Crucial roles of soil inherent Fe-bearing minerals in enhanced Cr(VI) reduction by biochar: The electronegativity neutralization and electron transfer mediation.

Biochar has been used for soil Cr(VI) remediation in the last decade due to its enriched redox functional groups and good electrochemical properties. However, the role of soil inherent Fe-bearing minerals during the reduction of Cr(VI) has been largely overlooked. In this study, biochar with different electron-donating capacities (EDCs) was produced at 400 °C (BC400) and 700 °C (BC700), and their performance for Cr(VI) reduction in soils with varied properties (e.g., Fe content) was investigated. The addition of BC400 caused around 14.2-36.0 mg g-1 Cr(VI) reduction after two weeks of incubation in red soil, paddy soil, loess soil, and fluvo-aquic soil, while a less Cr(VI) was reduced by BC700 (2.57-16.7 mg g-1) with smaller EDCs. The Cr(VI) reduction by both biochars in different soils was closely related to Fe content (R2=0.93-0.98), so red soil with the richest Fe (14.8% > 1.79-3.49%) showed the best reduction capability, and the removal of soil free Fe oxides (e.g., hematite) resulted in 71.9% decrease of Cr(VI) reduction by BC400. On one hand, Fe-bearing minerals could increase the soil acidity, neutralize the surface negative charge of biochar, enhance the contact between Cr(VI) and biochar, and thus facilitate the direct Cr(VI) reduction by biochar in soils. On the other hand, Fe-bearing minerals could also facilitate the indirect Cr(VI) reduction by mediating the electron from biochar to Cr(VI) with the cyclic transformation of Fe(II)/Fe(III). This study demonstrates the key role of soil Fe-bearing minerals in Cr(VI) reduction by biochar, which advances our understanding on the biochar-based remediation mechanism of Cr(VI)-contaminated soils.

Mineralogical transformation of arsenic at different copper smelting workshops: The impact on arsenic bioaccessibility.

Soil arsenic (As) contamination associated with the demolition of smelting plants has received increasing attention. Soil As can source from different industrial processes, and also participate in soil weathering, making its speciation rather complex. This study combined the usage of chemical sequential extraction and advanced spectroscopic techniques, e.g., time of flight secondary ion mass spectrometry (ToF-SIMS), to investigate the mineralogical transformation of soil As at different processing sites from a typical copper smelting plant in China. Results showed that the stability of arsenic species decreased following the processes of storage, smelting, and flue gas treatment. Arsenic in the warehouse area was incorporated into pyrite (FeS2) as well as its secondary minerals such as jarosite (KFe3(SO4)2(OH)6). At the smelting area, a large proportion of As was adsorbed by iron oxides from smelting slags, while some As existed in stable forms like orpiment (As2S3). At the acid-making area, more than half of As was adsorbed on amorphous iron oxides, and some were adsorbed on the flue gas desulfurization gypsum. More importantly, over 86% of the As belonged to non-specifically and specifically adsorbed fractions was found to be bioaccessible, highlighting the gypsum-adsorbed As one of the most hazardous species in smelting plant soils. Our findings indicated the importance of iron oxides in As retention and suggested the potential health risk of gypsum-adsorbed As. Such detailed knowledge of As speciation and bioaccessibility is vital for the management and remediation of As-contaminated soils in smelting plants.

A Critical Review of Groundwater Table Fluctuation: Formation, Effects on Multifields, and Contaminant Behaviors in a Soil and Aquifer System.

The groundwater table fluctuation (GTF) zone is an important medium for the hydrologic cycle between unsaturated soil and saturated aquifers, which accelerates the migration, transformation, and redistribution of contaminants and further poses a potential environmental risk to humans. In this review, we clarify the key processes in the generation of the GTF zone and examine its links with the variation of the hydrodynamic and hydrochemistry field, colloid mobilization, and contaminant migration and transformation. Driven by groundwater recharge and discharge, GTF regulates water flow and the movement of the capillary fringe, which further control the advection and dispersion of contaminants in soil and groundwater. In addition, the formation and variation of the reactive oxygen species (ROS) waterfall are impacted by GTF. The changing ROS components partially determine the characteristic transformation of solutes and the dynamic redistribution of the microbial population. GTF facilitates the migration and transformation of contaminants (such as nitrogen, heavy metals, non-aqueous phase liquids, and volatile organic compounds) through colloid mobilization, the co-migration effect, and variation of the hydrodynamic and hydrochemistry fields. In conclusion, this review illustrates the limitations of the current literature on GTF, and the significance of GTF zones in the underground environment is underscored by expounding on the future directions and prospects.

