Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

A synchronized amphibian metamorphosis assay as an improved tool to detect thyroid hormone disturbance by endocrine disruptors and apolar sediment extracts

Amphibian metamorphosis assays are used to evaluate potential effects of endocrine disrupting compounds on the thyroid hormone axis. In this study, Xenopus laevis tadpoles are kept in a solution of 0.2% thiourea (TU) to arrest and synchronise them in their development. The advantage of this synchronized amphibian metamorphosis assays is that synchronised tadpoles are available at any time to start metamorphosis experiments, and experimental groups are much more homogenous at the start of experimental exposure compared with groups selected from an untreated pool of animals. The water volume per animal was kept constant throughout the experimental period to overcome the influence of declining numbers of animals per aquarium due to metamorphosis and mortality on the density dependent development of the remaining tadpoles. Clophen A50 (a technical PCB mixture), the single congener 3,3',4,4'-tetrachlorobiphenyl (PCB 77) and apolar sediment extracts that were previously tested positive in the T-Screen, an in vitro proliferation assay for thyroid hormone disruption, were tested in the Synchronized Amphibian Metamorphosis Assay. Endpoints studied were mortality, malformations, body weight, and percentage of metamorphosed froglets at the end of the 60-day experimental period, percentage of tadpoles in different developmental stages, and developmental stage-dependent awarded penalty points. Dietary exposure to Clophen A50 (0.2-50mg/kg food) resulted in a significant increased percentage of tadpoles that did not pass metamorphosis at concentrations higher than 2mg/kg food. Time until metamorphosis in those animals that were able to metamorphose after the 60-days experimental period was significantly decreased. Dietary exposure to PCB 77, a congener that can be readily metabolised, did not result in significant effects in any exposure group (2-500 microg/kg food). Apolar sediment extracts from two of the three sites that are contaminated with a wide variety of chemicals significantly decreased the percentage of metamorphosed animals and significantly increased the number of tadpoles that remained in early and late metamorphic stages. These effects already occurred when the extracts where diluted more than 1000 times (on an organic carbon base) compared to environmental concentrations. The rank of potency was comparable to results obtained with the T-screen. This suggests the presence of thyroid hormone disrupting compounds in the aquatic environment and possible effects of such compounds on animal development in the wild.     

Risk assessment of linear alkylbenzene sulphonates, LAS, in agricultural soil revisited: robust chronic toxicity tests for Folsomia candida (Collembola), Aporrectodea caliginosa (Oligochaeta) and Enchytraeus crypticus (Enchytraeidae)

To obtain robust data on the toxicity of LAS, tests with the collembolan Folsomia candida L., the oligochaetes Aporrectodea caliginosa Savigny (earthworm) and Enchytraeus crypticus Westheide and Graefe (enchytraeid) were performed in a sandy loam soil. Additionally limited tests with LAS spiked to sewage sludge, and subsequently mixed into soil, were performed. For the endpoint of interest, reproduction in soil, we found an EC10 of 205 mg LAS kg(-1) soil [8.6-401] [95% confidence limits] for F. candida and an EC10 of 46 mg LAS kg(-1) soil [13-80] for A. caliginosa after 28 days. E. crypticus was not affected by concentrations up to 120 mg LAS kg(-1) soil. When adding (low contaminated) non-spiked sludge to soil, high stimulation of reproduction was observed for E. crypticus and A. caliginosa but not for F. candida. We argue that this difference in stimulative response between the tested species is related to the difference in feeding behaviour. Sludge spiked with LAS did not significantly affect the reproduction of F. candida (fertility: number of juvenile offspring) and A. caliginosa (fecundity: number of cocoons) (dose equivalent to 181 g and 91 g LAS kg(-1) sludge, respectively). Significantly reduced reproduction was observed for E. crypticus (at 120 mg LAS kg(-1) soil+sludge corresponding to 72 g LAS kg(-1) sludge) compared to non-spiked sludge. The reproduction by E. crypticus was, however, comparable to the reproduction observed in the control soil without sludge. Compared to LAS directly spiked to soil, the reproductive output of organisms exposed to spiked sludge was either not significantly different (F. candida, E. crypticus) or significantly improved (A. caliginosa). More studies are needed in order to make firm conclusions on the potential effect of artificially contaminated sludge in soil systems.     

Well water contaminated by acidic mine water from the Dabaoshan Mine, south China: chemistry and toxicity

An investigation into well water quality was carried out in a rural area subject to irrigation with acidic mine water from the Guangdong Dabaoshan Mine, southern China. The results of water pH measurements from 112 wells in two different seasons suggest that the well water has been contaminated to varying degrees in the investigated Shangba floodplain (approximately 11km south of the Guangdong Dabaoshan Mine). There is a trend that well water pH increased southwards, suggesting that the impacts of acidic irrigation water on groundwater decreased with increasing distance to the entry point of acidic irrigation water. Water quality monitoring results of the selected wells show that Cu and Cd in the water exceeded the limits set in the Chinese National Standards for Drinking Water (GB 5749-85) for the wells close to the irrigation water source. If the World Health Organization (WHO) standard was considered, Cd in some wells was almost 10 times as high as the WHO guideline value (0.003mg l(-1)). Water collected from the location closest to the acidic irrigation water source was acutely toxic to the test organism (Daphnia carinata) even after 51 time dilution. It is likely that the extremely high mortality rate of the local population reported for the study area is at least partly related to the high levels of heavy metals, particularly Cd in the drinking well water.     

