Dr Anitha Kunhikrishnan

The dynamics of trace elements in soils is dependent on both their physicochemical interactions with inorganic and organic soil constituents and their biological interactions linked to the microbial activities of soil-plant systems. Microorganisms control the transformation (microbial or biotransformation) of trace elements by several mechanisms that include oxidation, reduction, methylation, demethylation, complex formation, and biosorption. Microbial transformation plays a major role in the behavior and fate of toxic elements, especially arsenic (As), chromium (Cr), mercury (Hg), and selenium (Se) in soils and sediments. Biotransformation processes can alter the speciation and redox state of these elements and hence control their solubility and subsequent mobility. These processes play an important role in the bioavailability, mobility, ecotoxicity, and environmental health of these trace elements. A greater understanding of biotransformation processes is necessary to efficiently manage and utilize them for contaminant removal and to develop in situ bioremediation technologies. In this chapter, the key microbial transformation processes, including biosorption, redox reactions, and methylation/demethylation reactions controlling the fate and behavior of As, Cr, Hg, and Se, are addressed. The factors affecting these processes in relation to the bioavailability and remediation of trace elements in the environment are also examined, and possible future research directions are recommended.

With increasing demand for world water supply, wastewater reuse is a great opportunity to meet the water need, especially for agricultural and industrial development. Wastewater originates from many sources and hence its composition differs from origin and treatment processes. Wastewater rich in organic matter acts as a soil conditioner, thereby enhancing soil health. Wastewater also acts as a source of nutrient input in agriculture which in turn can reduce, or even eliminate the need for commercial fertilisers. However, wastewater usage in agriculture poses several threats like eutrophication, salinity, toxic chemicals (heavy metal(loids), pesticides), pathogen contamination, and most notably, nutrient leaching, and greenhouse gas (GHG) emission. These threats affect public health, soil and ground water resources, environment, crop quality, ecological, and property values. Biological degradation of the organic matter present in wastewater is considered one of the anthropogenic sources of major GHGs (carbon dioxide (CO ), nitrous oxide (N O), and methane (CH ). In this paper, an overview of various sources of wastewater, effects of wastewater application on GHG emission from soil, and the strategies to mitigate wastewater-induced GHG emission from soils is presented. © 2012 WIT Press. 2 2 4

Shooting range soils contain mixed heavy metal contaminants including lead (Pb), cadmium (Cd), and zinc (Zn). Phosphate (P) compounds have been used to immobilize these metals, particularly Pb, thereby reducing their bioavailability. However, research on immobilization of Pb's co-contaminants showed the relative importance of soluble and insoluble P compounds, which is critical in evaluating the overall success of in situ stabilization practice in the sustainable remediation of mixed heavy metal contaminated soils. Soluble synthetic P fertilizer (diammonium phosphate; DAP) and reactive (Sechura; SPR) and unreactive (Christmas Island; CPR) natural phosphate rocks (PR) were tested for Cd, Pb and Zn immobilization and later their mobility and bioavailability in a shooting range soil. The addition of P compounds resulted in the immobilization of Cd, Pb and Zn by 1.56¿76.2%, 3.21¿83.56%, and 2.31¿74.6%, respectively. The reactive SPR significantly reduced Cd, Pb and Zn leaching while soluble DAP increased their leachate concentrations. The SPR reduced the bioaccumulation of Cd, Pb and Zn in earthworms by 7.13¿23.4% and 14.3¿54.6% in comparison with earthworms in the DAP and control treatment, respectively. Bioaccessible Cd, Pb and Zn concentrations as determined using a simplified bioaccessibility extraction test showed higher long-term stability of P-immobilized Pb and Zn than Cd. The differential effect of P-induced immobilization between P compounds and metals is due to the variation in the solubility characteristics of P compounds and nature of metal phosphate compounds formed. Therefore, Pb and Zn immobilization by P compounds is an effective long-term remediation strategy for mixed heavy metal contaminated soils.

Co-composting biowastes such as manures and biosolids can be used to stabilize carbon (C) without impacting the quality of these biowastes. This study investigated the effect of co-composting biowastes with alkaline materials on C stabilization and monitored the fertilization and revegetation values of these co-composts. The stabilization of C in biowastes (poultry manure and biosolids) was examined by their composting in the presence of various alkaline amendments (lime, fluidized bed boiler ash, flue gas desulphurization gypsum, and red mud) for 6¿months in a controlled environment. The effects of co-composting on the biowastes¿ properties were assessed for different physical C fractions, microbial biomass C, priming effect, potentially mineralizable nitrogen, bioavailable phosphorus, and revegetation of an urban landfill soil. Co-composting biowastes with alkaline materials increased C stabilization, attributed to interaction with alkaline materials, thereby protecting it from microbial decomposition. The co-composted biowastes also increased the fertility of the landfill soil, thereby enhancing its revegetation potential. Stabilization of biowastes using alkaline materials through co-composting maintains their fertilization value in terms of improving plant growth. The co-composted biowastes also contribute to long-term soil C sequestration and reduction of bioavailability of heavy metals.

