Impacts of Forest Fire Ash on Aquatic Mercury Cycling.

Mercury (Hg) is a ubiquitous contaminant in the environment and its methylated form, methylmercury (MeHg), poses a worldwide health concern for humans and wildlife, primarily through fish consumption. Global production of forest fire ash, derived from wildfires and prescribed burns, is rapidly increasing due to a warming climate, but their interactions with aqueous and sedimentary Hg are poorly understood. Herein, we compared the differences of wildfire ash with activated carbon and biochar on the sorption of aqueous inorganic Hg and sedimentary Hg methylation. Sorption of aqueous inorganic Hg was greatest for wildfire ash materials (up to 0.21 µg g-1 or 2.2 µg g-1 C) among all of the solid sorbents evaluated. A similar Hg adsorption mechanism for activated carbon, biochar made of walnut, and wildfire ash was found that involves the formation of complexes between Hg and oxygen-containing functional groups, especially the -COO group. Notably, increasing dissolved organic matter from 2.4 to 70 mg C L-1 remarkably reduced Hg sorption (up to 40% reduction) and increased the time required to reach Hg-sorbent pseudo-equilibrium. Surprisingly, biochar and wildfire ash, but not activated carbon, stimulated MeHg production during anoxic sediment incubation, possibly due to the release of labile organic matter. Overall, our study indicates that while wildfire ash can sequester aqueous Hg, the leaching of its labile organic matter may promote production of toxic MeHg in anoxic sediments, which has an important implication for potential MeHg contamination in downstream aquatic ecosystems after wildfires.

Mitigating the accumulation of arsenic and cadmium in rice grain: A quantitative review of the role of water management.

Arsenic exposure through rice consumption is a growing concern. Compared to Continuous Flooding (CF), irrigation practices that dry the soil at least once during the growing season [referred to here as Alternate Wetting and Drying (AWD)] can decrease As accumulation in grain; however, this can simultaneously increase grain Cd to potentially unsafe levels. We modelled grain As and Cd from field studies comparing AWD and CF to identify optimal AWD practices to minimize the accumulation of As and Cd in grain. The severity of soil drying during AWD drying event(s), quantified as soil water potential (SWP), was the main factor leading to a reduction in grain total As and inorganic As, compared to CF. However, lower SWP levels were necessary to decrease grain inorganic As, compared to total As. Therefore, if the goal is to decrease grain inorganic As, the soil needs to be dried further than it would for decreasing total As alone. The main factor driving grain Cd accumulation was when AWD was practiced during the season. Higher grain Cd levels were observed when AWD occurred during the early reproductive stage. Further, higher Cd levels were observed when AWD spanned multiple rice growth stages, compared to one stage. If Cd levels are concerning, the minimum trade-off between total As and Cd accumulation in rice grain occurred when AWD was implemented at a SWP of -47 kPa during one stage other than the early reproductive. While these results are not meant to be comprehensive of all the interactions affecting the As and Cd dynamics in rice systems, they can be used as a first guide for implementing AWD practices with the goal of minimizing the accumulation of As and Cd in rice grain.

Enhanced removal of ammonium from water using sulfonated reed waste biochar-A lab-scale investigation.

The removal of excessive ammonium from water is vital for preventing eutrophication of surface water and ensuring drinking water safety. Several studies have explored the use of biochar for removing ammonium from water. However, the efficacy of pristine biochar is generally weak, and various biochar modification approaches have been proposed to enhance adsorption capacity. In this study, biochar obtained from giant reed stalks (300, 500, 700 °C) was modified by sulfonation, and the ammonium adsorption capabilities of both giant reed biochars (RBCs) and sulfonated reed biochars (SRBCs) were assessed. The ammonium adsorption rates of SRBCs were much faster than RBCs, with equilibrium times of ∼2 h and ∼8 h for SRBCs and RBCs, respectively. The Langmuir maximum adsorption capacities of SRBCs were 4.20-5.19 mg N/g for SRBCs, significantly greater than RBCs (1.09-1.92 mg N/g). Physical-chemical characterization methods confirmed the increased levels of carboxylic and sulfonic groups on sulfonated biochar. The reaction of ammonium with these O-containing functional groups was the primary mechanism for the enhancement of ammonium adsorption by SRBCs. To conclude, sulfonation significantly improved the adsorption performance of biochar, suggesting its potential application for ammonium mitigation in water.

Removal of phosphate from water by paper mill sludge biochar.

