Bioelectrochemical Chromium(VI) Removal in Plant-Microbial Fuel Cells.

Plant-microbial fuel cell (PMFC) is a renewable and sustainable energy technology that generates electricity with living plants. However, little information is available regarding the application of PMFC for the remediation of heavy metal contaminated water or soil. In this study, the potential for the removal of heavy metal Cr(VI) using PMFC was evaluated, and the performance of the PMFC at various initial Cr(VI) contents was investigated. The Cr(VI) removal efficiency could reached 99% under various conditions. Both the Cr(VI) removal rates and the removal efficiencies increased with the increasing initial Cr(VI) concentration. Furthermore, the long-term operation of the PMFC indicated that the system was stable and sustainable for Cr(VI) removal. The mass balance results and XPS analysis results demonstrate that only a small amount of soluble Cr(III) remained in the PMFC and that most Cr(III) precipitated in the form of the Cr(OH)3(s) or was adsorbed onto the electrodes. The PMFC experiments of without acetate addition also show that plants can provide carbon source for MFC through secrete root exudates and bioelectrochemical reduction of Cr(VI) was the main mechanism for the Cr(VI) removal. These results extend the application fields of PMFC and might provide a new insight for Cr(VI) removal from wastewater or soil.

FTIR and synchronous fluorescence heterospectral two-dimensional correlation analyses on the binding characteristics of copper onto dissolved organic matter.

Dissolved organic matter (DOM) is known to form strong complexes with heavy metals and thus governs the distribution, toxicity, bioavailability, and ultimate fate of heavy metals in the environment. The relevant aspects of metal-organic interactions remain unclear because the metal binding functionalities in DOM are substantially nonuniform and the availability of the models is limited. In this work, two-dimensional correlation spectroscopy (2DCOS) integrated with synchronous fluorescence and infrared absorption spectroscopy was used to explore the binding process of copper to DOM. A series of heterogeneous binding sites in humic acid (HA), a representative DOM, and the subsequent subtle changes of these sites within the molecular interactions were elucidated by the 2DCOS method. The band assignments and the correspondence between the results obtained by two spectral probes (synchronous fluorescence and infrared absorption spectra) were verified by hetero-2DCOS. Our results showed that, during the copper binding process, the carboxyl and polysaccharide groups gave the fastest responses to copper binding. Then fluorescence quenching of fluorescent humic-like moieties occurred with a vibrational change of the related functionalities, i.e., phenolic and aryl carboxylic groups, which further induces the fluorescence quenching of fulvic-like fractions. Finally, small amounts of amide and aliphatic groups participated in the copper binding after the fluorescence of the protein-like fraction decreased. With these promising results, a comprehensive picture of structural changes of HA during the copper binding process was developed, highlighting the superior potential of 2D heterospectral correlation spectroscopy in studying complex interactions in the environment.

Arsenic adsorption by carboxylate and amino modified polystyrene micro- and nanoplastics: kinetics and mechanisms.

We investigated adsorption characteristics of As(III) and As(V) onto two different functionalized polystyrene (PS) microplastics (MPs). Our results show that there is the potential for PS MPs to adsorb both As(III) and As(V). Using a particle size of 80-82 nm, maximum As(III) and As(V) adsorption capacities of 0.57 mg/g and 0.37 mg/g were obtained by PS-COOH MPs. These capacities were markedly higher than those for PS-NH2 MPs, which were 0.41 mg/g and 0.27 mg/g, respectively. The pseudo-second-order adsorption kinetic model was found to effectively describe the sorption kinetics of As(III)/As(V) on two different functionalized PS MPs. Langmuir isotherms better represented the equilibrium adsorption results. The kinetic models, XPS, and FTIR results indicate that hydrogen bonding, hydroxyl complexation, and outer-sphere surface complexation may have partly contributed to adsorption of As onto PS MPs. Adsorption capacity markedly decreases with increasing salinity or presence of humic acids (HA), suggesting an inhibiting effect of salinity and HA through outer-sphere complexation. These findings confirm that microplastics have great potential to adsorb As and hence are ultimately highly likely to affect the environmental behavior of As in an ecosystem.

Effects of microplastics on arsenic uptake and distribution in rice seedlings.

