Patterns and abiotic drivers of soil organic carbon in perennial tea (Camellia sinensis L.) plantation system of China.

Understanding soil organic carbon (SOC), the largest carbon (C) pool of a terrestrial ecosystem, is essential for mitigating climate change. Currently, the spatial patterns and drivers of SOC in the plantations of tea, a perennial leaf crop, remain unclear. Therefore, the present study surveyed SOC across the main tea-producing areas of China, which is the largest tea producer in the world. We analyzed the soil samples from tea plantations under different scenarios, such as provinces, regions [southwest China (SW), south China (SC), south Yangtze (SY), and north Yangtze (NY)], climatic zones (temperate, subtropical, and tropical), and cultivars [large-leaf (LL) and middle or small-leaf (ML) cultivars]. Preliminary analysis revealed that most tea-producing areas (45%) had SOC content ranging from 10 to 20 g kg-1. The highest SOC was recorded for Yunnan among the various provinces, the SW tea-producing area among the four regions, the tropical region among the different climatic zones, and the areas with LL cultivars compared to those with ML cultivars. Further Pearson correlation analysis demonstrated significant associations between SOC and soil variables and random forest modeling (RF) identified that total nitrogen (TN) and available aluminum [Ava(Al)] of soil explained the maximum differences in SOC. Besides, a large indirect effect of geography (latitude and altitude) on SOC was detected through partial least squares path modeling (PLS-PM) analysis. Thus, the study revealed a high spatial heterogeneity in SOC across the major tea-producing areas of China. The findings also serve as a basis for planning fertilization strategies and C sequestration policies for tea plantations.

Long-term nitrogen addition increases denitrification potential and functional gene abundance and changes denitrifying communities in acidic tea plantation soil.

The response of soil denitrification to nitrogen (N) addition in the acidic and perennial agriculture systems and its underlying mechanisms remain poorly understood. Therefore, a long-term (12 years) field trial was conducted to explore the effects of different N application rates on the soil denitrification potential (DP), functional genes, and denitrifying microbial communities of a tea plantation. The study found that N application to the soil significantly increased the DP and the absolute abundance of denitrifying genes, such as narG, nirK, norB, and nosZ. The diversity of denitrifying communities (genus level) significantly decreased with increasing N rates. Moreover, the denitrifying communities composition significantly differed among the soils with different rates of N fertilization. Further variance partitioning analysis (VPA) revealed that the soil (39.04%) and pruned litter (32.53%) properties largely contributed to the variation in the denitrifying communities. Dissolved organic carbon (DOC) and soil pH, pruned litter's total crude fiber (TCF) content and total polyphenols to total N ratio (TP/TN), and narG and nirK abundance significantly (VIP >1.0) influenced the DP. Finally, partial least squares path modeling (PLS-PM) revealed that N addition indirectly affected the DP by changing specific soil and pruned litter properties and functional gene abundance. Thus, the findings suggest that tea plantation is a major source of N2O emissions that significantly enhance under N application and provide theoretical support for N fertilizer management in an acidic tea plantation system.

Remediation of Cd-, Pb-, Cu-, and Zn-contaminated soil using cow bone meal and oyster shell meal.

To understand the environmental friendliness and high efficiency of organic materials during remediating soil polluted by heavy metals by assessing the feedback of soil ecosystems after organic materials were put into polluted soil. Incubation research was undertaken to examine the impact of amendments ranging from 0.1% to 3.0% (w/w), including single cow bone meal (BM), single oyster shell meal (OS), and a composite of 50% BM mixed with 50% OS (BO) on soil biochemical properties. The findings revealed that the implementation of BM and OS increased soil pH, the content of certain nutrients, and the activities of catalase (S-CAT), and urease (S-UE) while decreasing the availability of Cd, Pb, Cu, and Zn. Overall, the immobilization effect on Cd and Zn after a 108-day incubation was ranked as follows: BM group > OS group ≥ BO group, and the order of the immobilization effect of Pb and Cu was OS group > BO group > BM group. In addition, the dominant bacterial community flora shifted toward alleviating the re-dissolution of metal ions from the soil and promoting nutrient recycling in soil within 108 days of cultivation. RNA analyses showed that the strongest determinants for microbial communities between BM application and OS application at the genus level were soil pH, CEC, and heavy metal (Cd, Pb). These results increase our understanding of the leaching performance of Cd, Pb, Cu and Zn and the evolution trend of microorganisms when organic amendments remediate heavy metal contaminated soil.

