Mobilization of colloids in groundwater due to infiltration of water at a coal ash disposal site

We investigated groundwaters in the vicinity of a coal ash site near an electric generating station in the western U.S.A. The purpose of the study was to ascertain why fine particles or colloids appear in some subsurface water samples there. If such fine particles are merely introduced during bailing or pumping operations which suspend otherwise immobile soil colloids, we should exclude these particulate materials from the water samples before analysis intended to quantify what is moving through the aquifer. However, if the colloids were truly suspended and moving with the groundwater flow in situ, then we should includes their contribution to our assessment of the mobile loads.Application of very careful sampling techniques (slow pumping rates, no atmospheric exposure) did not cause the large quantities of colloids observed previously to disappear from well water in which they occured. Additionally, the same sampling procedures did not cause similar abundances of colloids to appear in waters collected from neighboring wells installed and developed in the same manner and in the same geologic strata. Thus we believe sampling artifacts do not explain the colloids' presence in the groundwater samples.On the other hand, the groundwater chemistry and the nature of the suspended colloids (size, composition) strongly suggest these fine particles were suspended and therefore moving with the groundwater flow. At wells exhibiting large amounts of suspended colloids (≈10–100 mg L⁻¹), the water was enriched in CO₂ and depleted in O₂ relative to nearby locations. The colloids were typically between 0.1 and 2 μm in size and were primarily silicates. These results suggest to us that, where infiltrating water is percolating through a site that has been mixed with coal ash, the secondary carbonate mineral in the soils are being dissolved; removal of this cementing carbonate phase may consequently release soil silicate colloids to be carried in the flowing water.Such processes may enhance contaminant transport in groundwater by augmenting the pollutant load moving in the groundwater, and increasing the permeability of the porous medium to pollutant infiltration with water water and/or rainwater.     

The ecotoxicology of vegetable versus mineral based lubricating oils: 3. Coral fertilization and adult corals

Biodegradable vegetable-derived lubricants (VDL) might be less toxic to marine organisms than mineral-derived oils (MDL) due to the absence of high molecular weight aromatics, but this remains largely untested. In this laboratory study, adult corals and coral gametes were exposed to various concentrations of a two-stroke VDL-1A and a corresponding MDL to determine which lubricant type was more toxic to each life stage. In the fertilization experiment, gametes from the scleractinian coral Acropora microphthalma were exposed to water-accommodated fractions (WAF) of VDL-1A and MDL for four hours. The MDL and VDL-1A WAFs inhibited normal fertilization of the corals at 200 microg l(-1) total hydrocarbon content (THC) and 150 microg l(-1) THC respectively. Disturbance of a stable coral-dinoflagellate symbiosis is regarded as a valid measure of sub-lethal stress in adult corals. The state of the symbiosis in branchlets of adult colonies of Acropora formosa was monitored using indicators such as dinoflagellate expulsion and dark-adapted photosystem II yields of dinoflagellate (using pulse amplitude modulation fluorescence). An effect on symbiosis was measurable following 48 h exposure to the lubricants at concentrations of 190 microg l(-1) and 37 microg l(-1) THC for the MDL and VDL-1A respectively. GC/MS revealed that the main constituent of the VDL-1A WAF was the compound coumarin, added by the manufacturer to improve odour. The fragrance containing coumarin was removed from the lubricant formulation and the toxicity towards adult corals re-examined. The coumarin-free VDL-2 exhibited significantly less toxicity towards the adult corals than all of the other oil types tested, with the only measurable effect being a slight but significant drop in photosynthetic efficiency at 280 microg l(-1).     

Gas chromatography/mass spectrometry of paraquat UV-ozonation products

The chromatographic and mass spectral properties of 13 compounds isolated from the reaction of UV and ozone on paraquat are described. The products were extracted from the acidified reaction mixture and converted to TMS derivatives. The identified products were the diTMS ester of oxalic acid (m/z 234), the TMS ester of 4-picolinic acid (m/z 195), the diTMS ester of succinic acid (m/z 262), the diTMS derivative of N-formylglycine, 4,4'-bipyridyl (m/z 156), the triTMS derivative of malic acid (m/z 350), and the diTMS derivative of a hydroxy-4-picolinic acid. Structural features and tentative identification of some of the remaining compounds are discussed. The most prominent peak on the chromatogram has a probable molecular ion at m/z 219, isomeric to the diTMS derivative of glycine. The structures presented suggest that demethylation, ring oxidation and fragmentation of one or both rings of the bipyridinium di-cation occur during UV-ozonation of paraquat.     

