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.

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.

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.

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.

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).

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.

A greenhouse experiment with two levels of Cd (0.5 and 10 mg Cd kg-¹, in the form of CdCl₂), and five salinity levels of irrigation water (0, 8.6, 17.1, 34.2 and 68.4 mM NaCl) in triplicate was conducted to determine the effect of NaCl-induced salinity on the solubility and availability of Cd in clay loam and sandy calcareous soils. Corn seeds (Zea mays L.) were sown in pots. Forty-five days after planting, the shoots were harvested, and their Cd concentration was determined. The post-harvest electrical conductivity (ECe), pH, and concentrations of cations and anions were determined in soil saturation paste extracts. Increasing irrigation water salinity resulted in significant increases in the total soluble Cd concentration in both studied soils. A positive correlation was found between the total soluble Cd and the chloride concentration in the soil solution.Solution speciation, calculated with MINEQL+ (a chemical equilibrium modeling system), predicted that Cd was present mainly as free Cd²⁺ ions followed by CdCl⁺ and [graphic removed] in the soils irrigated with deionized water. However, Cd species in the soil solution were significantly altered by increasing chloride concentration, with Cd-chloro complexes becoming the dominant Cd species in the soil solution. Increasing the salinity level resulted in significant decreases in the shoot dry matter and increases in the shoot Cd concentration. Shoot Cd concentration was positively correlated with both the total Cd and Cd-chloro complexes in the soil solution.

The retention and movement of water and atrazine (2-chloro-4-ethylamino-6- isopropylamino-s-triazine) was investigated in a calcareous soil (Krome) amended with three types of compost: (1) Clean organic waste (COW)- municipal solid waste cleaned of plastic materials and metal containers, (2) Biosolids (BSD)- sludge from municipal waste and (3) Bedminster (BDM)-a mixture containing 75% COW and 25% BSD. The research was conducted in two phases; a column-leaching study (dynamic) and a batch-equilibrium method (static). The column study demonstrated that while applying simulated rain, atrazine, leached out at a slower rate by 41, 24, and 18% from soil amended with BDM, BSD, and COW composts, respectively, during the first simulated storm event. BDM application resulted in lowest water movement and atrazine-leaching rate compared to the other composts tested. This study suggests that adding 134 t ha-1 of compost to the calcareous soil increased soil water holding capacity, reduced water movement and increased atrazine detention and reduced leaching potential of atrazine thereby reducing the potential for groundwater pollution. This study further demonstrates that soil amendment (particularly BDM) is effective in reducing the leaching potential of atrazine at the low rainfall amounts (corresponding to 0.5 pore volume). However, such amendment may not be effective in preventing leaching under more intense rain conditions or multiple rainfall events (corresponding to 3 or more pore volumes).

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.