Critical Functions of Soil Components for In Situ Persulfate Oxidation of Sulfamethoxazole: Inherent Fe(II) Minerals-Coordinated Nonradical Pathway.

Naturally occurring iron (Fe) minerals have been proved to activate persulfate (PS) to generate reactive species, but the role of soil-inherent Fe minerals in activating PS as well as the underlying mechanisms remains poorly understood. Here, we investigated sulfamethoxazole (SMX) degradation by PS in two Fe-rich soils and one Fe-poor soil. Unlike with the radical-dominant oxidation processes in Fe-poor soil, PS was effectively activated through nonradical pathways (i.e., surface electron-transfer) in Fe-rich soils, accounting for 68.4%-85.5% of SMX degradation. The nonradical mechanism was evidenced by multiple methods, including electrochemical, in situ Raman, and competition kinetics tests. Inherent Fe-based minerals, especially those containing Fe(II) were the crucial activators of PS in Fe-rich soils. Compared to Fe(III) minerals, Fe(II) minerals (e.g., ilmenite) were more liable to form Fe(II) mineral-PS* complexes to initiate the nonradical pathways, oxidizing adjacent SMX via electron transfer. Furthermore, mineral structural Fe(II) was the dominant component to coordinate such a direct oxidation process. After PS oxidation, low-crystalline Fe minerals in soils were transformed into high-crystalline Fe phases. Collectively, our study shows that soil-inherent Fe minerals can effectively activate PS in Fe-rich soils, so the addition of exogenous iron might not be required for PS-based in situ chemical oxidation. Outcomes also provide new insights into the activation mechanisms when persulfate is used for the remediation of contaminated soils.

Phosphorus Footprint in the Whole Biowaste-Biochar-Soil-Plant System: Reservation, Replenishment, and Reception.

Two phosphorus (P)-rich biowastes, sewage sludge (SS) and bone dreg (BD), were selected to clarify P footprints among biowaste, biochar, soil, and plants by introducing a novel "3R" concept model. Results showed that pyrolysis resulted in P transformation from an unstable-organic amorphous phase to a stable-inorganic crystalline phase with a P retention rate of 70-90% in biochar (P reservation). In soil, SSBC released more P in acid red soil and alkaline yellow soil than BDBC, while the opposite result appeared in neutral paddy soil. The P released from SSBC formed AlPO4 by combining with Al in soil, whereas P from BDBC transformed into Ca5(PO4)3F(or Cl) in conjunction with Ca in the soil (P replenishment). Various plants exhibited an uptake of approximately 2-6 times more P from biochar-amended soil than from the original soil (P reception). This study can guide the application of biochar in various soil-plant systems for effective nutrient reclamation.

Size-dependent influences of nanoplastics on microbial consortium differentially inhibiting 2, 4-dichlorophenol biodegradation.

Nanoplastics (NPs), as a type of newly emerging pollutant, are ubiquitous in various environmental systems, one of which is coexistence with organic pollutants in wastewater, potentially influencing the pollutants' biodegradation. A knowledge gap exists regarding the influence of microbial consortium and NPs interactions on biodegradation efficiency. In this work, a 2,4-dichlorophenol (DCP) biodegradation experiment with presence of polystyrene nanoplastics (PS-NPs) with particle sizes of 100 nm (PS100) or 20 nm (PS20) was conducted to verify that PS-NPs had noticeable inhibitory effect on DCP biodegradation in a size-dependent manner. PS100 at 10 mg/L and 100 mg/L both prolonged the microbial stagnation compared to the control without PS-NPs; PS20 exacerbated greater, with PS20 at 100 mg/L causing a noticeable 6-day lag before the start-up of rapid DCP reduction. The ROS level increased to 1.4-fold and 1.8-fold under PS100 and PS20 exposure, respectively, while the elevated LDH under PS20 exposure indicated the mechanical damage to cell membrane by smaller NPs. PS-NPs exposure also resulted in a decrease in microbial diversity and altered the niches of microbial species, e.g., they decreased the abundance of some functional bacteria such as Brevundimonas and Comamonas, while facilitated some minor members to obtain more proliferation. A microbial network with higher complexity and less competition was induced to mediate PS-NPs stress. Functional metabolism responded differentially to PS100 and PS20 exposure. Specifically, PS100 downregulated amino acid metabolism, while PS20 stimulated certain pathways in response to more severe oxidative stress. Our findings give insights into PS-NPs environmental effects concerning microflora and biological degradation.