Ecological management model for the improvement of soil fertility through the regulation of rare microbial taxa in tea (Camellia sinensis L.) plantation soils.

Agricultural management is essential to enhance soil ecosystem service function through optimizing soil physical conditions and improving nutrient supply, which is predominantly regulated by soil microorganisms. Several studies have focused on soil biodiversity and function in tea plantation systems. However, the effects of different agriculture managements on soil fertility and microbes remain poorly characterized, especially for what concerns perennial agroecosystems. In this study, 40 soil samples were collected from 10 tea plantation sites in China to explore the effects of ecological and conventional managements on soil fertility, as well as on microbial diversity, community composition, and co-occurrence network. Compared with conventional management, ecological management was found to significantly enhance soil fertility, microbial diversity, and microbial network complexity. Additionally, a significant difference in community composition was clearly observed under the two agriculture managements, especially for rare microbial taxa, whose relative abundance significantly increased under ecological management. Random forest modeling revealed that rare taxa (e.g., Rokubacteria and Mortierellomycota), rather than dominant microbial taxa (e.g., Proteobacteria and Ascomycota), were key variables for predicting soil fertility. This indicates that rare taxa might play a fundamental role in biological processes. Overall, our results suggest that ecological management is more efficient than conventional management in regulating rare microbial taxa and maintaining a good soil fertility in tea plantation systems.

Heavy Metal Sources, Contamination and Risk Assessment in Legacy Pb/Zn Mining Tailings Area: Field Soil and Simulated Rainfall.

This study investigated heavy metal(HM) soil pollution and evaluated the risk and sources at a legacy tailings pond's area in Meizhou, China. Result shows that HM accumulation in soil, particularly Cd, Pb, and Zn, were serious. Zn and Cd in tailing soil and all studied elements in field soil had a significant release potential. Four HM sources were identified by positive matrix factorization (PMF) model: cinder and vehicle emissions (11.3%), natural sources (16.3%), tailings pond and human activities (32.8%), tailings pond (39.7%). The soil was severely polluted with Cd, Pb, and Zn, which posed a high potential environmental risk near surrounding area. Column leaching tests showed that large quantities of HMs were released from the tailings soil during simulated rainfall with different pH. This study indicates that the study area has been severely polluted and continues to have a great risk of HM pollution under natural conditions.

Extracellular polymeric substance induces biogenesis of vivianite under inorganic phosphate-free conditions.

Vivianite is often found in reducing environments rich in iron and phosphorus from organic debris degradation or phosphorus mineral dissolution. The formation of vivianite is essential to the geochemical cycling of phosphorus and iron elements in natural environments. In this study, extracellular polymeric substances (EPS) were selected as the source of phosphorus. Microcosm experiments were conducted to test the evolution of mineralogy during the reduction of polyferric sulfate flocs (PFS) by Shewanella oneidensis MR-1 (S. oneidensis MR-1) at EPS concentrations of 0, 0.03, and 0.3 g/L. Vivianite was found to be the secondary mineral in EPS treatment when there was no phosphate in the media. The EPS DNA served as the phosphorus source and DNA-supplied phosphate could induce the formation of vivianite. EPS impedes PFS aggregation, contains redox proteins and stores electron shuttle, and thus greatly promotes the formation of minerals and enhances the reduction of Fe(III). At EPS concentration of 0, 0.03, and 0.3 g/L, the produced HCl-extractable Fe(II) was 107.9, 111.0, and 115.2 mg/L, respectively. However, when the microcosms remained unstirred, vivianite can be formed without the addition of EPS. In unstirred systems, the EPS secreted by S. oneidensis MR-1 could agglomerate at some areas, resulting in the formation of vivianite in the proximity of microbial cells. It was found that vivianite can be generated biogenetically by S. oneidensis MR-1 strain and EPS may play a key role in iron reduction and concentrating phosphorus in the oligotrophic ecosystems where quiescent conditions prevail.