Biochar modification by metals and metal oxides is considered a practical approach for enhancing the adsorption capacity of anionic compounds such as phosphate (P). This study obtained paper mill sludge (PMS) biochar (PMSB) via a one-step process by pyrolyzing PMS waste containing ferric salt to remove anionic P from water. The ferric salt in the sludge was transformed into ferric oxide and zero-valent-iron (Fe0) in N2 atmosphere at pyrolysis temperatures ranging from 300 to 800 °C. The maximum adsorption (Qm) of the PMSBs for P ranged from 9.75 to 25.19 mg P/g. Adsorption is a spontaneous and endothermic process, which implies chemisorption. PMSB obtained at 800 °C (PMSB800) exhibited the best performance for P removal. Fe0 in PMSB800 plays a vital role in P removal via adsorption and coprecipitation, such as forming the ≡Fe-O-P ternary complex. Furthermore, the possible chemical precipitation of P by CaO decomposed from calcite (CaCO3; an additive of paper production that remains in PMS) may also contribute to the removal of P by PMSB800. Moreover, PMSBs can be easily separated magnetically from water after application and adsorption. This study achieved a waste-to-wealth strategy by turning waste PMS into a metal/metal oxide-embedded biochar with excellent P removal capability and simple magnetic separation properties via a one-step pyrolysis process.

Natural and engineered clays and clay minerals for the removal of poly- and perfluoroalkyl substances from water: State-of-the-art and future perspectives.

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 clay­carbon (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.

Characterizing and Tuning the Properties of Polydiacetylene Films for Sensing Applications.

Self-assembled, polymerized diacetylene (DA) nanostructures and two-dimensional films have been studied over the past two decades for sensor applications because of their straightforward visual readout. DA monomers, when exposed to UV light, polymerize to produce a visibly blue polymer. Blue phase polydiacetylenes (PDAs) when exposed to an external stimuli, such as temperature or UV light, undergo a chromatic phase transition to a fluorescent, visibly red phase. The tunability of the monomer to blue to red chromatic phase transitions by choice of diacetylene monomer in the presence of metal cations is systematically and comprehensively investigated to determine their effects on the properties of PDA Langmuir films. The polymerization kinetics and domain morphology of the PDA films were characterized using polarized fluorescent microscopy, UV-vis-fluorescent spectroscopy, and Fourier transform infrared spectroscopy (FTIR). Increasing the monomer alkyl tail length was found to strongly increase the UV dose necessary to produce optimally blue films and fully red films. A decrease in the polymer domain size was also correlated with longer-tailed DA molecules. Metal cations have a diverse effect on the film behavior. Alkaline-earth metals such as Mg, Ca, and Ba have a negligible effect on the phase transition kinetics but can be used to tune PDA polymer domain sizes. The Ni and Fe cations increase the UV dose necessary to produce red phase PDA films and significantly decrease the polymer domain sizes. The Zn, Cd, and Cu ions exhibit strong directed interactions with the PDA carboxylic acid headgroups, resulting in quenched fluorescence and a unique film morphology. FTIR analysis provides insight into the metal-PDA binding mechanisms and demonstrates that the coordination between the PDA film headgroups and the metal cations can be correlated with changes in the film morphology and kinetics. The findings from these studies will have broad utility for tuning PDA-based sensors for different applications and sensitivity ranges.

Quantification of the sorption of organic pollutants to minerals via an improved mathematical model accounting for associations between minerals and soil organic matter.

The retention of organic pollutant (OP) in soils is commonly attributed to interactions with soil organic matter (SOM), perhaps overlooking substantial involvement of soil minerals. In this study, 36 soil samples with far-ranging ratios of clay to organic carbon were used to examine contribution of minerals on soil sorption of pentachlorophenol (PCP) and phenanthrene (PHE). Sorption isotherms (n = 216) were fit individually using three typical sorption models, with the most fitted Kd values screened out for quantification of the net mineral contribution to total sorption via development of mathematical model accounting for associations between minerals and SOM. Two mineral-relevant parameters [adsorption distribution coefficient (Kmin) and mineral contribution index (MCI)] were simultaneously defined. Previously reported soil sorption data of PCP, PHE and butachlor (13, 12 and 46, respectively) were also extracted and included to improve the credibility of mathematic model. The average MCI values were calculated as 0.421, 0.405 and 0.512 in PCP, PHE and butachlor treated soils, respectively, very close to or even over than the minerals dominant critical value (0.5). This suggested the significant, or even predominant, contribution of minerals - as compared to SOM. Significant dependence of MCI with four conventional parameters of soil property further offered the possibility to roughly evaluate mineral contributions based on estimated threshold values of soil property parameters (especially TOC). This study provides an accessible approach for predicting the contribution of minerals in soil OP retention, especially highlighting their predominant roles vs. SOM in regulating OP removal in most of subsurface soil or contaminated brownfields where organic carbon content of soil was very low, that was not like what previously believed.

