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The imprints of fireworks displays on the adjacent water body were investigated from the perspective of cogeneration of black carbon, metals and perchlorate (ClO4−). In particular, the mixing and dissipation of ClO4− were studied at Oak Lake, Lincoln, Nebraska, following fireworks displays in 2015 and 2016. Following the display, ClO4− concentration in the water increased up to 4.3 μg/L and 4.0 μg/L in 2015 and 2016, respectively. A first-order model generally provided a good fit to the measured perchlorate concentrations from which the rate of dissipation was estimated as 0.07 d−1 in 2015 and 0.43 d−1 in 2016. SEM images show imprints of soot and metal particles in aerosol samples. EDS analysis of the lake sediment confirmed the presence of Si, K, Ca, Zn and Ba, most of which are components of fireworks. The δ13C range of −7.55‰ to −9.19‰ in the lake water system closely resembles fire-generated carbon. Cogeneration of black carbon and metal with perchlorate was established, indicating that ClO4− is an excellent marker of fireworks or a burning event over all other analyzed parameters. Future microcosmic, aggregation and column-based transport studies on black carbon in the presence of perchlorate and metals under different environmental conditions will help in developing transport and fate models for perchlorate and black carbon particles.

by Jaehong Shim, Manish Kumar, Ritusmita Goswami,Payal Mazumder, Byung-Taek Oh and Patrick J. Shea

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated Fe(II) phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron Fe(II)/Fe(III) minerals. This was accomplished by quantifying the effects of initial Fe(II) concentration, pH, and the presence of aquifer solids (Fe(III) phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing Fe(II) concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous Fe(II) during HE treatment under anaerobic conditions. Geochemical modeling also predicted Fe(II) activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated Fe(II)/Fe(III) minerals in aqueous Fe(II) solutions play in the transformation of high explosives.

Activated carbon (AC) can help overcome toxicity of pollutants to microbes and facilitate soil bioremediation. We used this approach to treat a Histosol and an Alluvial soil historically contaminated with PCB (4190 and 1585 mg kg(-1), respectively; primarily tri-, tetra- and pentachlorinated congeners). Results confirmed PCB persistence; reductions in PCB extractable from control and AC-amended soils were mostly due to a decrease in tri- and to some extent tetrachlorinated congeners as well as formation of a bound fraction. Mechanisms of PCB binding by soil and AC were different. In addition to microbial degradation of less chlorinated congeners, we postulate AC catalyzed dechlorination of higher chlorinated congeners. A large decrease in bioavailable PCB in AC-amended soils was demonstrated by greater clover germination and biomass. Phytotoxicity was low in treated soils but remained high in untreated soils for the duration of a 39-month experiment. These observations indicate the utility of AC for remediation of soils historically contaminated with PCB.

Zerovalent iron (Fe 0 , ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe 0 (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24 h also restored ZVI reactivity, resulting in complete degradation within 8 h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl − and Br − was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br − was present in solution.

Soil properties impact pesticide persistence. Because these characteristics operate together in situ, identification of their clustered associations can help explain pesticide fate. Factor analysis was used to reduce the dimensionality of soil characteristics by grouping them into clustered independent factors, which were then related to the mineralization of atrazine and selected degradation intermediates. A Sharpsburg silty clay loam, Ortello sandy loam, and Hord silt loam were inoculated with a Hord soil that had a high capacity for atrazine mineralization. The soils were spiked with 14C-radiolabeled atrazine, deethylatrazine, hydroxyatrazine, N-isopropylammeline, N-isopropylammelide or cyanuric acid and sampled during incubation for 80 d (atrazine) or 40 d (degradation intermediates) at 22°C. Low mineralization in uninoculated soils demonstrated that the absence of atrazine-mineralizing microorganisms was most limiting. In inoculated soils, regression analysis indicated mineralization of atrazine (R2 ...

