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Tropical soils are often deeply weathered and vulnerable to degradation having low pH and unfavorable Al/Fe levels, which can constrain crop production. This study aims to examine nitrogen-enriched novel biochar co-composts prepared from rice straw, maize stover, and gram residue in various mixing ratios of the biochar and their feedstock materials for the amelioration of acidic tropical soil. Three pristine biochar and six co-composts were prepared, characterized, and evaluated for improving the chemical and biological quality of the soil against a conventional lime treatment. The pH, cation exchange capacity (CEC), calcium carbonate equivalence (CCE) and nitrogen content of co-composts varied between 7.78–8.86, 25.3–30.5 cmol (p+) kg−1, 25.5–30.5%, and 0.81–1.05%, respectively. The co-compost prepared from gram residue biochar mixed with maize stover at a 1:7 dry-weight ratio showed the highest rise in soil pH and CEC, giving an identical performance with the lime treatment and significantly better effect (p < .05) than the unamended control. Agglomerates of calcite and dolomite in biochar co-composts, and surface functional groups contributed to pH neutralization and increased CEC of the amended soil. The co-composts also significantly (p < .05) increased the dehydrogenase (1.87 µg TPF g−1 soil h−1), β-glucosidase (90 µg PNP g−1 soil h−1), and leucine amino peptidase (3.22 µmol MUC g−1 soil h−1) enzyme activities in the soil, thereby improving the soil’s biological quality. The results of this study are encouraging for small-scale farmers in tropical developing countries to sustainably reutilize crop residues via biochar-based co-composting technology.

Refereed/Peer-reviewed Silicon nanoparticles (SiNPs) have been widely used to immobilize toxic trace metal(loid)s (TTMs) in contaminated croplands. However, the effect and mechanisms of SiNP application on TTM transportation in response to phytolith formation and phytolith-encapsulated-TTM (PhytTTM) production in plants are unclear. This study demonstrates the promotion effect of SiNP amendment on phytolith development and explores the associated mechanisms of TTM encapsulation in wheat phytoliths grown on multi-TTM contaminated soil. The bioconcentration factors between organic tissues and phytoliths of As and Cr (> 1) were significantly higher than those of Cd, Pb, Zn and Cu, and about 10 % and 40 % of the total As and Cr that bioaccumulated in wheat organic tissues were encapsulated into the corresponding phytoliths under high-level SiNP treatment. These observations demonstrate that the potential interaction of plant silica with TTMs is highly variable among elements, with As and Cr being the two most strongly concentrated TTMs in the phytoliths of wheat treated with SiNPs. The qualitative and semi-quantitative analyses of the phytoliths extracted from wheat tissues suggest that the high pore space and surface area (≈ 200 m² g⁻¹) of phytolith particles could have contributed to the embedding of TTMs during silica gel polymerization and concentration to form PhytTTMs. The abundant Sisingle bondO functional groups and high silicate-minerals in phytoliths are dominant chemical mechanisms for the preferential encapsulation of TTMs (i.e., As and Cr) by wheat phytoliths. Notably, the organic carbon and bioavailable Si of soils and the translocation of minerals from soil to plant aerial parts can impact TTM sequestration by phytoliths. Thus, this study has implications for the distribution or detoxification of TTMs in plants via preferential PhytTTM production and biogeochemical cycling of PhytTTMs in contaminated cropland following exogenous Si supplementation.

Biochar, a potential alternative of infield crop residue burning, can prevent nutrient leaching from soil and augment soil fertility. However, pristine biochar contains low cation (CEC) and anion (AEC) exchange capacity. This study developed fourteen engineered biochar by treating a rice straw biochar (RBC-W) first separately with different CEC and AEC enhancing chemicals, and then with their combined treatments to increase CEC and AEC in the novel biochar composites. Following a screening experiment, promising engineered biochar, namely RBC-W treated with O3-HCl-FeCl3 (RBC-O-Cl), H2SO4-HNO3-HCl-FeCl3 (RBC-A-Cl), and NaOH-Fe(NO3)3(RBC-OH-Fe), underwent physicochemical characterization and soil leaching-cum nutrient retention studies. RBC-O-Cl, RBC-A-Cl, and RBC-OH-Fe recorded a spectacular rise in CEC and AEC over RBC-W. All the engineered biochar remarkably reduced the leaching of NH4+-N, NO3- -N, PO43--P and K+ from a sandy loam soil and increased retention of these nutrients. RBC-O-Cl at 4.46 g kg-1 dosage emerged as the most effective soil amendment increasing the retention of above ions by 33.7, 27.8, 15.0, and 5.74 % over a comparable dose of RBC-W. The engineered biochar could thus enhance plants' nutrient use efficiency and reduce the use of costly chemical fertilizers that are harmful to environmental quality. Refereed/Peer-reviewed

usc Microplastics have become a global concern, and soil acts as a major sink for plastic pollution. Due to rapid development of soil microplastics research, various analysis methods have been developed, but require proper consistency and standard procedures. The objective of this study was to appraise a quality assessment concerning soil microplastics from a methodological perspective. Nine studies were selected for the quality assessment exercise based on methodological investigations on soil microplastics and were evaluated based on the adapted Criteria for Reporting and Evaluating Ecotoxicity Data (CRED) method. The highest score obtained by an individual study was 21 while the lowest was 14, leaving a wide score gap which indicated inconsistency amongst the studies. Criterion with the highest average score of 2.0 was obtained for sample size and data reporting. The lowest average score of 0.89 was for the negative control. In conclusion, the total average scores for all eleven criteria were 1.56. Current quality assessment perceived that there was room for improvement and betterment of quality assurance for studies on microplastics and a form of guideline on methodological aspects of soil microplastics studies. It was suggested that future microplastics studies should methodically include quality assurance/quality control (QA/QC) protocols in every process to ensure that good quality data is produced and applied in the risk assessment process. Refereed/Peer-reviewed

Refereed/Peer-reviewed Humic substances with or without chemical modification can serve as environmentally benign and inexpensive adsorbents of potentially toxic trace elements (PTTEs) in the environment. The present study investigated the absorption of Pb, Zn, Cu and Ni by natural and potassium persulfate (K2S2O8) modified humic acids (HAs) isolated from a lowland peat through batch experiments. The adsorption of the studied PTTEs on the natural HA was satisfactorily described by the Langmuir isotherm model with maximum monolayer adsorption capacities of 318.2, 286.5, 225.0 and 136.8 mmol/kg for Pb, Cu, Zn and Ni, respectively. A thorough characterization of the natural and modified HA using 13C nuclear magnetic resonance spectroscopy demonstrated that the chemical modification of natural HA with K2S2O8 led to an increase in the content of carboxyl groups, and ketone and quinoid fragments in the HA structure. Consequently, the modified HA absorbed 16.3, 14.2, 10.6 and 6.9% more Pb, Ni, Zn and Cu, respectively, than the original natural HA. The isotherm data modeling together with adsorbent characterization suggested that the adsorption of PTTEs was controlled mainly by chemisorption mechanisms where inner-sphere complexations of metal ions with HA functional groups took place.

