Evaluation of a Watershed Model for Estimating Daily Flow Using Limited Flow Measurements1

Abstract: The Soil and Water Assessment Tool (SWAT) model was evaluated for estimation of continuous daily flow based on limited flow measurements in the Upper Oyster Creek (UOC) watershed. SWAT was calibrated against limited measured flow data and then validated. The Nash‐Sutcliffe model Efficiency (NSE) and mean relative error values of daily flow estimations were 0.66 and 15% for calibration, and 0.56 and 4% for validation, respectively. Also, further evaluation of the model’s estimation of flow at multiple locations was conducted with parametric paired t‐test and nonparametric sign test at a 95% confidence level. Among the five main stem stations, four stations were statistically shown to have good agreement between predicted and measured flows. SWAT underestimated the flow of the fifth main stem station possibly because of the existence of complex flood control measures near to the station. SWAT estimated the daily flow at one tributary station well, but with relatively large errors for the other two tributaries. The spatial pattern of predicted flows matched the measured ones well. Overall, it was concluded from the graphical comparisons and statistical analyses of the model results that SWAT was capable of reproducing continuous daily flows based on limited flow data as is the case in the UOC watershed.     

Pilot sample risk analysis for underground coal mine fires and explosions using MSHA citation data

After three decades of sustained continuous improvement of mine safety performances in the US, mine disasters in 2006 and 2007 compromised an excellent record and presented new challenges and vulnerabilities for the underground coal mining industry. In the aftermath of the incidents, formal investigations and new scrutiny of mine safety by the US Congress and expert study groups followed. The US Congress passed the Mine Improvement and New Emergency Response Act of 2006 (MINER Act), which mandated new laws to address the issues, including those related to mine fires and explosions from which miners must be protected. The National Mining Association-sponsored Mine Safety Technology and Training Commission report highlighted the role of risk analysis and management in identifying and controlling major hazards, such as fires and explosions. In this paper an approach is given for analyzing the risks for fires and explosions based on the Mine Safety and Health Administration citation database. Using 2006 citation data and focusing on subsystem failures, the methodology is applied to a database for a pilot sample of underground coal mines stratified by mine size and state.     

The hydrochemistry of groundwater in the Densu River Basin, Ghana

Hydrochemical analyses of groundwater samples were used to establish the hydrochemistry of groundwater in the Densu River Basin. The groundwater was weakly acidic, moderately mineralized, fresh to brackish with conductivity ranging from of 96.6 μS cm^???1 in the North to 10,070 μS cm^???1 in the South. Densu River basin have special economic significance, representing the countries greatest hydrostructure with freshwater. Chemical constituents are generally low in the North and high in the South. The order of relative abundance of major cations in the groundwater is Na^?+??> Ca^2?+??> Mg^2?+??> K^?+? while that of anions is Cl^????> HCO $_{3}^{-} >$ SO $_{4}^{2-} >$ NO $_{3}^{-}$ . Four main chemical water types were delineated in the Basin. These include Ca–Mg–HCO₃, Mg–Ca–Cl, Na–Cl, and mixed waters in which neither a particular cation nor anion dominates. Silicate weathering and ion exchange are probably the main processes through which major ions enter the groundwater system. Anthropogenic activities were found to have greatly impacted negatively on the quality of the groundwater.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Linking ground-water age and chemistry data along flow paths: implications for trends and transformations of nitrate and pesticides