Viromes outperform total metagenomes in revealing the spatiotemporal patterns of agricultural soil viral communities.

Viruses are abundant yet understudied members of soil environments that influence terrestrial biogeochemical cycles. Here, we characterized the dsDNA viral diversity in biochar-amended agricultural soils at the preplanting and harvesting stages of a tomato growing season via paired total metagenomes and viral size fraction metagenomes (viromes). Size fractionation prior to DNA extraction reduced sources of nonviral DNA in viromes, enabling the recovery of a vaster richness of viral populations (vOTUs), greater viral taxonomic diversity, broader range of predicted hosts, and better access to the rare virosphere, relative to total metagenomes, which tended to recover only the most persistent and abundant vOTUs. Of 2961 detected vOTUs, 2684 were recovered exclusively from viromes, while only three were recovered from total metagenomes alone. Both viral and microbial communities differed significantly over time, suggesting a coupled response to rhizosphere recruitment processes and/or nitrogen amendments. Viral communities alone were also structured along an 18 m spatial gradient. Overall, our results highlight the utility of soil viromics and reveal similarities between viral and microbial community dynamics throughout the tomato growing season yet suggest a partial decoupling of the processes driving their spatial distributions, potentially due to differences in dispersal, decay rates, and/or sensitivities to soil heterogeneity.

Chemical composition of soil-associated ash from the southern California Thomas Fire and its potential inhalation risks to farmworkers.

The increasing frequency and severity of wildfires poses human health risks, especially for those within burnt regions. The potential health effects of fire ash on farmworkers in orchards via inhalation exposure after fire is rarely studied. After the 2017 Thomas Fire, in Ventura County (California, USA), fire ash and corresponding soil samples were collected from several impacted orchards and analyzed for eight trace elements (TEs) and 16 polycyclic aromatic hydrocarbons (PAHs). Results indicate that except for mercury (Hg), the concentrations of TEs and PAHs were higher in ash samples compared with the corresponding soil samples. In general, ash samples showed greater potential to expose farmworkers to health risks than the corresponding soil samples. One site had particularly high concentrations of As (778 mg kg-1), Cr (629 mg kg-1), and Cu (499 mg kg-1) in the ash. This location corresponds to a house which was burned during the Thomas Fire, which might have contained chromated copper arsenate as a wood preservative. Therefore, the existence of construction materials in orchards could add hazardous materials to ash deposited on soil. Furthermore, a monitored dust generation experiment was designed to obtain the particle emission factors (PEF) of soil and ash, which is an essential parameter for the calculation of inhalation health risks. A two-fold difference in the PEFs was found between ash and the corresponding soil sample. Hence, health risks through inhalation exposure from fire ash may be underestimated if the default PEF suggested by the US Environmental Protection Agency is used.

Impact of biochar on plant growth and uptake of ciprofloxacin, triclocarban and triclosan from biosolids.

Application of municipal biosolids in agriculture present a concern with potential uptake and bioaccumulation of pharmaceutical compounds from biosolids into agronomic plants. We evaluated the efficacy of biochar as a soil amendment to minimize uptake of antimicrobial agents (ciprofloxacin, triclocarban, and triclosan) in lettuce (Lactuca sativa) and carrot (Daucus carota) plants. Biochar reduced the concentration of ciprofloxacin and triclocarban in lettuce leaves and resulted in a 67% reduction of triclosan in carrot roots. There was no substantial difference in pharmaceutical concentrations in carrot and lettuce plant matter at low (2.0 g kg-1 soil) and high (20.4 g kg-1 soil) rates of applied biochar. The co-amendment of biochar and biosolids increased soil pH and nutrient content which were positively correlated with an increase in lettuce shoot biomass. Our results demonstrate the potential efficacy of using walnut shell biochar as a sorbent for pharmaceutical contaminants in soil without negatively affecting plant growth.

Evaluating biochar and its modifications for the removal of ammonium, nitrate, and phosphate in water.

