Remediation performance and mechanisms of Cu and Cd contaminated water and soil using Mn/Al-layered double oxide-loaded biochar

The combined pollution of heavy metals is ubiquitous worldwide. Mn/Al-layered double oxide-loaded crab shells biochar (LDO/BC) was prepared, so as to remediate the combined pollution of Cd and Cu in soil and water. The pristine and used LDO/BC were characterized and the results revealed that the layered double oxide was successfully loaded on crab shells biochar (BC) and metal element Ca in crab shells was beneficial to the formation of more regular layered and flake structure. The maximal adsorption capacity (Q_m) of LDO/BC for aqueous Cu²⁺ and Cd²⁺ was 66.23 and 73.47 mg/g, respectively. LDO/BC and BC were used to remediate e-waste-contaminated soil for the first time and exhibited highly efficient performance. The extraction amount of Cu and Cd in the contaminated soil by diethylene triamine penta-acetic acid (DTPA) after treating with 5% LDO/BC was significantly reduced from 819.84 to 205.95 mg/kg (with passivation rate 74.8%) and 8.46 to 4.16 mg/kg (with passivation rate 50.8%), respectively, inferring that the bioavailability of heavy metals declined remarkably. The experimental result also suggested that after remediation by LDO/BC the exchangeable and weak acid soluble Cu and Cd in soil translated to reducible, residual and oxidizable fraction which are more stable state. Precipitation, complexation and ion exchange were proposed as the possible mechanisms for Cd and Cu removal. In general, these experiment results indicate that LDO/BC can be a potentially effective reagent for remediation of heavy metal contaminated water and soil.     

Remediation of Cu and As contaminated water and soil utilizing biochar supported layered double hydroxide: Mechanisms and soil environment altering

Preparing materials for simultaneous remediation of anionic and cationic heavy metals contamination has always been the focus of research. Herein a biochar supported FeMnMg layered double hydroxide (LDH) composites (LB) for simultaneous remediation of copper and arsenic contamination in water and soil has been assembled by a facile co-precipitation approach. Both adsorption isotherm and kinetics studies of heavy metals removal by LB were applied to look into the adsorption performance of adsorbents in water. Moreover, the adsorption mechanisms of Cu and As by LB were investigated, showing that Cu in aqueous solution was removed by the isomorphic substitution, precipitation and electrostatic adsorption while As was removed by complexation. In addition, the availability of Cu and As in the soil incubation experiments was reduced by 35.54%–63.00% and 8.39%–29.04%, respectively by using LB. Meanwhile, the addition of LB increased the activities of urease and sucrase by 93.78%–374.35% and 84.35%–520.04%, respectively, of which 1% of the dosage was the best. A phenomenon was found that the richness and structure of microbial community became vigorous within 1% dosage of LB, which indirectly enhanced the passivation and stabilization of heavy metals. These results indicated that the soil environment was significantly improved by LB. This research demonstrates that LB would be an imaginably forceful material for the remediation of anionic and cationic heavy metals in contaminated water and soil.     

Dairy manure as a potential source of crop nutrients and environmental contaminants

Although animal manure is applied to agricultural fields for its nutrient value, it may also contain potential contaminants. To determine the variability in such contaminants as well as in valuable nutrients, nine uncomposted manure samples from Idaho dairies collected during 2.5 years were analyzed for macro- and micro-nutrients, hormones, phytoestrogens, antibiotics, veterinary drugs, antibiotic resistance genes, and genetic elements involved in the spread of antibiotic resistance. Total N ranged from 6.8 to 30.7 (C:N of 10 to 21), P from 2.4 to 9.0, and K from 10.2 to 47.7 g/kg manure. Zn (103 – 348 mg/kg) was more abundant than Cu (56 – 127 mg/kg) in all samples. Phytoestrogens were the most prevalent contaminants detected, with concentrations fluctuating over time, reflecting animal diets. This is the first study to document the presence of flunixin, a non-steroidal anti-inflammatory drug, in solid stacked manure from regular dairy operations. Monensin was the most frequently detected antibiotic. Progesterones and sulfonamides were regularly detected. We also investigated the relative abundance of several types of plasmids involved in the spread of antibiotic resistance in clinical settings. Plasmids belonging to the IncI, IncP, and IncQ1 incompatibility groups were found in almost all manure samples. IncQ1 plasmids, class 1 integrons, and sulfonamide resistance genes were the most widespread and abundant genetic element surveyed, emphasizing their potential role in the spread of antibiotic resistance. The benefits associated with amending agricultural soils with dairy manure must be carefully weighed against the potential negative consequences of any manure contaminants.     

