Dr Balaji Seshadri

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.

Acid mine drainage (AMD) from both active and abandoned mine sites is a major environmental issue for the mining industry in environmentally concerned regions of the world (Gray 1997, Lindsay et al. 2015). The term is used to describe any seepage, leachate, or drainage affected by the oxidation products of sulfide minerals in mine sites when exposed to air and water (Figure 3.1). Both chemical reactions and biological transformations are recognized as being responsible for generating AMD (Lindsay et al. 2015). AMD is typically characterized by low pH and high levels of dissolved metal salts, as well as high concentrations of acidity, sulfate, iron, and other metals (Gray 1997). Once the AMD process begins, it is difficult to control, often accelerates, and is likely to persist for decades or centuries. In the absence of natural or added neutralizing materials 34(carbonate minerals such as calcite or dolomite), the AMD is likely to contain toxic levels of heavy metals such as Fe, Al, Mn, Cu, Pb, Zn, and Cd, which can cause serious environmental problems in soil and water systems (Sengupta 1994)

Spoil to Soil: Mine Site Rehabilitation and Revegetation presents both fundamental and practical aspects of remediation and revegetation of mine sites. Through three major themes, it examines characterization of mine site spoils; remediation of chemical, physical and biological constraints of mine site spoils, including post mine-site land-use practices; and revegetation of remediated mine site spoils. Each theme includes chapters featuring case studies involving mine sites around the world. The final section focuses specifically on case studies with successful mine site rehabilitation. The book provides a narrative of how inert spoil can be converted to live soil. Instructive illustrations show mine sites before and after rehabilitation. The purpose of this book is to provide students, scientists, and professional personnel in the mining industry sensible, science-based information needed to rehabilitate sustainably areas disturbed by mining activities. This book is suitable for undergraduate and graduate students majoring in environmental, earth, and soil sciences; environmental and soil scientists; and mine site environmental engineers and regulators

The Australian beef cattle industry is one of the most efficient and ranks third largest in beef export in the world, contributing 4% of beef supply. As on 2013, the meat value produced from beef cattle, in Australia is estimated to be $12.3 billion (Fastfacts, 2013). Beef cattle production ranges from intensive farms on fertile lands to extensive range lands. With the increase in human population and increase in affordability of meat-based food, the demand for beef cattle is also increasing

¿Mining¿ refers to the excavation of economically important resources from terrestrial landmasses, thereby generating a large quantity of valuable precursors for commercial and industrial activities. Mineral products such as coal, aluminum, copper, iron, gold, and mineral sand are examples from the mining industry. Though mining advances global economic prosperity, this industry severely disturbs the land, water resources, and the environment (Figure 4.1). Mined waste materials such as tailings, subsoils, oxidized wastes, and fireclay are the main causes for land disturbance. Presence of potentially hazardous substances such as heavy metals in elevated concentrations in the mined waste materials has caused land contamination. Poor soil characteristics such as low-level organic matter and poor soil texture and structure have resulted in deterioration of the land, adversely affecting the establishment of plants and soil microbial flora and fauna (Boyer et al. 2011, Johnson 2003, Larney and Angers 2012, Sopper 1992). Disturbed mine sites are known to contaminate water resources 60 61in many countries, mainly from acid mine drainage (Bolan et al. 2003, Lindsay et al. 2015, Taylor et al. 1997). Therefore, these sites need to be rehabilitated to minimize potential environmental consequences, thereby enhancing their utilization. Revegetation of mine sites is one of the potential strategies that can be applied to improve these disturbed land masses. Here, infertile soil properties are improved by a series of processes such as land application of biowastes

Soils are a prime and very important natural resource, and soil fertility is a major concern for sustainable agriculture and economic development of any country. In recent decades, problems of contaminated land sites, water bodies, groundwater, and air worldwide have increased manyfold due to anthropogenic activities. Mining is one of the anthropogenic activities that cause pollution problems in, around, and outside of mining areas. It results in the mobilization of metals and organic and inorganic substances into the environment, which causes pollution of air, soils, sediments, vegetation, and surface and groundwater. It also increases the morbidity and mortality of plant and animal species and results in the loss of visual, aesthetic characteristics of landscapes (Bolan et al. 2003; Pavli et al. 2015)

Degradation of land resources as a result of mining activities poses serious threat to the environment. It has been estimated that around 0.4 × 10 km area of land is impacted by mining activities around the world (Hooke and Martín-Duque 2012). Unfortunately, a significant percentage of this area has never been reclaimed, which poses health risks to ecosystems and humans. Often, these wastes contain hazardous substances such as heavy metals, organic contaminants, radionuclides, and crushed limestone, where the latter could become a potential source of atmospheric CO emission. Thus, they not only pose serious risk to the groundwater and surface water, but also to the atmosphere (Wijesekara et al. 2016). In order to tackle the issues related to mine wastes and manage the affected sites sustainably, an appropriate physical, chemical, and biological characterization of waste materials becomes very prudent. Due to the lack of both above- and below-ground biodiversity, mine waste sites are very poor in organic matter content. This in return leads to poor seed germination, plant growth, and vegetation establishment. In many cases, the associated toxic contaminants also seriously compromise the soil health, microbial life, and plant growth (Castillejo and Castelló 2010, Larney and Angers 2012). This chapter describes the physicochemical characteristics of mine wastes, including spoil, tailings, and overburden, by underpinning their source-property relationships. The value of readily available biowaste resources, including biosolids, composts, and manures, in improving such physicochemical properties of mining-impacted soils/sites is also discussed 6 2 2

