Nitrate Remediation: The Importance of the Advanced Nitrogen Cycle in Remedy Selection

Nitrate has become an increased regulatory concern due to gradual deterioration of surface and groundwater quality primarily related to widespread fertilizer use. Remediation of nitrate is a relatively straightforward process; however, nitrate impacts to groundwater are often a symptom of a sustained source from another nitrogen form (e.g., ammonia, ammonium nitrate, urea), analogous to how nonaqueous phase liquid can serve as a long‐term source of volatile organic compounds in groundwater. Understanding the various nitrogen transformation reactions when selecting, implementing, or documenting a remedy associated with nitrate is therefore critical to successfully reaching remedial endpoints. Case studies are presented that highlight in situ remedial successes with nitrogen‐impacted groundwater and discuss the key considerations that should be factored into remedy application. ©2015 Wiley Periodicals, Inc.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Fractionation and extractability of sulfur, iron and trace elements in sulfidic sediments

This study describes iron and sulfur fractionation, and the related extractability of selected trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) in estuarine sediments. The sediments were sulfidic, with moderately high concentrations of pore-water sulfide (200-600 micromol l(-1)) and acid-volatile sulfide (AVS; 9.9-129 micromol g(-1)). Pyrite-S concentrations increased with depth, with 63-251 micromol g(-1) at site W1 and 312-669 micromol g(-1) at site W2. The degree of sulfidisation was generally high (>80%), indicating that Fe may be limiting pyrite accumulation. The ratios of AVS to pyrite-S increased with sediment depth, as expected for the pyritisation of solid-phase AVS. Cadmium, Pb and Zn extractability in 1M HCl indicated that these elements are not significantly sequestered during pyritisation, whereas sequestration may be important for As, Cu and possibly Ni. Extractability trends for Cr suggest that diagenesis in sulfidic sediments may enhance Cr reactivity. Overall, replacement of AVS by pyrite during diagenesis may enhance the reactivity of Cd, Cr, Pb and Zn, whereas As, Cu and possibly Ni may be rendered less reactive.     

A Framework for Geographically Sensitive and Efficient Recycling Networks

This paper has three primary objectives. First, it seeks to demonstrate that recycling is an important component of sustainable human systems, particularly in the case of electronics, where environmental impacts of disposal are potentially severe. Second, it presents a methodology that could be used to estimate the volumes of electronics or other consumer durable goods that are available for recycling. Third and last, it illustrates, through a case study of Atlanta focused on computers, that metropolitan areas may fruitfully be viewed as opportune centres from which to mine, recycle and reuse cast-off electronic goods. From an environmental and economic development policy perspective, doing so presents an important opportunity to provide new economic opportunities in the most distressed portions of metropolitan areas which have been disproportionately impacted by previous environmentally destructive industrialization practices.     

Improved understanding of hyperaccumulation yields commercial phytoextraction and phytomining technologies

This paper reviews progress in phytoextraction of soil elements and illustrates the key role of hyperaccumulator plant species in useful phytoextraction technologies. Much research has focused on elements which are not practically phytoextracted (Pb); on addition of chelating agents which cause unacceptable contaminant leaching and are cost prohibitive; and on plant species which offer no useful phytoextraction capability (e.g., Brassica juncea Czern). Nickel phytoextraction by Alyssum hyperaccumulator species, which have been developed into a commercial phytomining technology, is discussed in more detail. Nickel is ultimately accumulated in vacuoles of leaf epidermal cells which prevents metal toxicity and provides defense against some insect predators and plant diseases. Constitutive up-regulation of trans-membrane element transporters appears to be the key process that allows these plants to achieve hyperaccumulation. Cadmium phytoextraction is needed for rice soils contaminated by mine wastes and smelter emissions with 100-fold more soil Zn than Cd. Although many plant species can accumulate high levels of Cd in the absence of Zn, when Cd/Zn>100, only Thlaspi caerulescens from southern France has demonstrated the ability to phytoextract useful amounts of Cd. Production of element-enriched biomass with value as ore or fertilizer or improved food (Se) or feed supplement may offset costs of phytoextraction crop production. Transgenic phytoextraction plants have been achieved for Hg, but not for other elements. Although several researchers have been attempting to clone all genes required for effective hyperaccumulation of several elements, success appears years away; such demonstrations will be needed to prove we have identified all necessary processes in hyperaccumulation.     

Trends In Regulatory Acceptance Of Risk-Based Cleanup Goals And Natural Attenuation For Site Closure

Since 1994, there has been a significant regulatory shift toward risk-based cleanup standards based on the site-specific risk of the more toxic and mobile compounds; namely, benzene, ethyl benzene, toluene, and xylene (BTEX). This regulatory shift has been accompanied by a growing acceptance of natural attenuation as an important component of petroleum site remediation. This article briefly reviews regulatory progress toward risk-based remediation and describes the successful application of risk-based corrective actions (RBCAs) at two fuel contaminated sites on Air Force installations. By developing site-specific cleanup goals, and combining natural attenuation, source reduction, and land use controls, innovative risk-based closure plans have been implemented on these sites.