The potential of microplastics (MPs) and nanoplastics (NPs) to act as a carrier for heavy metals derived from the environment is of rising concern to the health of global ecosystems. Here, we investigated the effects of particle size of polystyrene micro/nano plastics on the uptake, accumulation, and toxicity of As in rice seedlings in a hydroponic system. Significant differences in As uptake and accumulation in different plant tissue were observed between the plants co-exposed to 82 nm NPs + As and 200 nm MPs + As. The NPs + As co-exposure led to higher As accumulation in rice leaves (12.4-36.7 %), while larger sized MPs + As(V) treatment reduced As accumulation in rice leaves. Furthermore, the co-exposure of NPs/MPs + As mitigated the rice growth inhibition caused by As toxicity. These results will provide insight into elucidating the potentially effects of nano/microplastics on As uptake and accumulation in crop plants for assessing the hazards of micro-and nanoplastics as pollutants in the food chain and environment.

Insights into the interaction mechanism of ofloxacin and functionalized nano-polystyrene.

Nano-plastics (NPs), an emerging contaminant in the environment, have a larger specific surface area and can act as a carrier of other contaminants. Thus, insights into the interaction mechanisms between NPs and other pollutants are crucial for the assessment of environmental impacts of NPs in the ecosystems. In this study, the interaction mechanism between NPs and ofloxacin (OFL) were investigated via kinetics, fluorescence quenching, and two-dimensional correlation spectroscopy (2DCOS). The adsorption kinetics of OFL on carboxyl-modified polystyrene (PS-COOH) and amine modified polystyrene (PS-NH2) closely fitted the pseudo-second-order kinetics model (R2 = 0.99). Adsorption kinetics indicated that chemical adsorption is dominant mechanism, and the Fourier Transform Infrared Spectrometer (FT-IR) and X-ray photoelectron spectroscopy (XPS) results showed that the electronic interaction, π-π, and H-binding were also involved in the adsorption process. OFL showed strong fluorescence quenching in the presence of NPs. Stern-Volmer quenching was negatively related with the temperature, which was dominated by the static type of quenching. 2DCOS indicated that the π-π conjugation was dominant in the interaction process, and the interaction process was dependent on the solution pH and salinity. Overall, this work provides new insights into the interaction mechanism of NPs and antibiotics in the aquatic ecosystems.

Fe-modified fly ash/cotton stalk biochar composites for efficient removal of phosphate in water: mechanisms and green-reuse potential.

Excessive phosphate content input into natural water can lead to the waste of resource and eutrophication. Biochar is a kind of low-cost adsorbent. However, its adsorption capacity for phosphate is low. In order to solve this problem, Fe compound-modified fly ash/cotton stalk biochar composites (Fe-FBC) were prepared through co-pyrolyzed fly ash and cotton stalk at 800℃, followed by infiltration of FeSO4 solution. The samples were characterized by scanning electron microscopy, Brunauer-Emmett-Teller, X-ray diffraction, Fourier transform infrared spectroscopy, and zeta potential. After modification, the hydrophilicity and polarity of Fe-FBC increased. In addition, the pore volume, specific surface area, and surface functional groups were significantly improved. The adsorption behavior of Fe-FBC for the removal of phosphate from water can be well fitted by the pseudo-second-order kinetic and Sips isotherm adsorption model, with a maximum adsorption capacity of 47.91 mg/g. Fe-FBC maintained a high adsorption capacity in the pH range of 3-10. The coexisting anions (NO3-, SO42-, and Cl-) had negligible effects on phosphate adsorption. The adsorption mechanisms of Fe-FBC include electrostatic attraction, ligand exchange, surface complexation, ion exchange, chemical precipitation, and hydrogen bonding. Moreover, the desorption process of phosphate was investigated, indicating that the phosphate-saturated Fe-FBC could use as slow-release phosphate fertilizer. This study proposed a potentially environmental protection and recycling economy approach, which consists of recycling resources and treating wastes with wastes.

Phytoextraction, accumulation, and toxicological effects of 1-tetradecyl-3-methylimidazolium ionic liquid in ryegrass (Lolium perenne L.).

