Applying mineral phosphorus (P) fertilizers introduces a considerable input of the toxic heavy metal cadmium (Cd) into arable soils. This study investigates the fate of P fertilizer derived Cd (Cddff) in soil-wheat systems using a novel combination of enriched stable Cd isotope mass balances, sequential extractions, and Bayesian isotope mixing models. We applied an enriched ¹¹¹Cd labeled mineral P fertilizer to arable soils from two long-term field trials with distinct soil properties (a strongly acidic pH and a neutral pH) and distinct past mineral P fertilizer application rates. We then cultivated wheat in a pot trial on these two soils. In the neutral soil, Cd concentrations in the soil and the wheat increased with increasing past mineral P fertilizer application rates. This was not the case in the strongly acidic soil. Less than 2.3% of freshly applied Cddff was taken up by the whole wheat plant. Most of the Cddff remained in the soil and was predominantly (>95% of freshly applied Cddff) partitioned into the easily mobilizable acetic acid soluble fraction (F1) and the potentially mobile reducible fraction (F2). Soil pH was the determining factor for the partitioning of Cddff into F1, as revealed through a recovery of about 40% of freshly applied Cddff in F1 in the neutral pH soil compared with about 60% in the strongly acidic soil. Isotope mixing models showed that F1 was the predominant source of Cd for wheat on both soils and that it contributed to over 80% of the Cd that was taken up by wheat. By tracing the fate of Cddff in entire soil-plant systems using different isotope source tracing approaches, we show that the majority of Cddff remains mobilizable and is potentially plant available in the subsequent crop cycle.

Elevated toxins in soybeans extensively threaten Asian residents and over one billion vegetarians worldwide. An integrated dataset of toxic trace metal(loid)s especially cadmium (Cd) analysis in soybean grain samples (n = 5217) from 12 countries/regions of origin was compiled for risk analysis. Worldwide grain Cd averaged 0.093 mg kg⁻¹, but mean values varied 16-fold between regions, with South China (0.32 mg kg⁻¹) > Argentina (0.15 mg kg⁻¹) = German (0.13 mg kg⁻¹) > Japan (0.11 mg kg⁻¹) > the United States (0.064 mg kg⁻¹) > Central-North China (0.020–0.60 mg kg⁻¹) ≥ Iran (0.042 mg kg⁻¹) = Brazil (0.023 mg kg⁻¹) = South Korea (0.020 mg kg⁻¹). Regression analysis suggested widespread contamination and acidic soil features significantly contributed the elevated food Cd contamination worldwide. Arsenic (As) and lead (Pb) are also of concern because excessive levels were often observed in grains. Given that soil Cd bioavailability is generally low in alkaline pH ranges, the feasibility of producing safe food from contaminated land was investigated by greenhouse experiments with one low-Cd soybean cultivar grown on 20 contaminated calcareous soils. Equilibrium-based approaches i.e., 0.01 M CaCl₂ and in-situ porewater extractions, and diffusion-based diffusive gradients in thin-films technique were used to determine the plant-available fractions of soil metal(loid)s to explain the bioaccumulation variation. The results suggested that soybean grains bioaccumulated mean 0.76 mg Cd kg⁻¹, ranging from 0.16 to 2.1 mg kg⁻¹, whereas As and Pb bioaccumulation was low. Cadmium accumulation was closely correlated with plant-available Cd fractions especially the 0.01 M CaCl₂-extractable Cd, but negatively correlated with soil pH. Even in the alkaline pH range, a slight decrease of soil pH would increase grain Cd significantly. Study region and those arable lands that have similar soil conditions are not recommended for growing soybean unless novel remediation strategies are developed.

