Dissolution rates of three high explosive compounds: TNT,RDX, and HMX

Incidental exposure to high explosive compounds can cause subtle health effects to which a population could be more susceptible than injury by detonation. Proper source characterization is a key requirement in the conduct of risk assessments. For nonvolatile solid explosives, dissolution is one of the primary mechanisms that controls fate and transport, resulting in exposure to these compounds remote from their source. To date, information describing dissolution rates of high explosives has been sparse. The objective of this study was to determine the dissolution rates of three high explosive compounds, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), in dilute aqueous solutions as a function of temperature, surface area, and energy input. To determine each variable's impact on dissolution rate, experiments were performed where one variable was changed while the other two were held constant. TNT demonstrated the fastest dissolution rate followed by HMX and then RDX. Dissolution rate correlation equations were developed for each explosive compound incorporating the three aforementioned variables, independently, and collectively in one correlation equation.     

Identification of dimethylchloroarsine near a former herbicide factory by headspace solid-phase microextraction gas chromatography-mass spectrometry

The application of an improved method based on multidetector gas chromatography to the determination of trace levels of organoarsines in complex matrices is described. The method using headspace-mode solid-phase microextraction (SPME) was applied to a carefully sampled and preserved freshwater sediment core obtained from central Green Bay, Lake Michigan. The sediment core was collected and fractionated in an inert atmosphere. A carboxen/ polydimethylsiloxane-coated SPME fiber (85 microm film thickness) was equilibrated (n = 4) for 60 min at 25 degrees C in the headspace of the sample vessel before introduction to the chromatograph. Conventional quadrupole ion trap mass spectrometry (electron impact ionization), electron capture detection, and pulsed flame photometric detection (arsenic mode) were employed for structure elucidation. A heretofore unidentified species in this region, dimethylchloroarsine (DMCA). was identified. The mass spectrum for DMCA is interpreted based on the observed fragmentation pattern. A bimodal vertical distribution of DMCA in the sediment core sample was observed and its interpretation based on Pb-210 dating is reported.     

Dibenzo-p-dioxins in the environment from ceramics and pottery produced from ball clay mined in the United States

Processed ball clay samples used in the production of ceramics and samples of the ceramic products were collected and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs). The processed ball clay had average PCDD concentrations of 3.2 ng/g toxic equivalents, a congener profile, and isomer distribution consistent with those found previously in raw ball clay. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. The final fired ceramic products were found to be free of PCDDs/PCDFs at the LODs. A consideration of the conditions involved in the firing process suggests that the PCDDs, if not destroyed, may be released to the atmosphere and could represent an as yet unidentified source of dioxins to the environment. In addition, the PCDDs in clay dust generated during manufacturing operations may represent a potential occupational exposure.     

Changes in water quality after addition of sea salts to fresh water: implications during toxicity testing

Sea salts (seven brands from six commercially-available sources) were dissolved in water to develop 30 g/l solutions, and selected water quality characteristics were then monitored for 96 h. One or more water quality characteristics changed significantly during the 96 h period in six of the reconstituted sea salts. Measured characteristics of sea water diluted to 30 g/l demonstrated no changes during the observation period. The sea salts from different sources also demonstrated differences in absolute concentrations of some characteristics measured. Application of the Biotic Ligand Model to predict copper toxicity to the bivalve Mytilus edulis in solutions of the salts tested yielded 96-h median-lethal concentrations that ranged from 2 to 13 μg/l. Since water quality affects toxicity of many environmental pollutants, the source of the sea salt and equilibration time should be considered when planning toxicity tests.     

Effects of dimethoate on honey bee foraging

Collection by honey bees of sucrose solutions treated with dimethoate continued uninterrupted until 2.9–3.9 μg/bee had been accumulated. This self-limiting dose was 20–25 times the oral LD₅₀ for honey bees. Therefore a mean of 45 collection trips involving 1 ppm dimethoate or 11 trips involving 5 ppm was possible before foraging ceased. Losses in pollinator effectiveness and adult and larval mortality are likely to result from dimethoate contamination of nectar.     

