Aided phytostabilisation of As- and Cu-contaminated soils using white lupin and combined iron and organic amendments.

An aided phytostabilisation strategy consisting of several composite amendments of iron sulphate and organic materials combined with Lupinus albus L. (white lupin) was evaluated for remediation of an As- and Cu-contaminated soil. Iron sulphate was combined with lime, paper mill sludge (PS), olive mill waste compost (OMWC) or holm oak biochar (BC) and applied to a slightly acidic soil with high concentration of As (∼2200 mg kg-1) and Cu (∼150 mg kg-1). White lupin was grown for 48 days in pots containing amended and non-amended soils and the effect of soil treatments on soluble and extractable trace elements, soil fertility and plant growth and composition was evaluated. The addition of the amendments raised soil pH and reduced soluble As (50-93%) and extractable As and Cu (50-89%). Despite the reduction of As- and Cu-extractable fractions, plant As and Cu uptake was not greatly affected by the amendments. Variations in soil pH and P-Olsen seemed to have influenced As dynamics in the treated soils, although they did not provoke its mobilisation with respect to the non-amended soil. Our results suggest that the freshly formed iron oxides resulting from addition of iron sulphate controlled As dynamics in the treated soils, avoiding its mobilisation due to application of organic materials. The combination of iron sulphate with OMWC and BC is shown as appropriate for aided phytostabilisation of metal(loid)s contaminated soils, as it improved soil fertility and plant nutrition while reduced As and Cu mobility.

Aided phytostabilisation over two years using iron sulphate and organic amendments: Effects on soil quality and rye production.

An outdoor macrocosm experiment using Fe-based and organic amendments over 2 years was set up to evaluate the effectiveness of aided-phytostabilisation. For that, a soil contaminated with As- and Cu-rich waste material (∼13000 mg As kg-1 and ∼500 mg Cu kg-1) was treated with combinations of iron sulphate (Fe) with lime, paper mill sludge (PS), holm-oak biochar (BC), olive mill waste compost (OMWC) or green waste compost (GWC). Rye (Secale cereale L.) was grown in the treated and non-treated soils 16 months after addition of the amendments. Arsenic and Cu dynamics in soil were assessed throughout the experiment and soil quality parameters (soil nutrients, organic matter and soil biology) were measured almost two years after addition of the amendments. All treatments resulted in a reduction of soluble and extractable Cu during the experiment and, despite the increase in soil pH (from 5 to 68) and DOC (from 10 up to 50 mg DOC L-1) provoked by the amendments, As was not significantly mobilised in the treated soils. Treatments combining Fe sulphate with the organic materials, especially biochar and both composts, resulted in an increase in soil available nutrients and enhanced rye growth. In this semi-field scale experiment, the combination of Fe sulphate with holm-oak biochar showed the most promising results in terms of soil fertility (nutrient availability), plant As and Cu uptake and soil C sequestration. Further research should focus on monitoring long-term effects of the soil amendments on crops, following repeated applications.

Biochar modification to enhance sorption of inorganics from water.

Biochar can be used as a sorbent to remove inorganic pollutants from water but the efficiency of sorption can be improved by activation or modification. This review evaluates various methods to increase the sorption efficiency of biochar including activation with steam, acids and bases and the production of biochar-based composites with metal oxides, carbonaceous materials, clays, organic compounds, and biofilms. We describe the approaches, and explain how each modification alters the sorption capacity. Physical and chemical activation enhances the surface area or functionality of biochar, whereas modification to produce biochar-based composites uses the biochar as a scaffold to embed new materials to create surfaces with novel surface properties upon which inorganic pollutants can sorb. Many of these approaches enhance the retention of a wide range of inorganic pollutants in waters, but here we provide a comparative assessment for Cd2+, Cu2+, Hg2+, Pb2+, Zn2+, NH4+, NO3-, PO43-, CrO42- and AsO43-.

Effect of Lupinus albus L. root activities on As and Cu mobility after addition of iron-based soil amendments.

Arsenic and Cu mobility was investigated in the rhizosphere of Lupinus albus L. grown in an iron-amended contaminated soil. White lupin was grown in rhizobags in contaminated soil either left untreated or amended with iron sulphate plus lime (Fe + lime) or biochar (Fe + BC). Porewater was monitored in rhizosphere and bulk soil throughout the experiment and the extractable fraction of several elements and As and Cu plant uptake was analysed after 48 days. The distribution of As, Cu, P and Fe in the lupin rhizosphere was evaluated with chemical images obtained by laser ablation-ICP-MS analysis of diffusive gradients in thin films (DGT) gels. The treatments effectively reduced the soluble and extractable As and Cu fractions in the bulk soil, but they did not affect plant uptake. In all cases, soluble As was slightly enhanced in the rhizosphere. This difference was more pronounced in the Fe + lime-treated rhizosphere soil, where an increase of pH as well as extractable As and Fe concentrations were also observed. Chemical imaging of the lupin rhizosphere also showed slightly higher As- and Fe-DGT fluxes around lupin roots grown in the non-amended soil. Our findings indicate As and Fe co-solubilisation by lupin root exudates, likely as a response to P deficiency. Arsenic mobilisation occurred only in the rhizosphere and was not decreased by the amendments.

