The number of products containing engineered nanomaterials (ENMs) has increased due to their high industrial relevance as well as their use in diverse consumer products. At the end of their life cycle ENMs might be released to the environment and therefore concerns arise regarding their environmental impact. In order to track their fate upon disposal, it is crucial to establish methods to trace ENMs in complex environmental samples and to differentiate them from naturally-occurring nanoparticles. The goal of this study was to distinctively trace ENMs by (non-invasive) detection methods. For this, fluorescent ENMs, namely quantum dots (QDs), were distinctively traced in complex aqueous matrices, and were still detectable after a period of two months using fluorescence spectroscopy. In particular, two water-dispersible QD-species, namely CdTe/CdS QDs with N-acetyl-l-cysteine as capping agent (NAC-QDs) and surfactant-stabilized CdSe/ZnS QDs (Brij®58-QDs), were synthesized to examine their environmental fate during disposal as well as their potential interaction with naturally-occurring substances present in landfill leachates. When QDs were spiked into a leachate from an old landfill site, alteration processes, such as sorption, aggregation, agglomeration, and interactions with dissolved organic carbon (DOC), led to modifications of the optical properties of QDs. The spectral signatures of NAC-QDs deteriorated depending on residence time and storage temperature, while Brij®58-QDs retained their photoluminescence fingerprints, indicating their high colloidal stability. The observed change in photoluminescence intensity was mainly caused by DOC-interaction and association with complexing agents, such as fulvic or humic acids, typically present in mature landfill leachates. For both QD-species, the results also indicated that pH of the leachate had no significant impact on their optical properties. As a result, the unique spectroscopic fingerprints of QDs, specifically surfactant-stabilized QDs, allowed distinctive tracing in complex aqueous waste matrices in order to study their long-term behavior and ultimate fate.

The sorption of selenite, SeO32−, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, Kd, determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. The results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.

Per- and polyfluoroalkyl substances (PFASs) were detected in the atmosphere of a source region in Tianjin, China. Fluorotelomer alcohols (FTOHs) were the dominant neutral PFASs in the atmosphere with total concentrations of 93.6-131 pg/m3 and 8:2 FTOH contributing the most, whereas perfluorooctane sulfonamide derivatives (PFOSAs) were two magnitudes lower or undetected. In comparison, ionic PFASs (perfluoroalkyl carboxyl acids (PFCAs)) in the atmosphere were detected at similar or even higher levels. At wastewater treatment plants (WWTPs), the air over influent was found with higher levels of FTOHs than over aeration tank and effluent; whereas in the air over the aeration tank, the concentrations of PFOSAs and nonvolatile ionic PFASs substantially increased, suggesting a possible direct release of ionic PFASs to the atmosphere besides the atmospheric conversion from volatile precursors. In the air phase, a low proportion (1-5%) of PFCAs was subjected to dry deposition in the source region. Interestingly, the dry-deposition-to-bulk-air ratios of PFCA analogues were the lowest at medium chain lengths (C8 and C9) and increased with either shorter or longer chain length. The extraordinary affinity of shorter-chain PFCAs (C6-C7) to particles was presumed to be due to their smaller molecular size favoring the interactions between the carboxyl head groups and specific sorption sites on particulate matter.

Biosolids are extensively used in agriculture as fertilizers while offering a practical solution for waste disposal. Many pharmaceutical and personal care products (PPCPs), such as triclosan and triclocarban, are enriched in biosolids. Biosolid amendment changes soil physicochemical properties, which may in turn alter the persistence of PPCPs and hence the risk for secondary contamination such as plant uptake. To delineate the effect of biosolids on PPCPs persistence, triclosan and triclocarban were used as model compounds in this study and their sorption (Kd) and persistence (t1/2) were determined in different soils before and after biosolid amendment. Biosolids consistently increased sorption of triclosan and triclocarban in soil. The Kd of triclosan increased by 3.9–21 times following amendment of a sandy loam soil with biosolids at 2–10%. The persistence of both compounds was prolonged, with t1/2 of triclosan increasing from 10 d in the unamended soil to 63 d after biosolid amendment at 10%. The relationship between t1/2 and Kd was further examined through a meta-analysis using data from this study and all relevant published studies. A significant linear relationship between t1/2 and Kd was observed for triclosan (r2 = 0.69, p < 0.01) and triclocarban (r2 = 0.38, p < 0.05) in biosolid-amended soils. On the average, when biosolid amendment increased by 1%, t1/2 of triclosan was prolonged by 7.5 d, while t1/2 of triclocarban was extended by 4.7 d. Therefore, biosolid amendment greatly enhances persistence of triclosan and triclocarban, likely due to enhanced sorption or decreased chemical bioavailability. This finding highlights the importance to consider the effect of biosolids when evaluating the environmental risks of these and other biosolid-borne PPCPs.

