Modification of biochar by low-cost iron sources has gained increasing attention to improve pollutants removal performance and reduce production costs compared to conventional chemical modifications. While such iron sources generally have complex compositions, their effects on properties of the iron-biochar composite are not well investigated. This study produced an iron-biochar (RBC) composite from co-pyrolysis of incinerated sewage sludge ash (ISSA) and peanut shell, and examined the role of silica with widespread existence in ISSA and other low-cost iron sources on properties of the iron-biochar composite relevant to As(III)/As(V) removal. Silica was found to react with iron during the pyrolysis process at 850 °C and formed iron silicon at the expense of producing zero valent iron and Fe₃O₄ which resulted in a poorer removal efficacy for As(III) and As(V) compared to the iron-biochar (FBC) made from pure Fe₂O₃ and peanut shell. Moreover, a high leaching of reactive silica from RBC was observed which affected the formation of corrosion products of ZVI and competed with arsenic for active adsorption sites. Despite this, RBC still exhibited a maximum adsorption capacity of 17.44 and 57.56 mg/g towards As(III) and As(V) respectively at pH 3.0. Overall, this study provides an interesting insight into upcycling ISSA into useful media for sorptive removal of arsenic from aqueous solutions.

The negative impact of antibiotic pollution on the agricultural system and human health is a hot issue in the world. However, little information is available on the antibiotics toxicity mechanism and the role of silicon (Si) to alleviate the antibiotics toxicity. In this study, strawberry (Fragaria ananassa) showed excitatory response to low-dose SMZ (1 mg L⁻¹), but strawberry root and photosynthetic efficiency were damaged under high level. When SMZ level exceeded 10 mg L⁻¹, H₂0₂, O₂⁻, MDA and relative conductivity increased, while SOD and CAT activities first increased and then decreased. SMZ accumulated more in roots and fruits, but less in stems, and the accumulation increased with the increase of SMZ-dose. Under 1 mg L⁻¹ SMZ, the SMZ accumulation in fruits was 110.54 μg kg⁻¹, which exceeded the maximum residue limit. SMZ can induce the expression of sul1, sul2 and intI1, and intI1 had the highest abundance. Exogenous application of Si alleviated the toxicity of SMZ, which is mainly related to the degradation of SMZ in soil and the reduction of SMZ absorption by strawberry. In addition, Si relieved root damage, promoted the increase of photosynthetic efficiency, and improved the antioxidant system to resist SMZ toxicity.

Industrial by-products provide materials for remediation measures. In this study, a silicon-iron amendment was prepared from residue originating from acid-extracted copper (Cu) tailings based on thermal activation at temperatures ranging from 550 °C to 1150 °C for 30 min with the use of additives (CaO, Na₂CO₃, NaOH). The remediation performance of the amendment was evaluated through soil incubation and greenhouse pot experiments with vetiver (Vetiveria zizanioides). The results showed that the highest levels of soluble Si (6.11% of the total Si) and Fe (2.3% of the total Fe) in the amendment were achieved with thermal activation at 1150 °C for 30 min using an optimal ratio between residue and additives (residue: CaO: Na₂CO₃: NaOH = 1: 0.4: 0.4: 0.2). Heavy metal release indicated that the amendment could be safely used for soil remediation. The incubation experiments showed that the DTPA-extractable Cd, Cr and Pb in contaminated soils decreased with increasing amendment rate, which was not observed for As. The amendment-induced decrease in the Cd, Cr and Pb availability in contaminated soils could be explained by pH-change induced immobilization, Fe-induced chemisorption, Si-induced co-precipitation, and Ca-induced ion exchange. Correlation analysis suggested that there were significant negative correlations between DTPA-extractable Cd, Cr and Pb and the pH, Fe, Si, and Ca in soil pore water and soil. The most suitable amendment rate was determined to be 1% by balancing the efficacy and wise utilization of the amendment. The pot experiment demonstrated that the amendment promoted the vetiver growth and stimulated the accumulation of Cd and Cr in the roots. The amendment was proved to be promising for the phytostabilization of Cd, Cr and Pb in contaminated soils. Further investigations are required to determine whether the amendment is a tool for the long-term remediation of multi-metal-contaminated soils at the field scale.

Agricultural soil is one of the main sink for both heavy metals and nanomaterials (NMs). Whether NMs can impact heavy metals uptake or bioaccumulation in plants is unknown. Here, cucumber plants were cultivated in a multi-heavy metals contaminated soil amended with four types of NMs (SiO2, TiO2, ZnS and MoS2) separately for four weeks. Physiological and biochemical parameters were determined to investigate the impact of NMs on plant growth. Inductively coupled plasma mass spectrometry was employed to determine the metal content in plants. Results showed that none of the tested NMs impacted plants biomass, but all the NMs showed different degrees of reduction in heavy metals bioaccumulation in plant roots, stems and leaves. However, four NMs showed different degrees of reduction in macro and micro nutrients uptake. MoS2 decreased the bioaccumulation of heavy metals (As, Cd, Cr, Cu, Ni, Al, Ti and Pb) for 36.4–60.6% and nutrients (Mg, Fe, K, Si and Mn) for 40.1%–50.1% in roots. Exposure to MoS2 NMs also significantly increased 23.4% of Si in leaves, 205.6% and 83.9% of Mo in roots and stems, respectively. In general, the results of this study showed promising potential for NMs to reduce uptake of heavy metals in crop plants, especially MoS2 NMs. However, the negative impacts of perturbing nutrients uptake should be paid attention as well.

