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The sorption of ionic and ionizable organic compounds (IOCs) (e.g., pharmaceuticals and pesticides) on carbonaceous materials plays an important role in governing the fate, transport and bioavailability of IOCs. The paradigms previously established for the sorption of neutral organic compounds do not always apply to IOCs and the importance of accounting for the particular sorption behavior of IOCs is being increasingly recognized. This review presents the current state of knowledge and summarizes the recent advances on the sorption of IOCs to carbonaceous sorbents. A broad range of sorbents were considered to evaluate the possibility to read across between fields of research that are often considered in isolation (e.g., carbon nanotubes, graphene, biochar, and activated carbon). Mechanisms relevant to IOCs sorption on carbonaceous sorbents are discussed and critically evaluated, with special attention being given to emerging sorption mechanisms including low-barrier, charge-assisted hydrogen bonds and cation-π assisted π–π interactions. The key role played by some environmental factors is also discussed, with a particular focus on pH and ionic strength. Overall the review reveals significant advances in our understanding of the interactions between IOCs and carbonaceous sorbents. In addition, knowledge gaps are identified and priorities for future research are suggested. [ABSTRACT FROM AUTHOR]

The study investigates the role of biochar and/or compost in mitigating the toxic effects of pyrene in soils using reproduction of nematodes and porewater concentration as measures of pyrene toxicity and bioavailability, respectively. Two soils were spiked with increasing levels of pyrene to achieve a concentration-response relationship for the reproduction of Caenorhabditis elegans . The observed EC50 values (pyrene concentration causing 50% inhibition of reproduction) were 14 mg/kg and 31 mg/kg (dry mass) for these soils, corresponding to equilibrium porewater concentrations of 37 μg/L and 47 μg/L, respectively. Differences in organic carbon content were not sufficient to explain the variability in toxicity between the different soils. Soils causing a significant inhibition of reproduction were further amended with 10%-compost, 5%-biochar, or both, and the effects on reproduction and porewater concentration determined. Combined addition of compost and biochar was identified as the most effective strategy in reducing pyrene concentration in soil porewater, which was also partly reflected in soil toxicity. However, porewater concentrations predicted only 52% of pyrene toxicity to nematodes, pointing to particle-bound or dietary exposure pathways. Capsule: Amending pyrene-spiked soil with biochar and compost effectively reduced pyrene porewater concentrations and toxicity to nematodes, which were significantly related. [ABSTRACT FROM AUTHOR]

• Overlooked contribution of PBMs towards the DBP formation was critically reviewed. • Elastomers, tire waste, polyelectrolytes, and MPs serve as potent DBP precursors. • Leached DOC and dissolved nitrogen from PBMs play a key role in DBP formation. • DBPs formation potential of polyelectrolytes was found as high as ∼2 mg/L. • DBPs formation potential of different microplastics ranged from 1.9 to 15,990 µg/L. Disinfection by-products (DBPs) are formed through the disinfection of water containing precursors such as natural organic matter or anthropogenic compounds (e.g., pharmaceuticals and pesticides). Due to the ever increasing use of plastics, elastomers, and other polymers in our daily lives, polymer-based materials (PBMs) are detected more frequently and at higher concentrations in water and wastewater. The present review provides a comprehensive and systematic analysis of the contribution of PBMs - including elastomers, tire waste, polyelectrolytes, and microplastics - as precursors of DBPs in water and wastewater. Literature shows that the presence of PBMs can lead to the leaching of dissolved organic matter (DOM) and subsequent formation of DBPs upon disinfection in aqueous media. The quantity and type of DBPs formed strongly depends on the type of polymer, its concentration, its age, water salinity, and disinfection conditions such as oxidant dosage, pH, temperature, and contact time. DOM leaching from elastomers and tire waste was shown to form N -nitrosodimethylamine up to concerning levels of 930 ng/L and 466,715 ng/L, respectively upon chemical disinfection under laboratory conditions. Polyelectrolytes can also react with chemical disinfectants to form toxic DBPs. Recent findings indicate trihalomethanes formation potential of plastics can be as high as 15,990 µg/L based on the maximum formation potential under extreme conditions. Our analysis highlights an overlooked contribution of DOM leaching from PBMs as DBP precursors during disinfection of water and wastewater. Further studies need to be conducted to ascertain the extent of this contribution in real water and wastewater treatment plants. [Display omitted] [ABSTRACT FROM AUTHOR]