Dicamba (3,6-dichloro-2-methoxybenzoicacid) is a highly mobile pre- and post-emergence herbicide that has been detected in ground water. We determined the potential of zerovalent iron (Fe 0 ) to remediate water contaminated with dicamba and its common biological degradation product, 3,6-dichlorosalicylic acid (DCSA). Mixing an aqueous solution of 100 lM dicamba with 1.5% Fe 0 (w/v) resulted in 80% loss of dicamba within 12 h. Solvent extraction of the Fe 0 revealed that dicamba removal was primarily through adsorption; however when the Fe 0 was augmented with Al or Fe(III) salts, dicamba was dechlorinated to an unidentified degradation product. In contrast to dicamba, Fe 0 treatment of DCSA resulted in removal with some dechlorination observed. When DCSA was treated with Fe 0 plus Al or Fe(III) salts, destruction was 100%. Extracts of this Fe 0 treatment contained the same HPLC degradation peak observed with the Fe 0 + Al or Fe(III) salt treatment of dicamba. Molecular modeling suggests that differences in removal and dechlorination rates between dicamba and DCSA may be related to the type of coordination complex formed on the iron surface. Experiments with 14 C-labeled dicamba confirmed that Fe-adsorbed dicamba residues are available for subsequent biological mineralization (11% after 125 d). These results indicate that Fe 0 could be potentially used to treat dicamba and DCSA-contaminated water. 2003 Elsevier Ltd. All rights reserved.

Activated carbon can be used to decrease 2,4,6-trinitrotoluene (TNT) toxicity and promote bioremediation of highly contaminated soil. Adding activated carbon at 0.25, 0.75, and 1.0% (w/w) to Sharpsburg soil contaminated with 500, 1,000, and 2,000 mg TNT/kg decreased concentrations of TNT and its transformation products in soil solution to 5 mg/L or less, resulting in low toxicity to corn plants (Zea mays L.) and soil microorganisms. As much as 50% of the added TNT was rapidly bound to the soil-activated carbon matrix. Simultaneous accumulation of 2,4,6-trinitrobenzaldehyde (TNBAld) indicated that the activated carbon promoted oxidation of TNT. Some of the TNBAld was further oxidized to 1,3,5-trinitrobenzene, followed by reduction to 3,5-dinitroaniline. Reversibly bound TNT was gradually transformed to 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene, and both were bound to the soil-activated carbon matrix. The transformation and binding of TNT to soil were further promoted by incorporating shredded corn plants after growing for 52 d in the activated carbon-amended soil. After 120 d, these amendments reduced extractable TNT and transformation products by 91% in soil containing 2,000 mg TNT/kg, compared to 55% in unamended soil. These results demonstrate the potential use of activated carbon in combination with plants to promote in situ bioremediation of soils highly contaminated with explosives.

The capacity of UV-catalyzed Fenton oxidation to destroy mono-, di- and trinitrotoluenes (MNT, DNT, TNT) in aqueous solution was evaluated. Mononitrotoluenes were rapidly destroyed by Fenton oxidation in the dark at pH 3.0 or by UV/Fenton oxidation without pH adjustment. UV/Fenton oxidation at pH 3.0 was most effective for DNT and TNT destruction. The number and position of nitro substitutions influenced oxidation rate: 2-nitrotoluene > 4-nitrotoluene > 2,4-dinitrotoluene > 2,6-dinitrotoluene > 2,4,6-trinitrotoluene. UV/Fenton oxidation mineralized more than 95% of the TNT in aqueous extracts of contaminated soil. While dissolved humic and fulvic acids differentially influenced destruction rate, total TNT destroyed after 4 h was not greatly affected. Our results demonstrated that UV-catalyzed Fenton oxidation effectively destroyed nitrotoluenes in water and aqueous extracts of contaminated soil.

It is estimated that explosives contaminate approximately 0.82 million cubic metres of soil at former military installations throughout the US; major contaminants often include 2,4,6-trinitrotoluene (TNT) and its degradation products. At some sites, phytoremediation may be a viable option to incineration or other costly remediation treatments. Grasses may be particularly suited for remediation because of their growth habit and adaptability to a wide range of soil and climate conditions. We characterized the effects of TNT on germination and early seedling development of switchgrass and smooth bromegrass to evaluate their potential use on contaminated sites. Switchgrass and smooth bromegrass seeds were germinated in nutrient-free agar containing 0 to 60 mg TNT litre(-1). Smooth bromegrass germination decreased as TNT concentration increased, while switchgrass germination was unaffected by TNT. Concentrations up to 15 mg TNT litre(-1) did not affect switchgrass root growth rate, but bromegrass root growth was reduced at TNT concentrations above 7.5 mg litre(-1). At 7.5 mg TNT litre(-1), however, shoot growth rate was reduced in both species. Examination at 20-fold magnification revealed switchgrass radicles were unaffected by TNT, while smooth bromegrass radicles appeared slightly swollen. Results indicate switchgrass is more tolerant of TNT than smooth bromegrass, but the establishment of both species may be limited to soil containing less than 50 mg kg(-1) of extractable TNT.