Ionic liquids are widely used in many fields due to their extremely tunable nature and exceptional properties. The extensive application of ionic liquids raises great concerns regarding their bioaccumulation potential and adverse effects on organisms. Green plants have a great potential for uptake of persistent xenobiotics from aquatic and terrestrial environment. However, the assimilation and bioaccumulation of 1-tetradecyl-3-methylimidazolium bromide ([C14mim]Br) have not been studied in plants yet. In order to explore the phytoaccumulation of [C14mim]+, ryegrass were exposed to [C14mim]Br with hydroponic experiment. The effects of [C14mim]Br dosages on growth index, chlorophyll content, malondialdehyde (MDA) content, and antioxidant enzyme activity of ryegrass were investigated. The toxic effects of [C14mim]Br on ryegrass growth increased with increasing initial concentration. The high initial concentration treatment resulted in rapid changes in physiological characteristics in ryegrass tissue. [C14mim]+ ions were mainly accumulated in root tissue and partly translocated to the above ground part of ryegrass. [C14mim]+ was observed in the highest concentration (314.35 µg/g in root and 101.42 µg/g in aboveground parts of ryegrass) with 10 mg/L of [C14mim]Br. Our results demonstrated that ryegrass can uptake and accumulate [C14mim]+ and is therefore a suitable species for phytoremediation of trace amount of [C14mim]+ and possibly other ionic liquids.

Benthic Biofilm Bacterial Communities and Their Linkage with Water-Soluble Organic Matter in Effluent Receivers.

Benthic biofilms are pioneering microbial aggregates responding to effluent discharge from wastewater treatment plants (WWTPs). However, knowledge of the characteristics and linkage of bacterial communities and water-soluble organic matter (WSOM) of benthic biofilms in effluent-receiving rivers remains unknown. Here, we investigated the quality of WSOM and the evolution of bacterial communities in benthic biofilm to evaluate the ecological impacts of effluent discharge on a representative receiving water. Tryptophan-like proteins showed an increased proportion in biofilms collected from the discharge area and downstream from the WWTP, especially in summer. Biofilm WSOM showed weak humic character and strong autochthonous components, and species turnover was proven to be the main factor governing biofilm bacteria community diversity patterns. The bacterial community alpha diversity, interspecies interaction, biological index, and humification index were signally altered in the biofilms from the discharge area, while the values were more similar in biofilms collected upstream and downstream from the WWTP, indicating that both biofilm bacterial communities and WSOM characters have resilience capacities. Although effluent discharge simplified the network pattern of the biofilm bacterial community, its metabolic functional abundance was basically stable. The functional abundance of carbohydrate metabolism and amino acid metabolism in the discharge area increased, and the key modules in the non-random co-occurrence network also verified the important ecological role of carbon metabolism in the effluent-receiving river. The study sheds light on how benthic biofilms respond to effluent discharge from both ecological and material points of view, providing new insights on the feasibility of utilizing benthic biofilms as robust indicators reflecting river ecological health.

Alkyl chain length affecting uptake of imidazolium based ionic liquids by ryegrass (Lolium perenne L.).

Imidazolium based ionic liquids (ILs) have been extensively used in the various industrial fields, however, the dependence of their structure on toxicity and bioavailability by plants is not clear. Thus, in this study, uptake of imidazolium based ILs with different alkyl chain lengths (e.g., [C2mim]+ and [C8mim]+) by ryegrass and their toxicity to plant growth were investigated. Results show that the two ILs could be removed by ryegrass with high efficiencies, and a higher uptake efficiency and accumulation was observed for [C2mim]+ with shorter chain length compared with that for [C8mim]+. A higher growth inhibition of ryegrass by [C8mim]+ was observed compared with that by [C2mim]+, indicating the long alkyl chain length of ILs had a negative effect on the plant growth. ILs taken up by ryegrass was retained in the roots and their translocation from roots to shoots was restricted. The IL concentration in roots was 0.68 mg/g-fresh weight for [C2mim]+ and 0.08 mg/g- fresh weight for [C8mim]+ when the ryegrass was exposed to 10 mg/L ILs. This study proved that plant assimilation of ILs depended on their alky chain lengths, which would be useful for understanding the fate of ILs with various structures in phytoremediation for ILs-contaminated water.

Adsorption of ciprofloxacin to functionalized nano-sized polystyrene plastic: Kinetics, thermochemistry and toxicity.