Acidity and metallic elements release from AMD-affected river sediments: Effect of AMD standstill and dilution.

In acid mine drainage (AMD) polluted rivers, considerable fraction of potential toxic elements are temporarily sequestered by sediments. There are two main potential environmental hazards associated with the sediments, acidity liberation and re-mobilization of metallic elements, during environmental conditions change. The effects of AMD standstill and water dilution on metallic elements migration were assessed in an AMD standstill test and a dialysis experiment. Maintaining AMD standstill, often occurring in AMD damming process, could induce the occurrence of iron secondary minerals precipitation along with attenuation of dissolved elements and a decrease in water pH value. Both field sediments and lab precipitates were confirmed as being dominant with schwertmannite which was the most important source and sink for acidity and metallic elements. The mechanism of cation heavy metals scavenging implied by FTIR results mostly depended on the exchanging of H+ from surface hydroxyl groups (-OH) in schwertmannite-rich sediments. For arsenic oxyanion, its adsorption included surface complexation with iron hydroxyl groups at the mineral surface, as well as anion exchange of SO42- present in the structure. The quantities of acidity release differed significantly from 20 to 3714 mol H+/t depending on the iron hydroxyl minerals type and their contents in the corresponding sediments in 35 d dialysis, with the release rate well fitted by the second order model. Slight degree of phase transformation in schwertmannite dominant sediment had resulted in a high risk of metallic element release during the 35 d dilution duration. The significant risk of metallic elements release was ranked in the order of Cd > Mn > Zn > Pb, and with more than 89% of Cd released from FS6 and 82% from LPS1. Relatively, Cu and As in sediments were much more stable. Overall, damming was an effective and low cost pretreatment strategy for AMD pollution control. Knowledge of the characteristics of iron secondary minerals in river sediments is essential premise for both comprehensive assessment of site contamination status and effective remediation strategy decision.

Dissimilatory iron and sulfate reduction by native microbial communities using lactate and citrate as carbon sources and electron donors.

The bacterial (dissimilatory) iron and sulfate reduction (BIR and BSR) are intimately linked to the biogeochemical cycling of C, Fe, and S in acid mine drainage (AMD) environments. This study examined the response of native microbial communities to the reduction of iron and sulfate in bench experimental systems. Results showed that the reduction of ferric iron and sulfate took place when the electron acceptors coexist. Existence of Fe(III) can postpone the reduction of sulfate, but can enhance the reduction rate. Cultures grown in the presence of 10 mM iron can reach the final level of sulfate bio-reduction rate (~100%) after 35 days incubation. 16 S rDNA -based microbial community analysis revealed that the three genera Anaeromusa, Acinetobacter and Bacteroides were dominated in the ferric-reducing conditions. SRB (Desulfobulbus, Desulfosporosinus and Desulfovibrio) were dominated in the sulfate reduction process. Results in this study highlighted the highly coupled nature of C, Fe, and S biogeochemical cycles in AMD and provided insights into the potential of environmental remediation by native microbial.

Degradation of tris(2-chloroethyl) phosphate (TCEP) in aqueous solution by using pyrite activating persulfate to produce radicals.

Organophosphorus esters (OPEs), as one kind of emerging and toxic contaminant are ubiquitous in various environments. This study investigated the degradation of tris(2-chloroethyl) phosphate (TCEP) as a category OPEs by pyrite (FeS2)-activated persulfate (PS). The result shows that near-100% degradation of TCEP was achieved after 120 min in FeS2-PS system. The important role of Fe2+ in the activation mechanism was confirmed by the introduction of Fe2+ into the PS only system. Radical scavengers experiment and electron paramagnetic resonance (EPR) confirmed the presence of SO4·- and ·OH，which revealed that ·OH and SO4·- played major roles in TCEP degradation. The effect of various environmental factors, including pyrite and oxidant dosage, inorganic ions and pH were investigated. The result indicated that Fe3+ and Cl- can accelerate the degradation rate of TCEP and the reaction between TCEP and FeS2-PS favors acidic conditions (pH>9). In addition, due to the acidification of pyrite, this system can be applied with a wide pH range. Besides, two oxidation products, C4H9Cl2O4P and C2H6ClO4P were identified, which suggest that hydroxylation was probably the main mechanism. This study greatly improves our understanding on TCEP removal in FeS2-PS system.