Bacteria transport and deposition under unsaturated conditions: the role of the matrix grain size and the bacteria surface protein

Unsaturated (80% water saturated) packed column experiments were conducted to investigate the influence of grain size distribution and bacteria surface macromolecules on bacteria (Rhodococcus rhodochrous) transport and deposition mechanisms. Three sizes of silica sands were used in these transport experiments, and their median grain sizes were 607, 567, and 330 microm. The amount of retained bacteria increased with decreasing sand size, and most of the deposited bacteria were found adjacent to the column inlet. The deposition profiles were not consistent with predictions based on classical filtration theory. The experimental data could be accurately characterized using a mathematical model that accounted for first-order attachment, detachment, and time and depth-dependent straining processes. Visual observations of the bacteria deposition as well as mathematical modelling indicated that straining was the dominant mechanism of deposition in these sands (78-99.6% of the deposited bacteria), which may have been enhanced due to the tendency of this bacterium to form aggregates. An additional unsaturated experiment was conducted to better deduce the role of bacteria surface macromolecules on attachment and straining processes. In this case, the bacteria surface was treated using a proteolitic enzyme. This technique was assessed by examining the Fourier-transform infrared spectrum and hydrophobicity of untreated and enzyme treated cells. Both of these analytical procedures demonstrated that this enzymatic treatment removed the surface proteins and/or associated macromolecules. Transport and modelling studies conducted with the enzyme treated bacteria, revealed a decrease in attachment, but that straining was not significantly affected by this treatment.     

Catalyst deterioration over the lifetime of small utility engines

In this paper, the deterioration of catalysts in small, four-stroke, spark-ignition engines is described. The laboratory testing performed followed a proven test method that mimics the lifetime of a small air-cooled utility engine operating under normal field conditions. The engines used were single-cylinder, 6.5-hp, side-valve engines. These engines have a nominal 125-hr lifetime. The effectiveness of the catalysts was determined by testing exhaust emissions before and after the catalyst to determine the catalyst's efficiency. This was done several times during the lifetime of the engines to determine the deterioration in the performance of the catalysts at lowering pollutant emissions. Additional testing was performed on the catalysts to determine wear patterns, contamination, and recoverable activity. The results indicate that considerable catalyst deterioration is occurring over the lifetime of the engine. The results reveal that soot buildup, poisons, and active surface loss appear to be the contributing factors to the deterioration. These results were determined after analyzing the exhaust emissions data, scanning electron microscope results analysis, and the impact of regeneration attempts. An ANOVA statistical analysis was performed, and it was determined that the emissions are also impacted, to some degree, by time and the engine itself.     

Synthesis of polyhydroxyalkanoates in municipal wastewater treatment.

Biologically derived polyesters known as polyhydroxyalkanoates (PHAs) represent a potentially "sustainable" replacement to fossil-fuel-based thermoplastics. However, current commercial practices that produce PHA with pure microbial cultures grown on renewable, but refined, feedstocks (i.e., glucose) under sterile conditions do not represent a sustainable commodity. Here, we report on PHA production with a mixed microbial consortium indigenous to an activated sludge process on carbon present in municipal wastewaters. Reactors operated under anaerobic/aerobic and aerobic-only mode and fed primary solids fermenter liquor maintained a mixed microbial consortium capable of synthesizing PHA at 10 to 25% (w/w), while reducing soluble COD by approximately 62 to 71%. More critically, an aerobic batch reactor seeded from the anaerobic/aerobic reactor and fed fermenter liquor achieved approximately 53% PHA (w/w). Results presented suggest that environmentally benign production of biodegradable polymers is feasible. We further used PHA-rich biomass to produce a natural fiber-reinforced thermoplastic composite that can be used to offset advanced wastewater treatment costs.     

Characterization of PM2.5 aerosols dominated by local pollution and Asian dust observed at an urban site in Korea during aerosol characterization experiments (ACE)--Asia Project

Daily fine particulate matter (PM2.5) samples were collected at Gwangju, Korea, during the Aerosol Characterization Experiments (ACE)-Asia Project to determine the chemical properties of PM2.5 originating from local pollution and Asian dust (AD) storms. During the study period, two significant events occurred on April 10-13 and 24-25, 2001, and a minor event occurred on April 19, 2001. Based on air mass transport pathways identified by back-trajectory calculation, the PM2.5 dataset was classified into three types of aerosol populations: local pollution and two AD aerosol types. The two AD types were transported along different pathways. One originated from Gobi desert area in Mongolia, passing through Hunshandake desert in Northern Inner Mongolia, urban and polluted regions of China (AD1), and the other originated in sandy deserts located in the Northeast Inner Mongolia Plateau and then flowed southward through the Korean peninsula (AD2). During the AD2 event, a smoke plume that originated in North Korea was transported to our study site. Mass balance closures show that crustal materials were the most significant species during both AD events, contributing -48% to the PM2.5 mass; sulfate aerosols (19.1%) and organic matter (OM; 24.6%) were the second greatest contributors during the AD1 and AD2 periods, respectively, indicating that aerosol properties were dependent on the transport pathway. The sulfate concentration constituted only 6.4% (4.5 microg/m3) of the AD2 PM2.5 mass. OM was the major chemical species in the local pollution-dominated PM2.5 aerosols, accounting for 28.7% of the measured PM2.5 mass, followed by sulfate (21.4%), nitrate (15%), ammonium (12.8%), elemental carbon (8.9%), and crustal material (6.5%). Together with substantial enhancement of the crustal elements (Mg, Al, K, Ca, Sc, Ti, Mn, Fe, Sr, Zr, Ba, and Ce), higher concentrations of pollution elements (S, V, Ni, Zn, As, Cd, and Pb) were observed during AD1 and AD2 than during the local pollution period, indicating that, in addition to crustal material, the AD dust storms also had a significant influence on anthropogenic elements.     

Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.