Removal of nitrogen (N) and phosphorus (P) from water through the use of various sorbents is often considered an economically viable way for supplementing conventional methods. Biochar has been widely studied for its potential adsorption capabilities for soluble N and P, but the performance of different types of biochars can vary widely. In this review, we summarized the adsorption capacities of biochars in removing N (NH4-N and NO3-N) and P (PO4-P) based on the reported data, and discussed the possible mechanisms and influencing factors. In general, the NH4-N adsorption capacity of unmodified biochars is relatively low, at levels of less than 20 mg/g. This adsorption is mainly via ion exchange and/or interactions with oxygen-containing functional groups on biochar surfaces. The affinity is even lower for NO3-N, because of electrostatic repulsion by negatively charged biochar surfaces. Precipitation of PO4-P by metals/metal oxides in biochar is the primary mechanism for PO4-P removal. Biochars modified by metals have a significantly higher capacity to remove NH4-N, NO3-N, and PO4-P than unmodified biochar, due to the change in surface charge and the increase in metal oxides on the biochar surface. Ambient conditions in the aqueous phase, including temperature, pH, and co-existing ions, can significantly alter the adsorption of N and P by biochars, indicating the importance of optimal processing parameters for N and P removal. However, the release of endogenous N and P from biochar to water can impede its performance, and the presence of competing ions in water poses practical challenges for the use of biochar for nutrient removal. This review demonstrates that progress is needed to improve the performance of biochars and overcome challenges before the widespread field application of biochar for N and P removal is realized.

Influences of feedstock sources and pyrolysis temperature on the properties of biochar and functionality as adsorbents: A meta-analysis.

Biochar is a porous, amorphous, stable, and low-density carbon material derived from the carbonization of various biological residues. Biochars have multifunctional properties that make them promising adsorbents for the remediation of organic and inorganic contaminants from soil and water. High temperature treatment (HTT) and the properties of feedstocks are key factors influencing the properties of biochars. Feedstocks have distinctive physicochemical properties due to variations in elemental and structural composition, and they respond heterogeneously to specific pyrolysis conditions. The criteria for the selection of feedstocks and pyrolysis conditions for designing biochars for specific sorption properties are inadequately understood. We evaluated the influence of pyrolysis temperature on a wide range of feedstocks to investigate their effects on biochar properties. With increasing HTT, biochar pH, surface area, pore size, ash content, hydrophobicity and O/C vs. H/C (ratios that denote stability) increased, whereas, hydrophilicity, yield of biochar, O/C, and H/C decreased. Discriminant analysis of data from 533 published datasets revealed that biochar derived from hardwood (HBC) and softwood generally have greater surface area and carbon content, but lower content of oxygen and mineral constituents, than manure- (MBC) and grass-derived biochars (GBC). GBC and MBC have abundant oxygen-containing functional groups than SBC and HBC. The sequence of stability and aromaticity of feedstocks was MBC < GBC < SBC < HBC. Therefore, SBC and HBC are suitable for sorption of hydrophobic molecules. Biochars produced from low HTT are suitable for removal of ionic contaminants, whereas those produced at high HTT are suitable for removal of organic contaminants. The influences of biochar properties on sorption performance of heavy metals and organic contaminants are critically reviewed.

Modification of pyrogenic carbons for phosphate sorption through binding of a cationic polymer.

This study reports on the development of modified pyrogenic carbonaceous materials (PCMs) for recovering orthophosphate (PO4-P). The PCMs include softwood and hardwood biochars and a commercial granular activated carbon (GAC) that were modified by irreversible adsorption of the quaternary ammonium polymer, poly(diallyldimethylammonium) chloride (pDADMAC), which reverses electrokinetic charge and increases PO4-P sorption. MgO-doped biochars were prepared by a literature method for comparison. Imaging and spectroscopic analyses characterize pDADMAC coverage, MgO doping, and binding of PO4-P. At environmentally relevant concentrations, PO4-P sorption by the pDADMAC-treated biochars was ~100 times greater than that of the corresponding unmodified biochars, and was comparable to that of the corresponding MgO-doped biochars on a coating content basis. The pDADMAC-coated carbons bind PO4-P by ion exchange, while the MgO-doped biochars bind PO4-P principally by forming an amorphous Mg phosphate species. Susceptibility to competition from other relevant anions (Cl-, NO3-, HCO3-/CO32-, SO42-) and poultry and dairy manure extracts was moderate and comparable for the two types of modified softwood biochars. Sorption to the pDADMAC-treated biochars appears to be more reversible than to the MgO-doped biochars using stepwise water extraction. Greater reversibility may be advantageous for trapping and recycling phosphate.