Digestive fluid components affect speciation and bioaccessibility and the subsequent exposure risk of soil chromium from stomach to intestinal phase in in-vitro gastrointestinal digestion.

The simulated in-vitro gastrointestinal method provides a simple way to evaluate the health risk of human body exposed to soil contaminants. Several in-vitro methods have been successfully established for soil As, Pb, and Cd. However, the method development for soil Cr failed up to now, which could be resulted from alteration in the species of Cr (e.g., Cr(VI)/Cr(III)) caused by the gastrointestinal digestion components, ultimately affecting the accessibility of Cr. This study explored the transformation and bioaccessibility of Cr in two Cr-contaminated soils during the physiologically based extraction test. The water-soluble and exchangeable Cr in soil was dissolved in gastrointestinal tract, accompanied with reduction of Cr(VI) into Cr(III), and the reduction occurred after the chemical extraction in two soils rather than during the extraction. Pepsin and organic acids in gastric phase could reduce Cr(VI) into Cr(III) and reduction efficiency were 20.4%- 53.0%, while in intestinal phase, pancreatin and bile salt had little effect on the Cr(VI) reduction, instead, more Cr(VI) was released from soil. In the gastric solution, Cr(VI) was mainly present as HCrO4- and Cr(III) as free Cr3+ ion. In the intestinal phase, Cr(VI) mainly occurred as CrO42- and Cr(III) as Cr(OH)3 (aq). Cr in the soil solid phase was dominated as the precipitates of Cr-Fe oxide, which was hardly extracted. Bioaccessibility of Cr in gastric phase increased as extraction duration increased and decreased in the intestinal phase, the contrary trend was observed for the hazard quotient of Cr in two phases due to Cr(VI)/Cr(III) transformation. This study indicates that the gastrointestinal components could influence the Cr transformation and subsequently affect the Cr bioaccessibility, which would help for a successful establishment of in vitro determination method for soil Cr bioaccessibility.

New Insight into the Natural Detoxification of Cr(VI) in Fe-Rich Surface Soil: Crucial Role of Photogenerated Silicate-Bound Fe(II).

Photoexcitation of natural semiconductor Fe(III) minerals has been proven to generate Fe(II), but the photogeneration of Fe(II) in Fe-rich surface soil as well as its role in the redox biogeochemistry of Cr(VI) remains poorly understood. In this work, we confirmed the generation of Fe(II) in soil by solar irradiation and proposed a new mechanism for the natural reductive detoxification of Cr(VI) to Cr(III) in surface soil. The kinetic results showed that solar irradiation promoted the reduction of Cr(VI) in Fe-rich soils, while a negligible Cr(VI) reduction was observed in the dark. Fe(II), mainly in the form of silicate-bound Fe(II), was generated under solar irradiation and responsible for the reduction of Cr(VI) in soils, which was evidenced by sequential extraction, transmission electron microscopy with electron energy loss spectroscopy, and electron transfer calculation. Photogenerated silicate-bound Fe(II) resulted from the massive clay-iron (hydr)oxide associations, consisting of iron (hydr)oxides (e.g., hematite and goethite) and kaolinite. These associations could generate Fe(II) under solar irradiation either via intrinsic excitation to produce photoelectrons or via the ligand-to-metal charge transfer process after the formation of clay-iron (hydr)oxide-organic matter complexes, which was proven by photoluminescence spectroscopy and X-ray photoelectron spectroscopy. These findings highlight the important role of photogenerated Fe(II) in Cr(VI) reduction in surface soil, which advances a fundamental understanding of the natural detoxification of Cr(VI) as well as the redox biogeochemistry of Cr(VI) in soil.

The aggregated biofilm dominated by Delftia tsuruhatensis enhances the removal efficiency of 2,4-dichlorophenol in a bioelectrochemical system.