Oxidation of diclofenac by birnessite: Identification of products and proposed transformation pathway

Diclofenac(DCF), a widely used non-steroidal anti-inflammatory, reacted readily with birnessite under mild conditions, and the pseudo first order kinetic constants achieved 8.84 × 10^-2 hr^-1. Five products of DCF including an iminoquinone product(2,5-iminoquinone-diclofenac) and four dimer products were observed and identified by tandem mass spectrometry during the reaction. Meanwhile, 2,5-iminoquinone-diclofenac was identified to be the major product, accounting for 83.09% ...     

Adsorption mechanisms of PFOA onto activated carbon anchored with quaternary ammonium/epoxide-forming compounds: A combination of experiment and model studies

When wood-based activated carbon was tailored with quaternary ammonium/epoxide (QAE) forming compounds (QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid (PFOA) from groundwater. With favorable tailoring, QAE-AC removed PFOA from groundwater for 118,000 bed volumes before half-breakthrough in rapid small scale column tests, while the influent PFOA concentration was 200 ng/L. The tailoring involved pre-dosing QAE at an array of proportions onto this carbon, and then monitoring bed life for PFOA removal. When pre-dosing with 1 mL QAE, this PFOA bed life reached an interim peak, whereas bed life was less following 3 mL QAE pre-dosing, then PFOA bed life exhibited a steady rise for yet subsequently higher QAE pre-dosing levels. Large-scale atomistic modelling was used herein to provide new insight into the mechanism of PFOA removal by QAE-AC. Based on experimental results and modelling, the authors perceived that the QAE's epoxide functionalities cross-linked with phenolics that were present along the activated carbon's graphene edge sites, in a manner that created mesopores within macroporous regions or created micropores within mesopores regions. Also, the QAE could react with hydroxyls outside of these pore, including the hydroxyls of both graphene edge sites and other QAE molecules. This latter reaction formed new pore-like structures that were external to the activated carbon grains. Adsorption of PFOA could occur via either charge balance between negatively charged PFOA with positively charged QAE, or by van der Waals forces between PFOA's fluoro-carbon tail and the graphene or QAE carbon surfaces.     

Effects of reductive inorganics and NOM on the formation of chlorite in the chlorine dioxide disinfection of drinking water

Chlorine dioxide (ClO₂) disinfection usually does not produce halogenated disinfection by-products, but the formation of the inorganic by-product chlorite (ClO₂^–) is a serious consideration. In this study, the ClO₂^– formation rule in the ClO₂ disinfection of drinking water was investigated in the presence of three representative reductive inorganics and four natural organic matters (NOMs), respectively. Fe²⁺ and S^2– mainly reduced ClO₂ to ClO₂^– at low concentrations. When ClO₂ was consumed, the ClO₂^– would be further reduced by Fe²⁺ and S^2–, leading to the decrease of ClO₂^–. The reaction efficiency of Mn²⁺ with ClO₂ was lower than that of Fe²⁺ and S^2–. It might be the case that MnO₂ generated by the reaction between Mn²⁺ and ClO₂ had adsorption and catalytic oxidation on Mn²⁺. However, Mn²⁺ would not reduce ClO₂^–. Among the four NOMs, humic acid and fulvic acid reacted with ClO₂ actively, followed by bovine serum albumin, while sodium alginate had almost no reaction with ClO₂. The maximum ClO₂^– yields of reductive inorganics (70%) was higher than that of NOM (around 60%). The lower the concentration of reductive substances, the more ClO₂^– could be produced by per unit concentration of reductive substances. The results of the actual water samples showed that both reductive inorganics and NOM played an important role in the formation of ClO₂^– in disinfection.     

