Although biochar supports were widely adopted to fabricate the biochar (BC) supported layered double hydroxides (LDHs) composites (LDH-BC) for efficient environmental remediation, few studies focus on the important role of biochar support in alleviating the stacking of LDHs and enhancing LDH-BC's performance. Through the analysis of the material structure-performance relationship, the “support effect” of fine biochar prepared by ball milling was carefully explored. Compared with the original LDHs on LDH-BC, the LDHs on ball milled biochar (LDH-BMBC) had smaller particle size (from 1123 nm to 586 nm), crystallite size (from 20.5 nm to 6.56 nm), more abundant O-containing functional groups, and larger surface area (370 m² g⁻¹) and porous structure. The Langmuir model revealed that the maximum theoretical phosphate adsorption capacity of LDH-BMBC (56.2 mg P g⁻¹) was significantly higher than that of LDH-BC (27.6 mg P g⁻¹). The leaching experiment proved that the addition of LDH-BMBC in calcareous soil could significantly reduce the release of soil total phosphate (46.1%) and molybdate reactive phosphate (40.4%), even though pristine BC and BMBC significantly enhanced the soil phosphate leaching. This work fabricated high-performance and eco-friendly LDH-BMBC for phosphate adsorption in solution and phosphate retention in soil and also provide valuable insights into fine biochar support effect on LDHs exfoliation, extending the practical use of the engineered ball milled biochars in environment remediation.

In China, excessive phosphorus (P) application in protected vegetable fields has led to high legacy P stores. Soil amendment with alum or dolomite is one of many best management practices (BMPs) used to reduce P losses in calcareous soils. However, both the kinetics and mechanisms of P sorption and soil available P in amended soils are understudied. Herein, both aspects were looked at under controlled conditions. Firstly, a sorption study which coupled P concentrations with poorly-crystalline Al hydroxides and dolomite was conducted. Results from this batch experiment showed that P sorption on poorly-crystalline Al hydroxides was homogenous and occurred mainly via displacement of inner-sphere hydroxyl (Al–OH) instead of the formation of AlPO₄. However, the amount of sorbed P reached maximum sorption of 73.1 mg g⁻¹ and did not change with further increase in P concentration. It was observed that P adsorbed onto the dolomite surface at low P concentrations, whereas hydroxyl replacement and uneven cluster precipitation of Ca₃(PO₄)₂ occurred at high P concentrations. A second 90 day incubation experiment investigated changes to soil available P and sorption-desorption across variable rates of amendments (0–50 g kg⁻¹). Results showed that alum amendment at a rate of 50 g kg⁻¹ decreased soil CaCl₂–P and Olsen-P concentrations by 91.9% and 57.8%, respectively. However, Olsen-P increased when the dolomite rates were <20 g kg⁻¹. Phosphorus sorption-desorption of the amended soil showed alum had higher P sorption efficiency than dolomite at low addition rates (<10 g kg⁻¹). However, soil amended with high dolomite rates (>10 g kg⁻¹) could sorb more P in comparison with alum when P concentrations were increased. The P status of the amended soil was closely connected to the P sorption mechanisms on mineral amendments, soil P concentrations and soil properties.

Synthetic inhibitors and organic amendment have been proposed for mitigating greenhouse gas N₂O emissions. However, their combined effect on the N₂O emissions and ammonia-oxidizer (ammonia-oxidizing bacteria and archaea, AOB and AOA) communities remains unclear in calcareous soils under climate warming. We conducted two incubation experiments (25 and 35 °C) to examine how N₂O emissions and AOA and AOB communities responded to organic amendment (urea plus cattle manure, UCM), and in combination with urease (N-(n-butyl) thiophosphoric triamide, NBPT) and nitrification inhibitor (nitrapyrin). The treatments of UCM + nitrapyrin and UCM + nitrapyrin + NBPT significantly lowered total N₂O emissions by average 64.5 and 71.05% at 25 and 35 °C, respectively, compared with UCM treatment. AOB gene abundance and α-diversity (Chao1 and Shannon indices) were significantly increased by the application of urea and manure (P < 0.05). However, relative to UCM treatment, nitrapyrin addition treatments decreased AOB gene abundance and Chao 1 index by average 115.4 and 30.4% at 25 and 35 °C, respectively. PCA analysis showed that UCM or UCM plus nitrapyrin notably shifted AOB structure at both temperatures. However, fertilization had little effects on AOA community (P > 0.05). Potential nitrification rate (PNR) was greatly decreased by nitrapyrin addition, and PNR significantly positively correlated with AOB gene abundance (P = 0.0179 at 25 °C and P = 0.0029 at 35 °C) rather than AOA (P > 0.05). Structural equation model analysis showed that temperature directly increased AOA abundance but decrease AOB abundance, while fertilization indirectly influenced AOB community by altering soil NH₄⁺, pH and SOC. In conclusion, the combined application of organic amendment, NBPT and nitrapyrin significantly lowered N₂O emissions via reducing AOB community in calcareous soil even at high temperature. Our findings provide a solid theoretical basis in mitigating N₂O emissions from calcareous soil under climate warming.