Migration and fate of metallic elements in a waste mud impoundment and affected river downstream: A case study in Dabaoshan Mine, South China.

Fate of metallic elements and their migration mechanisms in a waste mud impoundment and affected downstream were assessed. Physicochemical and mineralogical methods combined with PHREEQC calculation, statistical analysis and review of relevant literatures were employed. Results showed that the waste in mud impoundment had been severely weathered and acidized. Metallic elements exhibited high mobility and activity, with a mobility ranking order of Cd > Zn > Mn > Cu ≈ Cr > As ≈ Pb. Hydraulic transportation originating from elevation variation was the most important driving force for metallic elements migration. Although damming standstill was considered as an effective strategy for controlling coarse suspended particulate pollutants, metallic elements were still transported to the Hengshi River in both dissolved phase and fine suspended particle phase accompanied by the overflow of acid mine drainage. The concentrations of dissolved metallic elements were attenuated significantly along the Hengshi River within 41 km stretch. Precipitation/ co-precipitation of iron oxyhydroxides, especially schwertmannite, ferrihydrite and goethite minerals, were established as the most critical processes for metallic elements attenuation in river water. Accompanied by metals migration in the river, two pollution sensitive sites with notably high content of metals in the stretch of S6-S8 and S10, were identified in gently sloping river stretch.

Role of Dissolved Organic Matter in the Release of Chromium from Schwertmannite: Kinetics, Repartition, and Mechanisms.

Dissolved organic matter (DOM) is an important factor influencing mineral biogeochemistry, although the role of labile DOM in the release of chromium (Cr) from schwertmannite, a mineral with high surface area, is unclear. In this study, the interaction of DOM with synthetic CrO-schwertmannite was investigated to better understand the potential fate of Cr in high-DOM environments. Minerals and their products were analyzed using Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. Experiments were conducted at pH 3.2 or 6.5 for different lengths of time, with a shrinking core model developed to describe kinetic processes. The concentration of total Cr in solution reached a maximum when the pH was 6.5 and the concentration of L-tryptophan was 5 mM. The newly formed minerals were confirmed to be mixtures involving residual schwertmannite, goethite, ferrihydrite, and jarosite. A possible mechanism is proposed to be a ligand-controlled binary system, accompanied by possible reduction at acidic pH conditions (3.2), including mass transfer and charge transfer processes. This study gives a new perspective for understanding the reactivity and stability of schwertmannite in the environment; it also provides some predictions on the mobility and fate of Cr. These findings will help design remediation strategies for Cr contamination.

Removal of heavy metals from acid mine drainage using chicken eggshells in column mode.

Chicken eggshells (ES) as alkaline sorbent were immobilized in a fixed bed to remove typical heavy metals from acid mine drainage (AMD). The obtained breakthrough curves showed that the breakthrough time increased with increasing bed height, but decreased with increasing flow rate and increasing particle size. The Thomas model and bed depth service time model could accurately predict the bed dynamic behavior. At a bed height of 10 cm, a flow rate of 10 mL/min, and with ES particle sizes of 0.18-0.425 mm, for a multi-component heavy metal solution containing Cd2+, Pb2+ and Cu2+, the ES capacities were found to be 1.57, 146.44 and 387.51 mg/g, respectively. The acidity of AMD effluent clearly decreased. The ES fixed-bed showed the highest removal efficiency for Pb with a better adsorption potential. Because of the high concentration in AMD and high removal efficiency in ES fixed-bed of iron ions, iron floccules (Fe2(OH)2CO3) formed and obstructed the bed to develop the overall effectiveness. The removal process was dominated by precipitation under the alkaline reaction of ES, and the co-precipitation of heavy metals with iron ions. The findings of this work will aid in guiding and optimizing pilot-scale application of ES to AMD treatment.

Soil fluoride fractions and their bioavailability to tea plants (Camellia sinensis L.).