Bioelectrochemical system is a prospective strategy in organic-contaminated groundwater treatment, while few studies clearly distinguish the mechanisms of adsorption or biodegradation in this process, especially when dense biofilm is formed. This study employed a single chamber microbial electrolysis cell (MEC) with two three-dimensional electrodes for removing a typical organic contaminant, 2,4-dichlorophenol (DCP) from groundwater, which inoculated with anaerobic bacteria derived from sewage treatment plant. Compared with the single biodegradation system without electrodes, the three-dimensional electrodes with a high surface enabled an increase of alpha diversity of the microbial community (increased by 52.6% in Shannon index), and provided adaptive ecological niche for more bacteria. The application of weak voltage (0.6 V) furtherly optimized the microbial community structure, and promoted the aggregation of microorganisms with the formation of dense biofilm. Desorption experiment proved that the contaminants were removed from the groundwater mainly via adsorption by the biofilm rather than biodegradation, and compared with the reactor without electricity, the bioelectrochemical system increased the adsorption capacity from 50.0% to 74.5%. The aggregated bacteria on the surface of electrodes were mainly dominated by Delftia tsuruhatensis (85.0%), which could secrete extracellular polymers and has a high adsorption capacity (0.30 mg/g electrode material) for the contaminants. We found that a bioelectrochemical system with a three-dimensional electrode could stimulate the formation of dense biofilm and remove the organic contaminants as well as their possible more toxic degradation intermediates via adsorption. This study provides important guidance for applying bioelectrochemical system in groundwater or wastewater treatment.

Converting coastal silt into subgrade soil with biochar as reinforcing agent, CO2 adsorbent, and carbon sequestrating material.

Large amounts of coastal silt produced annually is urgent to be treated with a feasible strategy. This study converted it into subgrade soil by cement solidification for resource utilization. Biochar was used as exogenous additive for enhancing compressive strength of the product, simultaneously achieving carbon sequestration. Three biochars derived from peanut shells (PSBC), cow dung (CDBC) and sewage sludge (SSBC) at 300 °C, 500 °C and 700 °C pyrolysis, were added into raw materials with 1%, 2% and 5%, respectively. All biochars significantly improved the compressive strength of the subgrade soil by 20-110%. Biochar catalyzed cement hydration reactions to produce more Ca(OH)2, CaCO3 and calcium silicate hydrates (C-S-H gel). The catalytic capacity of different biochars followed the order of SSBC > PSBC > CDBC. Addition of 2% SSBC500 induced the greatest increase in 28 d-strength from only 1.0 MPa-2.1 MPa, which was due to that 500 °C biochar had a suitable specific surface area and porosity. Biochar facilitated CO2 capture (absorption) during the hydration reactions at the initial 48 h with 55-70 mg g-1. The high alkalinity and water holding capacity of biochar contributed to the absorption of CO2; the high content of minerals in SSBC compared to CDBC and PSBC promoted chemical conversion of CO2 to carbonate. Besides, the biochar itself as carbon rich material was encapsulated in the subgrade soil, which can be regarded as a long-term carbon sequestration strategy. Carbon budget analysis demonstrated that converting one ton dry silt into subgrade soil with addition of 2% biochar could increase CO2 sequestration from 11 kg to 36-94 kg. This study proposes a novel strategy of using biochar to strengthen the subgrade soil simultaneously achieve long-term carbon sequestration.

Electron donation of Fe-Mn biochar for chromium(VI) immobilization: Key roles of embedded zero-valent iron clusters within iron-manganese oxide.

The dense surface passivation layer on zero-valent iron (ZVI) restricts its efficiency for water decontamination, causing a poor economy and waste of resources. Herein, we found that the ZVI on Fe-Mn biochar could afford a high electron-donating efficiency for the Cr(VI) reduction and immobilization. Over 78.0% of Fe in the Fe-Mn biochar was used for the Cr(VI) reduction and immobilization, i.e., 56.2 - 161.7 times higher than the commercial ZVI (0.5%) and modified ZVI (0.9 -1.3%), indicating that the unique ZVI species in Fe-Mn biochar offered an outstanding Fe utilization efficiency. We proposed that oxygen atoms in the FeO in the FeMnO2 precursor were removed during pyrolysis with biochar while the MnO skeleton was preserved, forming the embedded ZVI clusters within Fe-Mn oxide. The unique structure inhibited the formation of the Fe-Cr complex on Fe(0), which would facilitate the electron transfer between core Fe(0) and Cr(VI). Moreover, the surface FeMnO2 inhibited the diffusion of Fe and facilitated its affinity with pollutants, thus supporting higher efficiency for pollutant immobilization. The preserved performance of Fe-Mn biochar was proved in industrial wastewater and after long-term oxidation process, and the economic benefit was evaluated. This work provides a new approach for developing active ZVI-based materials with high Fe utilization efficiency and economics for water pollution control.

