants (MPs) from water. The overarching aim of this research was to develop machine learning (ML) models to predict GAC performance from adsorbent, adsorbate, and background water matrix properties. For model calibration, MP breakthrough curves were compiled and analyzed to determine the bed volumes of water that can be treated until MP breakthrough reaches ten percent of the influent MP concentration (BV10). Over 400 data points were split into training, validation, and testing sets. Seventeen variables describing MP, background water matrix, and GAC properties were explored in ML models to predict log10-transformed BV10 values. Using the ML models on the testing set, predicted BV10 values exhibited mean absolute errors of ∼0.12 log units and were highly correlated with experimentally determined values (R2 ≥ 0.88). The top three drivers influencing BV10 predictions were the air-hexadecane partition coefficient and hydrogen bond acidity (Abraham parameters L and A) of the MPs and the dissolved organic carbon concentration of the GAC influent water. The model can be used to rapidly estimate the GAC bed life, select effective GAC products for a given treatment scenario, and explore the suitability of GAC treatment for remediating emerging MPs.

2.
Environ Sci Technol ; 2024 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-39319827

RESUMO

Per- and polyfluoroalkyl substances (PFAS) are known to be highly persistent in groundwater, making it vital to develop new approaches to important practical questions such as the time scale for future persistence of PFAS in contaminated groundwater. In the approach presented here, groundwater from beneath streambeds was analyzed for PFAS and age-dated using SF6 and 3H/3He. The results were coupled with groundwater flux measurements in a convolution approach to estimate past and future PFAS concentrations in groundwater discharge to the streams. At our test site near the Cape Fear River (CFR) of North Carolina, PFAS were detected in groundwater up to 43 years old, suggesting that some PFAS entered groundwater immediately or shortly after fluorochemical production began at the nearby Fayetteville Works. Results are consistent with little to no retardation in groundwater for perfluoroethers such as hexafluoropropylene oxide-dimer acid (HFPO-DA) and perfluoro-2-methoxypropanoic acid (PMPA), the two most abundant PFAS, with mean concentrations of 229 and 498 ng/L, respectively. Future PFAS concentrations in groundwater discharge to streams were estimated to remain above current MCL or health advisory levels through at least 2050 or 2060 (using 3H/3He and SF6, respectively). Recent atmospheric deposition data suggest lower but non-negligible amounts of PFAS may continue to enter groundwater, likely further extending PFAS persistence in groundwater and the adjacent CFR. This approach shows promise for giving an overall perspective on persistence of PFAS in groundwater discharge from a broad contaminated area.

3.
Environ Sci Technol ; 57(47): 18970-18980, 2023 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-37223990

RESUMO

Per- and polyfluoroalkyl substances (PFAS) are widely used anthropogenic chemicals. Because of the strength of the carbon-fluorine bond, PFAS are not destroyed in typical water treatment processes. Sulfate (SO4•-) and hydroxyl (•OH) radicals can oxidize some PFAS, but the behavior of per- and polyfluoroalkyl ether acids (PFEAs) in processes involving SO4•- and •OH is poorly understood. In this study, we determined second-order rate constants (k) describing the oxidation of 18 PFAS, including 15 novel PFEAs, by SO4•- and •OH. Among the studied PFAS, 6:2 fluorotelomer sulfonate reacted most readily with •OH [k•OH = (1.1-1.2) × 107 M-1 s-1], while polyfluoroalkyl ether acids containing an -O-CFH- moiety reacted more slowly [k•OH = (0.5-1.0) × 106 M-1 s-1]. In the presence of SO4•-, polyfluoroalkyl ether acids with an -O-CFH- moiety reacted more rapidly [kSO4•- = (0.89-4.6) × 106 M-1 s-1] than perfluoroalkyl ether carboxylic acids (PFECAs) and a chloro-perfluoro-polyether carboxylic acid (ClPFPECA) [kSO4•- = (0.85-9.5) × 104 M-1 s-1]. For homologous series of perfluoroalkyl carboxylic acids, linear and branched monoether PFECAs, and multiether PFECAs, PFAS chain length had little impact on second-order rate constants. SO4•- reacted with the carboxylic acid headgroup of perfluoroalkyl carboxylic acids and PFECAs. In contrast, for polyfluoroalkyl ether carboxylic and sulfonic acids with an -O-CFH- moiety, the site of SO4•- attack was the -O-CFH- moiety. Perfluoroalkyl ether sulfonic acids were not oxidized by SO4•- and •OH under the conditions evaluated in this study.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Éter , Radical Hidroxila , Sulfatos , Fluorocarbonos/análise , Éteres , Ácidos Sulfônicos , Ácidos Carboxílicos , Poluentes Químicos da Água/análise
4.
Environ Sci Technol ; 57(13): 5203-5215, 2023 04 04.
Artigo em Inglês | MEDLINE | ID: mdl-36962006