Drinking teas containing high fluoride (F) imposes fluorosis risk. The soil F bioavailability is an important factor influencing its uptake and contents in teas. The present work was conducted to investigate F fractions in soil and their bioavailability to tea plants. Tea seedlings were cultivated on 6 typical soils treated with a mixture consisting of dolomite, lime, peat and KCl at variable rates in the pot experiment. Soils and young shoots were collected in pairs from 63 sites of 21 plantations in a field experiment. Soil fluoride was sequentially separated into hot water soluble [Formula: see text], exchangeable [Formula: see text] (by 1 mol L-1 MgCl2, pH = 7.0), F bound to Mn and Fe hydroxides [F(oxides,s)], and organic matter [F(OM,s)] or extracted independently by water [Formula: see text] or 0.01 mol L-1 CaCl2 solution [Formula: see text]. Averaged [Formula: see text], [Formula: see text], F(oxides,s) and F(OM,s) accounted for 51, 14, 5 and 30 % of the total sequential extracts, respectively. There were significant correlations among [Formula: see text], [Formula: see text] and F(OM,s). Fluoride contents in leaves correlated with [Formula: see text] (r = 0.71, p < 0.001), [Formula: see text] (r = 0.93, p < 0.001) and F(OM,s) (r = 0.69, p < 0.01) but not other fractions in the pot experiment and with [Formula: see text] (r = 0.43-0.57, p < 0.001) and [Formula: see text] (r = 0.42-0.79, p < 0.001) in the field experiment. It was concluded that 0.01 M CaCl2 extractable fluoride can be a good indicator of soil F bioavailability to tea plants. The significant correlations among some of the F fractions suggested that F in solution, AlF complexes (AlF2+, AlF2+) and those bound to organic matter likely represent the available pools to tea plants.

The Effect of Pollination on Cd Phytoextraction From Soil by Maize (Zea mays L.).

A pot experiment was conducted to investigate the effects of pollination on cadmium (Cd) phytoextraction from soil by mature maize plants. The results showed that the unpollinated maize plants accumulated 50% more Cd than that of the pollinated plants, even though the dry weight of the former plants was 15% less than that of the latter plants. The Cd accumulation in root and leaf of the unpollinated maize plant was 0.47 and 0.89 times higher than that of the pollinated plant, respectively. The Cd concentration in the cob was significantly decreased because of pollination. Preventing pollination is a promising approach for enhancing the effectiveness of phytoextraction in Cd-contaminated soils by maize. This study suggested that in low Cd-contaminated soil pollination should be encouraged because accumulation of Cd in maize grains is very little and maize seeds can bring farmers economic benefits, while in high Cd-contaminated soil, inhibition of pollination can be applied to enhance phytoextraction of Cd from soil by maize plant.

Turning harmful Mn2+ to treasure: In-situ formed ε-MnO2 for removing heavy metals from acid mine drainage.

Acid mine drainage (AMD) contains high concentrations of heavy metals, causing serious environmental pollution. Current neutralization techniques fail to recover and utilize valuable heavy metals, and generate large quantities of hazardous sludge. Manganese (Mn) is generally present at high levels in AMD. Therefore, this paper proposed a technology to recover Mn from AMD, by adding KMnO4 to converting Mn into ε-MnO2. Ultra-Violet C (UVC) was used to photolyze the residual KMnO4. The study then evaluated the processes and mechanisms involved in the technology. The photolysis of KMnO4 in strong acidic conditions was determined, and new mechanisms were proposed. MnO2 produced by the photolysis process was formed through the reaction between Mn(III) and KMnO4. In the absence of KMnO4, Mn(III) underwent further photolysis and was reduced to Mn2+. The maximum adsorption capacities of in-situ formed ε-MnO2 for Pb2+, Cd2+, and Fe3+ were 449.80, 122.05, and 779.88 mg/g, respectively. Higher Mn-OH levels and MnO2 regeneration were crucial in improving adsorption performance. Proton exchange and inner-circle complexation were the main pathways for Pb2+ and Cd2+ adsorption by in-situ formed ε-MnO2. A phase transformation occurred when a substantial amount of Fe3+ was adsorbed, leading to the gradual transformation to MnFe binary oxides. When applying in-situ formed ε-MnO2 technology for actual AMD treatment, 98.62 % of Mn in AMD was recovered within 24 h in the presence of ε-MnO2 for possible further reuse in industries, with a final recovery of 0.76 kg/m3. Further, this technique removed other heavy metals and reduced the sludge volume by 20.99 % when used as a pre-treatment step for neutralization. These results demonstrated the broad potential of this treatment technology.