Enhanced microbial reduction of Cr(VI) in soil with biochar acting as an electron shuttle: Crucial role of redox-active moieties.

Biochar has been proven to participate in the biotic reduction of hexavalent chromium (Cr(VI)) in environment since its involvement may accelerate the extracellular electron transfer (EET). However, roles of the redox-active moieties and the conjugated carbon structure of biochar in this EET process remain unclear. In this study, 350 °C and 700 °C were selected to produce biochar with more O-containing moieties (BC350) or more developed conjugated structures (BC700), and their performances in the microbial reduction of soil Cr(VI) were investigated. Our results showed that BC350 presented a 241% increase of Cr(VI) microbial reduction after 7-day incubation, much higher than that of BC700 (39%), suggesting that O-containing moieties might play more important roles in accelerating the EET process. Biochar, especially BC350 could serve as an electron donor for microbial anaerobic respiration, but its contribution (73.2%) as an electron shuttle for EET was dominant to the enhanced Cr(VI) reduction. The positive correlation between electron exchange capacities (EECs) of pristine and modified biochars and the corresponding maximum reduction rates of Cr(VI) evidenced the crucial role of redox-active moieties in electron shuttling. Moreover, EPR analysis suggested the nonnegligible contribution of semiquinone radicals in biochars to the accelerated EET process. This study demonstrates the crucial role of redox-active moieties, i.e., O-containing moieties in mediating the EET process during the microbial reduction of Cr(VI) in soil. Findings obtained will advance the current understanding of biochar as an electron shuttle participating in the biogeochemical processes of Cr(VI).

Calcium enhances phosphorus reclamation during biochar formation: Mechanisms and potential application as a phosphorus fertilizer in a paddy soil.

Transformation of phosphorus (P) species during pyrolytic production of biochar from P-rich biowastes with a subsequent soil amendment is important to P reclamation. Aiming at increasing the content of plant-available P and restraining the formation of easily mobile P in pyrolysis product, this study used exogenous calcium ions (20 wt% CaCl2) addition prior to pyrolysis to regulate the pyrolytic transformation of P chemical fractions from sewage sludge and bone dreg. Results showed that active Ca catalyzed the decomposition of organic P to transform into inorganic orthophosphate. Based on Hedley's sequential extraction method, this study found that addition of Ca ions remarkably reduced the content of soluble P, exchange P, Fe/Al bound P, and occluded P in biochar, while increased Ca bound P from 78 to 85% to 85-96%. Liquid 31P NMR indicated that exogenous Ca induced the crack of the P-O-P bond in pyrophosphate to become orthophosphates. It also explained why new orthophosphates including chlorapatite (Ca5(PO4)3Cl) and calcium hydroxyapatite (Ca10(PO4)6(OH)2) appeared in the Ca-composite biochar compared to pristine biochar. Combined with rapid P-release test in paddy soil (pH 6.27) and 30-days rice seedling growth test under flooded condition (10 wt% biochar addition ratio), it was confirmed that compared to pristine biochar, Ca-composite biochar released more P in paddy soil, but also promoted more P to be taken in by rice root and stalk. These results suggested that pretreating biowaste with Ca ion was a friendly approach to enhance P reclamation during biochar formation, making it a promising P fertilizer.

Immobilization of arsenic in different contaminated soils by zero-valent iron-embedded biochar: Effect of soil characteristics and treatment conditions.

