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Heavy metals are potentially toxic to human life and the environment. Metal toxicity depends on chemical associations in soil. Understanding the chemical association of trace elements in soils amended with biosolids is very important since it determines their availability within rhizosphere and mobility beyond the rhizosphere. A sequential extraction method was used to determine the various chemical associations [labile (exchangeable + sorbed), organic, carbonates, and sulfides] of Cu, Zn, Cd, Cr, and Pb at the end of sorghum-sudan grass growth (65d) in Candler fine sand (pH = 6.8) and in Ogeechee loamy sand (pH = 5.2) amended with wastewater treatment sludge (WWTS) obtained from two different sources at application rates of 0, 24.7, 49.4, 98.8, and 148.2 Mg ha(-1). Results of this study indicated that irrespective of the soil type, Cu, Cd, Cr, and Pb in the labile fractions (exchangeable + sorbed) were in the range of 0-3.0 mg kg(-1) and the amount for Zn was in the range of 0.2-6.6 mg kg(-1). Therefore, their availability to plants and mobility beyond rhizosphere would be substantially low unless further transformations occur from other fractions. Results also indicated that the presence of substantial amounts of trace elements studied were in sulfide (HNO3) fraction and in organic (NaOH) fraction irrespective of soil type with the exception of Pb which was mainly present as carbonate (Na2EDTA) fraction and the remaining Pb equally as sulfide (HNO3) and organic (NaOH) fractions. Furthermore, results indicated that Cd was mainly present as carbonate (Na2EDTA) fraction. Irrespective of soil type, source and rate of WWTS application, summation of quantities of various fractions of all the trace elements studied through sequential extraction procedure were 1 to 25 % lower than that of total recoverable quantities of these trace elements determined on acid digestion described by US EPA method 3050 B. It was further evident that growing sorghum sudan grass for 65-d following the application of WWTS either depleted labile fractions or shifted the solid phases containing the trace elements in soils away from those extractable with more severe reagents, such as 4M HNO3 to those extractable with milder reagents such as dilute NaOH and Na2EDTA.

The explosive compounds hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) are widespread environmental contaminants commonly found as co-pollutants on military training ranges. TNT is a toxic carcinogen which remains tightly bound to the soil, whereas RDX is highly mobile leaching into groundwater and threatening drinking water supplies. We have engineered Arabidopsis plants that are able to degrade RDX, whilst withstanding the phytotoxicity of TNT. Arabidopsis thaliana (Arabidopsis) was transformed with the bacterial RDX-degrading xplA, and associated reductase xplB, from Rhodococcus rhodochrous strain 11Y, in combination with the TNT-detoxifying nitroreductase (NR), nfsI, from Enterobacter cloacae. Plants expressing XplA, XplB and NR remove RDX from soil leachate and grow on soil contaminated with RDX and TNT at concentrations inhibitory to XplA-only expressing plants. This is the first study to demonstrate the use of transgenic plants to tackle two chemically diverse organic compounds at levels comparable with those found on contaminated training ranges, indicating that this technology is capable of remediating concentrations of RDX found in situ. In addition, plants expressing XplA and XplB have substantially less RDX available in aerial tissues for herbivory and potential bioaccumulation., (© 2011 The Authors. New Phytologist © 2011 New Phytologist Trust.)

Background: Speciation analysis is essential when evaluating risks from arsenic (As) exposure. In an oral exposure scenario, the importance of presystemic metabolism by gut microorganisms has been evidenced with in vivo animal models and in vitro experiments with animal microbiota. However, it is unclear whether human microbiota display similar As metabolism, especially when present in a contaminated matrix., Objectives: We evaluated the metabolic potency of in vitro cultured human colon microbiota toward inorganic As (iAs) and As-contaminated soils., Methods: A colon microbial community was cultured in a dynamic model of the human gut. These colon microbiota were incubated with iAs and with As-contaminated urban soils. We determined As speciation analysis using high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry., Results: We found a high degree of methylation for colon digests both of iAs (10 microg methylarsenical/g biomass/hr) and of As-contaminated soils (up to 28 microg/g biomass/hr). Besides the formation of monomethylarsonic acid (MMA(V)), we detected the highly toxic monomethylarsonous acid (MMA(III)). Moreover, this is the first description of microbial thiolation leading to monomethylmonothioarsonic acid (MMMTA(V)). MMMTA(V), the toxicokinetic properties of which are not well known, was in many cases a major metabolite., Conclusions: Presystemic As metabolism is a significant process in the human body. Toxicokinetic studies aiming to completely elucidate the As metabolic pathway would therefore benefit from incorporating the metabolic potency of human gut microbiota. This will result in more accurate risk characterization associated with As exposures.