Results from earlier laboratory and field experiments were interrogated for the possibilities of sequestration, or long term accumulation, of carbon from excess greenhouse gases in the atmosphere. In the laboratory study, samples of three (top)soils dominated by kaolinite and illite (together), smectite, and allophane were examined for the adsorption and desorption of dissolved organic carbon (DOC). Adsorption and desorption of DOC were carried out on clay fractions extracted physically and after first native organic matter and then iron oxides were removed chemically. Labeled organic material was added to the soils to assess the priming effect of organic carbon (OC). In the field, changes in OC were measured in sandy soils that had been amended by additions of clay for between 3 and 17 years, both through incorporation of exogenous clay and delving of in situ clay. The laboratory experiments demonstrated that a portion of DOC was held strongly in all soils. The amount of DOC adsorbed depended on clay mineral types, including Fe oxides. Much adsorbed DOC was lost by desorption in water and a substantial amount of native OC was lost on priming with new OC. Addition of clay to soils led to increased OC. Therefore, addition of clay to soil may enhance net sequestration of C. Organic carbon close to mineral surfaces or within micro aggregates is held most strongly. Carbon sequestration may occur in subsoils with unsaturated mineral surfaces. However, incorporation of carbon into macroaggregates from enhanced plant growth might be most effective in removing excess carbon from the atmosphere, albeit over the short-term. Refereed/Peer-reviewed

Nanoplastics are drawing a significant attention as a result of their propensity to spread across the environment and pose a threat to all organisms. The presence of nanoplastics in water is given attention nowadays as the transit of nanoplastics occurs through the aquatic ecosphere besides terrestrial mobility. The principal removal procedures for macro-and micro-plastic particles are effective, but nanoparticles escape from the treatment, increasing in the water and significantly influencing the society. This critical review is aimed to bestow the removal technologies of nanoplastics from aquatic ecosystems, with a focus on the treatment of freshwater, drinking water, and wastewater, as well as the importance of transit and its impact on health concerns. Still, there exists a gap in providing a collective knowledge on the methods available for nanoplastics removal. Hence, this review offered various nanoplastic removal technologies (microorganism-based degradation, membrane separation with a reactor, and photocatalysis) that could be the practical/effective measures along with the traditional procedures (filtration, coagulation, centrifugation, flocculation, and gravity settling). From the analyses of different treatment systems, the effectiveness of nanoplastics removal depends on various factors, source, size, and type of nanoplastics apart from the treatment method adopted. Combined removal methods, filtration with coagulation offer great scope for the removal of nanoplastics from drinking water with >99 % efficiency. The collected data could serve as base-line information for future research and development in water nanoplastics cleanup. Refereed/Peer-reviewed

Purpose: Similar to fresh- and brackish water aquaculture ponds, commercial shrimp farming in degraded saline areas holds the potential to bury carbon (C) in the sediments. However, studies on the mechanisms of sediment C dynamics and C-flux in response to inland saline aquaculture management practices are still scarce. Therefore, the objectives of the present study are to quantify the C burial rate in inland saline aquaculture ponds and assess the impact of inland saline aquaculture on sensitive C fractions in the bottom sediment of the ponds. Materials and methods: The sediment samples (n = 12 from each pond) were collected from six shrimp farming ponds (1000 m2 area of each pond) of different ages. The sediment depth, sediment accumulation rate and the levels of total carbon (TC), total organic carbon (TOC) and sediment oxidizable organic carbon (SOC) and its different fractions were determined using standard procedures. The data were analysed by one-way analysis of variance (ANOVA), followed by the Duncan's multiple range test for comparing the means, and the Pearson correlation test was used to assess the relationship between the different pond sediment parameters and SOC content. Results and discussion: The results revealed that the annual C accumulation rates varied from 902 to 1346 kg C ha−1 year−1 in 7-year-old earthen ponds (EPs) and bottom cemented ponds (BCPs), respectively. The sediment C fractions, including TC, TOC, SOC and its fractions (very labile, VLc; labile, Lc; less labile, LLc), and non-labile carbon (NLc)) were progressively increased over the pond age. The inland saline aquaculture practices over the years increased both active (AC) and passive carbon (PC) pools in the pond sediments, helped in the restoration and improvement of sediment quality and enhanced C sequestration potential of the sediments. Furthermore, a significant increase in the level of particulate organic carbon (POC) in BCPs justified that the non-ploughing practices at BCPs facilitated the formation of macro- and micro-aggregates, thereby increasing the C retention and stability of the pond sediments. Conclusion: This study suggested that the shrimp farming ponds in semi-arid saline soils represented considerable C burial hotspots, enhanced the stable passive C pools and improved the sediment quality. Refereed/Peer-reviewed

Fast weathering of parent materials and rapid mineralization of organic matter because of prevalent climatic conditions, and subsequent development of acidity and loss/exhaustion of nutrient elements due to intensive agricultural practices have resulted in the degradation of soil fertility and productivity in the vast tropical areas of the world. There is an urgent need for rejuvenation of weathered tropical soils to improve crop productivity and sustainability. For this purpose, biochar has been found to be more effective than other organic soil amendments due to biochar's stability in soil, and thus can extend the benefits over long duration. This review synthesizes information concerning the present status of biochar application in highly weathered tropical soils highlighting promising application strategies for improving resource use efficiency in terms of economic feasibility. In this respect, biochar has been found to improve crop productivity and soil quality consistently through liming and fertilization effects in low pH and infertile soils under low-input conditions typical of weathered tropical soils. This paper identifies several advance strategies that can maximize the effectiveness of biochar application in weathered tropical soils. However, strategies for the reduction of costs of biochar production and application to increase the material's use efficiency need future development. At the same time, policy decision by linking economic benefits with social and environmental issues is necessary for successful implementation of biochar technology in weathered tropical soils. This review recommends that advanced biochar strategies hold potential for sustaining soil quality and agricultural productivity in tropical soils. Refereed/Peer-reviewed

Chromium (Cr) contamination in soil and water poses high toxicity risks to organisms and threatens food and water security worldwide. Biochar has emerged as a promising material for cleaning up Cr contamination owing to biochar's strong capacity to immobilize Cr. This paper synthesizes information on biochar modification for the efficient remediation of Cr contamination in soil and water, and critically reviews mechanisms of Cr adsorption on pristine and modified biochars. Biochar modification methods include physical activation via ball milling or ultraviolet irradiation, chemical activation via magnetization, alkali/acid treatment, nano-fabrication or loading of reductive agents, and biological activation via integrating biochars with microorganisms and their metabolites. Modified biochars often have multi-fold enhancement in Cr adsorption/reduction capacity than pristine biochars. Iron (Fe)-supported magnetic biochars have the most promising Cr removal abilities with high reusability of the biochars. Pre-pyrolysis modification with Fe could load Fe3O4 micro-/nanoparticles on biochars, and increase the surface area and electrostatic attraction between chromate anions and biochar surfaces, and reduce Cr(VI) to Cr(III). Post-pyrolysis modification could enrich oxygen-containing functional groups such as Cdouble bondO and –OH on biochar surfaces and promote Cr reduction and adsorption. Future research directions for Cr mitigation using advanced biochar products are discussed in this review. Refereed/Peer-reviewed

Poly- and perfluoroalkyl substances (PFAS) are synthetic chemicals, which reach terrestrial and aquatic environments through anthropogenic activities. Major sources of PFAS in the environment include fire-fighting foams (aqueous film forming foam (AFFF)), wastewater sources, biosolids, and composts. Limited information is available about PFAS in wastewater, which is the focus of this review. PFAS wastewater sources include domestic effluents, industrial effluents, landfill leachates, stormwater, and agricultural effluents through their use in various applications. Land application of PFAS-contaminated wastewater can lead to the contamination of soil and groundwater, thereby reaching the food chain through plant uptake and consumption of potable water. Landfill leachates and industrial effluents contain the highest concentrations of PFAS, posing serious risks to surrounding waterways. Transformation of PFAS precursors can occur through abiotic and biotic processes within the treatment of wastewater, resulting in the formation of harmful PFAS compounds. Currently, there is limited data reported on novel short-chain and ultra-short chain PFAS and PFAS precursors. The strong thermal and chemical stability of PFAS and the complex nature of PFAS mixtures makes the remediation of PFAS in wastewater challenging. However, the review examines and compares current technologies which can treat and remove PFAS from wastewaters. In this review, the distribution, transformation, and remediation of PFAS and their substitutes in wastewater sources are covered. Refereed/Peer-reviewed

In this study, a pristine biochar (BC) and MgCl2-modified biochar (MBC) were prepared using Pennisetum sp. straw for removing Cd2+ from aqueous solutions. Scanning electron microscope (SEM) imaging combined with energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), as well as the surface area and porosity analyses were used to reveal the physico-chemical characteristics of the pristine and modified adsorbents. Results suggested that MgCl2 impregnation during the synthesis had enhanced the specific surface area and pore volume of the biochar. Batch adsorption experiments indicated that the Cd2+ adsorption data of MBC fitted the Langmuir isothermal and pseudo-second order kinetic models, indicating a chemical adsorption was undergoing in the system. The maximum adsorption capacity of Cd2+ on MBC was 763.12 mg/g, which was 11.15 times higher than that of the pristine BC. The Cd2+ removal by MBC was mainly attributed to the mechanisms in an order: Cd(OH)2 precipitation (73.43%) > ion exchange (22.67%) > Cd2+-π interaction (3.88%), with negligible contributions from functional group complexation, electrostatic attraction and physical adsorption. The MBC could thus be used as a promising adsorbent for Cd2+ removal from aqueous solutions.