Although zero-valent iron-embedded biochar (ZVI-BC) has been proposed as an effective amendment for arsenic (As)-contaminated soils, the impacts of soil characteristics and treatment conditions on the remediation process remained poorly understood. Herein, the immobilization of As in four As-contaminated soils (i.e., smelting soil, storage soil, agricultural soil, and mining soil) by ZVI-BC under different amendment dosages, cultivation temperatures, and soil moisture contents were investigated. ZVI-BC showed high As immobilization capacity in all four soils via forming the AsFe co-precipitation, and the liable As was reduced by 82.4-97.0 % with a 2 % (w/w) amendment. The higher temperature could raise the concentration of liable As in all four soils, especially for the storage soil, in which liable As at 35 °C was almost 3 times of that at 25 °C after 50-days treatment, because the elevated temperature enhanced the destruction of the generated AsFe coprecipitation as well as the desorption of As in soils. Too much soil moisture was unfavorable for the As immobilization after 50-days treatment. Flooding tended to inhibit the community diversity of As-detoxicated bacteria, e.g., Halomonas, Bryobacter, and Anaerolinea, thus resulting in the release of liable As. According to the correlation analysis, the crucial influencing factor for As immobilization was different in four soils, which was determined by the soil properties and proportion of liable As. Our study indicates that ZVI-BC is an effective amendment for As immobilization under various conditions, and the biogeochemical processes of As-associated Fe minerals determine the As immobilization during amendment.

Fate and transport of chromium in industrial sites: Dynamic simulation on soil profile.

Direct discharge of chromium-containing waste water and improper disposal of waste residues in industrial sites may lead to the vertical migration of metals into aquifers, posing serious threat to soil-groundwater system. The heterogeneity in soil profile further aggravates the complexity and unpredictability of this transport process. However, topsoil was the main focus of most studies. Herein, the vertical transport and transformation of Cr in soils at different depths in three industrial sites (i.e., Shijiazhuang, Zhuzhou, and Guangzhou) were investigated to delineate Cr transport and retention characteristics under complex conditions. Regional and vertical differences in soil properties led to the specificity in Cr migration behaviors among these three sites. Correlation analysis showed that soil pH (r = -0.909, p < 0.05) and Fe content (r = 0.949, p < 0.01) were the major controlling factors of Cr(VI) migration and transformation in aquifers. Furthermore, the soil of Zhuzhou site showed the maximum adsorption capacity for Cr(VI) (0.225 mol/kg), and the strongest reduction ability of Cr(VI) was observed in the Guangzhou soil. Results of model-based long-term forecast indicated that the Cr(III) concentration in the liquid phase of Guangzhou subsoil could reach 0.08 mol/m3 within 20 years. Heavier rainfall condition exacerbated the contamination due to an increased pollutant flux and enhanced convection. Specially, Cr was fixed in the topsoil of Zhuzhou site with the formation of PbCrO4 and presented least vertical migration risk. The conclusions above can provide scientific theoretical guidance for heavy metal pollution prevention and control in industrial contaminated regions.

Transport and transformation of arsenic in coastal aquifer at the scenario of seawater intrusion followed by managed aquifer recharge.

Release of contaminants from aquifers at the coastal area is of increasing concern, but remains unclear due to the complex groundwater dynamics and hydrochemistry. Specifically, frequently occurring seawater intrusion and the subsequent engineering measures of managed aquifer recharge (MAR) could alter the groundwater regime, which might affect the fate and behaviors of contaminants. In this work, we investigated the transport and transformation of arsenic (As) in the coastal aquifer at the scenario of seawater intrusion followed by the injection-based MAR process. Results showed that seawater intrusion induced 10.3% more release of aqueous As in aquifers, which was attributed to the competitive desorption as a result of elevated anion concentration and pH, and the reduction of As(V) to As(III) due to the reduced redox potential and enriched As-reducing bacteria. Furthermore, seawater intrusion inhibited the recrystallization of iron (hydr)oxides and instead facilitated its conversion to iron sulfide with lower affinity to As. The subsequent MAR introduced oxygenated recharge water into aquifers and increased the redox potential, leading to the dissolution of iron sulfide followed by formation of amorphous iron (hydr)oxides. However, the competitive desorption of As with rich HCO3- under increased pH dominated continuous increase in the aquifer aqueous As during MAR process. A constructed numerical model for describing As transport based on the experimental data showed that As transported along the interface between seawater and freshwater, and MAR enhanced the release of As and expanded the spread range of As. Our findings reveal that both seawater intrusion and subsequent MAR could cause the release, transport, and transformation of As, which provides new insight on the understanding of geochemical process of As in coastal aquifers.

Constructing the active surface soil layer with ZVI-biochar amendment for simultaneous immobilization of As and Zn in both contaminated soil and groundwater: Continuous versus intermittent infiltration mode.