Thermal degradation of fluorotelomer treated articles and related materials

This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical combustion conditions of time, temperature, and excess air level in a municipal incinerator, with an average temperature of 1000 degrees C or greater over approximately 2s residence time. The results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer-based acrylic polymer is destroyed and no detectable amount of perfluorooctanoic acid (PFOA) is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source of PFOA in the environment.     

Investigation of sources of atmospheric aerosol at a hot spot area in Dhaka, Bangladesh

Samples of fine and coarse fractions of airborne particulate matter were collected at the Farm Gate area in Dhaka from July 2001 to March 2002. Dhaka is a hot spot area with very high pollutant concentrations because of the proximity of major roadways. The samples were collected using a "Gent" stacked filter unit in two fractions of 0- to 2.2-microm and 2.2- to 10-microm sizes. The samples were analyzed for elemental concentrations by particle-induced X-ray excitation (PIXE) and for black carbon by reflectivity methods, respectively. The data were analyzed by positive matrix factorization (PMF) to identify the possible sources of atmospheric aerosols in this area. Six sources were found for both the coarse and fine PM fractions. The data sets were also analyzed by an expanded model to explore additional sources. Seven and six factors were obtained for coarse and fine PM fractions, respectively, in these analyses. The identified sources are motor vehicle, soil dust, emissions from construction activities, sea salt, biomass burning/brick kiln, resuspended/fugitive Pb, and two-stroke engines. From the expanded modeling, approximately 50% of the total PM2.2 mass can be attributed to motor vehicles, including two-stroke engine vehicle in this hot spot in Dhaka, whereas the PMF modeling indicates that 45% of the total PM2.2 mass is from motor vehicles. The PMF2 and expanded models could resolve approximately 4% and 3% of the total PM2.2 mass as resuspended/fugitive Pb, respectively. Although, Pb has been eliminated from gasoline in Bangladesh since July 1999, there still may be substantial amounts of accumulated lead in the dust near roadways as well as fugitive Pb emissions from battery reclaimation and other industries. Soil dust is the largest component of the coarse particle fraction (PM2.2-10) accounting for approximately 71% of the total PM2.2-10 mass in the expanded model, whereas from the PMF modeling, the dust (undifferentiated) contribution is approximately 49%.     

Waterborne and sediment toxicity of fluoxetine to select organisms

Ecological risk assessments of pharmaceuticals are currently difficult because little-to-no aquatic hazard and exposure information exists in the peer-reviewed literature for most therapeutics. Recently several studies have identified fluoxetine, a widely prescribed antidepressant, in municipal effluents. To evaluate the potential aquatic toxicity of fluoxetine, single species laboratory toxicity tests were performed to assess hazard to aquatic biota. Average LC(50) values for Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas were 0.756 (234 microg/l), 2.65 (820 microg/l), and 2.28 microM (705 microg/l), respectively. Pseudokirchneriella subcapitata growth and C. dubia fecundity were decreased by 0.044 (14 microg/l) and 0.72 microM (223 microg/l) fluoxetine treatments, respectively. Oryias latipes survival was not affected by fluoxteine exposure up to a concentration of 28.9 microM (8.9 mg/l). An LC(50) of 15.2 mg/kg was estimated for Chironomus tentans. Hyalella azteca survival was not affected up to 43 mg/kg fluoxetine sediment exposure. Growth lowest observed effect concentrations for C. tentans and H. azteca were 1.3 and 5.6 mg/kg, respectively. Our findings indicate that lowest measured fluoxetine effect levels are an order of magnitude higher than highest reported municipal effluent concentrations.     

A physical-chemical screening model for anticipating widespread contamination of community water supply wells by gasoline constituents

Continuing modifications of fuels like gasoline should include evaluations of the proposed constituents for their potential to damage environmental resources such as subsurface water supplies. Consequently, we developed a screening model to estimate well water concentrations and transport times for gasoline components migrating from underground fuel tank (UFT) releases to typical at-risk community water supply wells. Representative fuel release volumes and hydrogeologic characteristics were used to parameterize the transport calculation. Subsurface degradation processes were neglected in the model in order to make risk-conservative assessments. The model was tailored to individual compounds based on their abundances in gasoline, gasoline-water partition coefficients (Kgw), and organic matter-water partition coefficients (Kom). Transport calculations were conducted for 20 polar and 4 nonpolar compounds found in gasoline, including methyl tert-butyl ether (MTBE) and other ether oxygenates, ethanol, methanol, and some aromatic hydrocarbons. With no calibration, the screening model successfully captured the reported magnitude of MTBE contamination of at-risk community supply wells. Such screening indicates that other oxygenates would cause similar widespread problems unless they were biodegradable. Stochastic analysis of field parameter variability concluded that community supply well contamination estimates had order-of-magnitude reliability. This indicated that such pre-manufacturing analyses may reasonably anticipate widespread environmental problems and/or inspire focused investigations into chemical properties (e.g., biodegradability) before industrial adoption of new fuel formulations.     