Plastic debris is ubiquitous in aquatic systems and has been proven vehicles for the transport of various pollutants including trace organic compounds. Nanoplastics have large specific surface area and hydrophobic characteristics and therefore are capable of adsorbing other organic or inorganic chemicals from the environment. Antibiotics, as another class of emerging contaminants, have raised significant research concern in recent years as they pose threats to the ecosytems and human health. Nevertheless, little information is available on the adsorption behaviors of antibiotics onto nano-sized plastics. The toxicity of combined nanoplastics and antibiotics is also largely unknown. In this study, the physicochemical and thermodynamic interactions between representative nanoplastics, which containing a carboxyl functional group of polystyrene nanoplastics (PS-COOH), and typical antibiotic, i.e., ciprofloxacin (CIP) were investigated in a batch adsorption experiment. The specific thermodynamic correlation function of PS-COOH combined with CIP was obtained through isothermal titration microcalorimetry (ITC) analysis. The adsorption kinetics and isotherm of CIP on PS-COOH closely fit the pseudo-second-order kinetic model (r2 = 0.99) and Freundlich isotherm (r2 = 0.99). The ITC results showed that the adsorption reaction of PS-COOH with CIP was a spontaneous exothermic reaction. The adsorption of antibiotics on nanoplastics may aggravate the negative impacts of these two pollutants on aqueous ecosystems, and we hypothesized that would be reflected in the survival rate of model organism of Caenorhabditis elegans when exposed to this combination. This work used a mechanistic approach to unravel the adsorption behavior of antibiotics on nanoplastics and shed light on their potential impact on aquatic ecosystems.

Chemical speciation of ciprofloxacin in aqueous solution regulates its phytotoxicity and uptake by rice (Oryza sativa L.).

Ciprofloxacin (CIP), a widely used fluoroquinolone antibiotic, is frequently detected in aqueous environments, and could be assimilated by vegetable plants to possess potential threats to human and animal health through food chains. However, plant uptake of CIP in different chemical speciation has still far from clear now. Thus, the toxicity and uptake of CIP by rice plants were investigated under different solution pH, owing to its contribution to different chemical speciation of CIP. Results display that high pH-driven changes of CIP from cation (CIP+) to anion (CIP-) decreased its adsorption and uptake by excised roots and intact plants, respectively. However, CIP concentrations in roots, stems and leaves all exhibited no significant differences with increasing solution pH. Moreover, six intermediates of CIP were detected and two possible transformation pathways were proposed in rice plants, including firstly oxidation and following consecutive cleavage of piperazine ring. After accumulated in plant tissues, CIP significantly inhibited the plant growth, decreased the photosynthetic pigments contents and enhanced the antioxidant enzyme activities in a concentration-dependent manner. Besides, high pH exacerbated the growth inhibition and changed the oxidative damage responses of rice plants to CIP. These findings indicate that the uptake and toxicity of CIP in rice plants were influenced by solution pH-driven changes of its chemical speciation.

Uptake and accumulation of imidazolium ionic liquids in rice seedlings: Impacts of alkyl chain length.

The uptake and accumulation of three imidazolium ionic liquids with different alkyl chain lengths ([C2min]Br, [C4min]Br, [C8min]Br) in rice seedlings were investigated. All three different ILs were primarily accumulated in roots, while only a little amount of ILs were translocated and accumulated in stems and leaves. Accumulation and transportation of ILs in rice depend on the concentration and the alkyl chain length of ILs. ILs contents in the roots, stems and leaves decreased as ILs alkyl chain length increased. Growth inhibition results showed that the toxic effects of ILs on rice growth depends on the alkyl chain length: [C8min]Br >[C4min]Br >[C2min]Br. As markers of defense and phytotoxicity, the plant antioxidant enzymes and biochemical stress responses were also assessed. All different ILs significantly increased malondialdehyde (MDA), catalase (CAT), peroxidase (POD) and dismutase (SOD) activities in rice tissue. Compared to the control group, the contents of chlorophyll a reduced by 59.56%, 62.28% and 69.74% after addition of [C2min]Br, [C4min]Br, and [C8min]Br, respectively. This study provides important information for a better understanding on the uptake and accumulation of imidazolium ILs by agricultural plants.