Historically, mining of metalliferous ore bodies was a relatively dispersed activity, with numerous small mines occurring throughout many western countries including the United States, the United Kingdom, and Australia (Soucek et al. 2000, Grant et al. 2002, Mayes et al. 2009). Many metalliferous mine sites began operation in the late eighteenth and early nineteenth centuries and were abandoned in most instances before the environmental movement in Western countries. As such, there was very little recognition of the potential impacts caused by the dispersal of metal toxicants such as arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) into the surrounding environments from these sites. Many of these contaminants are cariogenic in humans (e.g., As), cause a range of human health-related impacts (Pb, Cd), and are toxic to ecological receptors in nearby streams and surrounding terrestrial environments (Cu, Zn, Mn, Ni). As a result of the lack of regard for potential impacts, much of the mining waste was discarded carelessly throughout mining sites, and in some cases, directly into nearby watercourses

In the era of global competition, mineral exploitation has been significantly increased resulting in pressure on the environment in the form of massive deforestation, soil pollution, and erosion. Despite global economic importance, mineral industries have adversely affected the ecosystems across the world. The impact of mine waste in soil depends on its type and composition, commodity being mined, type of ore, and technologies used to process the ore. Mining types and activities are several, which include surface mining, underground mining, openpit mining, in situ mining, pillar mining, slope mining, block caving, and quarrying. And thus mine waste materials vary in their physical and chemical composition and potential for soil contamination. The different 96types of mine waste materials are overburden, waste rock, tailings, slags, mine water, sludge, and gaseous wastes. Overburden includes the soil and rock that are removed to gain access to the ore deposits at openpit mines. It is usually dumped on the surface at mine sites where it will not hinder further expansion of the mining operation. Waste rock contains minerals in concentrations considered too low to be extracted at a profit. It is often stored in heaps on the mine site. Tailings are finely ground rock and mineral waste products of mineral processing operations. They also contain leftover processing chemicals, and usually are deposited in the form of water-based slurry into tailings ponds. Slags are nonmetallic by-products from metal smelting. Mine water is produced in a number of ways at mine sites and varies in its quality and potential for environmental contamination. Sludge is produced at active water treatment plants used at some mine sites and consists of the solids that have been removed from the water as well as any chemicals. Gaseous wastes are produced during high-temperature chemical processing such as smelting, and consist of particulate matter and oxides of sulfur

While landfilling provides a simple and economic means of waste disposal, it causes environmental impacts including leachate generation and greenhouse gas emissions. Increasingly, revegetation is practiced on traditionally managed landfill sites to mitigate environmental degradation. It also provides a source of biomass for energy production. Biomass from landfill sites can be converted to bioenergy through biochemical and thermochemical processes. Selection of suitable biomass-producing plants (high-yielding crops), pretreatments (e.g., removal of lignin) and providing ideal conditions for the conversion processes (e.g., temperature and pressure) influence the quantity and quality of energy generated. This chapter provides an overview of the potential volumes of biomass produced from landfills and the various methods of biomass energy conversion.

This chapter discusses the soil quality aspect of biofuel production. The production of biofuel crops might simultaneously affect a combination of soil properties and stipulating severe human-driven soil quality threats, out of which the decline of soil organic matter (SOM), the increase of erosion risks, and onand off-site pollution and nutrient losses are the most pronounced. The chapter analyzes differences between annual and perennial crops out of the effects of management and land-use change (LUC), including an issue of soil organic carbon (SOC) budget and sustainable removal of crop residues for energy production. Consequently, it focuses on soil quality under biofuel crop production as affected by these threats to provide essential soil services. The chapter further concentrates on the challenges of the soil quality aspect of sustainable biofuel crop production, which include by-product management, soil remediation potential, and utilization of idle and degraded soils for biofuels. This edition first published 2013 © 2013 John Wiley & Sons, Inc.