Modeling field-scale multiple tracer injection at a low-level waste disposal site in fractured rocks: effect of multiscale heterogeneity and source term uncertainty on conceptual understanding of mass transfer processes

Multiple factors may affect the scale-up of laboratory multi-tracer injection into structured porous media to the field. Under transient flow conditions and with multiscale heterogeneities in the field, previous attempts to scale-up laboratory experiments have not answered definitely the questions about the governing mechanisms and the spatial extent of the influence of small-scale mass transfer processes such as matrix diffusion. The objective of this research is to investigate the effects of multiscale heterogeneity, mechanistic and site model conceptualization, and source term density effect on elucidating and interpreting tracer movement in the field. Tracer release and monitoring information previously obtained in a field campaign of multiple, conservative tracer injection under natural hydraulic gradients at a low-level waste disposal site in eastern Tennessee, United States, is used for the research. A suite of two-pore-domain, or fracture-matrix, groundwater flow and transport models are calibrated and used to conduct model parameter and prediction uncertainty analyses. These efforts are facilitated by a novel nested Latin-hypercube sampling technique. Our results verify, at field scale, a multiple-pore-domain, multiscale mechanistic conceptual model that was used previously to interpret only laboratory observations. The results also suggest that, integrated over the entire field site, mass flux rates attributable to small-scale mass transfer are comparable to that of field-scale solute transport. The uncertainty analyses show that fracture spacing is the most important model parameter and model prediction uncertainty is relatively higher at the interface between the preferred flow path and its parent bedrock. The comparisons of site conceptual models indicate that the effect of matrix diffusion may be confined to the immediate neighborhood of the preferential flow path. Finally, because the relatively large amount of tracer needed for field studies, it is likely that source term density effect may exaggerate or obscure the effect of matrix diffusion on the movement of tracers from the preferred flow path into the bedrock.     

Perchlorate in water, soil, vegetation, and rodents collected from the Las Vegas Wash, Nevada, USA

Water, soil, vegetation, and rodents were collected from three areas along the Las Vegas Wash, a watershed heavily contaminated with perchlorate. Perchlorate was detected at elevated concentrations in water, soil, and vegetation, but was not frequently detected in rodent liver or kidney tissues. Broadleaf weeds contained the highest concentrations of perchlorate among all plant types examined. Perchlorate in rodent tissues and vegetation was correlated with perchlorate concentrations in soil as expected, however rodent residues were not highly correlated with plant perchlorate concentrations. This indicates that soil may be a greater source, or a more constant source of perchlorate exposure in rodents than vegetation.     

Deforestation alters phytotelm habitat availability and mosquito production in the Peruvian Amazon.

We quantified the effects of deforestation, and subsequent cultivation and forest regeneration, on the abundance and composition of mosquito larval habitats, specifically phytotelmata (plant-held waters), in the western Amazon basin. Recently deforested sites were characterized by increased phytotelm density (1.6 phytotelmata/m2) and greater relative abundance of fallen-plant-part phytotelmata (76%) compared to intact forests (0.9 phytotelmata/m2 and 25% fallen plant parts). As a result, the total volume of colonizable phytotelm water was significantly larger in new clearings. Subsequent cultivation of cleared land with mixed crops including pineapple and plantain had similar consequences: phytotelm density (2.2 units/m2) was significantly larger in plantations than in forests due to greater relative abundance of water-filled plant axils (71% vs. 39% in forest). Such axils are the preferred larval habitats for Wyeomyia spp. mosquitoes, which showed a similarly significant increase in production in plantations (0.25 larvae/m2) vs. forests (0.04 larvae/m2). Likewise, Limatus spp. mosquitoes were an order of magnitude more abundant in altered landscapes (especially in recently deforested and cultivated areas) than in mature forest, due to increased abundance of fallen-plant-part phytotelmata, in which they are typically the most common colonists. Because they are potential vectors of pathogens in a region of high endemic and emergent virus activity, increases in local abundance of Limatus spp. and Wyeomyia spp. due to large-scale deforestation and agriculture may influence rates of disease transmission.