A spatially explicit framework for quantifying downstream hydrologic conditions

Continued improvements in spatial datasets and hydrological modeling algorithms within Geographic Information Systems (GISs) have enhanced opportunities for watershed analysis. With more detailed hydrology layers and watershed delineation techniques, we can now better represent and model landscape to water quality relationships. Two challenges in modeling these relationships are selecting the appropriate spatial scale of watersheds for the receiving stream segment, and handling the network or pass-through issues of connected watersheds. This paper addresses these two important issues for enhancing cumulative watershed capabilities in GIS. Our modeling framework focuses on the delineation of stream-segment-level watershed boundaries for 1:24 000 scale hydrology, in combination with a topological network model. The result is a spatially explicit, vector-based, spatially cumulative watershed modeling framework for quantifying watershed conditions to aid in restoration. We demonstrate the new insights available from this modeling framework in a cumulative mining index for the management of aquatic resources in a West Virginia watershed.     

Diamondback terrapins as indicator species of persistent organic pollutants: Using Barnegat Bay, New Jersey as a case study

The diamondback terrapin’s (Malaclemys terrapin) wide geographic distribution, long life span, occurrence in a variety of habitats within the saltmarsh ecosystem, predatory foraging behavior, and high site fidelity make it a useful indicator species for contaminant monitoring in estuarine ecosystems. In this study fat biopsies and plasma samples were collected from males and females from two sites within Barnegat Bay, New Jersey, as well as tissues from a gravid female and blue mussels (Mytilus edulis), which are terrapin prey. Samples were analyzed for persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), chlorinated pesticides, and methyl-triclosan. Terrapins from the northern site, Spizzle Creek, closest to influences from industrial areas, had higher POP concentrations for both tissues than terrapins from the less impacted Forsythe National Wildlife Refuge. Sex differences were observed with males having higher contaminant concentrations in fat and females in plasma. PCB patterns in terrapin fat and plasma were comparable to other wildlife. An atypical PBDE pattern was observed, dominated by PBDEs 153 and 100 instead of PBDEs 47 and 99, which has been documented in only a few other turtle species. The typical PBDE patterns measured in mussels, terrapin prey, suggests that the terrapin may efficiently biotransform or eliminate PBDE 47 and possibly PBDE 99. Plasma contaminant concentrations significantly and positively correlated with those in fat. This study addresses several aspects of using the terrapin as an indicator species for POP monitoring: site and sex differences, tissue sampling choices, maternal transfer, and biomagnification.     

Aluminum water treatment residuals as permeable reactive barrier sorbents to reduce phosphorus losses

Two aluminum water treatment residuals (Al-WTRs) from water treatment plants in Manatee County, FL and Punta Gorda, FL were evaluated as potential permeable reactive barrier (PRB) media to reduce groundwater phosphorus (P) losses. Short-term (<24 h) P sorption kinetics and long-term P sorption capacity were determined using batch equilibration studies. Phosphorus desorption was characterized following P loadings of 10, 20, 30, 40 and >70 g kg⁻¹. Sorption and desorption studies were conducted on the <2.0 mm material and three size fractions within the <2.0 mm material. The effect of dissolved organic carbon (DOC) on P retention was determined by reacting Al-WTRs with P-spiked groundwater samples of varying initial DOC concentrations. Phosphorus sorption kinetics were rapid for all size fractions of both Al-WTRs (>98% P sorption effectiveness at shaking times ?2 h). The effect of DOC was minimal at <150 mg DOC L⁻¹, but modest reductions (<22%) in P sorption effectiveness occurred at 587 mg DOC L⁻¹. The P sorption capacities of the Manatee and Punta Gorda Al-WTRs (<2.0 mm) are ∼44 g kg⁻¹ and >75 g kg⁻¹, respectively, and the lifespan of an Al-WTR PRB is likely many decades. Desorption was minimal (<2% of the P sorbed) for cumulative P loadings <40 g kg^-l, but increased (<9% of the P sorbed) at cumulative P loads >70 g kg⁻¹. The <2.0 mm Manatee and Punta Gorda Al-WTRs are regarded as ideal PRB media for P remediation.     

Application of OMI observations to a space-based indicator of NOx and VOC controls on surface ozone formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the “Ratio”) from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios <1 and NO_x at Ratios >2; both NO_x and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria, the OMI data indicate that ozone formation became: 1. more sensitive to NO_x over most of the United States from 2005 to 2007 because of the substantial decrease in NO_x emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO₂, and 2. more sensitive to NO_x with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g., Chicago), the data clearly indicate that ozone formation became more sensitive to NO_x from 2005 to 2007. In cities with relatively high isoprene emissions (e.g., Atlanta), we found that the increase in the Ratio due to decreasing NO_x emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.     