Soil bacterial population dynamics were examined in several crude-oil-contaminated soils to identify those organisms associated with alkane degradation and to assess patterns in microbial response across disparate soils. Seven soil types obtained from six geographically distinct areas of the United States (Arizona, Oregon, Indiana, Virginia, Oklahoma, and Montana) were used in controlled contamination experiments containing 2% (wt/wt) crude oil spiked with [1-(14)C]hexadecane. Microbial populations present during hydrocarbon degradation were analyzed using both 16S rRNA gene sequence analysis and by traditional methods for cultivating hydrocarbon-oxidizing bacteria. After a 50-day incubation, all seven soils showed comparable hydrocarbon depletion, where >80% of added crude oil was depleted and approximately 40 to 70% of added [(14)C]hexadecane was converted to (14)CO(2). However, the initial rates of hydrocarbon depletion differed up to 10-fold, and preferential utilization of shorter-chain-length n-alkanes relative to longer-chain-length n-alkanes was observed in some soils. Distinct microbial populations developed, concomitant with crude-oil depletion. Phylogenetically diverse bacterial populations were selected across different soils, many of which were identical to hydrocarbon-degrading isolates obtained from the same systems (e.g., Nocardioides albus, Collimonas sp., and Rhodococcus coprophilus). In several cases, soil type was shown to be an important determinant, defining specific microorganisms responding to hydrocarbon contamination. However, similar Rhodococcus erythropolis-like populations were observed in four of the seven soils and were the most common hydrocarbon-degrading organisms identified via cultivation.

Arsenic is a contaminant at more than one-third of all Superfund Sites in the United States. Frequently this contamination appearsto resultfrom geochemical processes rather than the presence of a well-defined arsenic source. Here we examine the geochemical processes that regulate arsenic levels at the Coakley Landfill Superfund Site (NH), a site contaminated with As, Cr, Pb, Ni, Zn, and aromatic hydrocarbons. Long-term field observations indicate that the concentrations of most of these contaminants have diminished as a result of treatment by monitored natural attenuation begun in 1998; however, dissolved arsenic levels increased modestly over the same interval. We attribute this increase to the reductive release of arsenic associated with poorly crystalline iron hydroxides within a glaciomarine clay layer within the overburden underlying the former landfill. Anaerobic batch incubations that stimulated iron reduction in the glaciomarine clay released appreciable dissolved arsenic and iron. Field observations also suggest that iron reduction associated with biodegradation of organic waste are partly responsible for arsenic release; over the five-year study period since a cap was emplaced to prevent water flow through the site, decreases in groundwater dissolved benzene concentrations at the landfill are correlated with increases in dissolved arsenic concentrations, consistent with the microbial decomposition of both benzene and other organics, and reduction of arsenic-bearing iron oxides. Treatment of contaminated groundwater increasingly is based on stimulating natural biogeochemical processes to degrade the contaminants. These results indicate that reducing environments created within organic contaminant plumes may release arsenic. In fact, the strong correlation (>80%) between elevated arsenic levels and organic contamination in groundwater systems at Superfund Sites across the United States suggests that arsenic contamination caused by natural degradation of organic contaminants may be widespread.