The effect of goethite aging on Cd adsorption: Constraints of mineral condensation and surface site density.

Iron (hydr)oxides, as natural geosorbents, play a crucial role in retaining toxic heavy metals, and their aging process greatly influences heavy metals distributions and migration in soil systems. However, limited attention has been given to the interaction between heavy metals and crystalline-aged goethite. In this study, we investigated the sorption behavior and sorption mechanism of cadmium (Cd) with freshly synthesized or aged goethite. We quantified the total Cd sorption load, as well as the proportion of Cd with different sorption strengths on minerals. It has been found that in different aged goethite samples, approximately 71.3-84.7 % of Cd is strongly bound (bidentate inner-sphere complexes) and 16.0 % to 26.4 % of Cd is weakly bound (electrostatic adsorption and partially through monodentate inner-sphere complexes) by goethite. This observation is consistent with the distribution characteristics of Cd species fitted by the charge distribution and multisite surface complexation model. Additionally, the total Cd load and strongly bound Cd content on goethite aged at pH 7.5 decreased with extended aging time. Upon combining the mineral characterization analysis and surface hydroxyl density calculation, we found that the morphology transformation and the deterioration in sorption ability on goethite results from a condensation process through a surface hydroxyl oxolation reaction on the {110} facet between adjacent goethite crystals during the aging process at pH 7.5. This condensation process causes goethite to lose many hydroxyl sites, which is the dominant reason for the decrease in inner-sphere complexed Cd. The amount of weakly bound Cd decreases slightly with aging, because the decrease in inner-sphere complexed Cd is not conducive to balancing the positively charged mineral surface, resulting in a slight reduction in the amount of Cd adsorbed through electrostatic attractions.

Effects of Fe(II) bio-oxidation rate and alkali control on schwertmannite microstructure and adsorption of oxyanions: Characteristics, performance and mechanism.

Schwertmannite has attracted increasing interest for its excellent sorption of oxyanions such as AsO43-, CrO42-, and Sb(OH)6-. Controlling biomineralization by adjusting the Fe(II) oxidation rate and implementing alkali control can enhance the yield and adsorption performance of schwertmannite. However, the adsorption improvement mechanism is still unclear. The morphology, crystallinity, specific surface area (SSA) and oxyanion adsorption of schwertmannite synthesized with alkali control of solution pH and different Fe(II) oxidation rates were analyzed in this study. The differences in the adsorption mechanisms of As(V), Cr(VI) and Sb(V) on schwertmannite obtained under different synthesis conditions were also studied. Reducing the Fe(II) oxidation rate or maintaining the solution pH through alkali control significantly increased the SSA of schwertmannite and the proportion of outer-sphere sulfate. Alkali-controlled schwertmannite (Sch-C) exhibited superior As(V) and Sb(V) adsorption performance and slightly greater Cr(VI) adsorption than non-alkali-controlled schwertmannite. The As(V) and Sb(V) adsorption capacities of Sch-C greatly improved because the ultra-high SSA increased the surface hydroxyl content and reduced the passivation effect of amorphous precipitates on the mineral surface, allowing continuous sulfate exchange at inner mineral sites. An increased surface hydroxyl content had little effect on Cr(VI) adsorption, but an increased proportion of outer-sphere sulfate caused a slight increase in Cr(VI) adsorption. Sb(V) has a stronger hydroxyl exchange ability than As(V), but due to its octahedral structure, it exchanges only with outer-sphere sulfate on schwertmannite and hardly exchanges with inner-sphere sulfate.

Temporal and spatial evolution of different heavy metal fractions and correlation with environmental factors after prolonged acid mine drainage irrigation: A column experiment.