Soil serves as both a ‘source’ and ‘sink’ for contaminants. As a source, contaminants are derived from both ‘geogenic’ and ‘anthropogenic’ origins. Typically, while some of the inorganic contaminants including potentially toxic elements are derived from geogenic origin (e.g. arsenic and selenium) through weathering of parent materials, the majority of organic (e.g. pesticides and microplastics) as well as inorganic (e.g. lead, cadmium) contaminants are derived from anthropogenic origin. As a sink, soil plays a critical role in the transformation of these contaminants and their subsequent transfer to environmental compartments, including groundwater (e.g. pesticides), surface water (phosphate and nitrate), ocean (e.g. microplastics) and atmosphere (e.g. nitrous oxide emission). A complex transformation process of contaminants in soil involving adsorption, precipitation, redox reactions and biodegradation control the mobility, bioavailability and environmental toxicity of these contaminants. Soil also plays a major role in the decontamination of contaminants, and the ‘cleaning’ action of soil is controlled primarily by the physico-chemical interactions of contaminants with various soil components, and the biochemical transformations facilitated by soil microorganisms. In this article, we examine the geogenic and anthropogenic sources of contaminants reaching the soil, and discuss the role of soil in the sequestration and decontamination of contaminants in relation to various physico-chemical and microbial transformation reactions of contaminants with various soil components. Finally, we propose future actions that would help to maintain the role of soils in protecting the environment from contaminants and delivering sustainable development goals. This article is part of the theme issue ‘The role of soils in delivering Nature's Contributions to People’.

Refereed/Peer-reviewed Arsenic (As) poses a tremendous threat to human health due to exposure through arsenic-contaminated drinking water and/or food. We aimed to develop organically modified clay adsorbents for the removal of As from aqueous solution. We modified a smectite sample using three organic agents, namely hexadecyl trimethylammonium (HDTMA), chitosan and citric acid, and characterized the products using X-ray diffraction, infrared spectroscopy, and scanning electron microscopy techniques. The characterization techniques suggested successful organic modifications of the smectite sample. The surfactant-modified smectite was the most efficient (66.9%) As removing adsorbent with a maximum adsorption capacity of 473.2 μg g⁻¹. Kinetic study showed that the adsorbents reached As adsorption equilibrium within 3 h, and the data fitted reasonably well to power function and simple Elovich equations (R² > 0.89). The adsorption data were explained well by the Freundlich and Sips isothermal models. The surfactant-modified and chitosan-grafted organoclays adsorbed As by electrostatic attraction and anion exchange, whereas the citric acid activated smectite followed ligand exchange and simple anion exchange mechanisms. This study thus demonstrated the potential of surfactant-modified clays in removing As from contaminated waters.

Refereed/Peer-reviewed Biochar (BC) exhibits a great potential as an adsorbent in decontamination of water. To improve the adsorption capabilities and impart the particular functionalities of BC, various methods (chemical modification, physical modification, impregnation with different materials, and magnetic modification) have been developed. As compared to surface modifications, BC-based composites provide various technical and environmental benefits because they require fewer chemicals, lesser energy, and confer enhanced contaminant removal capacity. Therefore, this review focuses on BC composites prepared by the combination of BC with different additives including metals, metal oxides, clay minerals, and carbonaceous materials, which greatly alter the physico-chemical properties of BC and broaden its adsorption potential for a wide range of aquatic contaminants. Techniques for the preparation of BC composites, their adsorption potentials for a variety of inorganic and organic environmental contaminants, factors affecting BC properties and the adsorption process, and the mechanisms involved in adsorption are also discussed. Modification typically alters the surface properties and functionalities of BC composites including surface area, pore volume, pore size, surface charge, and surface functional groups. Hence, modification enhances the adsorption capacity of BC for most organic and inorganic compounds and ions. Nevertheless, some modifications negatively affect the adsorption of certain contaminants because of various factors including obstruction of pores due to over coating and development of same charge as contaminant on the surface of BC. However, the use of BC composites in environmental remediation is still in its infancy, and further research and development is needed to reach scalability and commercialization of the new technology.

Nitrate (NO3−) and bicarbonate (HCO3−) are harmful for the water quality and can potentially create negative impacts to aquatic organisms, crops and humans. This study deals with the removal of NO3− and HCO3− from contaminated wastewater using Fe-exchanged nano-bentonite and Fe3O4 nanoparticles. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, surface area measurement and particle size analysis revealed that the adsorbents fall under the nano-scale size range with high specific surface area, and Fe was successfully exchanged in the nano-bentonite clay. The kinetics of adsorption was well defined by pseudo-first order and pseudo-second order kinetic models for both NO3− and HCO3−. The Fe-exchanged nano-bentonite was a better performing adsorbent of the oxyanions than Fe3O4 nanoparticles. According to the Sips isothermal model, the Fe-exchanged nano-bentonite exhibited the highest NO3− and HCO3− adsorption potential of 64.76 mg g-1 and 9.73 meq g-1, respectively, while the respective values for Fe3O4 nanoparticles were 49.90 mg g-1 and 3.07 meq g-1. Thus, inexpensiveness and easy preparation process of Fe-exchanged nano-bentonite make it attractive for NO3− and HCO3− removal from contaminated wastewater with significant environmental and economic benefits.

Refereed/Peer-reviewed The beneficial role of biochar on improvement of soil quality, C sequestration, and enhancing crop yield is widely reported. As such there is not much consolidated information available linking biochar modulated soil condition improvement and soil nutrient availability on crop yields. The present review paper addresses the above issues by compilation of world literature on biochar and a new dimension is introduced in this review by performing a meta-analysis of published data by using multivariate statistical analysis. Hence this review is a new in its kind and is useful to the broad spectrum of readers. Generally, alkalinity in biochar increases with increase in pyrolysis temperature and majority of the biochar is alkaline in nature except a few which are acidic. The N content in many biochar was reported to be more than 4% as well as less than 0.5%. Poultry litter biochar is a rich source of P (3.12%) and K (7.40%), while paper mill sludge biochar is higher in Ca content (31.1%) and swine solids biochar in Zn (49810 mg kg(-1)), and Fe (74800 mg kg(-1)) contents. The effect of biochar on enhancing soil pH was higher in Alfisol, Ferrosol and Acrisol. Soil application of biochar could on an average increase (78%), decrease (16%), or show no effect on crop yields under different soil types. Biochar produced at a lower pyrolysis temperature could deliver greater soil nutrient availabilities than that prepared at higher temperature. Principal component analysis (PCA) of available data shows an inverse relationship between [pyrolysis temperature and soil pH], and [biochar application rate and soil cation exchange capacity]. The PCA also suggests that the original soil properties and application rate strongly control crop yield stimulations via biochar amendments. Finally, biochar application shows net soil C gains while also serving for increased plant biomass production that strongly recommends biochar as a useful soil amendment. Therefore, the application of biochar to soils emerges as a 'win-win strategy' for sustainable waste management, climate change mitigation and food security.