The internalized speciation of lead in roots and leaves of Sesbania drummondii, a lead hyperaccumulator, grown in lead nitrate solution was studied using x-ray absorption near-edge structure and extended x-ray absorption fine structure. Lead was predominantly present as lead acetate in both plant tissues. The other dominant forms of accumulation were lead-sulfur compounds. Whereas lead sulfate and sulfide were found in leaves, only lead sulfide was detected in root samples. These observations indicate that S. drummondii is able to biotransform lead nitrate in the nutrient solution to lead acetate and sulfate in its tissues. Complexation with acetate and sulfate may be a lead detoxification strategy in this plant. Transmission-electron microscopy revealed the pattern of lead distribution in and around the cells. Dense distributions of lead grains were detected in root cell walls and plasma membranes, whereas evidence for vacuolar transport of lead was noticed in the stem cells.

The use of green plants to remove, contain, inactivate, or degrade harmful environmental contaminants (generally termed phytoremediation) is an emerging technology. In this paper, an overview is given of existing information concerning the use of plants for the remediation of metal-contaminated soils. Both site decontamination (phytoextraction) and stabilization techniques (phytostabilization) are described. In addition to the plant itself, the use of soil amendments for mobilization (in case of phytoextraction) and immobilization (in case of phytostabilization) is discussed. Also, the economical impacts of changed land-use, eventual valorization of biomass, and cost-benefit aspects of phytoremediation are treated. In spite of the growing public and commercial interest and success, more fundamental research is needed still to better exploit the metabolic diversity of the plants themselves, but also to better understand the complex interactions between metals, soil, plant roots, and micro-organisms (bacteria and mycorrhiza) in the rhizosphere. Further, more demonstration experiments are needed to measure the underlying economics, for public acceptance and last but not least, to convince policy makers.

Development of degradation rate information for crop protection products in soil is typically a time consuming and costly process. Therefore, development of methodology that would allow extrapolation of limited degradation information to wider field conditions in a predictive fashion would be desirable. This study presents an approach that uses a modified heat unit model to estimate organic compound degradation time using limited datasets. The model requires daily soil or air temperature and volumetric water content. Predictions based on the model for three different compounds in five different field studies were within 80% of measured values based on soil analysis. Results from this research indicate that the model was able to predict compound half-life values across all sites with r2 = 0.99.

The use of plant based systems in hazardous waste management or site clean up is growing at a rapid rate. Major hurdles to implementation will be encountered by proponents if essential regulatory policies and regulations are not understood or addressed early in the project development. Understanding the regulatory requirements or issues as they relate to innovative clean up approaches such as phytotechnologies are critical to the successful implementation and long-term monitoring of these technologies. This chapter will address the issues that regulators may have in applying phytotechnologies to site conditions or contaminants, designing phytoremediation projects, monitoring or maintaining the systems for the long-term, establishing performance criteria, and demonstrating achievement of performance goals.

Application of herbicides in autumn is of interest to land managers who seek to reduce the number of field operations during spring in the northern Corn Belt. A limited number of herbicides, however, posses the physical characteristics that are required to minimize loss from soil over winter. This study examined the fate of one of these herbicides, metolachlor, during three consecutive winters (1994-1995, 1995-1996, and 1996-1997) near Morris, MN. Metolachlor was applied to the top 5 cm of a clay loam that was packed into a 1.8-m long plastic pipe. The pipe was then set inside a larger diameter 1.8-m long plastic pipe that was buried vertically in the field. The gap between the pipes was insulated along the sides and sealed at the top; this configuration allowed collection of leachate and extraction of the smaller diameter pipe while the field soil was frozen. The experimental design was replicated thrice with sample date (date that the smaller diameter pipes were extracted from the field) as the main treatment. Pipes were extracted from the field at least twice during winter and sectioned into 2 cm or larger increments. The soil contained within these sections was then analyzed for metolachlor. Downward movement of metolachlor occurred in the soil profile during the autumn, but only in 1995. This movement was likely caused by exclusion during pore ice formation as the soil froze. At the time of complete soil thaw in spring, the majority of metolachlor was still detected in the zone of application (0-5 cm depth). Some metolachlor, however, was detected 1 to 3 cm below the zone of application in all three years. Downward movement during thaw was due primarily to infiltration of snowmelt and rain. Metolachlor was most vulnerable to degradation during spring, but some loss occurred in autumn prior to freeze-up. This study suggests that autumn-applied metolachlor moves little in a repacked clay loam profile during winter. Further studies are warranted in evaluating movement under a range of soil physical properties and management practices.