Assessing the combination of iron sulfate and organic materials as amendment for an arsenic and copper contaminated soil. A chemical and ecotoxicological approach.

The efficiency of combining iron sulfate and organic amendments (paper mill sludge, olive mill waste compost and olive tree pruning biochar) for the remediation of an As- and Cu-contaminated soil was evaluated. Changes in As and Cu fractionation and solubility due to the application of the amendments was explored by leachate analysis, single and sequential extractions. Also, the effects on Arrhenatherum elatius growth, germination of Lactuca sativa and toxicity to the bacteria Vibrio fischeri were assessed. The combination of iron sulfate and the organic amendments efficiently reduced As solubility and availability through the formation of amorphous iron oxides, while organic matter did not seem to mobilize As. At the same time, copper fractionation was strongly affected by soil pH and organic matter addition. The soil pH significantly influenced both As and Cu mobility. Within all the amendments tested, FeSO4 in combination with compost showed to be the most suitable treatment for the overall remediation process, as it reduced As and Cu availability andenhanced soil nutrient concentrations and plant growth. In sipte of contradictory trends between chemical analyses and ecotoxicity tests, we can still conclude that the application of organic amendments in combination with reactive iron salts is a suitable approach for the remediation of soils contaminated by Cu and As.

Iron plaque formed under aerobic conditions efficiently immobilizes arsenic in Lupinus albus L roots.

Arsenic is a non-threshold carcinogenic metalloid. Thus, human exposure should be minimised, e.g. by chemically stabilizing As in soil. Since iron is a potential As immobiliser, it was investigated whether root iron plaque, formed under aerobic conditions, affects As uptake, metabolism and distribution in Lupinus albus plants. White lupin plants were cultivated in a continuously aerated hydroponic culture containing Fe/EDDHA or FeSO4 and exposed to arsenate (5 or 20 µM). Only FeSO4 induced surficial iron plaque in roots. LA-ICP-MS analysis accomplished on root sections corroborated the association of As to this surficial Fe. Additionally, As(V) was the predominant species in FeSO4-treated roots, suggesting less efficient As uptake in the presence of iron plaque. Fe/EDDHA-exposed roots neither showed such surficial FeAs co-localisation nor As(V) accumulation; in contrast As(III) was the predominant species in root tissue. Furthermore, FeSO4-treated plants showed reduced shoot-to-root As ratios, which were >10-fold lower compared to Fe/EDDHA treatment. Our results highlight the role of an iron plaque formed in roots of white lupin under aerobic conditions on As immobilisation. These findings, to our knowledge, have not been addressed before for this plant and have potential implications on soil remediation (phytostabilisation) and food security (minimising As in crops).

Biochar addition to an arsenic contaminated soil increases arsenic concentrations in the pore water but reduces uptake to tomato plants (Solanum lycopersicum L.).

Arsenic (As) concentrations in soil, soil pore water and plant tissues were evaluated in a pot experiment following the transplantation of tomato (Solanum lycopersicum L.) plantlets to a heavily As contaminated mine soil (~6000 mg kg(-1) pseudo-total As) receiving an orchard prune residue biochar amendment, with and without NPK fertiliser. An in-vitro test was also performed to establish if tomato seeds were able to germinate in various proportions of biochar added to nutrient solution (MS). Biochar significantly increased arsenic concentrations in pore water (500 µg L(-1)-2000 µg L(-1)) whilst root and shoot concentrations were significantly reduced compared to the control without biochar. Fruit As concentrations were very low (<3 µg kg(-1)), indicating minimal toxicity and transfer risk. Fertilisation was required to significantly increase plant biomass above the control after biochar addition whilst plants transplanted to biochar only were heavily stunted and chlorotic. Given that increasing the amount of biochar added to nutrient solution in-vitro reduced seed germination by up to 40%, a lack of balanced nutrient provision from biochar could be concluded. In summary, solubility and mobility of As were increased by biochar addition to this soil, but uptake to plant was reduced, and toxicity-transfer risk was negligible. Therefore leaching rather than food chain transfer appears the most probable immediate consequence of biochar addition to As contaminated soils.