Efficiency and the preservation of soil functions are key requirements for sustainable remediation of contaminated soil. Microbial decomposition and conversion of substrates is a fundamental soil function. Pilot-scale EDTA-based soil washing recycled chelant generated no wastewater and removed 78% of Pb from acidic farmland soil with 860 mg kg⁻¹ Pb and 60% of Pb from calcareous garden soil with 1030 mg kg⁻¹ Pb. Remediation had an insignificant effect on microbial respiration in acidic soil induced by sequential additions of glucose, micro-cellulose, starch and alfa-alfa sprout powder (mimicking litter components, C-cycle). In contrast, remediation of calcareous soil reduced cumulative CO₂ production after glucose (simple) and alfalfa (complex substrate) addition, by up to 40%. Remediation reduced the nitrification rate (denoting the N-cycle) in acidic soil by 30% and halved nitrification in calcareous soil. Remediation in both soils slightly or positively affected dehydrogenase and β-glucosidase activity (associated with C-cycle), and decreased urease activity (N-cycle). Generally, EDTA remediation modestly interfered with substrate utilisation in acidic soil. A more prominent effect of remediation on the functioning of calcareous soil could largely be attributed to the use of a higher EDTA dose (30 vs. 100 mmol kg⁻¹, respectively).

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction.

Low wheat production is linked to soil degradation, low organic matter, temperature variation, and nutrient depletion in soils of semiarid regions. Nitrogen is mostly applied as urea to meet crop requirements; however, excessive N application may pollute the environment and contaminate groundwater. The current studies explored possible ways for decreasing N losses (NH₃ volatilization and NO₃ leaching) and improving N availability for wheat production in alkaline soil. The ZnO was coated on urea (1% Zn coating) to get zinc-coated urea (ZnU), and both urea and ZnU were incubated in laboratory at recommended rate (RR), i.e., 150 kg N ha⁻¹ and 80% (N of RR), after further coating with inhibitors [N-(n-butyl) thiophosphoric triamide (NBPT) at 1% of urea and 4-amino-1,2,4-triazole (ATC) at 2% of urea], thus creating six treatments. The results showed higher NH₃–N loss at day 4 and thereafter a decreasing trend reaching to minimum at day 14. The cumulative NH₃–N volatilization from urea alone was found higher (28.99%), except ATC treatments producing statistically similar losses due to restriction in nitrification process. In greenhouse, the treatments were tested in wheat cultivars (Faisalabad 2008 and Lasani) for crop growth, nutrient (N, P, K, and Zn) uptake, and yield parameters, where 80% of RR treatment, i.e., NBPT + ZnU₈₀, was found at par with full RR as commercial products, especially comparable to ZnU (at RR) that produced the highest chlorophyll (53.65unit value), net leaf photosynthetic rate (19.64 μmol CO₂ m⁻² s⁻¹), plant biomass (208.13 g/pot), grain yield (63.65 g/pot), and nutrient (NPK and Zn) accumulation in grain of Fsd-2008 cultivar. In field trial, NBPT + ZnU₈₀ also outperformed and produced the highest physiological efficiency (PE), agronomic efficiency (AE), and nitrogen recovery efficiency (REN); the treatment also found statistically similar with ZnU (at RR) that produced the maximum plant height (95.4 cm), plant biomass (11.58 t/ha), grain yield (4.69 t/ha), and 1000-grain weight (42.55 g). The relative NO₃ leaching was found lower in 80% N treatments, yet leaching was not significant from either treatment at the three stages of crop growth. Overall, current studies revealed the effectiveness of NBPT-amended urea (followed by ZnU) with 20% saving of N inputs through higher N availability for plant uptake that could benefit growers as well as conserve environment.