Impact of pre-oxidation on the formation of byproducts in algae-laden water disinfection: Insights from fluorescent and molecular weight

Pre-oxidation has been reported to be an effective way to remove algal cells in water, but the released algal organic matter (AOM) could be oxidized and lead to the increment in disinfection by-product (DBP) formation. The relationship between pre-oxidation and AOM-derived DBP formation needs to be approached more precisely. This study compared the impact of four pre-oxidants, ozone (O₃), chlorine dioxide (ClO₂), potassium permanganate (KMnO₄) and sodium hypochlorite (NaClO), on the formation of nitrogenous (N-) and carbonaceous (C-) DBPs in AOM chlorination. The characterization (fluorescent properties, molecular weight distribution and amino acids concentration) on AOM samples showed that the characterization properties variations after pre-oxidation were highly dependent on the oxidizing ability of oxidants. The disinfection experiments showed that O₃ increased DBP formation most significantly, which was consistent with the result of characterization properties variations. Then canonical correspondent analysis (CCA) and Pearson's correlation analysis were conducted based on the characterization data and DBP formation. CCA indicated that C-DBPs formation was highly dependent on fluorescent data. The formation of haloacetic acids (HAAs) had a positive correlation with aromatic protein-like component while trichloromethane (TCM) had a positive correlation with fulvic acid-like component. Pearson's correlation analysis showed that low molecular weight fractions were favorable to form N-DBPs. Therefore, characterization data could provide the advantages in the control of DBP formation, which further revealed that KMnO₄ and ClO₂ were better options for removing algal cells as well as limiting DBP formation.     

Complex interplay between formation routes and natural organic matter modification controls capabilities of C60 nanoparticles (nC60) to accumulate organic contaminants

Accumulation of organic contaminants on fullerene nanoparticles (nC₆₀) may significantly affect the risks of C₆₀ in the environment. The objective of this study was to further understand how the interplay of nC₆₀ formation routes and humic acid modification affects contaminant adsorption of nC₆₀. Specifically, adsorption of 1,2,4,5-tetrachlorobenzene (a model nonionic, hydrophobic organic contaminant) on nC₆₀ was greatly affected by nC₆₀ formation route – the formation route significantly affected the aggregation properties of nC₆₀, thus affecting the available surface area and the extent of adsorption via the pore-filling mechanism. Depending on whether nC₆₀ was formed via the “top-down” route (i.e., sonicating C₆₀ powder in aqueous solution) or “bottom-up” route (i.e., phase transfer from an organic solvent) and the type of solvent involved (toluene versus tetrahydrofuran), modification of nC₆₀ with Suwannee River humic acid (SRHA) could either enhance or inhibit the adsorption affinity of nC₆₀. The net effect depended on the specific way in which SRHA interacted with C₆₀ monomers and/or C₆₀ aggregates of different sizes and morphology, which determined the relative importance of enhanced adsorption from SRHA modification via preventing C₆₀ aggregation and inhibited adsorption through blocking available adsorption sites. The findings further demonstrate the complex mechanisms controlling interactions between nC₆₀ and organic contaminants, and may have significant implications for the life-cycle analysis and risk assessment of C₆₀.     

Formation of sulfur oxide groups by SO2 and their roles in mercury adsorption on carbon-based materials

The presence of SO₂ display significant effect on the mercury (Hg) adsorption ability of carbon-based sorbent. Yet the adsorption and oxidation of SO₂ on carbon with oxygen group, as well as the roles of different sulfur oxide groups in Hg adsorption have heretofore been unclear. The formation of sulfur oxide groups by SO₂ and their effects on Hg adsorption on carbon was detailed examined by the density functional theory. The results show that SO₂ can be oxidized into SO₃ by oxygen group on carbon surface. Both C-SO₂ and C-SO₃ can improve Hg adsorption on carbon site, while the promotive effect of C-SO₂ is stronger than C-SO₃. Electron density difference analyses reveal that sulfur oxide groups enhance the charge transfer ability of surface unsaturated carbon atom, thereby improving Hg adsorption. The experimental results confirm that surface active groups formed by SO₂ adsorption is more active for Hg adsorption than the groups generated by SO₃.     

New methods for identification of disinfection byproducts of toxicological relevance: Progress and future directions

Disinfection byproducts (DBPs) represent a ubiquitous source of chemical exposure in disinfected water. While over 700 DBPs have been identified, the drivers of toxicity remain poorly understood. Additionally, ever evolving water treatment practices have led to a continually growing list of DBPs. Advancement of analytical technologies have enabled the identification of new classes of DBPs and the quantification of these chemically diverse sets of DBPs. Here we summarize advances in new workflows for DBP analysis, including sample preparation, chromatographic separation with mass spectrometry (MS) detection, and data processing. To aid in the selection of techniques for future studies, we discuss necessary considerations for each step in the strategy. This review focuses on how each step of a workflow can be optimized to capture diverse classes of DBPs within a single method. Additionally, we highlight new MS-based approaches that can be powerful for identifying novel DBPs of toxicological relevance. We discuss current challenges and provide perspectives on future research directions with respect to studying new DBPs of toxicological relevance. As analytical technologies continue to advance, new strategies will be increasingly used to analyze complex DBPs produced in different treatment processes with the aim to identify potential drivers of toxicity.     