Tracer-based ground-water ages, along with the concentrations of pesticides, nitrogen species, and other redox-active constituents, were used to evaluate the trends and transformations of agricultural chemicals along flow paths in diverse hydrogeologic settings. A range of conditions affecting the transformation of nitrate and pesticides (e.g., thickness of unsaturated zone, redox conditions) was examined at study sites in Georgia, North Carolina, Wisconsin, and California. Deethylatrazine (DEA), a transformation product of atrazine, was typically present at concentrations higher than those of atrazine at study sites with thick unsaturated zones but not at sites with thin unsaturated zones. Furthermore, the fraction of atrazine plus DEA that was present as DEA did not increase as a function of ground-water age. These findings suggest that atrazine degradation occurs primarily in the unsaturated zone with little or no degradation in the saturated zone. Similar observations were also made for metolachlor and alachlor. The fraction of the initial nitrate concentration found as excess N2 (N2 derived from denitrification) increased with ground-water age only at the North Carolina site, where oxic conditions were generally limited to the top 5 m of saturated thickness. Historical trends in fluxes to ground water were evaluated by relating the times of recharge of ground-water samples, estimated using chlorofluorocarbon concentrations, with concentrations of the parent compound at the time of recharge, estimated by summing the molar concentrations of the parent compound and its transformation products in the age-dated sample. Using this approach, nitrate concentrations were estimated to have increased markedly from 1960 to the present at all study sites. Trends in concentrations of atrazine, metolachlor, alachlor, and their degradates were related to the timing of introduction and use of these compounds. Degradates, and to a lesser extent parent compounds, were detected in ground water dating back to the time these compounds were introduced.     

Effects of repeated exposure to malathion on growth, food consumption, and locomotor performance of the western fence lizard (Sceloporus occidentalis)

Effects of repeated pollutant exposure on growth, locomotor performance, and behavior have rarely been evaluated in reptiles. We administered three doses of malathion (2.0, 20, or 100mg/kg body weight) to western fence lizards (Sceloporus occidentalis) over an 81day period. Eight and 23% mortality occurred at 20 and 100mg/kg (p=0.079) and 85% of lizards in the 100mg/kg group exhibited clinical symptoms of poisoning. Growth, food consumption, body condition index, and terrestrial locomotor performance were not significantly influenced by malathion. However, arboreal sprint velocity was significantly reduced in lizards receiving 100mg/kg. Fifty percent of lizards in the 100mg/kg group also refused to sprint in the arboreal setting (p=0.085). Based on these results, arboreal locomotor performance was the most sensitive metric of exposure we evaluated. Further study of compounds such as malathion is warranted due to highly variable application rates and exposure scenarios.     

Spatial distribution of metals within the liver acinus and their perturbation by PCB126

Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.     

Comparison of Stream Invertebrate Response Models for Bioassessment Metrics1

Waite, Ian R., Jonathan G. Kennen, Jason T. May, Larry R. Brown, Thomas F. Cuffney, Kimberly A. Jones, and James L. Orlando, 2012. Comparison of Stream Invertebrate Response Models for Bioassessment Metrics. Journal of the American Water Resources Association (JAWRA) 48(3): 570-583. DOI: 10.1111/j.1752-1688.2011.00632.x Abstract: We aggregated invertebrate data from various sources to assemble data for modeling in two ecoregions in Oregon and one in California. Our goal was to compare the performance of models developed using multiple linear regression (MLR) techniques with models developed using three relatively new techniques: classification and regression trees (CART), random forest (RF), and boosted regression trees (BRT). We used tolerance of taxa based on richness (RICHTOL) and ratio of observed to expected taxa (O/E) as response variables and land use/land cover as explanatory variables. Responses were generally linear; therefore, there was little improvement to the MLR models when compared to models using CART and RF. In general, the four modeling techniques (MLR, CART, RF, and BRT) consistently selected the same primary explanatory variables for each region. However, results from the BRT models showed significant improvement over the MLR models for each region; increases in R² from 0.09 to 0.20. The O/E metric that was derived from models specifically calibrated for Oregon consistently had lower R² values than RICHTOL for the two regions tested. Modeled O/E R² values were between 0.06 and 0.10 lower for each of the four modeling methods applied in the Willamette Valley and were between 0.19 and 0.36 points lower for the Blue Mountains. As a result, BRT models may indeed represent a good alternative to MLR for modeling species distribution relative to environmental variables.