RESUMO

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 Kia data for compounds exhibiting evidence of rate-limited partitioning. Experimental results suggest a Freundlich isotherm best describes PFAS air-water partitioning at environmentally relevant concentrations (101-106 ng/L). A multiparameter regression analysis for Kia prediction was performed for the 15 PFASs for which equilibrium Kia values 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 (R2 values of 0.92 and 0.83) were developed using an assumed average Freundlich n value 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.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Água , Fluorocarbonos/análise , Éteres , Poluentes Químicos da Água/análise , Concentração Osmolar
5.
Environ Sci Technol ; 57(41): 15348-15355, 2023 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-37801709

RESUMO

To estimate half-lives for novel fluoroethers, the GenX Exposure Study obtained two serum measurements for per- and polyfluoroalkyl substances (PFAS) for 44 participants of age 12-86 years from North Carolina, collected 5 and 11 months after fluoroether discharges into the drinking water source were controlled. The estimated half-lives for these compounds were 127 days (95% confidence interval (95% CI) = 86, 243 days) for perfluorotetraoxadecanoic acid (PFO4DA), 296 days for Nafion byproduct 2 (95% CI = 176, 924 days), and 379 days (95% CI = 199, 3870 days) for perfluoro-3,5,7,9,11-pentaoxadodecanoic acid (PFO5DoA). Using these estimates and the literature values, a model was built that predicted PFAS half-lives using structural properties. Three chemical properties predicted 55% of the variance of PFAS half-lives based on 15 PFAS. A model with only molecular weight predicted 69% of the variance. Some properties can predict the half-lives of PFAS, but a deeper understanding is needed. These fluoroethers had biological half-lives longer than published half-lives for PFHxA and PFHpA (30-60 days) but shorter than those for PFOA and PFOS (800-1200 days). These are the first and possibly only estimates of human elimination half-lives of these fluoroethers.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Humanos , Criança , Adolescente , Adulto Jovem , Adulto , Pessoa de Meia-Idade , Idoso , Idoso de 80 Anos ou mais , Éteres , Poluentes Químicos da Água/análise , Caprilatos , Fluorocarbonos/análise
6.
Environ Sci Technol ; 57(48): 20159-20168, 2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-37934924

RESUMO

Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.


Assuntos
Anguilla , Fluorocarbonos , Água Subterrânea , Poluentes Químicos da Água , Animais , Fluorocarbonos/análise , Água Subterrânea/química , Água , Flúor/análise , Flúor/química , Poluentes Químicos da Água/análise
7.
Environ Res ; 237(Pt 2): 117020, 2023 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-37673120