Soil microorganisms are an important indicator of soil fertility and health. However, our state of knowledge about soil microbial activities, community compositions and carbon use patterns under metal contaminations is still poor. This study aimed to evaluate the influences of heavy metals (Cd and Pb) on soil microorganisms by investigating the microbial community composition and carbon use preferences. Metal pollution was approached both singly and jointly with low (25 and 2500 mg kg−1) and high (50 and 5000 mg kg−1) concentrations of Cd and Pb, respectively, in an artificially contaminated soil. In a laboratory incubation experiment, bio-available and potentially bio-available metal concentrations, selected soil properties (pH, electrical conductivity, total organic carbon and total nitrogen), and microbial parameters (microbial activity as basal respiration, microbial biomass carbon (MBC) and microbial functional groups) were determined at two sampling occasions (7 and 49 days). Metal contamination had no effect on the selected soil properties, while it significantly inhibited both microbial activity and MBC formation. Contaminated soils had higher microbial quotient (qCO2), suggesting there was higher energy demand with less microbially immobilized carbon as MBC. Notably, the efficiency of microbial carbon use was repressed as the metal concentration increased, yet no difference was observed between metal types (p > 0.05). Based on the microbial phospholipid fatty acids (PLFA) analysis, total PLFAs decreased significantly under metal stress at the end of incubation. Heavy metals had a greater negative influence on the fungal population than bacteria with respective 5–35 and 8–32% fall in abundances. The contaminant-driven (metal concentrations and types) variation of soil PLFA biomarkers demonstrated that the heavy metals led to the alteration of soil microbial community compositions and their activities, which consequently had an adverse impact on soil microbial carbon immobilization. Keywords: Heavy metals, Soil organic carbon, Microbial carbon decomposition, Microbial activity, Microbial community composition, PLFAs

usc Hexavalent chromium (Cr[VI]) is one of the major environmental concerns due to its excessive discharge through effluents from the leather tanning industry. Peanut production leads to the generation of residual shells as waste calling for sustainable disposal. In this study, we employed an innovative approach of applying peanut-shell-derived pristine and engineered biochar for the remediation of Cr-contaminated wastewater and soil. The peanut shell waste was converted to biochar, which was further engineered with cetyltrimethylammonium bromide (CTAB, a commonly used cationic surfactant). The biochars were then used for the adsorption and immobilization of Cr(VI) in water and soil, respectively. The adsorption experiments demonstrated high Cr(VI) removal efficiency for the engineered biochar (79.35%) compared with the pristine biochar (37.47%). The Langmuir model best described the Cr(VI) adsorption onto the biochars (R² > 0.97), indicating monolayer adsorption. Meanwhile, the adsorption kinetics indicated that chemisorption was the dominant mechanism of interaction between the Cr(VI) and the biochars, as indicated by the best fitting to the pseudo-second-order model (R² > 0.98). Adsorption through the fixed-bed column also presented higher Cr(VI) adsorption onto the engineered biochar (qeq = 22.93 mg gˉ¹) than onto the pristine biochar (qeq = 18.54 mg gˉ¹). In addition, the desorption rate was higher for the pristine biochar column (13.83 mg gˉ¹) than the engineered biochar column (10.45 mg gˉ¹), indicating that Cr(VI) was more strongly adsorbed onto the engineered biochar. A higher immobilization of Cr(VI) was observed in the soil with the engineered biochar than with the pristine biochar, as was confirmed by the significant decreases in the Cr(VI) bioavailability (92%), leachability (100%), and bioaccessibility (97%) compared with the control (soil without biochar). The CTAB-engineered biochar could thus potentially be used as an efficient adsorbent for the removal and the immobilization of Cr(VI) in water and soil, respectively. Refereed/Peer-reviewed

The aim of this study was to evaluate the effect of raw (RawBC) and iron (Fe)-modified biochar (FeBC) derived from Platanus orientalis Linn branches on the plant growth, enzyme activity, and bioavailability and uptake of As, Cd, and Pb by rice in a paddy soil with continuously flooded (CF) or alternately wet and dry (AWD) irrigation in a pot experiment. Application of RawBC (3%, w/w) significantly increased soil pH, while FeBC decreased it. The FeBC was more effective in reducing As and Pb bioavailability, particularly under the AWD water regime, while RawBC was more conducive in reducing Cd bioavailability under the CF water regime. The FeBC decreased As concentration, but increased concentrations of Cd and Pb in the straw and brown rice, as compared to the untreated soil. Soil catalase and urease activities were enhanced by RawBC, but decreased by FeBC treatment. The FeBC increased the grain yield by 60% and 32% in CF and AWD treatments, respectively. The FeBC can be recommended for immobilization of As in paddy soils, but a potential human health risk from Cd and Pb in FeBC treated soils should be considered due to increased uptake and translocation of the metals to brown rice. usc Refereed/Peer-reviewed

In this study, typical animal- and plant-derived biochars derived from pig carcass (PB) and green waste (GWB), and their iron-engineered products (Fe-PB and Fe-GWB) were added at the dose of 3% (w/w) to an acidic (pH = 5.8) soil, and incubated to test their efficacy in improving soil quality and immobilizing arsenic (As = 141.3 mg kg−1) and lead (Pb = 736.2 mg kg−1). Soil properties, microbial activities, and the geochemical fractions and potential availabilities of As and Pb were determined in the non-treated (control) and biochar-treated soil. Modification of PB (pH = 10.6) and GWB (pH = 9.3) with Fe caused a decrease in their pH to 4.4 and 3.4, respectively. The application of PB and GWB significantly increased soil pH, while Fe-PB and Fe-GWB decreased soil pH, as compared to the control. Application of Fe-GWB and Fe-PB decreased the NH4H2PO4-extractable As by 32.8 and 35.9%, which was more effective than addition of GWB and PB. However, PB and GWB were more effective than Fe-PB and Fe-GWB in Pb immobilization. Compared to the control, the DTPA-extractable Pb decreased by 20.6 and 21.7%, respectively, following PB and GWB application. Both biochars, particularly PB significantly increased the 16S rRNA bacterial gene copy numbers, indicating that biochar amendments enhanced the bacterial abundance, implying an alleviation of As and Pb bio-toxicity to soil bacteria. The results demonstrated that pristine pig carcass and green waste biochars were more effective in immobilizing Pb, while their Fe-engineered biochars were more effective in As immobilization in co-contaminated soils. Refereed/Peer-reviewed

Refereed/Peer-reviewed High cost of synthetic fertilizers and their hazardous effects catapult the exploration of alternative nutrient formulations and soil amendments. This study aimed to synthesize a novel biochar-mineral-complex (BMC), and evaluate its nutrient supplying and soil improvement performances. In a hydrothermal reaction, the BMC was prepared using a biochar derived from distillation waste of Lemongrass (Cymbopogon flexuosus) and farmyard manure, for the first time via fortification with low-grade rock phosphate and waste mica. The BMC showed improved physico-chemical properties and nutrient availability than the pristine biochar. When applied to a deeply weathered acidic soil, the BMC significantly (P < 0.05) improved the herbage and bioactive compound (sennoside) yields of a medicinal plant (senna; Cassia angustifolia Vahl.) compared to the pristine biochar, farmyard manure, vermicompost, and chemical fertilizers. The BMC also improved the soil quality by increasing nutrient and carbon contents, and microbial activities. Soil quality improvement facilitated greater nutrient uptake in senna plants under BMC compared to the pristine biochar, and conventional organic and chemical fertilizer treatments. This study thus encourages the development of BMC formulations not only to overcome the limitation of sole biochar application to soils, but also to phaseout chemical fertilizers in agriculture. Moreover, BMC could bestow resilience and sustainability to crop production via value-added recycling of waste biomass and low-grade mineral resources