Contaminated water and soil at active or abandoned munitions plants is a serious problem since these compounds pose risks to human health and can be toxic to aquatic and terrestrial life. Our objective was to determine if zero-valent iron (Fe(0)) could be used to promote remediation of water and soil contaminated with 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). As little as 1% Fe(0) (w/v) removed 70 mg TNT litre(-1) from aqueous solution within 8 h and removed 32 mg RDX litre(-1) within 96 h. Treating slurries (1:5 soil:water) of highly contaminated soil (5200 mg TNT and 6400 mg RDX kg(-1) soil) from the former Nebraska Ordnance Plant (NOP) with 10% Fe(0) (w/w soil) reduced CH(3)CN-extractable TNT and RDX concentrations below USEPA remediation goals (17.2 mg TNT and 5.8 mg RDX kg(-1)). Sequential treatment of a TNT-contaminated solution (70 mg TNT litre(-1) spiked with (14)C-TNT) with Fe(0) (5% w/v) followed by H(2)O(2) (1% v/v) completely destroyed TNT and removed about 94% of the (14)C from solution, 48% of which was mineralized to (14)CO(2) within 8 h. Fe(0)-treated TNT also was more susceptible to biological mineralization. Our observations indicate that Fe(0) alone, Fe(0) followed by H(2)O(2), or Fe(0) in combination with biotic treatment can be used for effective remediation of munitions-contaminated water and soil.

Nitrate and atrazine (ATR) occur in combination in some drinking-water supplies and might react to form N-nitrosoatrazine (NNAT), which is reportedly more toxic than nitrate, nitrite, or ATR. Current evidence from population-based studies indicates that exposure to nitrate, nitrite, and nitrosatable compounds increases the risk of congenital defects and/or rate of embryo lethality. To test the hypothesis that NNAT induces malformations during embryogenesis, chicken embryos were examined for lethality and developmental abnormalities after treating fertilized eggs with 0.06-3.63 μg NNAT. After 5 d of incubation (Hamburger and Hamilton stage 27), 90% of embryos in NNAT-treated eggs were alive, of which 23% were malformed. Malformations included heart and neural-tube defects, caudal regression, gastroschisis, microphthalmia, anophthalmia, and craniofacial hypoplasia. The findings from this investigation suggest further studies are needed to determine the mechanisms underlying NNAT-induced embryotoxicity.

Phenol and heavy metals in petroleum waste are environmental and human health concerns, but physicochemical removal is often cost-prohibitive and can produce toxic secondary products and treatment residues. An environmentally benign alternative combines corn cob silica with alginate and immobilized bacteria into beads for treating contaminated water. The concentration of phenol was decreased >92% by Pseudomonas putida YNS1 on aliginate-silica beads (2%, w/v) after equilibrating for 96h with water containing 214mg phenol/L. GC-MS analysis indicated formation of benzoquinone and other polar products. Beads containing corn cob silica decreased Cu concentrations by 84-88% and Cd by 83-87% within 24h. In a mixture of 114mg phenol, 43mg Cu and 51mg Cd/L, phenol removal (93% within 96h) only occurred with beads containing the silica and bacterial strain. Beads containing corn cob silica removed >97% of the Cu and >99% of the Cd, critical for reducing toxicity to the bacteria. Beads with the immobilized strain removed phenol when zeolite was used instead of corn cob silica, but beads with silica were more effective for Cu and Cd removal. Results show the potential of corn cob silica combined with alginate and immobilized bacteria for removing phenol and heavy metals from contaminated water.

A secondary analysis of 1999-2002 Nebraska case-control data was conducted to assess the risk of non-Hodgkin lymphoma (NHL) associated with exposure to nitrate- and atrazine-contaminated drinking water. Water chemistry data were collected and weighted by well contribution and proximity of residence to water supply, followed by logistic regression to determine odds ratios (OR) and 95% confidence intervals (CI). We found no association between NHL risk and exposure to drinking water containing atrazine or nitrate alone. Risk associated with the interaction of nitrate and atrazine in drinking water was elevated (OR, 2.5; CI, 1.0-6.2). Risk of indolent B-cell lymphoma was higher than risk of aggressive B-cell lymphoma (indolent: OR, 3.5; CI, 1.0-11.6 vs. aggressive: OR, 1.9; CI, 0.6-5.58). This increased risk may be due to in vivo formation and subsequent metabolism of N-nitrosoatrazine. A larger study is warranted to confirm our findings.

