Vesicles exhibit high-performance removal of per-and polyfluoroalkyl substances (PFAS) depending on their hydrophobic groups.

The removal of per- and polyfluoroalkyl substances (PFAS) from drinking water is urgently needed. Here, we demonstrated high performance of vesicles on PFAS adsorption. Vesicles used in this study were enclosed amphiphile bilayers keeping their hydrophobic groups inside and their hydrophilic groups outside in water. The distribution coefficient Kd of perfluorooctane sulfonic acid (PFOS) for vesicles was 5.3 × 105 L/kg, which is higher than that for granulated activated carbon (GAC), and Kd of perfluorooctanoic acid (PFOA) for vesicles was 103-104 L/kg. The removal efficiencies of PFOA and PFOS adsorption on DMPC vesicles were 97.1 ± 0.1% and 99.4 ± 0.2%, respectively. The adsorption behaviors of PFOA and PFOS on vesicles were investigated by changing the number of cis-double bonds in the hydrophobic chains of the vesicle constituents. Moreover, vesicles formed by membranes in the different phases were also tested. The results revealed that, when vesicles are formed of a membrane in the liquid-crystalline (liquid-like) phase, the adsorption amounts of both PFOA and PFOS increased as the cis-double bond in the hydrocarbon chains decreased, which is considered due to molecular shape similarity. When vesicles are formed of a membrane in the gel (solid-like) phase, they do not adsorb PFAS as much as in the liquid-crystalline phase, even though the hydrocarbon chains do not have any cis-double bond. Our findings demonstrate that vesicles can be utilized as PFAS adsorbents by optimizing the structure of vesicle constituents and their thermodynamical phase. Indeed, the vesicles (DMPC) were demonstrated that they can adsorb PFOA and PFOS, and be coagulated by a coagulant even in environmental water. The coagulation will enable the removal of PFOA and PFOS from the water after adsorption.

Molecularly imprinted resin modified with ionic liquid for dispersive filter extraction and determination of perfluoroalkyl acids in eggs.

Perfluoroalkyl acids (PFAAs) are emerging pollutants that endangers food safety. Developing methods for the selective determination of trace PFAAs in complex samples remains challenging. Herein, an ionic liquid modified porous imprinted phenolic resin-dispersive filter extraction-liquid chromatography-tandem mass spectrometry (IL-PIPR-DFE-LC-MS/MS) method was developed for the determination of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in eggs. The new IL-PIPR adsorbent was prepared at room temperature, which avoids the disorder and instability of the template at high temperatures. The imprinting factor of IL-PIPR for PFOA and PFOS exceeded 7.3. DFE, combined with IL-PIPR (15 mg), was used to extract PFOA and PFOS from eggs within 15 min. The established method exhibits low limits of detection (0.01-0.02 ng/g) and high recoveries (84.7%-104.7%), which surpass those of previously reported methods. This work offers a new approach to explore advanced imprinted adsorbents for PFAAs, efficient sample pretreatment technique, and analytical method for pollutants in foods.

Synthesis of magnetic chitosan biopolymeric spheres and their adsorption performances for PFOA and PFOS from aqueous environment.

Due to numerous applications and excellent environmental stability, long-chain perfluorinated chemicals (PFCs) are ubiquitous in water across the world and adversely affect the living organisms. Thus, this study focused on the mitigation of the most frequently used long-chain PFCs namely perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) from water using reduced graphene oxide modified zinc ferrite immobilized chitosan beads (rGO-ZF@CB) as an adsorbent. The results from the adsorption isotherm and kinetic studies revealed that the adsorption data fitted well to the Langmuir and the pseudo-second-order models. According to the Langmuir isotherm, the rGO-ZF@CB possessed the maximum adsorption capacity of 16.07 mg/g for PFOA and 21.64 mg/g for PFOS. Both the electrostatic attractions and hydrophobic interactions have driven the removal of PFOA and PFOS by prepared rGO-ZF@CB. Eventually, the rGO-ZF@CB could be considered as an efficient adsorbent for the effective removal of PFOA and PFOS molecules from the aqueous environment.

PFAS Degradation in Ultrapure and Groundwater Using Non-Thermal Plasma.