Nanoscale zero-valent iron (NZVI) and NZVI supported onto montmorillonite (NZVI-Mt) were synthetized and used in this study to remove Se-VI and As-V from water in monoand binary-adsorbate systems. The adsorption kinetics and isotherm data for Se-VI and As-V were adequately described by the pseudo-second-order (PSO) (r(2)>0.94) and Freundlich (r(2)>0.93) equations. Results from scanning electron microscopy showed that the dimension of the NZVI immobilized on the Mt was smaller than pure NZVI. Using 0.05 g of adsorbent and an initial 200 mg L-1 As-V and Se-VI concentration, the maximum adsorption capacity (q(max)) and partition coefficient (PC) for As-V on NZ(VI)-Mt in monocomponent system were 54.75 mg g(-1) and 0.065 mg g(-1).mu M-1, which dropped respectively to 49.91 mg g(-1) and 0.055 mg g(-1).mu M-1 under competitive system. For Se-VI adsorption on NZ(VI)-Mt in monocomponent system, q(max) and PC were 28.63 mg g(-1) and 0.024 mg g(-1).mu M-1, respectively. Values of q(max) and PC were higher for NZVI-Mt than NZVI and montmorillonite, indicating that the nanocomposite contained greater adsorption sites for removing both oxyanions, but with a marked preference for As-V. Future research should evaluate the effect of different operational variables on the removal efficiency of both oxyanions by NZVI-Mt. usc Refereed/Peer-reviewed

A large amount of plastic waste released into natural waters and their demonstrated toxicity have made the transformation of microplastics (MPs; < 5 mm) and nanoplastics (NPs; < 100 nm) an emerging environmental concern. Aggregation is one of the most important environmental behaviors of MPs, especially in aquatic en-vironments, which determines the mobility, distribution and bioavailability of MPs. In this paper, the sources and inputs of MPs in aquatic environments were first summarized followed by the analytical methods for investigating MP aggregation, including the sampling, visualization, and quantification procedures of MP' particle sizes. We critically evaluated the sampling methods that still remains a methodological gap. Identification and quantification of MPs were mostly carried out by visual, spectroscopic and spectrometric techniques, and modeling analysis. Important factors affecting MP aggregation in natural waters and environmental implications of the aggregation process were also reviewed. Finally, recommendations for future research were discussed, including (1) conducting more field studies; (2) using MPs in laboratory works representing those in the en-vironment; and (3) standardizing methods of identification and quantification. The review gives a comprehensive overview of current knowledge for MP aggregation in natural waters, identifies knowledge gaps, and provides suggestions for future research. usc Refereed/Peer-reviewed

The term "Total petroleum hydrocarbons" (TPH) is used to describe a complex mixture of petroleum-based hydrocarbons primarily derived from crude oil. Those compounds are considered as persistent organic pollutants in the terrestrial environment. A wide array of organic amendments is increasingly used for the remediation of TPH-contaminated soils. Organic amendments not only supply a source of carbon and nutrients but also add exogenous beneficial microorganisms to enhance the TPH degradation rate, thereby improving the soil health. Two fundamental approaches can be contemplated within the context of remediation of TPH-contaminated soils using organic amendments: (i) enhanced TPH sorption to the exogenous organic matter (immobilization) as it reduces the bioavailability of the contaminants, and (ii) increasing the solubility of the contaminants by supplying desorbing agents (mobilization) for enhancing the subsequent biodegradation. Net immobilization and mobilization of TPH have both been observed following the application of organic amendments to contaminated soils. This review examines the mechanisms for the enhanced remediation of TPH-contaminated soils by organic amendments and discusses the influencing factors in relation to sequestration, bioavailability, and subsequent biodegradation of TPH in soils. The uncertainty of mechanisms for various organic amendments in TPH remediation processes remains a critical area of future research. usc Refereed/Peer-reviewed

Poly- and perfluoroalkyl substances (PFAS) present globally in drinking-, waste-, and groundwater sources are contaminants of emerging concern due to their long-term environmental persistence and toxicity to organisms, including humans. Here we review PFAS occurrence, behavior, and toxicity in various water sources, and critically discuss their removal via mineral adsorbents, including natural aluminosilicate clay minerals, oxidic clays (Al, Fe, and Si oxides), organoclay minerals, and clay-polymer and clay‑carbon (biochar and graphene oxide) composite materials. Among the many remediation technologies, such as reverse osmosis, adsorption, advanced oxidation and biologically active processes, adsorption is the most suitable for PFAS removal in aquatic systems. Treatment strategies using clay minerals and oxidic clays are inexpensive, eco-friendly, and efficient for bulk PFAS removal due to their high surface areas, porosity, and high loading capacity. A comparison of partition coefficient values calculated from extracted data in published literature indicate that organically-modified clay minerals are the best-performing adsorbent for PFAS removal. In this review, we scrutinize the corresponding plausible mechanisms, factors, and challenges affecting the PFAS removal processes, demonstrating that modified clay minerals (e.g., surfactant, amine), including some commercially available products (e.g., FLUORO-SORB®, RemBind®, matCARE™), show good efficacy in PFAS remediation in contaminated media under field conditions. Finally, we propose future research to focus on the challenges of using clay-based adsorbents for PFAS removal from contaminated water due to the regeneration and safe-disposal of spent clay adsorbents is still a major issue, whilst enhancing the PFAS removal efficiency should be an ongoing scientific effort. Refereed/Peer-reviewed

This review summarizes the adsorptive removal of Fluoroquinolones (FQ) from water and wastewater. The influence of different physicochemical parameters on the adsorptive removal of FQ-based compounds is detailed. Further, the mechanisms involved in the adsorption of FQ-based antibiotics on various adsorbents are succinctly described. As the first of its kind, this paper emphasizes the performance of each adsorbent for FQ-type antibiotic removal based on partition coefficients of the adsorbents that is a more sensitive parameter than adsorption capacity for comparing the performances of adsorbents under various adsorbate concentrations and heterogeneous environmental conditions. It was found that 7C-7C electron donor-acceptor interactions, electrostatic interactions, and pore-filling were the most prominent mechanisms for FQ adsorption by carbon and clay-based adsorbents. Among all the categories of adsorbents reviewed, graphene showed the highest performance for the removal of FQ antibiotics from water and wastewater. Based on the current state of knowledge, this review fills the gap through methodolically understanding the mechanism for further improvement of FQ antibiotics adsorption performance from water and wastewater. usc Refereed/Peer-reviewed

Particulate plastics (

Swine and chicken manures are abundant solid wastes that can be converted into carbonaceous materials through hydrothermal carbonization (HTC). Owing to their unique biochemical compositions, co-HTC of these two types of manures may have significant implications for the generated products. We investigated the co-HTC of swine manure and chicken manure to understand the influence of the interaction between contrasting manures on the properties of the derived products. The results indicated that co-HTC treatment enhanced the formation of solid product and improved the C and N contents, heating value, and energy yield of the resulting hydrochar. Regarding the ignition temperature and comprehensive combustion index, the combustion properties of the hydrochar were enhanced owing to the mutual effect of the HTC intermediates. Additionally, the interaction of the intermediates significantly impacted the transfer of nitrogenous species and generation of organic acids and organic polymers with fused-ring structures. Therefore, co-HTC processing of animal manures could potentially provide a sustainable pathway for the conversion of animal waste into solid products with improved characteristics compared to those produced by treating the two feedstocks separately Refereed/Peer-reviewed

Excess phosphorous (P) in aquatic systems causes adverse environmental impacts including eutrophication. This study fabricated Fe(III) loaded chitosan-biochar composite fibers (FBC-N and FBC-C) from paper mill sludge biochar produced under N-2 (BC-N) and CO2 (BC-C) conditions at 600 degrees C for adsorptive removal of phosphate from water. Investigations using SEM/EDX, XPS, Raman spectroscopy, and specific surface area measurement revealed the morphological and physico-chemical characteristics of the adsorbent. The Freundlich isotherm model well described the phosphate adsorption on BC-N, while the Redlich-Peterson model best fitted the data of three other adsorbents. The maximum adsorption capacities were 9.63, 8.56, 16.43, and 19.24 mg P g(-1) for BCN, BC-C, FBC-N, and FBC-C, respectively, indicating better adsorption by Fe(III) loaded chitosan-biochar composite fibers (FBCs) than pristine biochars. The pseudo-first-order kinetic model suitably explained the phosphate adsorption on BC-C and BC-N, while data of FBC-N and FBC-C followed the pseudo-second-order and Elovich model, respectively. Molecular level observations of the P K-edge XANES spectra confirmed that phosphate associated with iron (Fe) minerals (Fe-P) were the primary species in all the adsorbents. This study suggests that FBCs hold high potential as inexpensive and green adsorbents for remediating phosphate in contaminated water, and encourage resource recovery via bio-based management of hazardous waste. usc Refereed/Peer-reviewed

