A new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78-120%) and solid samples (83-100%). Determination of SAS was carried out by high or ultra performance liquid chromatography e mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where SAS concentrations below 1 mg L 1 were measured in surface water, and from 72 to 9737 mg kg 1 in sediments. Differential partitioning was observed for SAS homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that SAS measured levels were not harmful to the aquatic community in the sampling area.

This research is focused on secondary alkane sulfonates (SAS), anionic surfactants widely used in household applications that access aquatic environments mainly via sewage discharges.We studied their sorption capacity and anaerobic degradation in marine sediments, providing the first data available on this topic. SAS partition coefficients increased towards those homologues having longer alkyl chains(from up to 141 L kg 1 for C14 to up to 1753 L kg 1 for C17), which were those less susceptible to undergo biodegradation. Overall, SAS removal percentages reached up to 98% after 166 days of incubation using anoxic sediments. The degradation pathway consisted on the formation of sulfocarboxylic acids after an initial fumarate attack of the alkyl chain and successive b-oxidations. This is the first study showing that SAS can be degraded in absence of oxygen, so this new information should be taken into account for future environmental risk assessments on these chemicals.

Biosolids containing per- and polyfluoroalkyl substances (PFAS) could contaminate the receiving environments once they are land applied. In this study, we evaluated the feasibility of controlling the bioavailability of PFAS in biosolids to timothy-grass through stabilization or mobilization approaches. Stabilization was accomplished by adding a sorbent (i.e. granular activated carbon (GAC), RemBind, biochar) to biosolids, while mobilization was achieved by adding a surfactant, sodium dodecyl sulphate (SDS), to biosolids. The results showed that the ΣPFAS concentration in grass shoots grown in biosolids amended soil treated by GAC or RemBind at 2% was only 2.77% and 3.35% of the ΣPFAS concentration detected in shoots grown in biosolids amended soil without a sorbent, respectively, indicating the effectiveness of GAC and RemBind for stabilizing PFAS and reduce their bioavailability. On the other hand, mobilization by adding SDS to biosolids at a dose range of 10–100 mg/kg significantly increased the plant uptake of ΣPFAS by 15.48%–108.57%. Thus, mobilization by adding SDS could be a valuable approach for enhancing the PFAS removal if phytoremediation is applied. Moreover, higher rate of PFAS uptake took place after grass cutting was observed in this study. Thus, proper mowing and regrowth of timothy-grass could lead to efficient and cost-effective removal of PFAS from biosolids amended soil through phytoremediation and leave the site clean to be used for other purposes.

Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qₑ = 3.55·10⁻⁶ mol/m²), which could be explained by a higher surface area (600 m²/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100–500 m²/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qₑ = 1.72·10⁻⁶ mol/m²). However, the best experimental results of this study were obtained using synthesized graphenic materials.

Aquatic pollution from emerging organic contaminants (EOCs) is of key environmental importance in India and globally, particularly due to concerns of antimicrobial resistance, ecotoxicity and drinking water supply vulnerability. Here, using a broad screening approach, we characterize the composition and distribution of EOCs in groundwater in the Gangetic Plain around Patna (Bihar), as an exemplar of a rapidly developing urban area in northern India. A total of 73 EOCs were detected in 51 samples, typically at ng.L⁻¹ to low μg.L⁻¹ concentrations, relating to medical and veterinary, agrochemical, industrial and lifestyle usage. Concentrations were often dominated by the lifestyle chemical and artificial sweetener sucralose. Seventeen identified EOCs are flagged as priority compounds by the European Commission, World Health Organisation and/or World Organisation for Animal Health: namely, herbicides diuron and atrazine; insecticides imidacloprid, thiamethoxam, clothianidin and acetamiprid; the surfactant perfluorooctane sulfonate (and related perfluorobutane sulfonate, perfluorohexane sulfonate, perfluorooctanoic acid and perfluoropentane sulfonate); and medical/veterinary compounds sulfamethoxazole, sulfanilamide, dapson, sulfathiazole, sulfamethazine and diclofenac. The spatial distribution of EOCs varies widely, with concentrations declining with depth, consistent with a strong dominant vertical flow control. Groundwater EOC concentrations in Patna were found to peak within ∼10 km distance from the River Ganges, indicating mainly urban inputs with some local pollution hotspots. A heterogeneous relationship between EOCs and population density likely reflects confounding factors including varying input types and controls (e.g. spatial, temporal), wastewater treatment infrastructure and groundwater abstraction. Strong seasonal agreement in EOC concentrations was observed. Co-existence of limited transformation products with associated parent compounds indicate active microbial degradation processes. This study characterizes key controls on the distribution of groundwater EOCs across the urban to rural transition near Patna, as a rapidly developing Indian city, and contributes to the wider understanding of the vulnerability of shallow groundwater to surface-derived contamination in similar environments.