Low pH and aluminum (Al)-toxicity often coexist in acidic soils. Citrus sinensis seedlings were treated with nutrient solution at a pH of 2.5, 3.0, 3.5 or 4.0 and an Al concentration of 0 or 1 mM for 18 weeks. Thereafter, malate, citrate, isocitrate, acid-metabolizing enzymes, and nonstructural carbohydrates in roots and leaves, and release of malate and citrate from roots were measured. Al concentration in roots and leaves increased under Al-toxicity, but it declined with elevating nutrient solution pH. Al-toxicity increased the levels of glucose, fructose, sucrose and total soluble sugars in leaves and roots at each given pH except for a similar sucrose level at pH 2.5–3.0, but it reduced or did not alter the levels of starch and total nonstructural carbohydrates (TNC) in leaves and roots with the exception that Al improved TNC level in roots at pH 4.0. Levels of nonstructural carbohydrates in roots and leaves rose with reducing pH with a few exceptions with or without Al-toxicity. A potential model for the possible role of root organic acid (OA) metabolism (anions) in C. sinensis Al-tolerance was proposed. With Al-toxicity, the elevated pH upregulated the OA metabolism, and increased the flow of carbon to OA metabolism, and the accumulation of malate and citrate in roots and subsequent release of them, thus reducing root and leaf Al and hence eliminating Al-toxicity. Without Al-toxicity, low pH stimulated the exudation of malate and citrate, an adaptive response of Citrus to low pH. The interactive effects of pH and pH on OA metabolism were different between roots and leaves.

The immobilization effectiveness between Pb and phosphorus in soil varies with soil types. To clarify the effect of phosphate on the availability of Pb in agricultural soil, a culture experiment with three types of paddy soil was performed with potassium dihydrogen phosphate (KDP) added. EDTA, DGT and in-situ solution extraction methods were used to represent different available Pb content. Results showed that the concentration of EDTA-Pb in HN soil was slightly elevated after exogenous KDP added. The supplement of 300 mg/kg KDP significantly increased the content of soluble Pb in both acid silty clay loam soil and neutral silty loam soil (increased by 104.65% and 65.12%, respectively). However, there was no significant influence of KDP on the concentration of DGT extracted Pb. XANES results showed that Pb(OH)2, PbHPO4, humic acid-Pb and GSH-Pb were the major speciation of Pb in soil colloids. The proportion of Pb(OH)2 and humic acid-bounded Pb in soil colloids were elevated after exogenous KDP added. Our results indicated that there was a mobilization effect of KDP on Pb by increasing the amount of colloidal Pb in soil solution, especially in acid silty clay loam paddy soil. Such colloid-facilitated transport might promote the uptake of Pb in rice and pose a potential threat to human health.

Nitrous oxide (N2O) is a devastating greenhouse gas mainly released from soils to the atmosphere. Pasture soils, particularly acidic in nature, are large contributors of atmospheric N2O through deposition of urine-N. Devising strategies for reducing N2O emissions in acidic soils are the utmost need of the time. Therefore, the present study was carried out to investigate the possible efficacy of dolomite application to reduce N2O emissions from urine treated acidic soil. Application of urine to soil enlarged the production of NH4+-N, NO3−-N, microbial biomass C (MBC) and dissolved organic C (DOC), resulting in higher N2O emissions as compared to the control (soil only). The highest N2O emission rate (1.35 μg N2O-N kg−1 h−1) and cumulative flux (408 μg N2O-N kg−1) occurred in urine only treated soil. Dolomite addition, especially higher application dose, greatly reduced N2O emissions through improved soil pH. The results suggest that increasing pH of acidic soils is a good applicable approach for reducing N2O emissions from urine-treated soils.

