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.

Roxarsone (ROX), the primary aromatic arsenical additive (AAA) used in animal feeding operations, is of increasing concern to environmental and human health due to land application of ROX-laden animal manure. Few studies have investigated the phytotoxicity, uptake mechanisms, and speciation of AAA in crop plants. In this study, wheat seedlings were employed to address these issues under hydroponic conditions. Compared to inorganic arsenic, ROX was less toxic to wheat root elongation. Wheat roots were more sensitive to ROX stress than shoots. For the first time, metabolized inorganic arsenic was detected in plants, although ROX was the predominant detected arsenic species in wheat seedlings. ROX uptake and toxicity to roots were inhibited by humic acid at concentrations higher than 50 mg/L due to interaction with ROX. Phosphate enhanced ROX uptake, but no trends were observed for ROX uptake in the presence of glycerol at concentrations lower than 250 mM. In addition, ROX uptake was significantly decreased by silicate (Si(IV), 0.5–10 mM) and the metabolic inhibitor, 2,4-dinitrophenol (0.5–2 mM), indicating that ROX transport into wheat roots was actively mediated by Si(IV)-sensitive transporters. These findings provide important insights into the fate and speciation of AAA in soil-water-plant systems relevant to human health.

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.

Steroidal estrogens (SEs), widespread in aquatic systems, have a potential to disrupt the endocrine system of wildlife species and humans. In our experiments, the performance of ε-MnO2 nanorods in transforming 17β-estradiol (E2) was investigated, and the effect of humic acid (HA) on the reaction behaviors was systematically characterized. Reconfiguration of humic molecules was also investigated by high-performance size exclusion chromatography (HPSEC). Results indicated that ε-MnO2 nanomaterials ensured efficient removal of E2 from the aqueous solution. The presence of HA hindered the transformation of E2, while enhanced the cross-coupling between E2 and humic molecules. In particular, we used a mixture of un-labeled E2 and 13C3-labeled E2 at a 1: 1 set ratio (w/w) to probe the reaction products via high-resolution mass spectrometry (HRMS). The combination of HRMS and 13C3-labeling revealed the intermediate products including estrone (E1), and hydroxylated, quinone-like, and ring-opened species, as well as E2 dimer and trimer. More importantly, possible cross-coupling products between E2 and HA were also identified. A reaction mechanism including two-electron oxidation and single-electron oxidation was proposed. The applied analytical approach using HRMS along with 13C3-labeling for reaction-product identification is crucial to understanding the role of HA in the transformation of SEs.

Adsorption is an efficient method for removal of pharmaceuticals and personal care products (PPCPs). Magnetic resins are efficient adsorbents for water treatment and exhibit potential for PPCP removal. In this study, the magnetic hypercrosslinked resin Q100 was used for adsorption of PPCPs. The adsorption behavior of this resin was compared with those of two activated carbons, namely, Norit and F400D. Norit exhibited the fastest adsorption kinetics, followed by Q100. Norit featured a honeycomb shape and long-range ordered pore channels, which facilitated the diffusion of PPCPs. Moreover, the large average pore size of Q100 reduced diffusion resistance. The adsorbed amounts of 11 PPCPs on the three adsorbents increased with increasing adsorbate hydrophobicity. For Q100, a significant linear correlation was observed between the adsorption performance for PPCPs and hydrophobicity (logD value) of adsorbates (R2 = 0.8951); as such, PPCPs with high logD values (>1.69) could be efficiently removed. Compared with those of Norit and F400D, the adsorption performance of Q100 was less affected by humic acid because of the dominant hydrophobic interaction. Furthermore, Q100 showed improved regeneration performance, which renders it promising for PPCP removal in practical applications.

Graphene oxide (GO) and reduced graphene oxide (RGO) materials contain a variety of surface O-functional groups that are chemically reactive. When released into the environment these materials may significantly affect the abiotic transformation of organic contaminants, and therefore, may alter their fate and risks. We found that two GO and five RGO materials that varied in C/O ratio, hydrophobicity, and type/distribution of surface O-functionality all had catalytic effects on the dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA). Even though the catalytic effects of the materials originated from their deprotonated surface O-functional groups, which served as conjugated bases to catalyze the reaction, the catalytic efficiencies of the materials did not correlate strongly with their surface O contents. The spectroscopic evidence (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy), surface charge data, and adsorption experiments demonstrated that the catalytic efficiencies of the GO/RGO materials were controlled by a complex interplay of the type and distribution of surface O-functionality, as well as adsorption affinity of the materials. Both Ca2+ and Mg2+ inhibited the catalytic efficiency of the materials by binding to the surface O-functional groups, and consequently, decreasing the basicity of the functional groups. At an environmentally relevant concentration of 10 mg/L, Suwannee River humic acid (used as a model dissolved organic matter) alone had little effect on the dehydrochlorination of TeCA. However, it could inhibit the catalytic efficiency of the GO/RGO materials by coating on their surface and thus, decreasing the adsorption affinity of these materials for TeCA. The findings further underline the potentially important impacts of nanomaterials on contaminant fate and effects in the environment.