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and pefluorooctanesulfonic acid (PFOS) using a custom-built non-thermal plasma generator. A modified full factorial design (with 2 levels, 3 variables and the central point in which both quadratic terms and interactions between couple of variables were considered) was used to investigate the effect of plasma discharge frequency, distance between the electrodes and water conductivity on treatment efficiency. Then, the plasma treatment running on optimized conditions was used to degrade PFAS at ppb level both individually and in mixture, in ultrapure and groundwater matrices. PFOS 1 ppb exhibited the best degradation reaching complete removal after 30 min of treatment in both water matrices (first order rate constant 0.107 min-1 in ultrapure water and 0.0633 min-1 in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 83%, respectively. During plasma treatment, the production of reactive species in the liquid phase (hydroxyl radical, hydrogen peroxide) and in the gas phase (ozone, NOx) was investigated. Particular attention was dedicated to the nitrogen balance in solution where, following to NOx hydrolysis, total nitrogen (TN) was accumulated at the rate of up to 40 mgN L-1 h-1.

Separation and determination of alkyl sulfate surfactants in wastewater by capillary electrophoresis coupled with contactless conductivity detection after preconcentration by simultaneous adsorption using alumina beads.

The aim of the present study is to determine four anionic alkyl sulfate (AS) surfactants with different alkyl chains, namely, C8, C10, C12, and C14, in wastewater by CE with capacitively coupled contactless conductivity detection (CE-C4 D). The conditions effective for the separation of the four AS surfactants were systematically optimized and found to be in a Tris-His (50 mM/20 mM) BGE solution at a pH of 8.95, using a separation voltage of +15 kV, hydrodynamic injection by siphoning using a 20 cm injection height and an injection time of 20 s. The LODs for C8, C10, C12, and C14 were 2.58, 2.30, 2.08, and 3.16 mg/L, respectively. The conditions used to achieve the simultaneous adsorption and preconcentration of the AS surfactants using Al2 O3 beads were pH of 3 and 0.1 mM NaCl. The adsorption efficiencies were found to be 45.6, 50.8, 81.7, and 99.9%, while the desorption efficiencies reached 66.1, 70.4, 83.9, and 100.0% for C8, C10, C12, and C14, respectively. The concentrations of the AS surfactants in wastewater samples were quantified by CE-C4 D after preconcentration by simultaneous adsorption using Al2 O3 beads. The results obtained from the proposed method were consistent with those obtained by HPLC-MS/MS, with a deviation of less than 15%. Our results indicate that the CE-C4 D performed after preconcentration by an adsorption technique using Al2 O3 beads is a new, inexpensive, and suitable method for quantifying AS surfactants in wastewater samples.

Biochar sorption of PFOS, PFOA, PFHxS and PFHxA in two soils with contrasting texture.

The ability to immobilise PFAS in soil may be an essential interim tool while technologies are developed for effective long-term treatment of PFAS contaminated soils. Serial sorption experiments were undertaken using a pine derived biochar produced at 750 °C (P750). All experiments were carried out either in individual mode (solution with one PFAS at 5 µg/L) or mix mode (solution with 5 µg/L of each: PFOS, PFOA, PFHxS and PFHxA), and carried out in 2:1 water to soil solutions. Soils had biochar added in the range 0-5% w/w. Kinetic data were fitted to the pseudo-second order model for both amended soils, with equilibrium times ranging 0.5-96 h for all congeners. PFOS sorption was 11.1 ± 4.5% in the loamy sand compared to 69.8 ± 4.9% in the sandy clay loam. While total sorption was higher in the unamended loamy sand than sandy clay loam for PFHxA, PFOA and PFOS, the effect of biochar amendment for each compound was found to be significantly higher in amended sandy clay loam than in amended loamy sand. Application of biochar reduced the desorbed PFAS fraction of all soils. Soil type and experimental mode played a significant role in influencing desorption. Overall, the relationship between sorbent and congener was demonstrated to be highly impacted by soil type, however the unique physiochemical properties of each PFAS congener greatly influenced its unique equilibrium, sorption and desorption behaviour for each amended soil and mode tested.

Diatom-assisted biomicroreactor targeting the complete removal of perfluorinated compounds.

Persistent perfluorinated compounds (PFCs) have been recognized as a global environmental issue. Developing methods without leading to additional burden in nature will be essential for PFCs removal. Herein, we functionalized iron nanoparticles on living diatom (Dt) to efficiently enable the Fenton reaction and reactive oxygen species (ROS) production. Iron nanoparticles at the surface of living diatom act as promising catalytic agents to trigger OH radical generation from H2O2. Dt plays dual roles: i) as solid support for effective adsorption, and ii) it supplies oxygen and inherently produces ROS under stress conditions, which improves removal efficiency of PFCs. We also demonstrated its reusability by simple magnetic separation and 85% of decomposition efficiency could still be achieved. This newly developed diatom-assisted bioremediation strategy enables green and efficient PFC decomposition and shall be readily applicable to other persistent pollutants.