Sewage sludge (50% mineral), manure (29%) and wood (<1%) were pyrolyzed at 200, 350 and 500 °C with the aim to study the characteristics and sorption potential of materials undergoing pyrolysis across a wide range of mineral contents. A commercial plant-derived biochar (41% mineral) was also considered. The materials were extensively characterized and tested for their sorption towards the model sorbates benzene, naphthalene and pyrene. Plant-derived materials, regardless of their mineral content, developed micropores causing size exclusion of pyrene. Changes in properties and sorption behavior upon pyrolysis were generally consistent for the manure and wood series. A single regression equation developed on our data (including the sorbate hydrophobicity and sorbent polarity) provided excellent prediction of previously reported changes in sorption upon pyrolysis across a wide range of mineral content (up to 500 °C). The sewage sludge series, however, followed a particular behavior, possibly due to very high mineral content (up to 67%). [ABSTRACT FROM AUTHOR]

The effect of functionalization on the sorption behavior of carbon nanotubes (CNTs) remains poorly understood, especially when combined with other factors affecting dispersion. The sorption behavior of a series of functionalized CNTs towards pyrene has therefore been systematically evaluated over a wide range of concentrations and dispersion scenarios. When studied as purchased (in the absence of humic acids and sonication treatment), sorption isotherms showed that OH-, COOH- and NH 2 -CNTs exhibited significantly different sorption affinity for pyrene. Sonication greatly increased both the sorption affinity and the maximum capacity of all types of functionalized CNTs, to an extent that overwhelmed the differences initially observed (increase of up to 1.5 orders of magnitude lead to log K d values close to 9 L/kg). Results demonstrate that a significant proportion of the CNT surface was unavailable to pyrene prior to sonication. The presence of humic acids enhanced dispersion but decreased sorption, especially when combined with sonication. Sorption affinity, however, remained very high in all cases (log K d > 7.5 L/kg), suggesting that CNTs can act as strong sorbents under a wide range of conditions. [ABSTRACT FROM AUTHOR]

Abstract: The rapid developments in nanopesticide research over the last two years have motivated a number of international organizations to consider potential issues relating to the use of nanotechnology for crop protection. This analysis of the latest research trends provides a useful basis for identifying research gaps and future priorities. Polymer-based formulations have received the greatest attention over the last two years, followed by formulations containing inorganic nanoparticles (e.g., silica, titanium dioxide) and nanoemulsions. Investigations have addressed the lack of information on the efficacy of nanopesticides and a number of products have been demonstrated to have greater efficacy than their commercial counterparts. However, the mechanisms involved remain largely unknown and further research is required before any generalizations can be made. There is now increased motivation to develop nanopesticides that are less harmful to the environment than conventional formulations, and future investigations will need to assess whether any promising products developed are able to compete with existing formulations, in terms of both cost and performance. Investigations into the environmental fate of nanopesticides remain scarce, and the current state of knowledge does not appear to be sufficient for a reliable assessment to be made of their associated benefits and risks. A great deal of research will therefore be required over the coming years, and will need to include (i) the development of experimental protocols to generate reliable fate properties, (ii) investigations into the bioavailability and durability of nanopesticides, and (iii) evaluation of current environmental risk assessment approaches, and their refinement where appropriate. [Copyright &y& Elsevier]