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

Metabolic uptake of lead (Pb) is controlled by its bioaccessibility. Most studies have examined bioaccessibility of Pb in the absence of gut microbes, which play an important role in the metabolic uptake of nutrients and metal(loid)s in intestine. In this study, we examined the effect of three gut microbes, from various locations in the gut, on the bioaccessibility of soil ingested Pb. The gut microbes include Lactobacillus acidophilus, Lactobacillus rhamnosus and Escherichia coli. Lead toxicity to these three microbes was also examined at various pH values. Bioaccessibility of Pb was measured using gastric and intestinal extractions. Both Pb spiked and Pb-contaminated shooting range field soils were used to measure Pb bioaccessibility in the presence and absence of gut microbes. The results indicated that Pb toxicity to gut microbes, as measured by LD value, decreased with increasing pH, and was higher for Lactobacillus species. Gut microbes decreased the bioaccessible Pb; the effect was more pronounced at low pH, mimicking gastric conditions than in conditions closer to the intestine. Lead adsorption by these microbes increased at the higher pH tested, and E. coli adsorbed higher amounts of Pb than did the Lactobacillus species. The effect of gut microbes on reducing Pb bioaccessibility may be attributed to microbially-induced immobilization of Pb through adsorption, precipitation, and complexation reactions. The study demonstrates that bioaccessibility and subsequently bioavailability of metal(loid)s can be modulated by gut microbes, and it is important to undertake bioaccessibility measurements in the presence of gut microbes. 50

The term ¿Total petroleum hydrocarbons¿ (TPH) is used to describe a complex mixture of petroleum-based hydrocarbons primarily derived from crude oil. Those compounds are considered as persistent organic pollutants in the terrestrial environment. A wide array of organic amendments is increasingly used for the remediation of TPH-contaminated soils. Organic amendments not only supply a source of carbon and nutrients but also add exogenous beneficial microorganisms to enhance the TPH degradation rate, thereby improving the soil health. Two fundamental approaches can be contemplated within the context of remediation of TPH-contaminated soils using organic amendments: (i) enhanced TPH sorption to the exogenous organic matter (immobilization) as it reduces the bioavailability of the contaminants, and (ii) increasing the solubility of the contaminants by supplying desorbing agents (mobilization) for enhancing the subsequent biodegradation. Net immobilization and mobilization of TPH have both been observed following the application of organic amendments to contaminated soils. This review examines the mechanisms for the enhanced remediation of TPH-contaminated soils by organic amendments and discusses the influencing factors in relation to sequestration, bioavailability, and subsequent biodegradation of TPH in soils. The uncertainty of mechanisms for various organic amendments in TPH remediation processes remains a critical area of future research.

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.

© 2016 Elsevier LtdThe alkaline residue generated from the production of soda ash using the ammonia-soda method has been successfully used in removing phosphorus (P) from aqueous solution. But the accumulation of P-containing solid after P removal is an undesirable menace to the environment. To achieve the goal of recycling, this study explored the feasibility of reusing the P loaded alkaline residue as an amendment for immobilization of lead (Pb) in a shooting range soil. The main crystalline phase and micromorphology of amendments were determined using X-ray diffraction (XRD) and scanning electron microscopy-electron dispersion spectroscopy (SEM-EDS) methods. The toxicity characteristic leaching procedure (TCLP), sequential extraction procedure, and physiologically based extraction test (PBET) were employed to evaluate the effectiveness of Pb immobilization in soil after 45¿d incubation. Treatment with P loaded alkaline residue was significantly effective in reducing the TCLP and PBET extractable Pb concentrations in contrast to the untreated soil. Moreover, a positive change in the distribution of Pb fractions was observed in the treated soil, i.e., more than 60% of soil-Pb was transformed to the residual fraction compared to the original soil. On the other hand, P loaded amendments also resulted in a drastic reduction in phytoavailable Pb to the winter wheat and a mild release of P as a nutrient in treated soil, which also confirmed the improvement of soil quality.

The effluents derived from agricultural industries are major sources of wastewater with significant amounts of nutrients and organic load. Australia's agricultural industries have experienced rapid growth in recent years, with nearly 152 abattoirs, 1798 wine industries, 9256 dairy farms and 1835 piggeries in operation. Agricultural industries require huge volumes of water for processing the farm products towards commercial value and quality. For instance, around 200 L of water required for processing a cattle in an abattoir; around 2.4-2.5 L for producing 1 L of wine; 500-800 L for 1 L of milk; and 12-45 L for sow and litter management in piggeries. As a result, these industries generate huge volumes of wastewater. For example, Australian meat industries produce an average of 4000 m /day wastewater, with high concentration of nitrogen (N) and phosphorus (P). The annual average N and P loads in some of the farm effluents are: abattoir - 722 and 722 t; winery - 280 and 280 t; dairy - 150000 and 110000 t; and piggery - 72895 and 5075t. With Australia's average fertiliser consumption being 1 Mt N and 0.5 Mt P, the huge amounts of N and P from the agricultural effluents can be re-used as a potential alternative for fertiliser usage. Sustainable management of nutrients in the wastewater irrigated soil is a critical step to prevent contamination of both surface and ground-water. The available technologies for wastewater treatment require high investment. Hence, using high biomass-producing plants (e.g., Pennisetum purpureum and Arundo donax) as remediators, which also has the potential to uptake high amount of nutrients and heavy metals, can serve as a cost effective technology. Consequently, the plants used not only act as remediators, but also provide biomass that can also be used for energy generation, paper production and as a feed for animals. © 2012 WIT Press. 3