RESUMO

In 2017, people living in New Hanover County, North Carolina, learned that for ∼40 years they were unknowingly exposed to per- and polyfluoroalkyl substances (PFAS) through drinking water sourced by the Cape Fear River. Using data from the GenX Exposure Study, which measured serum PFAS levels in county residents, we aimed to understand questionnaire-measured factors associated with serum PFAS levels. Because most residents were served by the same municipal water source, we focused on surrogate factors of drinking water exposure that may contribute to variability in PFAS levels. Our analysis included 335 participants aged 6 and older. We included seven chemicals detected in ≥75% of the study population: four well-studied perfluoroalkyl acids (PFOA, PFOS, PFNA, PFHxS) and three understudied fluoroethers (Nafion byproduct 2, PFO4DA, PFO5DoA). For each PFAS, we evaluated associations of variables with serum PFAS levels adjusting for key demographic characteristics. Additionally, we developed predictive models for each PFAS. We used years of residence in the lower Cape Fear Region as a surrogate for water consumption. Duration of drinking water exposure was associated with higher serum levels of all seven PFAS. Drinking municipal water treated by home filters or other sources of water (non-city) were associated with lower PFAS concentrations for all seven PFAS compared to drinking municipal water without additional filtration. Males had higher levels of well-studied PFAS, but there was no difference for fluoroethers. For six PFAS, the predictive models explained ≥30% of the variance in serum PFAS levels. While some factors were significantly associated with levels of individual PFAS, their relative importance to overall prediction was low, such as microwave popcorn consumption. Consistently, water consumption-related variables were important for both the association and predictive investigations. These analyses provide additional evidence that drinking water is a primary source for serum PFAS concentrations among New Hanover County residents.


Assuntos
Ácidos Alcanossulfônicos , Água Potável , Poluentes Ambientais , Fluorocarbonos , Poluentes Químicos da Água , Masculino , Humanos , Água Potável/química , North Carolina , Poluentes Químicos da Água/análise , Ácidos Alcanossulfônicos/análise , Poluentes Ambientais/análise
8.
Environ Sci Technol ; 56(22): 15470-15477, 2022 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-36265138

RESUMO

Anion-exchange (AE) sorbents are gaining in popularity for the remediation of anionic per- and polyfluoroalkyl substances (PFAS) in water. However, it is unclear how hydrophobic and electrostatic interactions contribute to anionic PFAS retention. The goal of this study was to understand the effects of PFAS chain length and head group on electrostatic interactions between PFAS and an aminopropyl AE phase. Liquid chromatography-mass spectrometry (LC-MS) was used with an aminopropyl AE guard column to find relative retention times. The average electrostatic potential (EPavg) of each PFAS was calculated, which correlated positively with the PFAS chromatographic retention time, demonstrating the value of EPavg as a proxy for predicting electrostatic interactions between PFAS and the aminopropyl AE phase. The order of greatest to lowest PFAS AE affinity for an aminopropyl column based on chromatographic retention times and electrostatic interactions was n:3 fluorotelomer carboxylic acids (n:3 FtAs) > n:2 fluorotelomer carboxylic acids (n:2 FtAs) > perfluoroalkyl carboxylates (PFCAs) > perfluoroalkyl sulfonamides (FASAs) ∼ n:2 fluorotelomer sulfonates (n:2 FtSs) > perfluoroalkyl sulfonates (PFSAs). This study introduces a methodology for qualitatively characterizing electrostatic interactions between PFAS and AE phases and highlights that electrostatic interactions alone cannot explain the affinity of PFAS for AE resins in water treatment/remediation scenarios.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Purificação da Água , Fluorocarbonos/análise , Poluentes Químicos da Água/análise , Ácidos Carboxílicos/análise , Ânions
9.
Environ Sci Technol ; 56(10): 6103-6112, 2022 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-34734715