Insight into the mechanisms of trichloronitromethane formation by vacuum ultraviolet: QSAR model and FTICR-MS analysis

Vacuum ultraviolet(VUV) photolysis is recognized as an environmental-friendly treatment process. Nitrate(NO-3) and natural organic matter(NOM) are widely present in water source.We investigated trichloronitromethane(TCNM) formation during chlorination after VUV photolysis, because TCNM is an unregulated highly toxic disinfection byproduct. In this study:(1) we found reactive nitrogen species that is generated under VUV photolysis of NO-3react with organic matter to form nitrogen-containing compo...     

A review of gas-phase chemical mechanisms commonly used in atmospheric chemistry modelling

The atmospheric chemical mechanism is an essential component of airshed models used for investigating the chemical behaviors and impacts of species. Since the first tropospheric chemical mechanism was proposed in the 1960s, various mechanisms including Master Chemical Mechanism (MCM), Carbon Bond Mechanism (CBM), Statewide Air Pollution Research Center (SAPRC) and Regional Atmospheric Chemistry Mechanism (RACM) have been developed for different research purposes. This work summarizes the development and applications of these mechanisms, introduces their compositions and lumping methods, and compares the ways the mechanisms treat radicals with box model simulations. CBM can reproduce urban pollution events with relatively low cost compared to SAPRC and RACM, whereas the chemical behaviors of radicals and the photochemical production of ozone are described in detail in RACM. The photolysis rates of some oxygenated compounds are low in SAPRC07, which may result in underestimation of radical levels. As an explicit chemical mechanism, MCM describes the chemical processes of primary pollutants and their oxidation products in detail. MCM can be used to investigate certain chemical processes; however, due to its large size, it is rarely used in regional model simulations. A box model case study showed that the chemical behavior of OH and HO₂ radicals and the production of ozone were well described by all mechanisms. CBM and SAPRC underestimated the radical levels for different chemical treatments, leading to low ozone production values in both cases. MCM and RACM are widely used in box model studies, while CBM and SAPRC are often selected in regional simulations.     

Water-lifting and aeration system improves water quality of drinking water reservoirs: Biological mechanism and field application

Reservoirs have been served as the major source of drinking water for dozens of years. The water quality safety of large and medium reservoirs increasingly becomes the focus of public concern. Field test has proved that water-lifting and aeration system (WLAS) is a piece of effective equipment for in situ control and improvement of water quality. However, its intrinsic bioremediation mechanism, especially for nitrogen removal, still lacks in-depth investigation. Hence, the dynamic changes in water quality parameters, carbon source metabolism, species compositions and co-occurrence patterns of microbial communities were systematically studied in Jinpen Reservoir within a whole WLAS running cycle. The WLAS operation could efficiently reduce organic carbon (19.77%), nitrogen (21.55%) and phosphorus (65.60%), respectively. Biolog analysis revealed that the microbial metabolic capacities were enhanced via WLAS operation, especially in bottom water. High-throughput sequencing demonstrated that WLAS operation altered the diversity and distributions of microbial communities in the source water. The most dominant genus accountable for aerobic denitrification was identified as Dechloromonas. Furthermore, network analysis revealed that microorganisms interacted more closely through WLAS operation. Oxidation-reduction potential (ORP) and total nitrogen (TN) were regarded as the two main physicochemical parameters influencing microbial community structures, as confirmed by redundancy analysis (RDA) and Mantel test. Overall, the results will provide a scientific basis and an effective way for strengthening the in-situ bioremediation of micro-polluted source water.     

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur(DOS) by electrospray ionizationFourier transform ion cyclotron resonance mass spectrometry(ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ioni...     

Highly inhibited transport of dissolved thallium(I) in manganese oxide-coated sand: Chemical condition effects and retention mechanisms

Thallium contamination in water can cause great danger to the environment. In this study, we synthesized manganese oxide-coated sand (MOCS) and investigated the transport and retention behaviors of Tl(I) in MOCS under different conditions. Characterization methods combined with a two-site nonequilibrium transport model were applied to explore the retention mechanisms. The results showed that Tl(I) mobility was strongly inhibited in MOCS media, and the retention capacity calculated from the fitted model was 510.41 mg/g under neutral conditions. The retention process included adsorption and oxidative precipitation by the manganese oxides coated on the sand surface. Cotransport with the same concentration of Mn(II) led to halving Tl(I) retention due to competition for reactive sites. Enhanced Tl(I) retention was observed under alkaline conditions, as increasing pH promoted electronegativity on the media surface. Moreover, the competitive cation Ca²⁺ significantly weakened Tl(I) retention by occupying adsorption sites. These findings provide new insights into understanding Tl(I) transport behavior in water-saturated porous media and suggest that manganese oxide-coated sand can be a cost-effective filter media for treating Tl-contaminated water.     