A remote in situ monitor based on continuous flow analysis for the quantitation of sub-micromolar levels of hexavalent chromium in natural waters

We describe the design, optimization, and application of a small, lightweight, deployable monitoring instrument for accurately measuring parts-per-billion levels of hexavalent Cr in surface waters at hourly intervals. The monitor quantifies Cr(vi) using a standard molecular absorbance spectroscopic method, i.e. by formation of a complex with 1,5-diphenylcarbazide (DPC). The continuous flow analysis (CFA) design uses narrow conduits (0.90 mm) that are hot-forged onto poly(methyl methacrylate) ('Plexiglas') plates based on the method of Jannasch et al.(Anal. Chem., 1994, 66, 3352). The sample stream is drawn through the manifold at 25 microl min(-1) using a mini-peristaltic pump; osmotic pumps (10 microl h(-1)) are used to continuously inject reagent (2.0 mM DPC, 0.60 M HNO(3), 5.0% w/v acetone, and 0.10% w/v Brij-35) and to periodically introduce quality control standards and a cleaning solution (0.50 M HNO(3)). The 'Z-type' optical cell uses a liquid-core waveguide (10 mm) to collimate the light-emitting diode source beam (lambda(max) 574 nm) to a broadband photodiode detector. Figures of merit are: 7 min cycle time, response within 28 min and clear-down within 31 min, low waste generation (<40 ml d(-1)), detection limit (3sigma) of 48.4 microg l(-1) as Cr(vi) or 0.411 microM as chromic acid, 1.54% relative standard deviation at 100 microg l(-1), and selectivity for dissolved Cr(vi) in authentic surface water samples containing moderate levels (>0.21% w/v) of total particulate matter. Using a test chamber containing Milwaukee Harbor water that was periodically fortified with Cr(vi) standards, continuous testing over a 15 day period (354 h) yielded results that were in excellent agreement (<5% variation) with measurements made using an ICP-MS reference method. Drift in the calibration model over the test period was 1.23% and the variation in a 0.50 mg l(-1) Cr(vi) standard was 3.8%(n= 11). Known interferences to the DPC chemistry (Mo, V, and Hg at >5 mg l(-1)) were undetected in the harbor water by ICP-MS.     

Organochlorine contamination in shorebirds from Washington state and the significance for their falcon predators

Arctic-breeding shorebirds collected in western Washington state during winter and spring, and a comparative sample collected in coastal California during the winter were analyzed for organochlorine contaminants to determine the potential impact of these residues on populations of peregrine falcons (Falco peregrinus) and merlins (F. columbarius) which prey upon shorebirds in western Washington. Dunlins (Calidris alpina), an important winter prey for falcons in western Washington, were collected between 1975 and 1981. During winter 1980–81, dunlins carried low organochlorine residues; DDE levels ranged from 0.01 to 1.2 ppm, and PCB levels ranged from 0.02 to 0.82 ppm (wet weight). Levels of other organochlorine contaminants (HCB, Chlordane compounds, Dieldrin, and Heptachlor Epoxide), analyzed in a subsample of dunlins, were consistently lower than DDE and PCB levels, and ranged from 0.001 to 0.22 ppm (wet weight). Dunlins in western Washington did not significantly increase their DDE or PCB burdens over the 1980–81 winter. A decline in DDE residues between 1978 and 1981 was noted, and declines in PCB residues from both 1975 and 1978 to 1980–81 were noted. Residues in other wintering shorebirds from western Washington were similar. Wintering sanderlings (Calidris alba) from California, revealed much higher DDE contamination than in Washington (up to 32 ppm, wet weight). Spring migrant shorebirds in western Washington contained both low and very high DDE residues (up to 417 ppm, wet weight). There is evidence suggesting these high DDE concentrations are accumulated along the Pacific coast of North America.     

Ecology and seasonal variation of microalgal community in an oil refinery effluent holding pond: monitoring and assessment

The microalgal community as primary producers has to play a significant role in the biotic and abitoic interactions of anyaquatic ecosystem. Whenever a community is exposed to a pollutant, responses can occur because individuals acclimate topollutant caused changes and selection can occur favouring resistant genotypes within a population and selection among species can result in changes in community structure. The microalgal community of industrial effluent treatment systems arecontinuously exposed to pollutants and there is little data available on the structure and seasonal variation of microalgalcommunity of industrial effluent holding ponds, especially of acomplex effluent like that of refinery. The aim of the presentstudy was to investigate the annual variation in the ecology,biomass, productivity and community structure of the algalcommunity of a refinery effluent holding pond. The results ofthe study showed the pond to be a eutrophic system with a resistant microalgal community with distinct seasonal variation in species composition.