Environmental mobility of C60 fullerene can be significantly affected in the presence of naturally abundant α-FeOOH. However, α-FeOOH vary significantly in sizes, shapes and associated properties that can greatly influence the fate and transport of C60 fullerene in environmental media. Therefore, colloidal hetero-association between well crystallized low aspect (LAsp) α-FeOOH and nC60 fullerene may differ substantially to weakly crystallized high-aspect (HAsp) counterpart. In contrast to LAsp α-FeOOH, inherent crystal defects and surface charge generation in HAsp α-FeOOH facilitated strong Coulombic attraction and aggregation with fullerene in acidic pH. However, LAsp α-FeOOH demonstrated subtle entropic depletion mediated interaction with fullerene prevalent in hard rods. Humic acid (HA) encapsulation of HAsp α-FeOOH substantially blocked fullerene attachment. Minute enhancement in colloidal stability was detected for HA-coated HAsp α-FeOOH and fullerene mixture to HA-coated HAsp α-FeOOH alone. To investigate the interfacial assembly of α-FeOOH with fullerene “in situ” differential interference contrast (DIC) microscopic investigations were employed. This study showed significantly different interface behavior of the binary mixtures of fullerene and HAsp α-FeOOH NPs, and LAsp particles. On air-water interface, bare HAsp α-FeOOH displayed liquid crystalline packing. However, addition of fullerene to HAsp α-FeOOH suspension at pH5 produced closed-loop polygonal and circular ring structures. Head-to-tail alignment of magnetic dipoles as well as fullerene hydrophobicity facilitated such assembly formation. “Ex situ” AFM investigation revealed further the presence of magnetically derived ring structure which asserts that the formed “in situ” ensembles were not transient, hence, may abate fullerene transport through environmental interfaces. Barring hydrophobicity assisted attachment of fullerene to LAsp α-FeOOHs, the absence of any close-packed structures may unlikely abate fullerene transport as envisaged in case of HAsp α-FeOOH. Thus, aspect ratio variation and associated material properties of naturally abundant α-FeOOH may significantly impact fullerene transport through environmental media.

Silica nanoparticles (SiO2 NPs) can cause health hazard after their release into the environment. Adsorption of natural organic matter and biomolecules on SiO2 NPs alters their surface properties and cytotoxicity. In this study, SiO2 NPs were treated by bovine serum albumin (BSA) and humic acid (HA) to study their effects on the integrity and fluidity of model cell membranes. Giant and small unilamellar vesicles (GUVs and SUVs) were prepared as model cell membranes in order to avoid the interference of cellular activities. The microscopic observation revealed that the BSA/HA treated (BSA-/HA-) SiO2 NPs took more time to disrupt membrane than untreated-SiO2 NPs, because BSA/HA adsorption covered the surface SiOH/SiO- groups and weakened the interaction between NPs and phospholipids. The deposition of SiO2 NPs on membrane was monitored by a quartz crystal microbalance with dissipation (QCM-D). Untreated- and HA-SiO2 NPs quickly disrupted the SUV layer on QCM-D sensor; BSA-SiO2 NPs attached on the membranes but only caused slow vesicle disruption. Untreated-, BSA- and HA-SiO2 NPs all caused the gelation of the positively-charged membrane, which was evaluated by the generalized polarity values. HA-SiO2 NPs caused most serious gelation, and BSA-SiO2 NPs caused the least. Our results demonstrate that the protein adsorption on SiO2 NPs decreases the NP-induced membrane damage.

The effects of four types of dissolved organic matters (DOM) on the bioconcentration of perfluoroalkyl substances (PFASs) in Chironomus plumosus larvae have been studied. The PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The DOM included humic acid (HA), fulvic acid (FA), tannic acid (TA), and a protein, peptone (PEP), and their concentrations ranged from 0 to 50 mg L−1. The results showed that, upon bioconcentration equilibrium, the body burdens of longer perfluoroalkyl chain PFASs (PFOS, PFDA, PFUnA and PFDoA) decreased with PEP and HA concentrations while increased with FA and TA concentrations. When FA and TA concentrations increased from 0 to 50 mg L−1, body burdens of these PFASs increased by 7.5%–148.8% and 5.7%–37.1%, respectively. However, the DOM had no significant impact on the body burdens of shorter perfluoroalkyl chain PFASs (PFOA and PFNA). All of the four types of DOM lowered not only the uptake rate constants (ku) of PFASs due to the decrease of freely dissolved PFAS concentrations, but also the elimination rate constants (ke) due to the inhibition effect of DOM on the PFAS elimination from the larvae. The reduction in the two constants varied with both DOM and PFAS types. In the presence of PEP and HA with larger molecular weights, the ku values decreased more than ke, leading to the decreased body burdens of longer perfluoroalkyl chain PFASs. As for FA and TA with smaller molecular weights, the ke values decreased more than ku, resulting in increased body burdens of longer perfluoroalkyl chain PFASs. This study suggests that the effects of DOM on PFAS bioconcentration depend not only on the concentration but also on the molecule weight of DOM, which should be considered in the bioavailability assessment of PFASs.

Perfluoroalkyl acids (PFAAs) are highly stable, persistent, and ubiquitous in the environment with significant concerns growing with regards to both human and ecosystem health. Due to the high stability to both biological and chemical attack, the only currently feasible approach for their removal from water is adsorbent technology. The main objective of this study was to assess a covalent triazine-based framework (CTF) adsorbent for removal from aqueous solutions of perfluoro C4, C6, and C8 carboxylates and sulfonates including the two C8s most commonly monitored, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Adsorption affinity and capacity were quantified and compared to three commonly used sorbents: pulverized microporous activated carbon, single-walled carbon nanotubes, and Amberlite IRA-400 anion-exchange resin. CTF adsorbent exhibited pronouncedly higher adsorption affinity and capacity of PFAAs than other test sorbents. The remarkably strong adsorption to CTF can be attributed to the favored electrostatic interaction between the protonated triazine groups on the inner wall of the hydrophobic CTF pore and the negatively charged head groups of the PFAAs intercalated between the CTF layers. The homogeneous, nanosized pores (1.2 nm) of CTF hindered adsorption of a large-sized dissolved humic acid, thus minimizing the suppression of PFAA adsorption. Additionally, regeneration of CTF was easily accomplished by simply raising pH > 11, which inhibited the electrostatic adsorptive interaction of PFAAs.