Acid mine drainage (AMD) has global significance due to its low pH and elevated heavy metal content, which have received widespread attention. After AMD irrigation in mining areas, heavy metals are distributed among soil layers, but the influencing factors and mechanisms remain unclear. AMD contamination of surrounding soil is primarily attributed to surface runoff and irrigation and causes significant environmental degradation. A laboratory soil column experiment was conducted to investigate the temporal and spatial distribution of the heavy metals Cd and Cu, as well as the impact of key environmental factors on the migration and transformation of these heavy metals following long-term soil pollution by AMD. After AMD addition, the soil exhibited a significant increase in acidity, accompanied by notable alterations in various environmental parameters, including soil pH, Eh, Fe(II) content, and iron oxide content. Over time, Cd and Cu in the soil mainly existed in the exchangeable and carbonate-bound fractions. In spatial terms, exchangeable Cu increased with increasing depth. Pearson correlation analysis indicated significant negative correlations between pH and Cu, Cd, and Eh in pore water, as well as negative correlations between pH and the exchangeable fraction of Cd (F1), carbonate-bound fraction of Cd (F2), and exchangeable fraction of Cu (F1) in the solid phase. Additionally, a positive correlation was observed between pH and the residual fraction of Cu (F5). Furthermore, the soil total Cd content exhibited a positive correlation with pyrophosphate-Fe (Fep) and dithionite-Fe (Fed), while CdF1, CdF2, total Cu, and CuF1 displayed positive correlations with Fep. Our findings indicate that the presence of AMD in soil leads to alterations in the chemical fractions of Cd and Cu, resulting in enhanced bioavailability. These results offer valuable insights for developing effective remediation strategies for soils near mining sites.

Magnetic anaerobic granular sludge for sequestration and immobilization of Pb.

The development of magnetic adsorbents with high capacity to capture heavy metals has been the subject of intense research, but the process usually involves costive synthesis steps. Here, we propose a green approach to obtaining a magnetic biohybrid through in situ grown anaerobic granular sludge (AGS) with the help of magnetite, constituting a promising adsorbent for sequestration and immobilization of Pb in aqueous solutions and soils. The resultant magnetite-embedded AGS (M-AGS) was not only capable of promoting methane production but also conducive to Pb adsorption because of the large surface area and abundant function groups. The uptake of Pb on M-AGS followed the pseudo-second order, having a maximum adsorption capacity of 197.8 mg gDS-1 at pH 5.0, larger than 159.7, 170.3, and 178.1 mg gDS-1 in relation to AGS, F-AGS (ferrihydrite-mediated), and H-AGS (hematite-mediated), respectively. Mechanistic investigations showed that Pb binding to M-AGS proceeds via surface complexation, mineral precipitation, and lattice replacement, which promotes heavy metal capture and stabilization. This was evident from the increased proportion of structural Pb sequestrated from the aqueous solution and the enhanced percentage of the residual fraction of Pb extracted from the contaminated soils.

A coupled electrochemical process for schwertmannite recovery from acid mine drainage: Important roles of anodic reactive oxygen species and cathodic alkaline.

The increasing need for sustainable acid mine drainage (AMD) treatment has spurred much attention to strategic development of resource recovery. Along this line, we envisage that a coupled electrochemical system involving anodic Fe(II) oxidation and cathodic alkaline production will facilitate in situ synthesis of schwertmannite from AMD. Multiple physicochemical studies showed the successful formation of electrochemistry-induced schwertmannite, with its surface structure and chemical composition closely related to the applied current. A low current (e.g., 50 mA) led to the formation of schwertmannite having a small specific surface area (SSA) of 122.8 m2 g-1 and containing small amounts of -OH groups (formula Fe8O8(OH)4.49(SO4)1.76), whereas a large current (e.g., 200 mA) led to schwertmannite high in SSA (169.5 m2 g-1) and amounts of -OH groups (formula Fe8O8(OH)5.16(SO4)1.42). Mechanistic studies revealed that the reactive oxygen species (ROS)-mediated pathway, rather than the direct oxidation pathway, plays a dominant role in accelerating Fe(II) oxidation, especially at high currents. The abundance of •OH in the bulk solution, along with the cathodic production of OH-, were the key to obtaining schwertmannite with desirable properties. It was also found to function as a powerful sorbent in removal of arsenic species from the aqueous phase.