This study evaluates the arsenic adsorption behavior of Fe-exchanged smectite and phosphate-bound kaolinite, in soil, tap water and double distilled water in the presence of competing anions such as silicate, phosphate, and sulfate, and at variable pH values. The maximum amounts of As adsorbed in soil are 620.6 and 607.6 µg g–¹ at pH 5 by Fe-exchanged smectite and phosphate-bound kaolinite, respectively. The pH-modified Freundlich equation fits well (R² > 0.96) to the adsorption data, distinguishing the effect of pH on adsorption. The coefficients of pH-value are 0.04 and 0.05 for phosphate-bound kaolinite and Fe-exchanged smectite, suggesting that low pH is suitable for the adsorption. The As adsorption is decreased in tap water at low pH compared to the soil due to the presence of iron (Fe²⁺/³⁺), sulfate, and bicarbonate in tap water. Among the competing anions in distilled water, phosphate is the most interfering anion for As adsorption. The competition coefficients of As-phosphate binary adsorption derived from the Sheindorf equation are 3.93 and 0.56 for Fe-exchanged smectite and phosphate-bound kaolinite at pH 5. The Fe-exchanged smectite can be used more effectively than phosphate-bound kaolinite for As remediation in systems having low pH (pH ≈5) and high phosphate concentration. Refereed/Peer-reviewed

Pyrolysis is considered as a promising method to immobilize potentially toxic elements (PTEs) in animal manures. However, comparative study on characteristics and environmental risk of PTEs in biochar obtained by pyrolysis of animal manure at different reactors are lacking. In this study, swine manure was pyrolyzed at 300–600 °C in a lab-scale or pilot-scale reactor with the aim to investigate their effects on characteristics and environmental risk of As, Cd, Cu, Ni, Pb, and Zn in swine manure biochar. Results showed that biochars produced from pilot scale had lower pH and carbon (C) content but higher oxygen (O) content than those from lab scale. Biochars from pilot scale had higher total PTEs (except Cd) concentrations and releasable PTEs (except Pb) but lower CaCl2-extractable PTEs and phytotoxicity germination index (GI) to radish seedings than those from lab scale. Chemical speciation analysis indicated that PTEs in biochar produced from pilot-scale fast pyrolysis at 400 °C had higher percentage of more stable fraction (F5 fraction) and lower potential ecological risk index (RI) than those from lab-scale slow pyrolysis. These findings demonstrated that bioavailability and potential ecological risk of PTE in swine manure biochar were greatly decrease in the pilot-scale pyrolysis reactor and the optimum temperature was 400 °C considering the lowest potential ecological risk index. Refereed/Peer-reviewed

Conventional adsorbents for decontaminating arsenic exhibit low efficacy for the removal of arsenite (As(III)). This study aims to develop a robust As adsorbent from natural magnetite (M0) via a facile ball milling process, and evaluate their performance for decontaminating As(III) and As(V) in water and soil systems. The ball milling process decreased the particle size and crystallinity of M0, resulting in pronounced As removal by the ball-milled magnetite (Mm). Ball milling under air facilitated the formation of Fe-OH and Fe-COOH functional groups on Mm interface, contributing to effective elimination of As(III) and As(V) via hydrogen bonding and complexation mechanisms. Synergistic oxidation effects of hydroxyl and carboxyl groups, and reactive oxygen species (O2·-, and ·OH) on the transformation of As(III) to As(V) during the adsorption were proposed to explain the enhanced As(III) removal by Mm. A short-term soil incubation experiment indicated that the addition of Mm (10 wt%) induced a decrease in the concentration of exchangeable As by 30.25%, and facilitated the transformation of water-soluble As into residual fraction. Ball milling thus is considered as an eco-friendly (chemical-free) and inexpensive (scalable, one-stage process) method for upgrading the performance of natural magnetite towards remediating As, particularly for tackling the highly mobile As(III). Refereed/Peer-reviewed

Rhizoremediation potential of different wild plant species for total (aliphatic) petroleum hydrocarbon (TPH)-contaminated soils was investigated. Three-week-old seedlings of Acacia inaequilatera, Acacia pyrifolia, Acacia stellaticeps, Banksia seminuda, Chloris truncata, Hakea prostrata, Hardenbergia violacea, and Triodia wiseana were transplanted in a soil contaminated with diesel and engine oil as TPH at pollution levels of 4,370 (TPH1) and 7,500 (TPH2) mg kg−1, and an uncontaminated control (TPH0). After 150 days, the presence of TPH negatively affected the plant growth, but the growth inhibition effect varied between the plant species. Plant growth and associated root biomass influenced the activity of rhizo-microbiome. The presence of B. seminuda, C. truncata, and H. prostrata significantly increased the TPH removal rate (up to 30% compared to the unplanted treatment) due to the stimulation of rhizosphere microorganisms. No significant difference was observed between TPH1 and TPH2 regarding the plant tolerance and rhizoremediation potentials of the three plant species. The presence of TPH stimulated cluster root formation in B. seminuda and H. prostrata which was associated with enhanced TPH remediation of these two members of Proteaceae family. These results indicated that B. seminuda, C. truncata, and H. prostrata wild plant species could be suitable candidates for the rhizoremediation of TPH-contaminated soil. Refereed/Peer-reviewed

Biochar, an environmentally friendly soil conditioner, is produced using several thermochemical processes. It has unique characteristics like high surface area, porosity, and surface charges. This paper reviews the fertilizer value of biochar, and its effects on soil properties, and nutrient use efficiency of crops. Biochar serves as an important source of plant nutrients, especially nitrogen in biochar produced from manures and wastes at low temperature (≤ 400 °C). The phosphorus, potassium, and other nutrient contents are higher in manure/waste biochars than those in crop residues and woody biochars. The nutrient contents and pH of biochar are positively correlated with pyrolysis temperature, except for nitrogen content. Biochar improves the nutrient retention capacity of soil, which depends on porosity and surface charge of biochar. Biochar increases nitrogen retention in soil by reducing leaching and gaseous loss, and also increases phosphorus availability by decreasing the leaching process in soil. However, for potassium and other nutrients, biochar shows inconsistent (positive and negative) impacts on soil. After addition of biochar, porosity, aggregate stability, and amount of water held in soil increase and bulk density decreases. Mostly, biochar increases soil pH and, thus, influences nutrient availability for plants. Biochar also alters soil biological properties by increasing microbial populations, enzyme activity, soil respiration, and microbial biomass. Finally, nutrient use efficiency and nutrient uptake improve with the application of biochar to soil. Thus, biochar can be a potential nutrient reservoir for plants and a good amendment to improve soil properties. Refereed/Peer-reviewed

Imogolite and magnetic imogolite-Fe oxide nanocomposites (Imo-Fe50 and Imo-Fe25, at 50 and 25 % Fe loading (w/w), respectively) were synthesized and tested for the removal of aqueous copper (Cu), cadmium (Cd), and arsenic (As) pollutants. The materials were characterized by transmission electron microscopy, and specific surface area and isoelectric point measurements. The Fe-containing samples were additionally characterized by Mössbauer spectroscopy and vibrating-sample magnetometry. Significant differences were found in the morphological, electrophoretic, and magnetic characteristics between imogolite and the nanocomposites. The in-situ Fe-oxide precipitation process modified the active surface sites of the imogolite. The Fe–oxide, mainly magnetite, favored the contaminants’ adsorption over the pristine imogolite. The adsorption kinetics of these pollutants were adequately described by the pseudo-second order and intraparticle diffusion models. The kinetic models showed that surface adsorption was more important than intraparticle diffusion in the removal of the pollutants by all the adsorbents. The Langmuir-Freundlich model described the experimental adsorption data, and both nanocomposites showed greater adsorption capacity than the imogolite. The adsorption of Cu and Cd was sensitive to cationic competition, showing a decrease of the adsorption capacity when the two cations coexisted, while their adsorption increased in the presence of arsenate. Refereed/Peer-reviewed

