Enhanced Cu and Cd sorption after soil aging of woodchip-derived biochar: What were the driving factors?

Biochar (BC) is increasingly tested as a soil amendment for immobilization of heavy metals (HMs) and other pollutants. In our study, an acidic soil amended with wood chip-derived BC showed strongly enhanced Cu and Cd sorption after 15 months of aging under greenhouse conditions. X-ray absorption near edge structure suggested formation of Cu(OH)2 and CuCO3 and upon aging increasingly Cu sorption to the BC organic phase (from 9.2% to 40.7%) as main binding mechanisms of Cu on the BCs. In contrast, Cd was predominantly bound as CdCO3 on the BCs even after 15 months (82.7%). We found indications by mid-infrared spectroscopy that the formation of organic functional groups plays a role for increased HM sorption on aged BCs. Yet, our data suggest that the accessibility of BC's pore network and reactive surfaces is likely to be the overriding factor responsible for aging-related changes in HM sorption capacity, rather than direct interactions of HMs with oxidized functional groups. We observed highly weathered BC surface structures with scanning electron microscopy along with strongly increased wettability of the BCs after 15 months of soil aging as indicated by a decrease of water contact angles (from 62.4° to 4.2°).

Trace element biogeochemistry in the soil-water-plant system of a temperate agricultural soil amended with different biochars.

Various biochar (BC) types have been investigated as soil amendment; however, information on their effects on trace element (TE) biogeochemistry in the soil-water-plant system is still scarce. In the present study, we determined aqua-regia (AR) and water-extractable TEs of four BC types (woodchips (WC), wheat straw (WS), vineyard pruning (VP), pyrolyzed at 525 °C, of which VP was also pyrolyzed at 400 °C) and studied their effects on TE concentrations in leachates and mustard (Sinapis alba L.) tissue in a greenhouse pot experiment. We used an acidic, sandy agricultural soil and a BC application rate of 3% (w/w). Our results show that contents and extractability of TEs in the BCs and effectuated changes of TE biogeochemistry in the soil-water-plant system strongly varied among the different BC types. High AR-digestable Cu was found in VP and high B contents in WC. WS had the highest impact on TEs in leachates showing increased concentrations of As, Cd, Mo, and Se, whereas WC application resulted in enhanced leaching of B. All BC types increased Mo and decreased Cu concentrations in the plant tissue; however, they showed diverging effects on Cu in the leachates with decreased concentrations for WC and WS, but increased concentrations for both VPs. Our results demonstrate that BCs may release TEs into the soil-water-plant system. A BC-induced liming effect in acidic soils may lead to decreased plant uptake of cationic TEs, including Pb and Cd, but may enhance the mobility of anionic TEs like Mo and As. We also found that BCs with high salt contents (e.g., straw-based BCs) may lead to increased mobility of both anionic and cationic TEs in the short term.

Trace element concentrations in leachates and mustard plant tissue (Sinapis alba L.) after biochar application to temperate soils.

Biochar application to agricultural soils has been increasingly promoted worldwide. However, this may be accompanied by unexpected side effects in terms of trace element (TE) behavior. We used a greenhouse pot experiment to study the influence of woodchip-derived biochar (wcBC) on leaching and plant concentration of various TEs (Al, Cd, Cu, Pb, Mn, As, B, Mo, Se). Three different agricultural soils from Austria (Planosol, Cambisol, Chernozem) were treated with wcBC at application rates of 1 and 3% (w/w) and subsequently planted with mustard (Sinapis alba L.). Soil samples were taken 0 and 7 months after the start of the pot experiment, and leachate water was collected twice (days 0 and 54). The extractability (with NH4NO3) of cationic TEs was decreased in the (acidic) Planosol and Cambisol after wcBC application, whereas in the (neutral) Chernozem it hardly changed. In contrast, anionic TEs were mobilized in all three soils, which resulted in higher anion concentrations in the leachates. The application of wcBC had no effect on Al and Pb in the mustard plants, but increased their B and Mo concentrations and decreased their Cd, Cu and Mn concentrations. A two-way analysis of variance showed significant interactions between wcBC application rate and soil type for most TEs, which indicates that different soil types may react differently upon wcBC application. Correlation and partial correlation analyses revealed that TE behavior was primarily related to soil pH, whereas the involvement of other factors such as electrical conductivity (EC), organic carbon (OC) content and dissolved organic carbon (DOC) was found to be more soil and TE-specific. The application of wcBC may be a useful strategy for the remediation of soils with elevated levels of cationic TEs, but could lead to deficiencies of cationic micronutrients and enhance short-term translocation of anionic TEs towards the groundwater at high leaching rates.

Characterization of slow pyrolysis biochars: effects of feedstocks and pyrolysis temperature on biochar properties.

Biochars are increasingly used as soil amendment and for C sequestration in soils. The influence of feedstock differences and pyrolysis temperature on biochar characteristics has been widely studied. However, there is a lack of knowledge about the formation of potentially toxic compounds that remain in the biochars after pyrolysis. We investigated biochars from three feedstocks (wheat straw, poplar wood, and spruce wood) that were slowly pyrolyzed at 400, 460, and 525°C for 5 h (straw) and 10 h (woodchips), respectively. We characterized the biochars' pH, electrical conductivity, elemental composition (by dry combustion and X-ray fluorescence), surface area (by N adsorption), water-extractable major elements, and cation exchange capacity (CEC). We further conducted differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffractometry to obtain information on the biochars' molecular characteristics and mineralogical composition. We investigated trace metal content, total polycyclic aromatic hydrocarbon (PAH) content, and PAH composition in the biochars. The highest salt (4.92 mS cm) and ash (12.7%) contents were found in straw-derived biochars. The H/C ratios of biochars with highest treatment temperature (HTT) 525°C were 0.46 to 0.40. Surface areas were low but increased (1.8-56 m g) with increasing HTT, whereas CEC decreased (162-52 mmol kg) with increasing HTT. The results of DSC and FTIR suggested a loss of labile, aliphatic compounds during pyrolysis and the formation of more recalcitrant, aromatic constituents. X-ray diffractometry patterns indicated a mineralogical restructuring of biochars with increasing HTT. Water-extractable major and trace elements varied considerably with feedstock composition, with trace elements also affected by HTT. Total PAH contents (sum of EPA 16 PAHs) were highly variable with values up to 33.7 mg kg; irrespective of feedstock type, the composition of PAHs showed increasing dominance of naphthalene with increasing HTT. The results demonstrate that biochars are highly heterogeneous materials that, depending on feedstock and HTT, may be suitable for soil application by contributing to the nutrient status and adding recalcitrant C to the soil but also potentially pose ecotoxicological challenges.