Guanidinocalix[5]arene for sensitive fluorescence detection and magnetic removal of perfluorinated pollutants.

Perfluorinated alkyl substances, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are toxic materials that are known to globally contaminate water, air, and soil resources. Strategies for the simultaneous detection and removal of these compounds are desired to address this emerging health and environmental issue. Herein, we develop a type of guanidinocalix[5]arene that can selectively and strongly bind to PFOS and PFOA, which we use to demonstrate the sensitive and quantitative detection of these compounds in contaminated water through a fluorescent indicator displacement assay. Moreover, by co-assembling iron oxide nanoparticle with the amphiphilic guanidinocalix[5]arene, we are able to use simple magnetic absorption and filtration to efficiently remove PFOS and PFOA from contaminated water. This supramolecular approach that uses both molecular recognition and self-assembly of macrocyclic amphiphiles is promising for the detection and remediation of water pollution.

Bubble-Nucleation-Based Method for the Selective and Sensitive Electrochemical Detection of Surfactants.

We present the first bubble-nucleation-based electrochemical method for the selective and sensitive detection of surfactants. Our method takes advantage of the high surface activity of surfactant analyte to affect the electrochemical bubble nucleation and then transduces the change in nucleation condition to electrochemical signal for determining the surfactant concentration. Using this method, we demonstrate the quantitation of perfluorinated surfactants in water, a group of emerging environmental contaminants, with a remarkable limit of detection (LOD) down to 30 µg/L and a linear dynamic range of over 3 orders of magnitude. With the addition of a preconcentration step, we have achieved the LOD: 70 ng/L, the health advisory for perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) in drinking water established by the U.S. Environmental Protection Agency. The experimental results are in quantitative agreement with our theoretical model derived from classical nucleation theory. Our method also exhibits an exceptional specificity for the surfactant analytes even in the presence of 1000-fold excess of nonsurfactant interference. This method has the potential to be further developed into a universal electrochemical detector for surfactant analysis because of its simplicity and the surface-activity-based detection mechanism.

Combined UMBAF-MBAF process treating detergent wastewater.

A combined process of the upflow multimedium biological aerated filter (UMBAF) and the multimedia biological aerated filter (MBAF) treating detergent wastewater was investigated in this study. Results showed that the optimal filtration rate of the combined system was 1.4 m/hr while the optimized performance was observed at air to water ratio of 2:1. The average removal rate of chemical oxygen demand (COD), linear alkyl benzene sulfonate sodium (LAS), and total phosphate (TP) was up to 91.4%, 88.5%, and 40%, respectively, while the average effluent concentrations of COD, LAS, and TP under stable operation states were 35.0 mg/L, 7.0 mg/L, and 4.4 mg/L, respectively. UMBAF played a major role in TP removal; the removal of COD in the combined UMBAF and MBAF process was consistent with the general formula C = C0 e -(ah + b) , while the kinetic model of LAS removal in the combined UMBAF and MBAF process could be expressed by L = L0 e-(mh + n) . The combined UMBAF-MBAF process provides a promising technology for the treatment of detergent wastewater. The kinetic model of LAS removal in the UMBAF and MBAF units is helpful for the prediction of the treatment efficiency of organic pollutants. PRACTITIONER POINTS: A novel UMBAF-MBAF process was developed treating detergent wastewater. The average removal rate of COD, LAS, and TP by the combined process was up to 91.4%, 88.5%, and 40%, respectively. Kinetic models for the UMBAF-MBAF process were investigated.

Fast and sensitive determination of per- and polyfluoroalkyl substances in seawater.