The influence of biochar on the soil structure and aggregate stability has been debated in previous studies. To probe the action of biochar on soil aggregates, a 5-year field experiment was implemented in the brown earth soil of northeastern China. We determined the aggregate distribution (> 2000 μm, 250–2000 μm, 53–250 μm, and < 53 μm) and organic carbon (OC) and organo-mineral complex contents both in the topsoil (0–20 cm) and within the soil aggregates. Three treatments were studied as follows: control (basal application of mineral NPK fertilizer), biochar (biochar applied at a rate of 2.625 t ha−1), and stover (maize stover applied at a rate of 7.5 t ha−1), and all treatments received the same fertilization. The biochar and stover applications decreased the soil bulk and particle densities significantly (p < 0.05) and enhanced the soil total porosity. Both amendments significantly (p < 0.05) enhanced the total OC, heavy OC fractions, and organo-mineral complex quantities in the bulk soil as well as in all the studied aggregate fractions. Biochar and stover applications promoted the formation of small macroaggregates. A greater amount of organic matter was contained in the macroaggregates, which led to the formation of more organo-mineral complexes, thereby improving soil aggregate stability. However, the different mechanisms underlying the effect of biochar and stover on organo-mineral complexes need further research. Biochar and stover applications are both effective methods of improving the soil structure in Northeast China. Refereed/Peer-reviewed

This chapter provides an attempt to centralize and unify information on a plethora of techniques used for the analysis of particulate plastics in soil and water. Plastic production required to meet unabating demands was reported to increase from 0.5 million tons per year in 1960 to as high as 300 million tons in 2013. Microplastics can directly enter the environment from large plastic items that are continuously fragmenting until they attain micrometric dimensions. Microplastics tend to sediment after reaching soil and aquatic systems via effluents from wastewater treatment plants. Pressurized fluid extraction is another method used for extraction of microplastics (MP), which involves a sample preparation technique that employs elevated temperatures and pressure with liquid solvents to achieve rapid and efficient extraction of the analytes from the solid matrix. A new and improved, cost-effective oil extraction protocol was demonstrated as an alternative to density-based approaches by taking advantage of the oleophilic properties of MPs.

The knowledge about lead (Pb) sorption on soil-derived black carbons (SBCs) under different cultivation intensities of soils is limited. In this study, chemical and spectroscopic methods were applied to investigate the Pb sorption mechanisms on SBCs in soils from a forest land, a rubber plantation area, and a vegetable farm with none, less and highly intensive cultivation, respectively, that are located in the Hainan Island of China. Results showed that the specific surface area and cation exchange capacity of the SBCs from the less and highly intensive cultivation soils were 4.5- and 2.7-fold, and 1.3- and 1.8-fold higher compared to that of SBC from the no-cultivation soil, which subsequently enhanced the Pb sorption capacities of SBCs in iron exchange fraction. Ion exchange and hydrogen bonded Pb fractions together accounted for about 80% of total Pb sorbed on all SBCs at an externally added 1000 mg L−1 Pb solution concentration. The O[dbnd]C–O groups also played key roles in Pb sorption by forming complexes of O[dbnd]C–O–Pb–O and/or O[dbnd]C–O–Pb. Overall, SBCs in soils under all studied cultivation intensities showed high potential to sorb Pb (with the maximum absorbed Pb amount of 46.0–91.3 mg g−1), and increased Pb sorption capacities of the studied soils by 18.7–21.1 mg kg−1 in the stable fraction (complexation). Therefore, SBC might be a potential environment-friendly material to enhance the Pb immobilization capacity of soil Refereed/Peer-reviewed

Refereed/Peer-reviewed 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

Land‐based enhanced rock weathering (ERW) is a biogeochemical carbon dioxide removal (CDR) strategy aiming to accelerate natural geological processes of carbon sequestration through application of crushed silicate rocks, such as basalt, to croplands and forested landscapes. However, the efficacy of the approach when undertaken with basalt, and its potential co‐benefits for agriculture, require experimental and field evaluation. Here we report that amending a UK clay‐loam agricultural soil with a high loading (10 kg/m2) of relatively coarse‐grained crushed basalt significantly increased the yield (21 ± 9.4%, SE ) of the important C4 cereal Sorghum bicolor under controlled environmental conditions, without accumulation of potentially toxic trace elements in the seeds. Yield increases resulted from the basalt treatment after 120 days without P‐ and K‐fertilizer addition. Shoot silicon concentrations also increased significantly (26 ± 5.4%, SE ), with potential benefits for crop resistance to biotic and abiotic stress. Elemental budgets indicate substantial release of base cations important for inorganic carbon removal and their accumulation mainly in the soil exchangeable pools. Geochemical reactive transport modelling, constrained by elemental budgets, indicated CO2 sequestration rates of 2–4 t CO2/ha, 1–5 years after a single application of basaltic rock dust, including via newly formed soil carbonate minerals whose long‐term fate requires assessment through field trials. This represents an approximately fourfold increase in carbon capture compared to control plant–soil systems without basalt. Our results build support for ERW deployment as a CDR technique compatible with spreading basalt powder on acidic loamy soils common across millions of hectares of western European and North American agriculture.

The staggering production of rock dusts and quarry by-products of mining activities poses an immense environmental burden that warrants research for value-added recycling of these rock mineral powders (RMP). In this study, an incubation experiment was conducted to determine potassium (K) and micronutrients (Zn, Cu, Fe and Mn) release from a quarry RMP to support plant nutrition. Four different size fractions of the RMP were incubated with organic amendments (cow dung and legume straw) under controlled conditions for 90 days. Samples were collected at different intervals (7, 15, 30, 45, 60 and 90 days) for the analysis of available K and micronutrients in the mineral-OM mixtures and leachates. There was a significant (p

Halloysite nanoclay was utilized to retain aqueous oxytetracycline (OTC) which is extensively used in the veterinary industry. The micro-structure and functionality of the nanoclay were characterized through spectroscopic techniques before and after adsorption. The OTC removal experiments were performed at different pH conditions (pH 3.0-9.0), ionic strengths (0.001, 0.01, 0.1 M NaNO3) and contact time (up to 32 h) at an initial 25 mg/L OTC concentration with 1.0 g/L halloysite. Oxytetracycline adsorption was pH dependent, and the best pH was observed in the range of pH 3.5-5.5 at a 0.001 M ionic strength. At pH 3.5, the maximum OTC adsorption amount was 21 mg/g which translated to 68% removal of the initial OTC loading. Positively charged inner lumen and negatively charged outer lumen of the tubular halloysite structure led to form inner-sphere complexes with the anionic and cationic forms of OTC, respectively. A rapid adsorption of OTC was observed in the kinetic study where 62% OTC was adsorbed in 90 min.. Pseudo-second order equation obeyed by the kinetic data indicated that the adsorption was governed by chemisorption, whereas Hill isotherm equation was the most fitted with a maximum adsorption capacity of 52.4 mg/g indicating a cooperative adsorption phenomenon. usc Refereed/Peer-reviewed

This chapter provides an overview of particulate plastics as a source and sink for heavy metal(loid)s in the environment. Particulate plastics in the terrestrial and aquatic environments are a group of synthetic polymer fragments or beads ranging in diameter from roughly 5 mm down to the nano-meter scale. The accumulated particulate plastics in soil can be transported to the aquatic environment through soil erosion, which is one of the main processes that allows the transport of particulate plastics from the terrestrial to the aquatic ecosystem. Heavy metal(loid)s are elements that have properties in between metals and non-metals. Particulate plastics impact the dynamics of metal(loid)s in terrestrial and aquatic environments through both acting as a source and sink for metal(loid)s. In environmental toxicology, the “source” can be defined where pollution is emitted to the environment, or where the pollution originates. Particulate plastics act as a “source” when they release a pollutant into the environment.