Magnetic biochars (MW) prepared by chemical co-precipitation of Fe2+/Fe3+ on water hyacinth biomass followed by pyrolysis exhibited important potential in aqueous As(V) elimination. In comparison, MW2501 outperformed other MWs and exhibited the highest As(V) sorption capacity which was estimated to be 7.4 mg g−1 based on Langmuir-Freundlic model. With solution pH ranging from 3 to 10, As(V) removal efficiency by MW2501 kept stable and consistently higher than 90%. Besides, ∼100% removal of 0.5 mM As(V) can be obtained in the presence of P ≤ 0.1 mM or Cr/Sb ≤ 0.5 mM, indicating a wide applicability of MW2501 for treatment of As-containing water. The predominance of Fe3O4 on MW2501 surface was evidenced by XRD. Ligand exchange between As(V) anion and the hydroxylated surface of Fe3O4 as well as H bond was largely responsible for As(V) sorption as suggested by FTIR. XPS analysis further revealed the dominance of As(V) in the sorbed As on MW2501 surface with co-occurrence of a minor proportion of As(III) (11.45%). In parallel, oxidative transformation of Fe3O4 to Fe2O3 was also suggested by XPS. By a lab-scale column test, the potential and suitability of MW2501 in As-containing water treatment was further confirmed, which could also provide an alternative way to manage and utilize this highly problematic invasive species.

Biochar is a porous carbonaceous material with high alkalinity and rich minerals, making it possible for CO2 capture. In this study, biochars derived from pig manure, sewage sludge, and wheat straw were evaluated for their CO2 sorption behavior. All three biochars showed high sorption abilities for CO2, with the maximum capacities reaching 18.2–34.4 mg g−1 at 25 °C. Elevating sorption temperature and moisture content promoted the transition of CO2 uptake from physical to chemical process. Mineral components such as Mg, Ca, Fe, K, etc. in biochar induced the chemical sorption of CO2 via the mineralogical reactions which occupied 17.7%–50.9% of the total sorption. FeOOH in sewage sludge biochar was transformed by sorbed CO2 into Fe(OH)2CO3, while the sorbed CO2 in pig manure biochar was precipitated as K2Ca(CO3)2 and CaMg(CO3)2, which resulted in a dominant increase of insoluble inorganic carbon in both biochars. For wheat straw biochar, sorbed CO2 induced CaCO3 transformed into soluble Ca(HCO3)2, which led to a dominant increase of soluble inorganic carbons. The results obtained from this study demonstrated that biochar as a unique carbonaceous material could distinctly be a promising sorbent for CO2 capture in which chemical sorption induced by mineralogical reactions played an important role.

Although enantioselective sorption to soil particles has been proposed as a mechanism that can potentially influence the availability of individual chiral pesticide enantiomers in the environment, environmental fate studies generally overlook this possibility and assume that only biotic processes can be enantioselective, whereas abiotic processes, such as sorption, are non-enantioselective. In this work, we present direct evidence for the effect of the enantioselective sorption of a chiral pesticide in a natural soil on the availability of the single pesticide enantiomers for transport. Batch sorption experiments, with direct determination of the sorbed amounts, combined with column leaching tests confirmed previous observations that from non-racemic aqueous solutions the sorption of the chiral fungicide metalaxyl on the soil appeared to be enantioselective, and further demonstrated that the enantiomer that was sorbed to a greater extent (R-metalaxyl, Kd = 1.73 L/kg) exhibited retarded leaching compared to its optical isomer (S-metalaxyl, Kd = 1.15 L/kg). Interconversion and degradation of the pesticide enantiomers, which are potential experimental artifacts that can lead to erroneous estimates of sorption and its enantioselectivity, were discarded as possible causes of the observed enantioselective behavior. The results presented here may have very important implications for a correct assessment of the environmental fate of chiral pesticides that are incorporated into the environment as non-racemic mixtures, and also of aged chiral pesticide residues that have been transformed from racemic to non-racemic by biologically-mediated processes.

Superfund sites with sediments contaminated by hydrophobic organic compounds (HOCs) can be difficult to characterize because of the complex nature of sorption to sediments. Porewater concentrations, which are often used to model transport of HOCs from the sediment bed into overlying water, benthic organisms, and the larger food web, are traditionally estimated using sediment concentrations and sorption coefficients estimated using equilibrium partitioning (EqP) theory. However, researchers have begun using polymeric samplers to determine porewater concentrations since this method does not require knowledge of the sediment's sorption properties. In this work, polyethylene passive samplers were deployed into sediments in the field (in situ passive sampling) and mixed with sediments in the laboratory (ex situ active sampling) that were contaminated with polychlorinated biphenyls (PCBs). The results show that porewater concentrations based on in situ and ex situ sampling generally agreed within a factor of two, but in situ concentrations were consistently lower than ex situ porewater concentrations. Imprecision arising from in situ passive sampling procedures does not explain this bias suggesting that field processes like bioirrigation may cause the differences observed between in situ and ex situ polymeric samplers.

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

Cadmium (Cd) is a non-essential trace element that accumulates in agricultural soils through the application of Cd-rich phosphate fertiliser. Vegetables can accumulate Cd to concentrations that sometimes exceed food safety standards. We investigated the potential of low-cost soil amendments to reduce Cd uptake by spinach (Spinacia oleracea L.), lettuce (Lactuca sativa L.) and onion (Allium cepa L.). Batch sorption experiments revealed the relative sorption of Cd by biosolids, charcoal, lignite, sawdust, two types of compost, bentonite and zeolite. Lignite and compost had the greatest ability to sorb Cd and were subsequently selected for pot trials, which elucidated their effect on Cd uptake by onions, spinach and lettuce in two market garden soils with native Cd concentrations of 1.45 mg/kg and 0.47 mg/kg. The addition of 2.5% (dry w/w) municipal compost reduced the Cd concentration in onions, spinach and lettuce by up to 60% in both soils. The addition of lignite gave variable results, which depended on the soil type and rate of addition. This Cd immobilisation was offset by soil acidification caused by the lignite. The results indicate that municipal compost is a low-cost soil conditioner that is effective in reducing plant Cd uptake.