RESUMO

Per- and polyfluoroalkyl substances (PFASs) are widely used anthropogenic chemicals. For environmental and toxicological analysis, it is important to understand the stability of PFASs, including novel per- and polyfluoroalkyl ether acids (PFEAs), in commonly used solvents. In this study, we investigated the effects of PFAS characteristics, solvent type, water-to-organic solvent ratio, and temperature on the stability of 21 PFASs including 18 PFEAs. None of the studied PFASs showed measurable degradation in deionized water, methanol, or isopropyl alcohol over 30 days; however, nine PFEAs degraded in the polar aprotic solvents acetonitrile, acetone, and dimethyl sulfoxide (DMSO). PFEA degradation followed first-order kinetics, and first-order rate constants increased with increasing temperature and with decreasing water-to-organic solvent ratio. Monoethers with a carboxylic acid functional group adjacent to a tertiary carbon (>CF-COOH) degraded more rapidly than multiethers in which the carboxylic acid moiety was adjacent to repeating -CF2O- groups. In contrast, monoethers with a carboxylic acid moiety adjacent to a secondary carbon (-CF2-COOH) were stable in all tested solvents. Using high-resolution mass spectrometry, we determined that PFEAs with a >CF-COOH group were stoichiometrically decarboxylated in aprotic solvents and formed products with a >CFH group; e.g., hexafluoropropylene oxide-dimer acid (HFPO-DA or GenX), HFPO-trimer acid, and HFPO-tetramer acid were stoichiometrically converted to Fluoroethers E-1, E-2, and E-3, respectively. PFEA degradation results highlight the importance of solvent choice when preparing dosing solutions and performing extractions for environmental and toxicological assessments of PFEAs.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Carbono , Ácidos Carboxílicos , Éter , Éteres , Fluorocarbonos/análise , Solventes , Água , Poluentes Químicos da Água/análise
10.
Environ Sci Technol ; 55(9): 5848-5856, 2021 05 04.
Artigo em Inglês | MEDLINE | ID: mdl-33797238

RESUMO

We quantified per- and polyfluoroalkyl substance (PFAS) transport from groundwater to five tributaries of the Cape Fear River near a PFAS manufacturing facility in North Carolina (USA). Hydrologic and PFAS data were coupled to quantify PFAS fluxes from groundwater to the tributaries. Up to 29 PFAS were analyzed, including perfluoroalkyl acids and recently identified fluoroethers. Total quantified PFAS (ΣPFAS) in groundwater was 20-4773 ng/L (mean = 1863 ng/L); the range for stream water was 426-3617 ng/L (mean = 1717 ng/L). Eight PFAS constituted 98% of ΣPFAS; perfluoro-2-(perfluoromethoxy)propanoic acid (PMPA) and hexafluoropropylene oxide dimer acid (GenX) accounted for 61%. For PFAS discharge from groundwater to one tributary, values estimated from stream water measurements (18 ± 4 kg/yr) were similar to those from groundwater measurements in streambeds (22-25 ± 5 kg/yr). At baseflow, 32 ± 7 kg/yr of PFAS discharged from groundwater to the five tributaries, eventually reaching the Cape Fear River. Given the PFAS emission timeline at the site, groundwater data suggest the abundant fluoroethers moved through the subsurface to streams in ≪50 yr. Discharge of contaminated groundwater may lead to long-term contamination of surface water and impacts on downstream drinking water supplies. This work addresses a gap in the PFAS literature: quantifying PFAS mass transfer between groundwater and surface water using field data.


Assuntos
Fluorocarbonos , Água Subterrânea , Poluentes Químicos da Água , Fluorocarbonos/análise , Instalações Industriais e de Manufatura , North Carolina , Poluentes Químicos da Água/análise
11.
Environ Eng Sci ; 38(5): 298-309, 2021 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-34079203