In this work, a novel, fast, and sensitive method was developed for perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS) and PFOS precursor's determination in seawater. The proposed method consists in a vortex-assisted liquid-liquid microextraction (VALLME) combined with liquid chromatography (LC) and LTQ-Orbitrap high resolution mass spectrometry (LTQ-Orbitrap HRMS) determination. Several parameters affecting both the HPLC-LTQ Orbitrap HRMS determination and the VALLME were studied, with special attention to blank contamination problem. The use of LTQ-Orbitrap-HRMS in full mode, quantifying the target analytes using the exact mass, provides a very powerful detection in terms of sensitivity and specificity maintaining all the information provided by the full mass spectra, allowing, also, the identification of non-target substances. The use of matrix-matched calibration, together with labelled surrogate standards, minimize matrix effects and compensate potential recovery losses, resulting in recoveries between 95 and 105%, with excellent sensitivity (quantitation limit between 0.7 and 6 ng L-1) and precision (4-10%). The proposed method requires only 35 mL of sample and 100 µL of extracting solvent, is fast and avoids the use of other solvents to obtain the dispersive cloudy solution, simplifying the procedure and improving the existing procedures for the determination of per- and polyfluoroalkyl substances (PFASs) in seawater in terms of green analytical chemistry. The method was successfully validated by participating in a proficiency test assay provided by the National Measurement Institute of the Australian Government for the determination of PFOA, total PFOS and linear PFOS in waters. A revision of the state of the art in the last twelve years of methods for the analysis of PFASs in seawater and other types of water was performed, and a critical comparison between the developed method and the previously published was included. Finally, the method was applied to the analysis of samples from Ría de Vigo, a sensitive and semiconfined coastal area located in the northwest of Spain. PFOS, N-methyl perfluorooctanesulfonamide (n-MeFOSA) and N-ethyl perfluorooctanesulfonamide (n-EtFOSA) were detected in samples at levels lower than the maximum allowable concentration (MAC) established by Directive 2013/39/EU, but above the annual average (AA) levels.

Efficient removal of perfluorooctane sulfonate from aqueous film-forming foam solution by aeration-foam collection.

Aqueous film-forming foams (AFFFs) used in fire-fighting are one of the main contamination sources of perfluorooctane sulfonate (PFOS) to the subterranean environment, requiring high costs for remediation. In this study, a method that combined aeration and foam collection was presented to remove PFOS from a commercially available AFFF solution. The method utilized the strong surfactant properties of PFOS that cause it to be highly enriched at air-water interfaces. With an aeration flow rate of 75 mL/min, PFOS removal percent reached 96% after 2 h, and the PFOS concentration in the collected foam was up to 6.5 mmol/L, beneficial for PFOS recovery and reuse. Increasing the aeration flow rate, ionic strength and concentration of co-existing surfactant, as well as decreasing the initial PFOS concentration, increased the removal percents of PFOS by increasing the foam volume, but reduced the enrichment of PFOS in the foams. With the assistance of a co-existing hydrocarbon surfactant, PFOS removal percent was above 99.9% after aeration-foam collection for 2 h and the enrichment factor exceeded 8400. Aeration-foam collection was less effective for short-chain perfluoroalkyl substances due to their relatively lower surface activity. Aeration-foam collection was found to be effective for the removal of high concentrations of PFOS from AFFF-contaminated wastewater, and the concentrated PFOS in the collected foam can be reused.

Rapid and high-capacity adsorption of PFOS and PFOA by regenerable ammoniated magnetic particle.

Adsorption is well accepted as an effective method for perfluorinated compounds' (PFCs) removal from water among various conventional methods. However, development of adsorbents that combine good performance of PFC removal and regenerability has not yet been realized. This work demonstrated the fabrication and application of an ammoniated magnetic adsorbent for efficient and economical PFOS and PFOA removal. Functional ammonium groups and γ-Fe2O3 were effectively incorporated in the particle with the proposed method. These fabricated magnetic particles presented superior adsorption performance for PFOS and PFOA with short equilibrium time of 120 min and high adsorption capacity. The isotherms revealed that the adsorption process belonged to multilayer sorption with their intricate interactions including anion exchange and hydrophobic interaction. The magnetic particle maintained its removal efficacy over a wide pH range of 3-9 or with coexisting substances. Moreover, the regeneration and reuse of the magnetic particle were successfully carried out with PFOS and PFOA removal efficiency sustained higher than 80% in 15 consecutive treatment cycles. Along with the efficient adsorption and easy separation of adsorbents, we expect that this ammoniated magnetic particle can serve as an excellent alternative for PFOS and PFOA removal from water.

Identification and quantification of linear and branched isomers of perfluorooctanoic and perfluorooctane sulfonic acids in contaminated groundwater in the veneto region.