The watershed provides a physical basis for establishing linkages between aquatic contaminants, environmental health and human health. Current attempts to establish such linkages are limited by environmental and epidemiological constraints. Environmental limitations include difficulties in characterizing the temporal and spatial dynamics of agricultural runoff, in fully understanding the degradation and metabolism of these compounds in the environment, and in understanding complex mixtures. Epidemiological limitations include difficulties associated with the organization of risk factor data and uncertainty about which measurable endpoints are most appropriate for an agricultural setting. Nevertheless, it is our contention that an adoption of the watershed concept can alleviate some of these difficulties. From an environmental perspective, the watershed concept helps identify differences in land use and application of agrichemicals at a level of resolution relevant to human health outcomes. From an epidemiological perspective, the watershed concept places data into a construct with environmental relevance. In this perspectives paper, we discuss how the watershed can provide a conceptual framework for studies in environmental and human health.

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. Zerovalent iron (Fe0) has been shown to promote reductive dechlorination and nitro group reduction of a wide range of contaminants in soil and water. We employed Fe0 for on-site treatment of soil containing > 1000 mg metolachlor, > 55 mg alachlor, > 64 mg atrazine, > 35 mg pendimethalin, and > 10 mg chlorpyrifos kg(-1). While concentrations were highly variable within the windrowed soil, treatment with 5% (w/w) Fe0 resulted in > 60% destruction of the five pesticides within 90 d and increased to > 90% when 2% (w/w) Al2(SO4)3 was added to the Fe0. GC/MS analysis confirmed dechlorination of metolachlor and alachlor during treatment. Our observations support the use of Fe0 for ex situ treatment of pesticide-contaminated soil.

Activated carbon can remove 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB) from aqueous solution and promote oxidation of TNT. After equilibrating a 0.35 mM TNT solution with activated carbon (0.2-1% w/v), HPLC and GC/MS analysis confirmed the presence of 2,4,6-trinitrobenzaldehyde (TNBAld) and 2,4,6-trinitrobenzene (TNB), and provided strong evidence supporting 2,4,6-trinitrobenzyl alcohol (TNBAlc) as an intermediate of TNT oxidation. After 6 d, TNT and its oxidation products were strongly bound to the activated carbon, while TNB was extractable with acetonitrile. Observations indicate that activated carbon catalyzes TNT oxidation to TNBAlc, which is readily oxidized to TNBAld and TNB in the absence of activated carbon under dark conditions. While adsorbed TNB was extractable with acetonitrile, activated carbon promoted rapid TNT oxidation and formation of unextractable residues. Strong binding is attributed to catalyzed oxidation of the TNT methyl group, probably through a free radical mechanism, and subsequent chemisorption of oligomers and polymerized products that are not desorbed from micropores. Our observations indicate TNT oxidation and bound residue formation after sorption by activated carbon increases the effectiveness of activated carbon to decontaminate water.

Cost-effective and environmentally acceptable methods are needed to remediate munitions-contaminated soil. Some perennial grass species are tolerant of soil contaminants and may promote remediation because of their high water use and extensive fibrous root systems. The effects of 2,4,6-trinitrotoluene (TNT) and its reduction product, 4-amino-2,6-dinitrotoluene (4ADNT), on germination and early seedling development of tall fescue (Festuca arundinacea Schreb.) were determined. Tall fescue seeds were germinated in nutrient-free agar containing 0-60 mg TNT litre(-1) or 0-15 mg 4ADNT litre(-1). Germination decreased linearly as TNT concentration increased but was not significantly affected by 4ADNT at these concentrations. Concentrations less than 30 mg TNT litre(-1) or 7.5 mg 4ADNT litre(-1) had little effect on seedling growth and development. Higher TNT or 4ADNT concentrations substantially delayed seedling development, caused abnormal radicle tissue development, and reduced secondary root and shoot growth. Seedling respiration rates decreased linearly with increasing TNT concentration. Experiments indicate that tall fescue may be grown in soils that maintain soil solution concentrations of 30 mg TNT litre(-1) or less.