Biochar amendment as a remediation strategy for surface soils impacted by crude oil.

The impact of organic bulking agents on the biodegradation of petroleum hydrocarbons in crude oil impacted soils was evaluated in batch laboratory experiments. Crude oil impacted soils from three separate locations were amended with fertilizer and bulking agents consisting of biochars derived from walnut shells or ponderosa pine wood chips produced at 900 °C. The batch reactors were incubated at 25 °C and sampled at pre-determined intervals to measure changes in total petroleum hydrocarbons (TPH) over time. For the duration of the incubation, the soil moisture content was adjusted to 75% of the maximum water holding capacity (MWHC) and prior to each sampling event, the sample was manually stirred. Results show that the addition of fertilizer and bulking agents increased biodegradation rates of TPH. Soil samples amended with ponderosa pine wood biochar achieved the highest biodegradation rate, whereas the walnut shell biochar was inhibitory to TPH biodegradation. The beneficial impact of biochars on TPH biodegredation was more pronounced for a soil impacted with lighter hydrocarbons compared to a soil impacted with heavier hydrocarbons. This study demonstrates that some biochars, in combination with fertilizer, have the potential to be a low-technology and eco-friendly remediation strategy for crude oil impacted soils.

Sorption and abiotic transformation of monensin by iron and manganese oxides.

Monensin, an ionophore antibiotic, is commonly administered as a feed additive to cattle and poultry. A large percentage of the administered dose is excreted in animal waste, which is often applied to agricultural fields as fertilizer. The objective of this work is to gain insight into the fate of monensin in soil by investigating the interactions between monensin and common soil minerals, including sorption and transformation to unmonitored partial oxidation products. Batch sorption experiments across varying conditions (i.e., pH, ionic strength) and desorption experiments (i.e., methanol, PO43-, methyl tert-butyl ether) were used to determine the extent to which a selection of common redox-active soil minerals [birnessite (δ-MnO2), goethite (α-FeOOH), hematite (α-Fe2O3)] can bind and transform monensin. Monensin was bound by hematite (pH < 7.5, up to 7.5 mmol kg-1), goethite (pH < 7.5, up to 3.4 mmol kg-1), and birnessite (pH < 7, up to 0.1 mmol kg-1). Combined sorption and transformation were the greatest for hematite and the lowest for birnessite. Sorption to hematite was more reversible than to goethite. Each desorption from goethite recovered <10% of sorbed monensin, whereas desorption from hematite recovered up to 69% of sorbed monensin, dependent on the solution. The potential for iron and manganese (hydr)oxides to abiotically transform monensin through reductive dissolution to partial oxidation products was evaluated by mass spectral analysis following sorption experiments. Additionally, the dominant sorption mechanism was inferred through ATR-FTIR spectroscopy, via examination of the carboxylate peak separation differences, on goethite and hematite to be bridging bidentate.

Surface modification induced cuprous oxide nanoparticle toxicity to duckweed at sub-toxic metal concentrations.

Nanoparticle capping agents are critical for controlling the growth, oxidation state, and final particle size during aqueous synthesis. However, despite the known phytotoxicity of cetyltrimethylammonium bromide (CTAB) to plants, it is used to synthesize metal oxide nanoparticles of uniform size and with mesoporous structure. Among the few studies that have investigated how CTAB influences nanoparticle toxicity, CTAB has never been identified as the primary cause of nanoparticle toxicity in environmental systems; rather nanoparticle surface charge or morphology was identified as the driver of toxicity in environmentally relevant systems. In the current study, CTAB release from CTAB surface modified Cu2O nanoparticles (SM-Cu2O NPs) inhibited duckweed (Landoltia punctata) growth, even when administered at subtoxic Cu concentrations. Organic ligands, such as humic acid (HA) and ethylenediaminetetraacetic acid (EDTA), lessened growth inhibition associated with exposure to SM-Cu2O NPs, likely through electrostatic and hydrophobic interactions with CTAB. Such results highlight the need for a more holistic approach to nanoparticle surface modification and improved communication between toxicologists and synthetic chemists to develop green alternatives for nanoparticle synthesis.

Simultaneous removal of arsenic, cadmium, and lead from soil by iron-modified magnetic biochar.