Concentration- and nutrient-dependent cellular responses of microalgae Chlorella pyrenoidosa to perfluorooctanoic acid.

Perfluorooctanoic acid (PFOA), an emerging and persistent pollutant, could cause toxicity effects on aquatic organisms. However, this was generally assessed under high exposure concentrations of PFOA and nutrient-enriched conditions, which was not accordant with the actual environments. Therefore, to comprehensively understand the toxicity effects of PFOA on aquatic organisms, the cellular responses of microalgae, Chlorella pyrenoidosa, to PFOA under different concentrations (≤ 1.0 mg/L) and nutrient conditions were investigated in this study. Results show that PFOA at concentrations less than 1.0 mg/L had no significant effects on algal growth and chlorophyll contents, and no oxidative damages were generated to destroy membrane integrity and morphology. However, N,P-limited and -starved conditions significantly decreased algal growth and chlorophyll contents, and induced oxidative stresses to ruin the structure and function of cell membrane. Moreover, the deficiency of P had more severe negative effect on algae than that of N, and they both influenced the toxicity responses of microalgae to 1.0 mg/L PFOA. The adsorption and uptake percentages of PFOA by algal cells were both less than 10%, and increased adsorption but decreased uptake of PFOA amounts occurred under N,P-limited and -starved conditions. These findings will be useful to understand the toxicity effects of PFOA on microalgae in aquatic environments.

Synthesis of Fe3O4 nanocomposites for efficient separation of ultra-small oil droplets from hexadecane-water emulsions.

Eco-friendliness and low cost are critical when investigating new oil-water separation agents with high separation efficiencies for the treatment of emulsified oily wastewater in industrial applications, including crude oil exploitation. Treatment methods specifically suited to wastewater containing ultra-small oil droplets are lacking and urgently required. This study investigated the one-pot synthesis of humic acid and polydimethyldiallylammonium chloride coated Fe3O4 nanoparticles. A low dosage of the nanoparticles (375 µg mL-1) exhibited excellent separation efficiency (nearly 100%) and reusability when applied to hexadecane-water emulsions containing ultra-small droplets (200-300 nm). Electrostatic interactions and the strong interfacial activity of the nanoparticles played essential roles in achieving oil-water separation. This study provided an efficient extraction material synthesized by a facile and cheap method for separating ultra-small oil droplets from emulsions.

Mixture toxicity and uptake of 1-butyl-3-methylimidazolium bromide and cadmium co-contaminants in water by perennial ryegrass (Lolium perenne L.).

Ionic liquids, a kind of emerging and persistent organic contaminants, always coexist with heavy metals in aquatic and terrestrial environments. However, the feasibility of phytoremediation to remove ionic liquids and heavy metals co-contaminants is still unclear. Thus, in this study, the hydroponic experiment was conducted to investigate the combined effect of 1-butyl-3-methylimidazolium bromide ([C4mim]+Br-) and cadmium (Cd2+) on growth and physiological indictors of perennial ryegrass, together with their uptake and translocation by plants. Results show that the exposure of ryegrass to [C4mim]+ and Cd2+ mixture significantly inhibited the biomass growth and affected the photosynthetic pigments contents in leaves. The increases of lipid peroxidation and catalase, peroxidase activity were also observed under the co-exposure experiments. The mixture toxicity of [C4mim]+ and Cd2+ to ryegrass growth showed an additive effect predicted by concentration addition and independent action. [C4mim]+ uptake and acropetal translocation by ryegrass were significantly inhibited with dosing Cd2+. In contrast, [C4mim]+ had no obvious effect on Cd2+ uptake by ryegrass, while enhanced Cd2+ translocation from roots to shoots occurred with increasing [C4mim]+ dosages. These results indicate that the co-contamination of ionic liquids and heavy metals would affect their fates during phytoremediation.

Uptake, accumulation and metabolization of 1-butyl-3-methylimidazolium bromide by ryegrass from water: Prospects for phytoremediation.