RESUMO

Biochar adsorbent can be produced in low-resource settings using local materials and simple pyrolysis technology, and it has shown promise for uptake of micropollutants (MPs) such as pesticides, pharmaceuticals, industrial compounds, and chemicals released from consumer goods present in water at ng/L to µg/L levels. Accordingly, the use of biochar in water treatment applications where granular activated carbon (GAC) is economically or logistically infeasible is gaining interest. Monitoring treatment systems for individual MPs require laboratory analytical techniques that are typically cost-prohibitive and impractical for low-resource settings. Therefore, identification of surrogate parameters(s) for adsorbent bed life that can be measured inexpensively and in the field is a high priority. Background dissolved organic matter (DOM) is ubiquitous in natural and anthropogenic waters at concentrations typically 1,000 to 100,000 that of MPs. Some constituents of DOM foul the adsorbent and reduce bed life for removal of target contaminants. Aromatic DOM foulants absorb ultraviolet light at a wavelength of 254 nm (UVA254). Because DOM fouling directly affects MP adsorption capacity and DOM is a bulk water parameter that can be quantified using relatively inexpensive and portable instruments, it could be exploited as a surrogate for monitoring biochar adsorber bed life under field conditions. The objective of this study was to quantify removal of MPs from waters containing different types and concentrations of background DOM (surface water, wastewater, dump leachate) and thus exhibiting different UVA254 breakthrough profiles in bench-scale column experiments. Breakthrough profiles of weakly to moderately adsorbing MPs, including herbicides, pharmaceuticals and personal care products, and perfluoroalkyl acids, were collected using biochars generated under different pyrolysis conditions and a commercial GAC as a performance benchmark. Optimal conditions for biochar water treatment include using biochar produced from wood at ≥850°C under slightly aerobic conditions, empty bed contact times of ≥30 min, and upstream treatment processes to reduce DOM. Relative UVA254 breakthrough (C/C 0) up to 0.6-0.9 corresponded to ≥90% MP removal for most MP-water combinations studied.

12.
Anal Chem ; 92(6): 4427-4435, 2020 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-32011866

RESUMO

Per- and polyfluoroalkyl substances (PFAS) are an ensemble of persistent organic pollutants of global interest because of their associations with adverse health outcomes. Currently, environmental PFAS pollution is prolific as a result of the widespread manufacturing of these compounds and their chemical persistence. In this work, we demonstrate the advantages of adding ion mobility spectrometry (IMS) separation to existing LC-MS workflows for PFAS analysis. Using a commercially available drift tube IMS-MS, we characterized PFAS species and isomeric content in both analytical standards and environmental water samples. Molecular trendlines based on intrinsic mass and structural relationships were also explored for individual PFAS subclasses (e.g. PFSA, PFCA, etc.). Results from rapid IMS-MS analyses provided a link between mass and collision cross sections (CCS) for specific PFAS families and are linked to compositional differences in molecular structure. In addition, CCS values provide additional confidence of annotating prioritized features in untargeted screening studies for potential environmental pollutants. Results from this study show that the IMS separation provides novel information to support traditional LC-MS PFAS analyses and will greatly benefit the evaluation of unknown pollutants in future environmental studies.


Assuntos
Hidrocarbonetos Fluorados/análise , Polímeros/análise , Espectrometria de Mobilidade Iônica , Espectrometria de Massas , Estrutura Molecular
13.
Environ Sci Technol ; 53(10): 5987-5999, 2019 05 21.
Artigo em Inglês | MEDLINE | ID: mdl-31038939

RESUMO

Granular activated carbon (GAC) adsorption is well-established for controlling regulated disinfection byproducts (DBPs), but its effectiveness for unregulated DBPs and DBP-associated toxicity is unclear. In this study, GAC treatment was evaluated at three full-scale chlorination drinking water treatment plants over different GAC service lives for controlling 61 unregulated DBPs, 9 regulated DBPs, and speciated total organic halogen (total organic chlorine, bromine, and iodine). The plants represented a range of impacts, including algal, agricultural, and industrial wastewater. This study represents the most extensive full-scale study of its kind and seeks to address the question of whether GAC can make drinking water safer from a DBP perspective. Overall, GAC was effective for removing DBP precursors and reducing DBP formation and total organic halogen, even after >22 000 bed volumes of treated water. GAC also effectively removed preformed DBPs at plants using prechlorination, including highly toxic iodoacetic acids and haloacetonitriles. However, 7 DBPs (mostly brominated and nitrogenous) increased in formation after GAC treatment. In one plant, an increase in tribromonitromethane had significant impacts on calculated cytotoxicity, which only had 7-17% reduction following GAC. While these DBPs are highly toxic, the total calculated cytotoxicity and genotoxicity for the GAC treated waters for the other two plants was reduced 32-83% (across young-middle-old GAC). Overall, calculated toxicity was reduced post-GAC, with preoxidation allowing further reductions.