Perfluoroalkylated acids (PFAAs) are ubiquitous xenobiotic substances characterized by high persistency, bioaccumulation potential and toxicity. They have generated global concern because of their widespread presence both in water and biota compartments. In the past four years, alarming levels of these pollutants have been found in both surface and groundwater collected in an area covering more than 150 square kilometers in the south-western part of the province of Vicenza (Veneto region, Italy). One of the sources of the contamination recognized by local authorities is a fluorochemicals production plant that produced PFAAs since late sixties by electrochemical fluorination involving the obtainment of a complex mixture of linear and branched isomers. Branched isomers account for a significant part of total long chain homologues (22%-35%). Because of the potential threat to public health and the absence of specific limits set for these pollutants by Directive 98/83/EC, local authorities have established the following performance limits for drinking water: 90 ng L-1 for PFOA + PFOS, (reduced to 40 ng L-1 in the most contaminated municipalities), 30 ng L-1 for PFOS and 300 ng L-1 for the sum of all other PFAAs. Given the non-negligible incidence of branched isomers, it appears very important to correctly identify and quantify their contribution to total PFAAs. A liquid chromatography-electrospray ionization tandem spectrometry LC-MS/MS method, coupled with solid phase extraction, was developed to identify and quantify 25 PFAAs including six branched isomers of PFOS and four branched isomers of PFOA. Expanded uncertainty, recovery and precision were determined and found to agree with the reference EPA method 537:2009. The quantification limit is comprised in the 1-5 ng L-1 range.

Synthesis and evaluation of molecularly imprinted polymers with binary functional monomers for the selective removal of perfluorooctanesulfonic acid and perfluorooctanoic acid.

This work describes a novel method for the synthesis of molecularly imprinted polymers (MIPs) using 2-(trifluoromethyl) acrylic acid (TFMAA) and 4-vinyl pyridine (4-Vpy) as binary functional monomers, perfluorooctanoic acid (PFOA) as template, and ethyleneglycol dimethacrylate (EGDMA) as cross-linker in the presence of azobisisobutyronitrile (AIBN). The binary functional monomer MIPs were applied to selective recognition for PFOA and perfluorooctanesulfonic acid (PFOS) from aqueous environment. The MIPs were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and microscopic electrophoresis. Thereafter, the adsorption capacity and selectivity of the synthesized MIPs for PFOA and PFOS were evaluated by batch adsorption experiments. The maximum adsorption capacities of the MIPs for PFOA and PFOS were 6.42 and 6.27mg/g, respectively. It was also found that the adsorption capacities remained constant with increasing the solution pH in the range of 2.0-5.0, and then decreased when the pH was further increased. Finally, the novel MIPs can be reused after five cycles of adsorption-desorption-adsorption with no significant decrease of removal rate and have an effective performance in selective removal of PFOA and PFOS in real lake water samples. All the results indicate that the binary functional monomer MIPs have great potential to remove PFOA and PFOS in aqueous environment.

Behavior and mechanisms for sorptive removal of perfluorooctane sulfonate by layered double hydroxides.

Perfluorooctane sulfonate (PFOS) is known to be extremely persistent and is toxic to wildlife and humans. In this study, we evaluated the sorptive removal behavior of PFOS from aqueous solution using three forms of layered double hydroxides (LDHs), namely, nitrate-, carbonate- and chloride-intercalated LDHs. Batch experiments showed that the sorption process was very fast with an equilibrium time of 10-60 min. The nitrate-LDH had the greatest ability to remove PFOS with a removal rate of 99.7% at an initial concentration of 100 mg/L and the maximum uptake capacity reached 865 mg/g. The sorption kinetic and equilibrium data could be fitted well with the pseudo-second-order model and Langmuir model, respectively. The intraparticle diffusion model suggests that both external diffusion and intraparticle diffusion are the rate-limiting processes for PFOS sorption onto the LDHs. The initial pH, background electrolyte concentration and coexisting ions influenced the sorption of PFOS by the LDHs. It was concluded that both surface adsorption and anion exchange were involved in the PFOS sorption onto the LDHs.

Perfluorooctane sulfonate adsorption on powder activated carbon: Effect of phosphate (P) competition, pH, and temperature.