The change in land-use from woodland to crop production leads to increased nitrous oxide (N2O) emissions. An understanding of the main N2O sources in soils under a particular land can be a useful tool in developing mitigation strategies. To better understand the effect of land-use on N2O emissions, soils were collected from 5 different land-uses in southeast China: shrub land (SB), eucalyptus plantation (ET), sweet potato farmland (SP), citrus orchard (CO) and vegetable growing farmland (VE). A stable isotope experiment was conducted incubating soils from the different land use types at 60% water holding capacity (WHC), using 15NH4NO3 and NH415NO3 to determine the dominant N2O production pathway for the different land-uses. The average N2O emission rates for VE, CO and SP were 5.30, 4.23 and 3.36 μg N kg−1 dry soil d−1, greater than for SB and ET at 0.98 and 1.10 μg N kg−1 dry soil d−1, respectively. N2O production was dominated by heterotrophic nitrification for SB and ET, accounting for 51 and 50% of N2O emissions, respectively. However, heterotrophic nitrification was negligible (<8%) in SP, CO and VE, where autotrophic nitrification was a primary driver of N2O production, accounting for 44, 45 and 66% for SP, CO and VE, respectively. Denitrification was also an important pathway of N2O production across all land-uses, accounting for 35, 35, 49, 52 and 32% for SB, ET, SP, CO and VE respectively. Average N2O emission rates via autotrophic nitrification, denitrification and heterotrophic nitrification increased significantly with gross nitrification rates, NO3− contents and C:N ratios respectively, indicating that these were important factors in the N2O production pathways for these soils. These results contribute to our understanding and ability to predict N2O emissions from different land-uses in subtropical acidic soils and in developing potential mitigation strategies.

The effects of wastewater irrigation and sewage sludge on the dissipation behavior of the fungicide benalaxyl and its primary metabolite benalaxyl acid in soil were studied on an enantiomeric level during a 148-day exposure experiment. Chiral separation and analysis of the two pairs of enantiomers were achieved using HPLC-MS/MS with a chiralpak IC chiral column. Benalaxyl decreased with half-life of 16.1 days in soil under tap water irrigation with preferential residue of S-benalaxyl. Benalaxyl acid was formed with great preference of R-enantiomer before 21 days while enriched in S-enantiomer afterwards. The degradation of benalaxyl was restrained by both wastewater and treated wastewater irrigation, but the enantioselectivity in S-benalaxyl residue was enhanced. Benalaxyl acid was also formed with similar enantioselectivity as in tap water irrigation. Sewage sludge could accelerate benalaxyl degradation with shorter half-life. Surprisingly, the enantioselectivity with preference degradation of S-enantiomer in sewage sludge was opposite to that in soil. More benalaxyl acid was generated with EF values always lower than 0.5 and remained longer in sewage sludge than in soil. A sterilization experiment indicated that the conversion of benalaxyl to benalaxyl acid and the enantioselectivity were determined by the microorganisms in soil or sewage sludge. Farming practices like wastewater irrigation and sewage sludge application might not only influence the fate of pesticide, but also the enantioselectivity of chiral pesticide enantiomers and thus the risks of pesticide residues posed to the environment.

With the phaseout of perfluorooctane sulfonate (PFOS) production in most countries and its well known recalcitrance, there is a need to quantify the potential release of PFOS from precursors previously or currently being emitted into the environment. Aerobic biodegradation of N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) was monitored in two soils from Indiana, USA: an acidic forest silt loam (FRST-48, pH = 5.5) and a high pH agricultural loam (PSF-49, pH = 7.8) with similar organic carbon contents (2.4 and 2.6%) for 210 d and 180 d, respectively. At designated times, triplicate samples were sacrificed for which headspace samples were taken followed by three sequential extractions. Extracts were analyzed using HPLC-tandem mass spectrometry. Measured profiles of EtFOSE degradation and generation/degradation of subsequent metabolites were fitted to the Indiana soils data as well as to a previously published data set for a Canadian soil using an R-based model (KinGUII) to explore pathways and estimate half-lives (t1/2) for EtFOSE and metabolites. EtFOSE degradation ranged from a few days to up to a month. PFOS yields ranged form 1.06–5.49 mol% with the alkaline soils being four to five times higher than the acidic soil. In addition, a direct pathway to PFOS had to be invoked to describe the early generation of PFOS in the Canadian soil. Of all metabolites, the sulfonamidoacetic acids were the most persistent (t1/2 ≥ 3 months) in all soils. We hypothesized that while pH-pKa dependent speciation may have impacted rates, differences in microbial communities between the 3 soils arising from varied soil properties including pH, nutrient levels, soil management, and climatic regions are likely the major factors affecting pathways, rates, and PFOS yields.

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.