The octanol/water partition coefficient (Kow) for organic compounds is widely used in predictive environmental studies. A significant proportion of contaminants of surface and ground water are ionisable (e.g. many pesticides, pharmaceuticals, metabolites). Such compounds may be partially ionised dependent on the pH. Since the neutral and ionic species exhibit different polarities, the Kow value of ionisable pesticides is pH dependent. It is therefore essential to determine Kow values over the full range of pH that occurs in the environment in order to get appropriate predictors. Numerous methods are available to measure lipophilicity but only a few are appropriate for ionisable pesticides (e.g. pH metric and filter probe methods). Parameters such as pH and ionic strength need to be carefully controlled when working with ionisable compounds. Variation of these factors probably explains why literature can yield Kow values that differ by more than one order of magnitude for some compounds. In this article, Kow values obtained for six acidic pesticides with three different methods are compared as well (data from the literature, measured by pH metric method and calculated with five computer programs). The values used in predictive regression equations needs to be either measured with a suitable method or selected from the literature with great care. [Copyright &y& Elsevier]

• PFAS occurrence information is not available for most developing countries. • Monitoring is required for ultra-short chain and new generation replacement PFAS. • Majority of studies report higher PFAS concentrations in effluents than influents. • Biodegradation transforms PFAS precursors to PFAA at a secondary stage. • Adsorption, electrochemical, and filtration are the most studied PFAS treatments. Poly- and perfluoroalkyl substances (PFAS) comprise more than 4,000 anthropogenically manufactured compounds with widescale consumer and industrial applications. This critical review compiles the latest information on the worldwide distribution of PFAS and evaluates their fate in wastewater treatment plants (WWTPs). A large proportion (>30%) of monitoring studies in WWTPs were conducted in China, followed by Europe (30%) and North America (16%), whereas information is generally lacking for other parts of the world, including most of the developing countries. Short and long-chain perfluoroalkyl acids (PFAAs) were widely detected in both the influents (up to 1,000 ng/L) and effluents (15 to >1,500 ng/L) of WWTPs. To date, limited data is available regarding levels of PFAS precursors and ultra-short chain PFAS in WWTPs. Most WWTPs exhibited low removal efficiencies for PFAS, and many studies reported an increase in the levels of PFAAs after wastewater treatment. The analysis of the fate of various classes of PFAS at different wastewater treatment stages (aerobic and/aerobic biodegradation, photodegradation, and chemical degradation) revealed biodegradation as the primary mechanism responsible for the transformation of PFAS precursors to PFAAs in WWTPs. Remediation studies at full scale and laboratory scale suggest advanced processes such as adsorption using ion exchange resins, electrochemical degradation, and nanofiltration are more effective in removing PFAS (~95–100%) than conventional processes. However, the applicability of such treatments for real-world WWTPs faces significant challenges due to the scaling-up requirements, mass-transfer limitations, and management of treatment by-products and wastes. Combining more than one technique for effective removal of PFAS, while addressing limitations of the individual treatments, could be beneficial. Considering environmental concentrations of PFAS, cost-effectiveness, and ease of operation, nanofiltration followed by adsorption using wood-derived biochar and/or activated carbons could be a viable option if introduced to conventional treatment systems. However, the large-scale applicability of the same needs to be further verified. [Display omitted] [ABSTRACT FROM AUTHOR]

Per - and poly-fluoroalkyl substances (PFAS) have contaminated land and water at numerous sites worldwide that now require remediation. The most common approach for treating contaminated water currently relies on removal of PFAS by sorption. The spent sorbents loaded with PFAS can potentially be disposed of at landfills, provided the sorbed contaminants remain sequestered and certain risk criteria are met. Hence, it is essential that remediation sorbents (i) rapidly adsorb a large variety of PFAS under varying water chemistry conditions, and (ii) do not release the adsorbed PFAS in due course. This review aims at establishing the current state of knowledge about the potential release of PFAS that may occur during and after treatment. The scientific literature currently provides data for a very restricted range of long-chain PFAS. Our knowledge of the dynamics of PFAS adsorption processes on engineered sorbents is limited, and even less is known about their desorption processes. The sorption of PFAS can be strongly affected by changes in the solution pH, ionic strength and dissolved organic matter content, and the process is also subject to complex competition mechanisms in the presence of other PFAS as well as organic contaminants and inorganic salts. Several studies suggest that changes in one or several of these factors may trigger the release of PFAS from engineered sorbents. This phenomenon is more likely to occur for PFAS with shorter carbon chain lengths (