Phytoremediation is an attractive treatment technology for many contaminated sites due to its cost effectiveness and public acceptance. We present a sensitivity analysis of important parameters from a screening level model for phytoremediation by grass species of weathered petroleum-contaminated sites. The conceptual framework is that root movement through contaminated soil will enhance contaminant biodegradation by providing a local environment more favorable for petroleum degrading microorganisms--the so-called rhizosphere effect. Common questions in phytoremediation are, "What species should be planted?" and "What management practices should be followed?" These choices may affect degradation kinetics, root biomass (and therefore rhizosphere volume), and the root turnover. Important model parameters are the rate constants, rhizosphere volume, and the rate of root turnover. We present a sensitivity analysis with the aim of identifying the most important factors for improving phytoremediation effectiveness. For simulations of the phytoremediation of weathered diesel range organics, our results indicate that annual species, with higher root turnover, are preferred over perennial species with the caveat of equal degradation rate constants, that is, no species-dependent effects. In addition, the results suggest that the management of nonrhizosphere soil could play an important role in the overall effectiveness of phytoremediation. Finally, the effect of increasing root biomass or increasing the rhizosphere thickness is approximately equivalent with respect to the ultimate removal of the contaminants.

This paper proposes the hypothesis that microbial life chemically reduces levels of nitrogen (N(2)) and phosphorus (P) that are toxic and threaten human health and safety. Bio-remediation uses microorganisms to decontaminate a polluted system, in situ, requiring a minimal amount of space and equipment. Data strongly suggest that bio-stimulation can assist one microbe to multiply up to one billion microorganisms in 24 hours. Biochemical literature postulates that microbial life chemically biodegrades nitrates by one of two methods: (1) assimilative reduction; or (2) dissimilative reduction, also known as denitrification. Assimilative reduction results in construction of microbial cell walls, cell membranes and various forms of amino acids. It is proposed that denitrification includes the venting-off of the excess amounts of N(2)not required by the soil or needed for additional microbial development. Nitrate reduction by way of denitrification is a functional part of anaerobic respiration. Alternatively, the denitrification process supports oxidative phosphorylation, a mechanism similar to aerobic respiration. Thus, denitrification and phosphorylation may be considered as forms of respiration., (Copyright 2000 Harcourt Publishers Ltd.)

Sucrose polyesters (SPEs) were applied to soil at rates equivalent to 1062 to 1293 kg per hectare and incubated over periods of 100 to 403 days at 20 +/- 2 degrees C in darkness and at a soil moisture of 40% of the maximum water holding capacity. All applied forms of SPEs were aerobically biodegraded to some degree in both American and German soil. However, the mineralization rates varied considerably and were dependent on both SPE and soil type. For example, sucrose octaoleate underwent slow and limited mineralization in the German soils Speyer and Borstel as well as in the American soil Madera, reaching only 6.9-18.4% mineralisation after over 400 days incubation. The same material in the American soils Hollande, Thermal and Uvalde as well as in the German soil Speicherkoog, reached 35-52% after the same incubation period. Of the SPEs most realistic for use in food products, the more liquid (i.e. with the least saturated fatty acids) underwent the most rapid and extensive mineralization. However, the mineralization rates for these materials were distinctly lower than the corresponding ones for sucrose octaoleate. In all cases the extent of mineralization of the SPEs in soil was significantly lower than that of a control fat (synthetic triglyceride mixture HB307), which typically underwent over 50% mineralization in 60 days.

The Hazardous Substances Data Bank (HSDB), a factual data bank on the National Library of Medicine's (NLM) TOXNET (Toxicology Data Network) online system, provides information in areas such as chemical substance identification, chemical and physical properties, safety and handling, toxicology, pharmacology, environmental fate and transformation, regulations, and analytical methodology. This article discusses how environmental fate data is handled in HSDB.