Modern agricultural practices use a huge amount of agro-pesticides to control insect pests, pathogens, and unwanted weeds. Many of such agrochemicals persist in the soil and plant systems for long time and pose a risk of migration into the drinking water sources and food chain. Often these agrochemicals occur as a mixture of multiple compounds in the soil due to their simultaneous and/or subsequent seasonal applications. The mobility, fate, and transformation of agrochemicals depend largely on soil types, especially the type and content of soil clays, organic matter content, pH, and microbial activity. The sorption–desorption behaviors of agrochemicals on soil clays, which are the most reactive particle components of soils, may alter significantly when these compounds appear as a mixture. This chapter aims to discuss various soil attributes that control the sorption–desorption of agrochemical contaminants in soils under different soil–plant systems.

Lead (Pb(II)) pollution in water poses a serious threat to human health in many parts of the world. In the past decades, research has been aimed at developing efficient and cost-effective methods to address the problem. In this study, dimethyl sulfoxide (DMSO) and potassium acetate (K-Ac) intercalated kaolinite complexes were synthesized and subsequently utilized for Pb(II) removal from water. The intercalation of kaolinite with DMSO was found to be useful for expanding the interlayer space of the clay mineral from 0.72 to 1.12 nm. Kaolinite intercalation with K-Ac (KDK) increased the interlayer space from 1.12 to 1.43 nm. The surface area of KDK was found to be more than threefold higher as compared to natural kaolinite (NK). Batch experimental results revealed that the maximum Pb(II) uptake capacity of KDK was 46.45 mg g−1 which was higher than the capacity of NK (15.52 mg g−1). Reusability studies showed that KDK could be reused for 5 cycles without substantially losing its adsorption capacity. Furthermore, fixed-bed column tests confirmed the suitability of KDK in continuous mode for Pb(II) removal. Successful application of intercalated kaolinite for Pb(II) adsorption in batch and column modes suggests its application in water treatment (especially removal of divalent metals). Electronic supplementary material The online version of this article (10.1007/s11356-019-06845-w) contains supplementary material, which is available to authorized users.

Nickel (Ni) is a potentially toxic element that contaminates soil and water, threatens food and water security, and hinders sustainable development globally. Biochar has emerged as a promising novel material for remediating Ni-contaminated environments. However, the potential for pristine and functionalized biochars to immobilize/ adsorb Ni in soil and water, and the mechanisms involved have not been systematically reviewed. Here, we critically review the different dimensions of Ni contamination and remediation in soil and water, including its occurrence and biogeochemical behavior under different environmental conditions and ecotoxicological hazards, and its remediation using biochar. Biochar is effective in immobilizing Ni in soil and water via ion exchange, electrostatic attraction, surface complexation, (co)precipitation, physical adsorption, and reduction due to the biogeochemistry of Ni and the interaction of Ni with surface functional groups and organic/inorganic compounds contained in biochar. The efficiency for Ni removal is consistently greater with functionalized than pristine biochars. Physical (e.g., ball milling) and chemical (e.g., alkali/acidic treatment) activation achieve higher surface area, porosity, and active surface groups on biochar that enhance Ni immobilization. This review highlights possible risks and challenges of biochar application in Ni remediation, suggests future research directions, and discusses implications for environmental agencies and decision-makers. usc Refereed/Peer-reviewed

Aqueous film-forming foam, used in firefighting, and biowastes, including biosolids, animal and poultry manures, and composts, provide a major source of poly- and perfluoroalkyl substances (PFAS) input to soil. Large amounts of biowastes are added to soil as a source of nutrients and carbon. They also are added as soil amendments to improve soil health and crop productivity. Plant uptake of PFAS through soil application of biowastes is a pathway for animal and human exposure to PFAS. The complexity of PFAS mixtures, and their chemical and thermal stability, make remediation of PFAS in both solid and aqueous matrices challenging. Remediation of PFAS in biowastes, as well as soils treated with these biowastes, can be achieved through preventing and decreasing the concentration of PFAS in biowaste sources (i.e., prevention through source control), mobilization of PFAS in contaminated soil and subsequent removal through leaching (i.e., soil washing) and plant uptake (i.e., phytoremediation), sorption of PFAS, thereby decreasing their mobility and bioavailability (i. e., immobilization), and complete removal through thermal and chemical oxidation (i.e., destruction). In this review, the distribution, bioavailability, and remediation of PFAS in soil receiving solid biowastes, which include biosolids, composts, and manure, are presented. usc Refereed/Peer-reviewed

Mafic igneous rocks, such as basalt, are composed of abundant calcium- and magnesium-rich silicate minerals widely proposed to be suitable for scalable carbon dioxide removal (CDR) by enhanced rock weathering (ERW). Here, we report a detailed characterization of the mineralogy, chemistry, particle size and surface area of six mined basalts being used in large-scale ERW field trials. We use 1-D reactive transport modelling (RTM) of soil profile processes to simulate inorganic CDR potential via cation flux (Mg2+, Ca2+, K+ and Na+) and assess the release of the essential plant nutrients phosphorus (P) and potassium (K) for a typical clay-loam agricultural soil. The basalts are primarily composed of pyroxene and plagioclase feldspar (up to 71 wt%), with accessory olivine, quartz, glass and alkali feldspar. Mean crushed particle size varies by a factor of 10, owing to differences in the mining operations and grinding processes. RTM simulations, based on measured mineral composition and N-2-gas BET specific surface area (SSA), yielded potential CDR values of between c. 1.3 and 8.5 t CO2 ha(-1) after 15 years following a baseline application of 50 t ha(-1) basalt. The RTM results are comparative for the range of inputs that are described and should be considered illustrative for an agricultural soil. Nevertheless, they indicate that increasing the surface area for slow-weathering basalts through energy intensive grinding prior to field application in an ERW context may not be warranted in terms of additional CDR gains. We developed a function to convert CDR based on widely available and easily measured rock chemistry measures to more realistic determinations based on mineralogy. When applied to a chemistry dataset for >1300 basalt analyses from 25 large igneous provinces, we simulated cumulative CDR potentials of up to c. 8.5 t CO2 ha(-1) after 30 years of weathering, assuming a single application of basalt with a SSA of 1 m(2) g(-1). Our RTM simulations suggest that ERW with basalt releases sufficient phosphorus (P) to substitute for typical arable crop P-fertiliser usage in Europe and the USA offering potential to reduce demand for expensive rock-derived P. Refereed/Peer-reviewed

The use of modified clay minerals for adsorbing arsenic (As) in contaminated soils is an underexplored area of research. The adsorption behavior of As onto inorganically modified smectite and kaolinite both in aqueous and soil media was studied. X-ray diffraction, infra-red spectroscopy, scanning and transmission electron microscopy studies confirmed successful modification of smectite through Fe-exchange and Ti-pillaring, and kaolinite through phosphate binding. The modified smectites were more efficient than phosphate-bound kaolinite in adsorbing As both in water and soil systems. Kinetic study revealed that the clay products reached adsorption equilibrium within 3 h, and the data well fitted to the power function and simple Elovich equation (R 2 > 0.90). The Freundlich isotherm model best described the As adsorption data (R 2 > 0.86) of the modified clay products in both the systems. The Ti-pillared smectite exhibited the highest As adsorption capacity (156.54 μg g − 1 ) in the aqueous medium, while the Fe-exchanged smectite was the best material in the soil system (115.63 μg g − 1 ). The partition coefficient (K d ) and adsorption efficiency (%) data also maintained the similar trend. Precipitation of As and binuclear complex formation also took place in the soil system which made the metalloid non-labile as the time passed. The inorganically modified clay products reported here hold a great potential to adsorb As in contaminated groundwater, drinking water as well as soil. Refereed/Peer-reviewed