Due to their persistence and toxicity, per- and polyfluoroalkyl substances (PFAS) have become an issue of global concern. The public's perception is valuable in consultations about possible remediation of or mitigation against the use of PFAS. In this study, we investigated the source of PFAS information and factors (psycho-demographic characteristics) affecting public views. We performed an online survey with a demographically representative sample of Aotearoa New Zealand adults (n = 935). Results show that PFAS are known to nearly 45 % of the survey participants, yet, with misunderstandings. Amongst those aware of PFAS, the concern is high, especially for their use in products that contact skin or consumed orally. Individuals with the highest level of self-perceived PFAS knowledge (vs no knowledge) were most concerned but also the most accepting of PFAS-containing products. Males were self-perceived to be more knowledgeable and less concerned than females. Younger adults (aged 18–34) were more likely to indicate high perceived knowledge and more acceptance of consumer products containing PFAS than older adults. These findings identified crucial information gaps that will contribute to national and global regulation and policy decisions as well as inform public education campaigns, informing a more targeted education approach. • Most respondents heard about PFAS from the internet and television. • Most respondents wanted to learn more about PFAS, believing this would impact their behaviour. • Males perceived themselves more knowledgeable and less concerned about PFAS than females. • Females had less tolerance for PFAS in consumer products than males. • Younger people perceive themselves as more knowledgeable about PFAS, but they are not more concerned than older individuals. [ABSTRACT FROM AUTHOR]

Diffusely contaminated soils often remain untreated as classical remediation approaches would be disproportionately expensive. Adding compost can accelerate the biodegradation of organic contaminants and adding biochar can immobilize contaminants through sorption. The combined use of compost and biochar to reduce polycyclic aromatic hydrocarbon (PAH) and NSO-substituted PAH contamination has, however, not previously been systematically investigated. We have therefore investigated the processes involved (i) through sorption batch experiments, (ii) by monitoring changes in bacterial, fungal and archaeal communities using denaturing gradient gel electrophoresis, and (iii) through degradation experiments with fluorene, phenanthrene, pyrene, carbazole, dibenzothiophene, and dibenzofuran. Sorption coefficients for organic contaminants in soils increased tenfold following 10% compost addition and up to a hundredfold with further addition of 5% biochar. The rate of PAH and NSO-PAH degradation increased up to twofold following compost addition despite increased sorption, probably due to the introduction of additional microbial species into the autochthonous soil communities. In contrast, degradation of PAHs and NSO-PAHs in soil-compost-biochar mixtures slowed down up to tenfold due to the additional sorption, although some degradation still occurred. The combined use of biochar and compost may therefore provide a strategy for immobilizing PAHs and NSO-PAHs and facilitating degradation of remaining accessible contaminant fractions. [ABSTRACT FROM AUTHOR]

The surface area and pore volume of carbonaceous materials, which are commonly determined by N 2 and/or CO 2 gas-physisorption, are important parameters when describing environmental processes such as adsorption. Their measurement requires prior degassing of samples, which can change the nature of the material. Current guidelines for biochar characterization recommend different degassing temperatures. To investigate how degassing temperatures affect gas-physisorption we systematically degassed a range of materials (four biochars, carbon nanotubes, and Al 2 O 3 reference material) at different temperatures (105, 150, 200, 250 and 300 °C; for ≥ 14 h each). Degassing temperatures had no effect on Al 2 O 3 or carbon nanotubes but the measured surface areas and pore volumes of biochars increased by up to 300% with degassing temperature. An equation is presented for predicting surface area obtained at different degassing temperatures. Elemental analysis and results from sorption batch experiments suggest that surface area and pore volume may increase as biochar components volatilize during degassing. Our results showed that degassing temperatures change material properties and influence gas-physisorption measurements, and therefore need to be standardized. These results may also apply to the characterization of other complex materials, including carbon nanotubes coated with natural organic matter and fouled activated carbon. [ABSTRACT FROM AUTHOR]