In this study, the zero valent iron-biochar composite (ZVI-BC) was applied to construct an active surface soil layer for the simultaneous remediation of As-Zn contaminated soil and groundwater, focusing on the influence of the infiltration mode of pumped-up groundwater into soil. The active surface soil treated more contaminated groundwater for As (4.45-5.46 L kg-1 soil) than that for Zn (2.52-3.13 L kg-1 soil) under both continuous and intermittent infiltration modes, with about 98% As and 95% Zn removed from groundwater and retained in the soil. As(V) precipitated with Fe(III) due to ZVI oxidation, which was responsible for the As immobilization. The soil under the intermittent infiltration mode was enriched by the Sphingomonas with arsenate reductase gene, which promoted more reduction of As(V) into As(III) and facilitated coprecipitation of As(III) with Fe(III). The Mn oxide determined the sorption of Zn in the active soil layer, where the Hyphomicrobium, one type of manganese oxidizing bacteria, was much higher under the continuous infiltration mode, which accounted for the more Zn immobilization. After the remediation, both As and Zn immobilized in the active surface soil showed high stability, with the average downward migration rate of only 0.207-0.368 cm year-1 within 20-year rainfall exposure. Our findings indicate that this active surface soil layer is applicable for simultaneous immobilization of As and Zn in both contaminated soil and groundwater, and the groundwater intermittent infiltration could be a better option considering the remediation effectiveness, the immobilization mechanism, the long-term stability, and the energetic efficiency.

Numerical modeling investigations of colloid facilitated chromium migration considering variable-density flow during the coastal groundwater table fluctuation.

Fluctuation of the groundwater table in the coastal zone influences the migration of colloids in vadose zone, which can further carry contaminants to transport. To capture the variable-density water flow and the migration processes, this study developed a colloid-facilitated migration model by adjusting the adsorption coefficient and considering the relationship between colloid and salinity based on the experimental observations. This model was further applied to explore the effects of freshwater and seawater fluctuations on the migration and transformation of colloids and Cr in coastal vadose zones. The greater the hydraulic conductivity of the saturated aquifer was, the more Cr were discharged into the ocean by submarine groundwater discharge. Furthermore, the increase in the freshwater fluctuation amplitude expanded the pollution ranges of colloidal Cr and dissolved Cr. The rise of the seawater fluctuation amplitude had a more obvious reduction effect on the total solid retained Cr in the contaminant source, compared with that of the freshwater fluctuation. As the seawater fluctuation amplitude increased from 0.1 m to 0.8 m, the ratio of total solid retained Cr reduction in the contaminant source to the initial value increased from 1.8 % to 7.8 %. The results obtained from this study deepens our understanding of how colloids and contaminants migrate across a coastal area from vadose zone induced by the groundwater table fluctuation.

Enhancement of coal gangue performance by surface micro-crystalline glaze derived from mineral powder.

Coal gangue is a waste derived from coal mining, and its unreasonable disposal usually causes serious land occupation and environmental pollution. Using coal gangue as a substitute for natural aggregate is an effective recycling approach, however, the high water absorption and high crushing rate of coal gangue seriously weaken its performance. This study proposed a novel strategy to decrease the water absorption and crushing rate of coal gangue by co-calcining with mineral powders, including K-feldspar, wollastonite, blast furnace slag and fly ash, meanwhile clarified the improvement mechanisms. Results showed that after calcining with mineral powders, the crushing rate of coal gangue decreased from 16.8 % to 16.1-13.2 %, and water absorption decreased from 5.29 % to 2.74-3.90 %, among which the coal gangue treated by K-feldspar and blast furnace slag had the lowest water absorption (2.74 %), reducing by 48.2 % compared to raw coal gangue. Underlying mechanisms were that during calcination, mineral powders generated micro-crystalline glaze on gangue surface, which improved the pore size distribution of coal gangue and strengthened its hardness. Specifically, as for pores with 1-1000 nm diameter, the pore volume percentage decreased from 88.5 % to 43.2-71.3 %. Vickers hardness of coal gangue increased from 0.29 GPa to 6.37-6.79 GPa, and the fracture toughness increased significantly to 41.9-67.6 MPa m1/2. Under K-feldspar and blast furnace slag treatment, the approximate thickness of micro-crystalline glaze was about 32 µm. The main component of micro-crystalline glaze was silicate lattice derived from SiO2 and Al2O3, and abundant Fe2O3 and Fe3O4 crystalline were sealed in the glaze. This study provides an innovative approach to strengthen the performance of coal gangue, which is important to expand the resource utilization of coal gangue and control the environmental pollution.