The unique properties of ionic liquids make them attractive for a wide range of industrial applications, which makes it easy to be released into the environment and cause water or soil pollution. Phytoremediation of organic contaminants is a safe and important process for removing persistent pollutants from the environment. However, due to they are very chemically stable and potentially toxic to plants, whether they can be removed, assimilated and metabolized by plants remains unknown during phytoremediation process. In this study, ryegrass, Lolium perenne L., was used for imidazolium ionic liquid (1-butyl-3-methylimidazolium bromide, [C4mim]+) removal from water. The results show that [C4mim]+ could be taken up, accumulated and metabolized by plants in vivo with a high removal efficiency. Most of the [C4mim]+ was accumulated in the root tissue, with the root concentration fraction factors ranging from 4.9 to 51.5. Two hydroxylated metabolites 1-(4-hydroxybutyl)-3-methylimidazolium, and 1-(n-butyl)-3-(hydroxymethyl)-imidazolium, and two secondary metabolites were detected in the ryegrass after [C4mim]+ uptake. The metabolic mechanism was clarified using density functional theory calculations. Furthermore, [C4mim]+ at a high concentration was found to be high toxic to inhibit the growth of ryegrass markedly. In response, some oxidative stress was observed in the metabolic process, as indicated by increasing of catalase, super dismutase and peroxidase activities. Our results suggested that phytoremediation was an efficient technique for ionic liquids treatment from water.

Structural response of humic acid upon binding with lead: A spectroscopic insight.

Lead (Pb) is a widespread heavy metal that can cause damage to the ecosystem, and the ubiquitously existing dissolved organic matter (DOM) can significantly affect the environmental behavior of Pb. The present work explores the interaction process of Pb with humic acid (HA) through integration of synchronous fluorescence and log-transformed UV-vis absorption spectroscopy coupled with spectral slope calculation and two-dimensional correlation analyses. The spectral slope calculation results show that the carboxylic and phenolic groups in HA were the predominant binding sites to Pb, and the interaction process was highly dependent on solution pH. Correlation analyses confirmed a superior binding affinity of carboxylic groups in HA over phenolic groups. Integration of spectral slope calculation with two-dimensional correlation spectroscopy is a promising tool for better understanding the molecular structure of Pb-DOM complexes and the characteristics of Pb binding to DOM, which may provide new insights into the prevention, control, and remediation of Pb contamination in environment.

Microbial fuel cell driving electrokinetic remediation of toxic metal contaminated soils.

An investigation of the feasibility of in-situ electrokinetic remediation for toxic metal contaminated soil driven by microbial fuel cell (MFC) is presented. Results revealed that the weak electricity generated from MFC could power the electrokinetic remediation effectively. The metal removal efficiency and its influence on soil physiological properties were also investigated. With the electricity generated through the oxidation of organics in soils by microorganisms, the metals in the soils would mitigate from the anode to the cathode. The concentrations of Cd and Pb in the soils increased gradually through the anode to the cathode regions after remediation. After about 143days and 108 days' operation, the removal efficiencies of 31.0% and 44.1% for Cd and Pb at the anode region could be achieved, respectively. Soil properties such as pH and soil conductivity were also significantly redistributed from the anode to the cathode regions. The study shows that the MFC driving electrokinetic remediation technology is cost-effective and environmental friendly, with a promising application in soil remediation.

Copper release from copper nanoparticles in the presence of natural organic matter.

Copper nanoparticles (CuNPs) are widely used and inevitably released into aqueous environments, causing ecological and health risks. Ubiquitous natural organic matter (NOM) might affect the copper release behaviors from CuNPs and their toxicity. This work aims to elucidate how NOM affects copper release from CuNPs, with a focus on the impacts of NOM properties and the NOM-CuNPs interaction mechanism. The copper release kinetics and different copper fractions induced by representative NOMs were characterized. The presence of NOM led to a more dispersive state of CuNPs clusters. Copper release mainly resulted from complexation reactions between CuNPs and functional groups of NOM. Humic substances were more effective in releasing copper than sodium alginate and bovine serum albumin, due to a higher amount of functional groups and lower molecular weight, which facilitated the contact and complexion reactions. Chlorination treatment of NOM significantly decelerated copper release due to the destruction of functional groups and less attachment of NOM. However, the copper releasing ability of humic acid was not substantially affected by Ca²âº-induced coagulation. This study provides better understanding about the persistence and transformation of CuNPs in aquatic environments.