• Collated (im)mobilization and destruction techniques for PFAS remediation in soil. • Described interrelationships between soil PFAS dynamics and their remediation. • Ascribed soil amendments to PFAS bioavailability and mobility in relation to remediation. • Covered case studies of successful remediation techniques for PFAS contaminated soil. • Highlighted environmental implications of various soil PFAS remediation techniques. Poly- and perfluoroalkyl substances (PFASs) are synthetic chemicals, which are introduced to the environment through anthropogenic activities. Aqueous film forming foam used in firefighting, wastewater effluent, landfill leachate, and biosolids are major sources of PFAS input to soil and groundwater. Remediation of PFAS contaminated solid and aqueous media is challenging, which is attributed to the chemical and thermal stability of PFAS and the complexity of PFAS mixtures. In this review, remediation of PFAS contaminated soils through manipulation of their bioavailability and destruction is presented. While the mobilizing amendments (e.g., surfactants) enhance the mobility and bioavailability of PFAS, the immobilizing amendments (e.g., activated carbon) decrease their bioavailability and mobility. Mobilizing amendments can be applied to facilitate the removal of PFAS though soil washing, phytoremediation, and complete destruction through thermal and chemical redox reactions. Immobilizing amendments are likely to reduce the transfer of PFAS to food chain through plant and biota (e.g., earthworm) uptake, and leaching to potable water sources. Future studies should focus on quantifying the potential leaching of the mobilized PFAS in the absence of removal by plant and biota uptake or soil washing, and regular monitoring of the long-term stability of the immobilized PFAS. [ABSTRACT FROM AUTHOR]

• Engineered Ag 2 S-NPs showed high stability in simulated human gastrointestinal tract. • Stability of transformed Ag 2 S-NPs was affected by the sulfidation degree. • Ag 2 S-NPs primarily underwent transformations in the mouth phase. • Transformed Ag 2 S-NPs could release silver ion in the gastrointestinal tract. Engineered silver sulfide nanoparticles (e-Ag 2 S-NPs) are used in industry and can be released into the environment. Besides e-Ag 2 S-NPs, transformed silver sulfide nanoparticles (t-Ag 2 S-NPs) from silver nanoparticles are more likely to be the form that is widely distributed in the environment. Both e-Ag 2 S-NPs and t-Ag 2 S-NPs may be ingested and get into human gastrointestinal tract (GIT) through trophic transfer, posing a potential threat to human health. Nevertheless, knowledge of chemical stability of t-Ag 2 S-NPs and e-Ag 2 S-NPs in the human GIT is very limited. Herein e-Ag 2 S-NPs and a series of t-Ag 2 S-NPs with different degrees of sulfidation were selected as models for exposure to the simulated human GIT including mouth, stomach and small intestine phases under fed and fasted conditions. Silver ions were detected in the simulated saliva, gastric and small intestine fluids when t-Ag 2 S-NPs or e-Ag 2 S-NPs were incubated in the simulated GIT, but the amount (e.g., < 20 μg) of silver ion in each phase accounted for < 0.2‰ (w/w) of the silver added (i.e., 100 mg). Silver species of the residual particulate from each phase of the simulated GIT with t-Ag 2 S-NPs or e-Ag 2 S-NPs were thus analyzed through a developed analytical method that could selectively, successively and efficiently dissolve and quantify AgCl, Ag(0), and Ag 2 S in particulates. Both e-Ag 2 S-NPs and fully sulfidized t-Ag 2 S-NPs were shown to be highly stable in the simulated human GIT. Conversely, partially sulfidized t-Ag 2 S-NPs primarily underwent transformations in the mouth phase relative to stomach and small intestine phases regardless of fed or fasted status, wherein AgCl and Ag 2 S were observed besides Ag(0). The amount of Ag 2 S in the mouth phase negatively (r = −0.99, p < 0.001) correlated with the sulfidation degree of initial t-Ag 2 S-NPs. This work improved our understanding of potential transformations of t-Ag 2 S-NPs in the simulated human GIT, providing valuable information for future researches on evaluating health risks of ingested Ag 2 S-NPs. [ABSTRACT FROM AUTHOR]