Effective and economically viable method to remove elevated metal(loid)s from farm and industrial lands remains a major challenge. In this study, magnetic biochar-based adsorbents with Fe3O4 particles embedded in a porous biochar matrix was synthesized via iron (Fe) treated biochar or thermal pyrolysis of Fe treated cedar sawdust. Application and separation of the adsorbent to a multi-contaminated soil slurry simultaneously removed 20-30% of arsenic, cadmium and lead within 24 h. Fast removal of multi-metal(loid)s result from the decrease in all operationally defined fractions of metal(loid)s, not limited to the exchangeable fraction. The direct removal of arsenic-enriched soil particles was observed via micro X-ray fluorescence maps. Furthermore, through comparison of biochars with different production methods, it has been found that magnetization after pyrolysis treatment leads to stronger metals/metalloids adsorption with a higher qe (bound sorbate) than other treatments but pyrolysis after magnetization stabilized Fe oxides on the biochar surface, indicating a higher biochar recovery rate (∼65%), and thus a higher metal(loid)s removal efficiency. The stability of Fe oxides on the surface of biochar is the determining factor for the removal efficiency of metal(loid)s from soil.

A novel calcium-based magnetic biochar is effective in stabilization of arsenic and cadmium co-contamination in aerobic soils.

This study developed a novel calcium-based magnetic biochar by pyrolysing rice straw mixed with calcium carbonate and iron oxide for stabilization of contamination of multiple metals. A 160-day incubation study was conducted to investigate its performance in stabilization of cadmium and arsenic co-contamination in soil. Both biochar and Ca-MBC treatments increased soil pH, decreased the bioavailability of cadmium. Ca-MBC decreased but biochar enhanced the bioavailability of arsenic. The BCR (European Community Bureau of Reference) sequential extraction confirmed Ca-MBC facilitated the transformation of the unstable fraction of arsenic to stable fractions. The stabilization mechanisms were explored through synchrotron-based micro X-ray fluorescence and X-ray absorption near edge structure. The results show that Ca-MBC remediated the dual contamination of arsenic and cadmium through (1) elevated pH and cation exchange capacity (for Cd); (2) the formation of bi-dentate chelate and ternary surface complexes on the surface of iron oxide; (3) enhanced adsorption ability of porous biochar. In addition, Ca-MBC increased the abundance and diversity of bacterial community, and modified the relative abundances of bacterial taxa, leading to a shift of the composition. These new insights provide valuable information for stabilization of co-contamination of arsenic and cadmium in soil using the potential material Ca-MBC.

Influence of pH and Divalent Metals Relevant to California Rice Fields on the Hydroxide-Mediated Hydrolysis of the Insecticide Chlorantraniliprole.

The hydrolysis of chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was investigated over the pH range of 6-10, reflective of California rice field conditions, with variable additions of Cu2+, Zn2+, Mn2+, or Ni2+. Dissipation accelerated as pH increased with half-lives ranging from 26.9 to 2.2 days with slight inhibition in rice field water. The addition of divalent metals was not observed to catalyze the hydrolysis of CAP at pH 6, indicating that the insecticide is likely to remain recalcitrant to hydrolysis in neutral or acidic surface waters. However, Mn2+ and Ni2+ were observed to inhibit hydrolysis at pH 8 and 9. Attenuated total reflectance Fourier transform infrared analysis supports the conclusion that divalent metals may withdraw electron density from the amide nitrogen via interaction with the amide oxygen, though additional quantum chemical modeling is necessary to provide further mechanistic insights. Overall, the hydrolysis of CAP in California rice fields and their surrounding surface waters will be dominated by pH and inhibited by dissolved metal species.

Influence of Flooding, Salinization, and Soil Properties on Degradation of Chlorantraniliprole in California Rice Field Soils.

Chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was granted supplemental registration for use in rice cultivation in California through December, 2018. Previous work investigated the partitioning of CAP in California rice field soils; however, its degradation in soils under conditions relevant to California rice culture has not been investigated. The degradation of CAP in soils from two California rice fields was examined under aerobic and anaerobic conditions with varying salinity via microcosm experiments. Results indicate that soil properties governing bioavailability may have a greater influence on degradation than flooding practices or field salinization over a typical growing season. Differences between native and autoclaved soils (t1/2 = 59.0-100.2 and 78.5-171.7 days) suggest that biological processes were primarily responsible for CAP degradation; however, future work should be done to confirm specific biotic processes as well as to elucidate abiotic processes, such as degradation via manganese oxides and formation of nonextractable residues, which may contribute to its dissipation.