Complementary medicines have associated risks which include toxic heavy metal(loid) and pesticide contamination. The objective of this study was to examine the speciation and bioavailability of lead (Pb) in selected complementary medicines. Six herbal and six ayurvedic medicines were analysed for: (i) total heavy metal(loid) contents including arsenic (As), cadmium (Cd), Pb and mercury (Hg); (ii) speciation of Pb using sequential fractionation and extended x-ray absorption fine structure (EXAFS) techniques; and (iii) bioavailability of Pb using a physiologically-based in vitro extraction test (PBET). The daily intake of Pb through the uptake of these medicines was compared with the safety guidelines for Pb. The results indicated that generally ayurvedic medicines contained higher levels of heavy metal(loid)s than herbal medicines with the amount of Pb much higher than the other metal(loid)s. Sequential fractionation indicated that while organic-bound Pb species dominated the herbal medicines, inorganic-bound Pb species dominated the ayurvedic medicines. EXAFS data indicated the presence of various Pb species in ayurvedic medicines. This implies that Pb is derived from plant uptake and inorganic mineral input in herbal and ayurvedic medicines, respectively. Bioavailability of Pb was higher in ayurvedic than herbal medicines, indicating that Pb added as a mineral therapeutic input is more bioavailable than that derived from plant uptake. There was a positive relationship between soluble Pb fraction and bioavailability indicating that solubility is an important factor controlling bioavailability. The daily intake values for Pb as estimated by total and bioavailable metal(loid) contents are likely to exceed the safe threshold level in certain ayurvedic medicines. This research demonstrated that Pb toxicity is likely to result from the regular intake of these medicines which requires further investigation.

Regular application of phosphate (P) fertilisers has been identified as the main source of heavy metal(loid) contamination including cadmium (Cd) in agricultural soils. Some of these P fertilisers that act as a source of Cd contamination of soils have also been found to act as a sink for the immobilisation of this metal(loid). In paddy soils, redox reactions play an important role in the (im)mobilisation of nutrients and heavy metal(loid)s, as a result of flooding of the rice plains. Although a number of studies have examined the potential value of P compounds in the immobilisation of metals in contaminated soils, there has been no comprehensive review on the mechanisms involved in the P-induced (im)mobilisation of Cd in paddy soils. There are a number of factors that influences P induced Cd (im)mobilisation in paddy soils that include pH, redox reactions, liming effect, rhizosphere acidification and root iron plaques. Following a brief overview of the reactions of Cd and common P compounds that are used as fertiliser in soils, the review focuses on the above mentioned mechanisms for the (im)mobilisation of Cd by P compounds in paddy soils. The role of iron plaques on Cd status in soil and rice plants is also discussed followed by a summary and future research needs.

Arsenic (As) contamination of groundwater reservoirs is a global environmental and health issue given to its toxic and carcinogenic nature. Over 170 million people have been affected by As due to the ingestion of As-contaminated groundwater. Conventional methods such as reverse osmosis, ion exchange, and electrodialysis are commonly used for the remediation of As-contaminated water; however, the high cost and sludge production put limitations on their application to remove As from water. This review critically addresses the use of various agricultural waste materials (e.g., sugarcane bagasse, peels of various fruits, wheat straw) as biosorbents, thereby offering an eco-friendly and low-cost solution for the removal of As from contaminated water supplies. The effect of solution chemistry such as solution pH, cations, anions, organic ligands, and various other factors (e.g., temperature, contact time, sorbent dose) on As biosorption, and safe disposal methods for As-loaded biosorbents to reduce secondary As contamination are also discussed.

Heavy metals such as chromium (Cr) and arsenic (As) occur in ionic form in soil, with chromate [Cr(VI)] and arsenate As(V) being the most pre-dominant forms. The application of biochar to Cr(VI) and As(V) spiked and field contaminated soils was evaluated on the reduction processes [(Cr(VI) to Cr(III)] and [As(V) to As(III))], and subsequent mobility and bioavailability of both As(V) and Cr(VI). The assays used in this study included leaching, soil microbial activity and XPS techniques. The reduction rate of As(V) was lower than that of Cr(VI) with and without biochar addition, however, supplementation with biochar enhanced the reduction process of As(V). Leaching experiments indicated Cr(VI) was more mobile than As(V). Addition of biochar reversed the effect by reducing the mobility of Cr and increasing that of As. The presence of Cr and As in both spiked and contaminated soils reduced microbial activity, but with the addition of biochar to these soils, the microbial activity increased in the Cr(VI) contaminated soils, while it was further decreased with As(V) contaminated soils. The addition of biochar was effective in mitigating Cr toxicity by reducing Cr(VI) to Cr(III). In contrast, the conversion process of As(V) to As(III) hastened by biochar was not favourable, as As(III) is more toxic in soils. Overall, the presence of functional groups on biochar promotes reduction by providing the electrons required for reduction processes to occur as determined by XPS data.

Heavy metal contamination in rice paddies is a serious problem in monsoon Asia, and these fields require appropriate restoration measures. Although soil washing is a promising remediation technology, high cost for the treatment on soil washing leachate (wastewater) is one of the critical problems. This study sought to develop a simple method for the restoration of paddy fields by soil washing, with simplified wastewater treatment. Ferric chloride solution (FeCl ) was used as a washing chemical to extract Cd from a soil, which produced the wastewater containing Cd and other metals. Three alkali materials (NaOH, MgO, and CaCO ) were tested to treat the wastewater and determined MgO is optimal. In an on-site experiment, the target pH for wastewater treatment was controlled between 8 and 9 by using MgO. All metals in the wastewater could be effectively removed, reaching levels substantially lower than those permitted by Japanese standards. The treated wastewater could be discharged to agricultural canal. Therefore, our novel simplified method effectively removed heavy metals from the wastewater produced by on-site soil washing and contribute drive down the cost. 3 3

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO and PO , surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota. © 2013 Springer Science+Business Media Dordrecht. 4 4 f 2- 3-