The interaction mechanisms of co-existing polybrominated diphenyl ethers and engineered nanoparticles in environmental waters:A critical review

This review focuses on the occurrence and interactions of engineered nanoparticles(ENPs)and brominated flame retardants(BFRs) such as polybrominated diphenyl ethers(PBDEs)in water systems and the generation of highly complex compounds in the environment.The release of ENPs and BFRs(e.g. PBDEs) to aquatic environments during their usage and disposal are summarised together with their key interaction mechanisms. The major interaction mechanisms including electrostatic, van der Waals, hydrophobic, ...     

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

Roles of semivolatile and intermediate-volatility organic compounds in secondary organic aerosol formation and its implication: A review

Secondary organic aerosol(SOA) is a very important component of fine particulate matter(PM_2.5) in the atmosphere. However, the simulations of SOA, which could help to elucidate the detailed mechanism of SOA formation and quantify the roles of various precursors, remains unsatisfactory, as SOA levels are frequently underestimated. It has been found that the performance of SOA formation models can be significantly improved by incorporating the emission and evolution of semivolatile and ...     

Removal of antibiotic-resistant genes during drinking water treatment: A review

Once contaminate the drinking water source, antibiotic resistance genes (ARGs) will propagate in drinking water systems and pose a serious risk to human health. Therefore, the drinking water treatment processes (DWTPs) are critical to manage the risks posed by ARGs. This study summarizes the prevalence of ARGs in raw water sources and treated drinking water worldwide. In addition, the removal efficiency of ARGs and related mechanisms by different DWTPs are reviewed. Abiotic and biotic factors that affect ARGs elimination are also discussed. The data on presence of ARGs in drinking water help come to the conclusion that ARGs pollution is prevalent and deserves a high priority. Generally, DWTPs indeed achieve ARGs removal, but some biological treatment processes such as biological activated carbon filtration may promote antibiotic resistance due to the enrichment of ARGs in the biofilm. The finding that disinfection and membrane filtration are superior to other DWTPs adds weight to the advice that DWTPs should adopt multiple disinfection barriers, as well as keep sufficient chlorine residuals to inhibit re-growth of ARGs during subsequent distribution. Mechanistically, DWTPs obtain direct and inderect ARGs reduction through DNA damage and interception of host bacterias of ARGs. Thus, escaping of intracellular ARGs to extracellular environment, induced by DWTPs, should be advoided. This review provides the theoretical support for developping efficient reduction technologies of ARGs. Future study should focus on ARGs controlling in terms of transmissibility or persistence through DWTPs due to their biological related nature and ubiquitous presence of biofilm in the treatment unit.     

Thermal behaviors, combustion mechanisms, evolved gasses, and ash analysis of spent potlining for a hazardous waste management

An unavoidable but reusable waste so as to enhance a more circular waste utilization has been spent potlining (SPL) generated by the aluminum industry. The combustion mechanisms, evolved gasses, and ash properties of SPL were characterized dynamically in response to the elevated temperature and heating rates. Differential scanning calorimetric (DSC) results indicated an exothermic reaction behavior probably able to meet the energy needs of various industrial applications. The reaction mechanisms for the SPL combustion were best described using the 1.5-, 3- and 2.5-order reaction models. Fluoride volatilization rate of the flue gas was estimated at 2.24%. The SPL combustion emitted CO₂, HNCO, NO, and NO₂ but SO_x. The joint optimization of remaining mass, derivative thermogravimetry, and derivative DSC was achieved with the optimal temperature and heating rate combination of 783.5°C, and 5 °C/min, respectively. Interaction between temperature and heating rate exerted the strongest and weakest impact on DSC and remaining mass, respectively. The fluorine mainly as the formation of substantial NaF and CaF₂ in the residual ash. Besides, the composition and effect of environment of residual solid were evaluated. The ash slagging tendency and its mineral deposition mechanisms were elucidated in terms of turning SPL waste into a benign input to a circular waste utilization.