Soil properties and retention mechanisms affecting the relative mobility of aniline, benzoic acid, and toluene in Cecil sandy loam (clayey, kaolinitic, thermic Typic Hapludults), Holdredge silt loam (fine-silty, mixed, mesic Typic Argiustolls), Sharpsburg silty clay loam (fine, montmorillonitic, mesic Typic Argiudolls), and Valentine fine sand (mixed, mesic Typic Ustipsamments) were delineated in laboratory studies. The effect of the synthetic organic compounds (SOCs) was also determined on effective organic campounds (SOCs) was also determined on effective cation exchange capacity (ECEC) of the soils. Benzoic acid was most mobile of the SOCs but was retained in the Cecil soil by hydrogen bonds to Fe oxides. Toluene was least mobile and probably was hydrophobically sorbed to all soils. Aniline was electrostatically retained in protonated form to organic and inorganic exchange sites of the soils and reduced the ECEC of aniline-treated Holdredge and Sharpsburg soils.

In May 1981, acephate (O,S-dimethyl-acetylphosphoramidothioate) was applied at 0.85 kg [a.i. (active ingredient)]/ha in a ponderosa pine (Pinus ponderosa Douglas) forest of northern Arizona for suppression of a pandora moth (Coloradia pandora Blake) infestation. Brain cholinesterase (ChE) activity was determined in six species of wild birds, and brain and liver residues were determined in five species. Brain ChE was not inhibited on the day of spraying, but ChE was significantly inhibited 2 d after acephate application. The species of birds which presumably had the smallest territories and therefore would be more likely to be confined to the relatively small spray plots (about 250 ha) had the greatest ChE inhibition, both in magnitude and in numbers of birds with inhibition. Acephate and methamidophos (O,S-dimethyl-phosphoramidothioate) residues in brain and liver were highest on the day of spraying and decreased to undetectable concentrations 14 d after application. No correlation between brain ChE activities and brain or liver residue concentrations was found. The results of this study suggest that brain ChE inhibition found after acephate application is a better indicator of exposure than is tissue residue analysis. Brain ChE inhibition is probably due to a metabolite of acephate that is not detected by the methods used. Birds exposed to acephate in the wild may suffer as yet undetermined sublethal effects, but it is unlikely that acephate applied at 0.85 kg/ha or less will kill many birds.

American kestrels (Falco sparverius) were given a single acute dose of the insecticide acephate (50 mg/kg), either alone or superimposed on a moderate background level of DDE (35 ppm wet-weight in carcass homogenates). The combined DDE-acephate treatment was chosen to resemble exposure conditions for wild avian predators whose tissues may contain appreciable sublethal accumulations of organochlorine insecticides. Acephate produced similar cholinesterase (ChE) depression in both groups (39% median depression of serum ChE, 25% median brain ChE depression). Predatory vigilance and attack behavior, measured by frequency and speed of responses to a familiar moving prey model, were not altered by acephate administration in either group. Neither DDE nor acephate at these low dosages has appreciable effects on kestrels' responses to a prey stimulus with which they have had extensive prior contact.

The calculated, acute oral LD50 of acephate and methamidophos to dark-eyed juncos (Junco hyemalis) was 106 mg/kg and 8 mg/kg, respectively. Brain cholinesterase (ChE) activity in birds that died after acephate poisoning was depressed 80% below that of control birds. Birds that died of acute methamidophos poisoning had brain ChE depression of 60%. The birds killed by acephate had brain acephate residue concentrations greater than 2 mg/kg and methamidophos concentrations usually greater than 0.25 mg/kg. Eighty percent of the birds killed with methamidophos had brain methamidophos concentrations greater than 0.1 mg/kg. The five-day feeding LC50 for acephate was 1485 mg/kg. Brain ChE activities of birds which died early in the study were less depressed (51.5%) than those which died at a later date (69.6%). Brain residues of acephate and methamidophos were lower in these birds than in the birds of the acute oral LD50 studies. Brain ChE activity returned to normal within three days after the birds received a single sublethal dose of acephate. These studies indicate that the amount of acephate needed to produce the ChE depression found in other investigations in most dark-eyed juncos exposed to forest applications of insecticide is about one-fifth of the LD50; however, in a few birds the ChE activity may be depressed to near lethal levels.

Determination de l'importance de la depression de la cholinesterase cerebrale associee a diverses concentrations d'acephate, et du temps necessaire pour le retour de cette cholinesterase a la normale apres cette derpession. Etablissement des concentrations tissulaires d'acephate associees au parametre ci-dessus. Etude identique realisee avec le methamidophos a cause de la possibilite de ldesacylation de l'acephate en methamidophos