Tris(2-chloroethyl) phosphate (TCEP) is a widely found emerging pollutant due to its heavy usage as a flame retardant. It is chemically stable and is very difficult to removal from water. The goal of this study was to explore whether iron monosulfide (FeS) can be used for reductive transformation of TCEP as FeS can react with a variety of halogenated organic contaminants. We used batch reactor systems to quantify the transformation reactions in the absence and presence of cetyltrimethylammonium bromide (CTAB, a common surfactant in aquatic environments). The results showed that, in the presence of CTAB (100 mg L⁻¹), FeS exhibited much greater reactivity towards TCEP as 93% of initial TCEP had been transformed within 14 d of reaction. In the absence of CTAB, it required 710 d of reaction to achieve 97.3% reduction of initial TCEP. The enhancement of CTAB on TCEP transformation rate could be due to the facts that CTAB could stabilize FeS suspension against aggregation, protect FeS from rapid oxidation, and increase surface adsorption of TCEP on FeS. XPS analysis showed that both Fe(II) and S(-II) species on the FeS surface were involved in the reductive transformation of TCEP. Analysis of transformation products revealed that TCEP was reductively transformed into bis(2-chloroethyl) phosphate (BCEP), Cl⁻ and C₂H₄. These findings showed that FeS may play an important role in the reductive transformation of TCEP when TCEP coexisting with CTAB in aquatic environments.

Surfactants are known to enhance the degradation of halogenated organics by nanoscale zerovalent iron (n-ZVI) or n-ZVI-based bimetallic particles, but the mechanism of the promotion is not well understood. In this study, we used nanoscale Ag/Fe particles (n-Ag/Fe) to degrade 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) in different surfactant solutions. The results show that the nonionic surfactant TX-100 had the best promoting effect, which might be attributed to the decrease in particle agglomeration and improvement of mass transfer efficiency after the adsorption of TX-100 on n-Ag/Fe. The distribution analysis of BDE-47 in solid and liquid phases indicates that when the concentration of TX-100 in aqueous solution was above critical micelle concentration, BDE-47 started to dissolve in the liquid phase. Thus, TX-100 micelles can enhance the mass transfer efficiency of BDE-47. However, a too high concentration of TX-100 (above 1.0 mM) would influence the promotion effect of BDE-47 degration, which might be attributed to the excessive and thicker micelles of TX-100 hindering the contact between BDE-47 and n-Ag/Fe. We also studied the degradation pathway of BDE-47 and its products, and found that surfactants did not change the degradation pathway of BDE-47.

The problem of effective assessment of risk posed by complex mixtures of toxic chemicals in the environment is a major challenge for government regulators and industry. The biological effect of the individual contaminants, where these are known, can be measured; but the problem lies in relating toxicity to the multiple constituents of contaminant cocktails. The objective of this study was to test the hypothesis that diverse contaminant mixtures may cause a greater toxicity than the sum of their individual parts, due to synergistic interactions between contaminants with different intracellular targets. Lysosomal membrane stability in hemocytes from marine mussels was used for in vitro toxicity tests; and was coupled with analysis using the isobole method and a linear additive statistical model. The findings from both methods have shown significant emergent synergistic interactions between environmentally relevant chemicals (i.e., polycyclic aromatic hydrocarbons, pesticides, biocides and a surfactant) when exposed to isolated hemocytes as a mixture of 3 & 7 constituents. The results support the complexity-based hypothesis that emergent toxicity occurs with increasing contaminant diversity, and raises questions about the validity of estimating toxicity of contaminant mixtures based on the additive toxicity of single components. Further experimentation is required to investigate the potential for interactive effects in mixtures with more constituents (e.g., 50–100) at more environmentally realistic concentrations in order to test other regions of the model, namely, very low concentrations and high diversity. Estimated toxicant diversity coupled with tests for lysosomal damage may provide a potential tool for determining the toxicity of estuarine sediments, dredge spoil or contaminated soil.

The occurrence of a polyether trisiloxane surfactant in the ng L−1 range in German surface waters is reported for the first time. The studied surfactant does not ubiquitously occur in the aquatic environment but can reach surface waters on a local scale. As a first step towards the understanding of the environmental fate, the hydrolysis was studied according to the OECD guideline 111. It confirmed that the trisiloxane surfactant is sensitive to hydrolysis and that the hydrolysis rate strongly depends on the pH and the temperature. If one takes only into account the hydrolysis, the trisiloxane surfactant could persist several weeks in river water (the half-life in water is approximately 50 days at pH 7, 25 °C, and an initial concentration of 2 mg L−1). A degradation product, more polar than the initial trisiloxane surfactant, was identified by high resolution mass spectrometry.