Assuntos
Desinfetantes , Água Potável , Poluentes Químicos da Água , Purificação da Água , Desinfecção , Halogenação , Halogênios
17.
Environ Sci Technol ; 50(5): 2246-54, 2016 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-26829406

RESUMO

Recent U.S. Environmental Protection Agency data show that 1,4-dioxane is frequently detected in U.S. drinking water derived from both groundwater and surface water. 1,4-Dioxane is a likely human carcinogen, and an excess 10(-6) cancer risk is associated with a drinking water concentration of 0.35 µg/L. To support 1,4-dioxane occurrence investigations, source identification and exposure assessment, a rapid and sensitive analytical method capable of quantifying 1,4-dioxane over a wide concentration range in a broad spectrum of aqueous matrices was developed. The fully automated method is based on heated purge-and-trap preconcentration and gas chromatography/mass spectrometry with selected-ion storage and has a reporting limit of 0.15 µg/L. Quantification of 1,4-dioxane was accomplished by isotope dilution using mass-labeled 1,4-dioxane-d8 as internal standard. Matrix spikes yielded recoveries of 86-115% in drinking water, groundwater, surface water, and wastewater treatment plant (WWTP) effluent. Also, 1,3-dioxane can be distinguished from 1,4-dioxane. The method was applied to investigate 1,4-dioxane occurrence and sources in the Cape Fear River watershed of North Carolina. 1,4-Dioxane concentrations ranged from <0.15 µg/L in nonimpacted surface water to 436 µg/L downstream of a WWTP discharge. In WWTP effluent, 1,4-dioxane concentrations varied widely, with a range of 1.3-2.7 µg/L in one community and 105-1,405 µg/L in another. Discharges from three municipal WWTPs were primarily responsible for elevated 1,4-dioxane concentrations in the Cape Fear River watershed.


Assuntos
Dioxanos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Poluentes Químicos da Água/análise , Fosfatase Ácida , Monitoramento Ambiental/métodos , Água Subterrânea/análise , Temperatura Alta , Humanos , Isoenzimas , North Carolina , Rios/química , Fosfatase Ácida Resistente a Tartarato , Eliminação de Resíduos Líquidos , Águas Residuárias/química
18.
Environ Sci Technol ; 50(20): 11253-11262, 2016 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-27656757

RESUMO

Micropollutants in wastewater present environmental and human health challenges. Powdered activated carbon (PAC) can effectively remove organic micropollutants, but PAC production is energy intensive and expensive. Biochar adsorbents can cost less and sequester carbon; however, net benefits depend on biochar production conditions and treatment capabilities. Here, life cycle assessment was used to compare 10 environmental impacts from the production and use of wood biochar, biosolids biochar, and coal-derived PAC to remove sulfamethoxazole from wastewater. Moderate capacity wood biochar had environmental benefits in four categories (smog, global warming, respiratory effects, noncarcinogenics) linked to energy recovery and carbon sequestration, and environmental impacts worse than PAC in two categories (eutrophication, carcinogenics). Low capacity wood biochar had even larger benefits for global warming, respiratory effects, and noncarcinogenics, but exhibited worse impacts than PAC in five categories due to larger biochar dose requirements to reach the treatment objective. Biosolids biochar had the worst relative environmental performance due to energy use for biosolids drying and the need for supplemental adsorbent. Overall, moderate capacity wood biochar is an environmentally superior alternative to coal-based PAC for micropollutant removal from wastewater, and its use can offset a wastewater facility's carbon footprint.