Hardpans are massively indurated layers formed at the top layer of sulfidic tailings dams, which develop cementation structures and result in heavy metal immobilization. However, the micro-structural and complex forms of the cementing materials are not fully understood, as well as the mechanisms by which Zn and Pb are stabilized in the hardpans. The present study deployed synchrotron-based X-ray fluorescence microscopy (XFM) to have characterized the cementing structures, examined the distribution of Fe, Zn and Pb, and obtained laterally-resolved speciation of Zn within the hardpans using fluorescence X-ray absorption near-edge structure (XANES) imaging. The XFM analyses revealed that the Fe-rich cement layers consisted of Fe (oxyhydr)oxides coupled with amorphous Si materials, immobilizing Zn and Pb. Through laterally-resolved XANES imaging analyses, Zn-ferrihydrite-like precipitates were predicted to account for >76% of the total Zn within the Fe-rich cement layers. In contrast, outside of the cement layers, 9–63% of the Zn was estimated as labile ZnSO4.7H2O, with the remainder in the form of Zn-sulfide. These findings demonstrated that the Fe-rich cement layers were critical in immobilizing Zn and Pb within hardpans via mineral passivation and encapsulation, as the basis for long-term geochemical stability in the hardpan layer of sulfidic mine tailings.

Metals are released from biochar (BC) in either the free or dissolved organic carbon (DOC)-combined form. The complexation of metals with DOC influences their toxicity and bioavailability in the environment. The endogenous release of metal species with heterogeneous DOC from BC is very complex; this process has been neglected and remains unaddressed in the literature to date. In this study, the yield and chemical properties of labile DOC from BC were characterized, and the release of endogenous metal/metalloid elements (K, Mg, Mn, Fe, Al, Cu, and Si) and their species from BC with various pyrolysis temperatures and particle sizes were systematically investigated under various solution chemistries. The results showed that pyrolysis temperature of BC significantly influenced the yield and composition of DOC and DOC-metal/metalloid complexes, while particle size had lower impact. The yield of BC-derived DOC significantly decreased and the components gradually changed from low-molecular weight and low-aromaticity hydrophilic humic acid-like substances to complex high-molecular weight and high-aromaticity hydrophobic substances as pyrolysis temperature increased from 200 to 700 °C. The release of total dissolved metals decreased with increasing pyrolysis temperature, while the highest total dissolved Si was released from BC with the moderate pyrolysis temperature (500 °C). The metal elements were mainly released in the DOC-combined form, while the released Si was mainly in the free form in the neutral water environment. The release of DOC increased while that of dissolved metals decreased with increasing solution pH. The release of total dissolved metals/metalloids increased but the ratio of the DOC-combined metals/metalloids decreased with increasing solution ionic strength. These results provide new insight into the understanding of endogenous metal/metalloid release from BC in the natural environment.

Source samples including crustal dust, cement dust, coal combustion were sampled and ambient samples of PM₂.₅ and PM₁₀ were synchronously collected in Hefei from April to December 2014. The size distributions of the markers in the measured source profiles were incorporated into ME-2 solution to develop a new method, called the SDABB model (an advanced ABB three-way factor analysis model incorporating size distribution information). The performance of this model was investigated using three-way synthetic and ambient dataset. For the synthetic tests, the size distributions of markers estimated by the SDABB model were more consistent with true condition. The AAEs between estimated and observed contributions of the SDABB ranged from 15.2% to 29.0% for PM₁₀ and 19.9%–31.6% for PM₂.₅, which is lower than those of PMF2. For the ambient PM, six source categories were identified by SDABB for both sizes, although the profiles were different. The source contributions were sulphate (33.33% and 24.53%), nitrate and SOC (22.33% and 18.16%), coal combustion (19.01% and 18.23%), vehicular exhaust (12.99% and 12.07%), crustal dust (10.69% and 19.40%) and cement dust (1.65% and 5.39%) for PM₂.₅ and PM₁₀ respectively. In addition, the estimated ratios of Al, Si, Ti and Fe in CRD were 0.76, 0.84, 1.10 and 0.85; those of Al and Si in CC were 0.42 and 0.66; Ca and Si in CD were 0.95 and 1.10; NO₃⁻ and NH₄⁺ in nitrate were 1.11 and 1.01; and SO₄²⁻ and NH₄⁺ in sulphate were 0.96 and 1.16. These modeled ratios were consistent with the measured ratios. The size distribution of contributions also came close to reality. Thus, the advanced SDABB three-way model can better capture the characteristics of sources between sizes by effectively incorporating the size distributions of the markers as physical constraints.