The effective approaches to eliminate impacts of ethanol on the biodegradation of benzene, toluene, ethylbenzene, and xylene (BTEX) are concerned in the bioremediation of groundwater contaminated with ethanol-blended gasoline. In situ chemical oxidation (ISCO) is a common technique widely used for the remediation of contaminated groundwater. However, the selectivity of ISCO for BTEX and ethanol removal is poorly understood. Therefore, a batch experiment was performed with different aquifer materials, including calcareous soil, basalt soil, granite soil, dolomite, and sand. Gasoline was used to provide dissolved BTEX and ethanol reagent was used as additive to improve the quality of gasoline and to reduce the possibility of air pollution caused by gasoline. Persulfate (PS) was used as a chemical oxidant to oxidize organic contaminants. The target concentrations of BTEX and ethanol were 20 mg/L and 1000 mg/L, respectively. The results showed that ethanol could be preferentially degraded in the absence of PS and inhibit BTEX biodegradation. However, BTEX could be preferentially removed prior to ethanol in all aquifer materials used at ambient temperature, when PS was added at a PS/BTEX molar ratio of 150. Over 94% BTEX in sand, dolomite, and granite soil was preferentially removed with the first-order decay rate constants of 0.890–2.703 day⁻¹ within the first ~ 10 days, followed by calcareous and basalt soil at the constants of 0.123–0.371 day⁻¹. Ethanol could compete with BTEX for sulfate radical at the first-order decay rate constants of 0.005–0.060 day⁻¹ for the first 25 days, which was slower than that of BTEX. The pH quickly decreased to < 2.5 in dolomite, sand, and granite soil, but maintained > 6.2 in calcareous soil. Rich organic matter in calcareous and basalt soil had an inhibition effect on BTEX oxidation by PS. The pH buffer in calcareous soil may imply the potential of PS oxidation combined with bioremediation in carbonate rock regions.

The purpose of this study is to investigate the elution behavior of pool-dominated dense nonaqueous phase liquid (DNAPL) source zone mass during enhanced solubilization remediation. Flow-cell experiments were first conducted to investigate the performance of different solubilization agents on the DNAPL source zone mass removal in porous media. PCE was used as the model organic liquid, while sodium dodecyl sulfate and Tween 80 surfactants, methyl cyclodextrin (MCD) were selected as enhanced-flushing agents. The porous media considered were silica sand and natural calcareous soil. To gain further insight into the dynamics of source zone depletion, the flushing experiments were modeled using two approaches: a multiphase flow model and a simplified empirically based concentration mass discharge (CMD) model. Results of the flushing experiments indicated that the performance of solubilization agents on PCE source zone depletion was in the following order: Tween 80 > SDS > MCD > > Water. Both models reveal the non-ideal behavior observed during the flooding experiments. For all cases considered, the later stage of mass removal appears to be controlled by the portion poorly accessible mass associated with higher-saturation zones. The advantages and limitations of the two modeling approaches are discussed. It is shown that the two modeling approaches are complementary to each other. Whereas the multiphase model can reveal important aspects of the governing pore-scale processes, the latter approach can provide valuable source term depletion metrics, circumventing the need for detailed definition of DNAPL and porous media parameters.

For plant growth, cadmium (Cd) is a toxic and easily accumulated element but silicon (Si) is beneficial. To explore the alleviating effect of Si on Cd toxicity to plants in Cd-contaminated calcareous soil, the effect of Si on Cd absorption was investigated for cucumber organs in pot experiments. The Cd concentration of cucumber organs using an atomic absorption spectrophotometer. The Si significantly inhibited Cd uptake by cucumber organs and was most effective for Si application of 100–200 mg kg⁻¹. On the whole, the translocation factors of stems and leaves did not vary significantly, but substantially varied in fruit. The distribution pattern of Cd content in different cucumber organs follows: root > stem > leaf > > fruit. For Cd content in soil ≤ 3 mg kg⁻¹, the Cd content in cucumber fruit was lower than the maximum limit of Cd content in fresh vegetables in China (GB2762-2017) for Si application of 100–300 mg kg⁻¹. However, with the Cd treatment of 5 mg kg⁻¹, the content of Cd in cucumber fruit exceeded this limit, even though Si alleviated Cd toxicity to some extent. Therefore, Si had a substantial alleviating effect on Cd uptake in cucumber, effectively reduced Cd toxicity to cucumber in calcareous soil. The study may help us understand the mechanism for silicon-mediated Cd tolerance in calcareous soil and provide theoretical basis for the application of silicon in the production of crops in alkaline soil polluted by Cd.