19.
Water Res ; 249: 120956, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38103444

RESUMO

Anion exchange (IX) is a readily implementable water treatment method that can effectively remove per- and polyfluoroalkyl substances (PFAS). The overarching objective of this research was to predict PFAS removal in full- or pilot-scale packed-bed IX resin contactors from rapid small-scale column test (RSSCT) data. Specific objectives were to (1) assess the effects of IX resin crushing on total anion exchange capacity and packed bed density, (2) determine the effects of initial PFAS concentration on PFAS uptake capacity, (3) determine the rate-limiting step controlling PFAS uptake kinetics, (4) determine the effects of hydraulic loading rate on PFAS uptake capacity, and (5) link constant diffusivity RSSCT data to pilot test data to develop a scale-up protocol. Experiments were conducted with two single-use IX resins and three water matrices, including coagulated surface water and groundwater. Crushing IX resin did not substantially change the bed density and total anion exchange capacity, but the morphology of particles changed from almost perfectly spherical to irregularly shaped. PFAS uptake capacity was independent of influent PFAS concentrations in the 30-300 ng/L range. This finding facilitated the development of an RSSCT scale-up approach because influent PFAS concentrations in RSSCTs and corresponding pilot tests often differ. Biot number values and data from interrupted RSSCTs demonstrated that film diffusion or a combination of film diffusion and intraparticle diffusion controls the rate of PFAS uptake by IX resins. From RSSCTs with identical empty bed contact times but different hydraulic loading rates (vf), PFAS uptake capacity was found to be a function of the square root of the product of Sherwood number and particle shape factor (Sh×ϕ). Using a constant diffusivity RSSCT design with a reduced vf, full- or pilot-scale PFAS breakthrough data can therefore be predicted by multiplying the bed volumes of water treated in the RSSCT by a factor of (Shpilot×ϕpilot)/(ShRSSCT×ϕRSSCT) . This research will support the design of future IX treatment processes in the context of PFAS remediation and drinking water treatment.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Resinas de Troca Aniônica , Poluentes Químicos da Água/análise , Adsorção , Ânions
20.
Water Environ Res ; 96(8): e11091, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39072849

RESUMO

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are widespread groundwater contaminants and are present in over 7000 drinking water wells near a North Carolina (NC) PFAS plant (Chemours). To understand options available to affected residents, we used new and previously existing water quality data to investigate deeper aquifers as alternate drinking water supplies and compared the regulatory responses near Chemours and three other PFAS production facilities with nearby contaminated wells. Data from >100 wells show that GenX concentrations decrease with increasing depth through the four aquifers in the study area: surficial, Black Creek, Upper Cape Fear, and bedrock. This illustrates the extent of vertical PFAS penetration through the aquifer sequence following roughly 40 years of atmospheric emissions. Detailed data on 143 water quality parameters in nine deep wells (two Upper Cape Fear, seven bedrock) revealed only eight exceedances of drinking water standards (one each for arsenic, perfluorooctanoic acid [PFOA], iron, chloride, and gross alpha, and three for manganese) and nine exceedances of health advisories (all for sodium). Regulatory responses to PFAS contamination of wells in four states included mention of deeper wells as an alternate water source only for nonresidential users in NC and residential users in Vermont. The bedrock aquifer is currently used by some residents and may be a viable alternative to shallower groundwater, though arsenic treatment may be beneficial at some deep wells and long-term sustainability of the aquifer should be evaluated. PRACTITIONER POINTS: GenX concentrations decreased with increasing depth in four aquifers near a PFAS plant. A few exceedances of drinking water standards and health advisories were found in deep bedrock wells. New bedrock wells could be part of the response to PFAS issues in shallower wells. In the long term, deep bedrock wells might be a less expensive option for some residents.


Assuntos
Água Potável , Fluorocarbonos , Poluentes Químicos da Água , Poços de Água , North Carolina , Fluorocarbonos/análise , Poluentes Químicos da Água/análise , Água Potável/química , Monitoramento Ambiental , Qualidade da Água , Água Subterrânea/química
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