Powdered activated carbon (PAC), as an adsorbent, was applied to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Laboratory batch experiments were performed to investigate the influences of phosphate (P) competition, temperature, and pH for PFOS adsorption onto PAC. The results showed that higher temperature favored PFOS adsorption in single and binary systems. The kinetic data fitted very well to the pseudo second-order kinetic model. Thermodynamically, the endothermic enthalpy of the PFOS adsorption in single and binary systems were 125.07 and 21.25 kJ mol-1, respectively. The entropy of the PFOS adsorption in single and binary systems were 0.479 and 0.092 kJ mol-1 K-1, respectively. And the Gibbs constants were negative. These results indicated that the adsorption processes were spontaneous. The adsorption isotherms of PFOS agreed well with the Langmuir model. In the single system, PFOS adsorption decreased with increased pH value. The difference in the amount of PFOS adsorption between the single and binary systems increased at higher pH. Frustrated total internal reflection (FTIR) demonstrated that P competition increased the hydrophilicity of the PAC and the electrostatic repulsion between PFOS and PAC, then the PFOS adsorption amount decreased. It also demonstrated that, at higher temperature, increased PFOS adsorption was mainly due to the higher diffusion rate of PFOS molecules and greater number of active sites opened on the PAC surface.

Effects of hydraulic retention time, co-substrate and nitrogen source on laundry wastewater anionic surfactant degradation in fluidized bed reactors.

The aim of this study was to evaluate the influence of hydraulic retention time (HRT) on linear alkylbenzene sulfonate (LAS) removal in fluidized bed reactors (FBRs). FBR1 (HRT of 8h) and FBR2 (HRT of 12h) were fed laundry wastewater with 18.6±4.1 to 27.1±5.6mg/L of LAS in the following conditions: ethanol and nitrate addition (Phases I, II and III), nitrate (Phase IV), ethanol (Phase V) and laundry wastewater (Phase VI). LAS removal was 93±12% (FBR1) and 99±2% (FBR2). In FBR1, nitrate influenced significantly on LAS removal (99±3% - Phase IV) compared to the phase without nitrate (90±15% - Phase V). In FBR1 the absence of ethanol was more favourable for LAS removal (99±3% - Phase IV) compared to ethanol addition (87±16% - Phase II). In FBR2, 99±2% LAS removal was found up to 436days. By microbial characterization were identified bacteria as Acinetobacter, Dechloromonas, Pseudomonas and Zoogloea.

Evaluation of anionic surfactant removal in anaerobic reactor with Fe(III) supplementation.

The objective of this study was to evaluate the removal of linear alkylbenzene sulfonate (LAS) associated with Fe(III) supplementation using an expanded granular sludge bed (EGSB) reactor. The reactor was inoculated with a granular sludge and fed with synthetic wastewater containing a specific LAS load rate (SLLR) of 1.5 mg gVS-1 d-1 (∼16.4 mgLAS L-1 influent) and supplied with 7276 µMol L-1 of Fe(III). The biomasses from the inoculum and at the end of the EGSB-Fe operation (127 days) were characterized using 16S rRNA Ion Tag sequencing. An increase of 20% in the removal efficiency was observed compared to reactors without Fe(III) supplementation that was reported in the literature, and the LAS removal was approximately 84%. The Fe(III) reduction was dissimilatory (the total iron concentration in the influent and effluent were similar) and reached approximately 64%. The higher Fe(III) reduction and LAS removal were corroborated by the enrichment of genera, such as Shewanella (only EGSB-Fe - 0.5%) and Geobacter (1% - inoculum; 18% - EGSB-Fe). Furthermore, the enrichment of genera that degrade LAS and/or aromatic compounds (3.8% - inoculum; 29.6% - EGSB-Fe of relative abundance) was observed for a total of 20 different genera.

Polar stir bars for isolation and preconcentration of perfluoroalkyl substances from human milk samples prior to UHPLC-MS/MS analysis.

BACKGROUND: A new method for the determination of four perfluoroalkyl carboxylic acids (from C5 to C8) and perfluorooctane sulfonate in human milk samples using stir-bar sorptive extraction-ultra-HPLC-MS/MS has been accurately optimized and validated. METHODOLOGY: Polydimethylsiloxane and polyethyleneglycol modified silicone materials were evaluated. DISCUSSION: Overall, polyethyleneglycol led to a better sensitivity. After optimizing experimental variables, the method was validated reaching detection limits in the range of 0.05-0.20 ng ml(-1); recovery rates from 81 to 105% and relative standard deviations fewer than 13% in all cases. The method was applied to milk samples from five randomly selected women. All samples were positive for at least one of the target compounds with concentrations ranging between 0.8 and 6.6 ng ml(-1), being the most abundant perfluorooctane sulfonate.