Assessment of basin-scale hydrologic impacts of CO2 sequestration,Illinois basin

Idealized, basin-scale sharp-interface models of CO₂ injection were constructed for the Illinois basin. Porosity and permeability were decreased with depth within the Mount Simon Formation. Eau Claire confining unit porosity and permeability were kept fixed. We used 726 injection wells located near 42 power plants to deliver 80 million metric tons of CO₂/year. After 100 years of continuous injection, deviatoric fluid pressures varied between 5.6 and 18 MPa across central and southern part of the Illinois basin. Maximum deviatoric pressure reached about 50% of lithostatic levels to the south. The pressure disturbance (>0.03 MPa) propagated 10–25 km away from the injection wells resulting in significant well–well pressure interference. These findings are consistent with single-phase analytical solutions of injection. The radial footprint of the CO₂ plume at each well was only 0.5–2 km after 100 years of injection. Net lateral brine displacement was insignificant due to increasing radial distance from injection well and leakage across the Eau Claire confining unit. On geologic time scales CO₂ would migrate northward at a rate of about 6 m/1000 years. Because of paleo-seismic events in this region (M5.5–M7.5), care should be taken to avoid high pore pressures in the southern Illinois basin.     

Correlations of Eisenia fetida metabolic responses to extractable phenanthrene concentrations through time

Eisenia fetida earthworms were exposed to phenanthrene for thirty days to compare hydroxypropyl-β-cyclodextrin (HPCD) extraction of soil and ¹H NMR earthworm metabolomics as indicators of bioavailability. The phenanthrene 28-d LC₅₀ value was 750 mg/kg (632-891, 95% confidence intervals) for the peat soil tested. The initial phenanthrene concentration was 319 mg/kg, which biodegraded to 16 mg/kg within 15 days, at which time HPCD extraction suggested that phenanthrene was no longer bioavailable. Multivariate statistical analysis of ¹H NMR spectra for E. fetida tissue extracts indicated that phenanthrene exposed and control earthworms differed throughout the 30 day experiment despite the low phenanthrene concentrations present after 15 days. This metabolic response was better correlated to total phenanthrene concentrations (Q² = 0.59) than HPCD-extractable phenanthrene concentrations (Q² = 0.46) suggesting that ¹H NMR metabolomics offers considerable promise as a novel, molecular-level method to directly monitor the bioavailability of contaminants to earthworms in the environment.     

Safety climate: Leading or lagging indicator of safety outcomes?

This paper theorizes how and why safety climate can be conceived as both a leading and a lagging indicator of safety events (i.e., accidents, injuries). When safety climate is conceived as a leading indicator, a prospective design is utilized and safety climate data are correlated with accidents/injuries that occur in the future. When safety climate is conceived as a lagging indicator, retrospective designs are used in which safety climate data are correlated with prior accidents/injuries. We examine the research literature to reveal that safety climate has been investigated as both a leading and a lagging indicator, but it is usually only examined as one or the other within a given study and has been examined as a lagging indicator most frequently. Consistent with our theorizing, prospective designs yield stronger relationships than retrospective designs, suggesting that safety climate is a better leading indicator than lagging indicator; however, it is clearly both. Implications for safety climate research and study design are discussed.     

Evaluating landfill disposal of chromated copper arsenate (CCA) treated wood and potential effects on groundwater: evidence from Florida

Chromated copper arsenate (CCA) treated wood has been used for more than 50 years. Recent attention has been focused on appropriate disposal of CCA-treated wood when its service life ends. Groups in the US and Europe concerned with the possibility of arsenic migration to groundwater from disposed CCA-treated wood have proposed that consumers be required to dispose of the wood as a hazardous waste, in the most protective of landfills. We examined available data for evidence of arsenic migration from unlined construction and demolition (C&D) debris landfills in Florida, where CCA-treated wood is disposed. Florida was chosen because soil, groundwater, landfill design, weather, and levels of CCA-treated wood use make the state a uniquely sensitive indicator for observing arsenic migration from CCA-treated wood disposal sites, should it occur. We developed and quality-checked a CCA-treated wood disposal model to estimate the amount of wood and associated arsenic disposed. By 2000, an estimated 13 million kg of arsenic in CCA-treated wood was disposed in Florida; however, groundwater monitoring data do not indicate that arsenic is migrating from unlined C&D landfills. Our results provide evidence that highly stringent regulation of CCA-treated wood disposal, such as treatment as a hazardous waste, is unnecessary.     

Quantifying MTBE biodegradation in the Vandenberg Air Force Base ethanol release study using stable carbon isotopes

Compound-specific isotope analysis (CSIA) was used to assess biodegradation of MTBE and TBA during an ethanol release study at Vandenberg Air Force Base. Two continuous side-by-side field releases were conducted within a preexisting MTBE plume to form two lanes. The first involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene ("No ethanol lane"), while the other involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene and ethanol ("With ethanol lane"). The delta(13)C of MTBE for all wells in the "No ethanol lane" remained constant during the experiment with a mean value of -31.3 +/- 0.5 per thousand (n=40), suggesting the absence of any substantial MTBE biodegradation in this lane. In contrast, substantial enrichment in (13)C of MTBE by 40.6 per thousand, was measured in the "With ethanol lane", consistent with the effects of biodegradation. A substantial amount of TBA (up to 1200 microg/L) was produced by the biodegradation of MTBE in the "With ethanol lane". The mean value of delta(13)C for TBA in groundwater samples in the "With ethanol lane" was -26.0 +/- 1.0 per thousand (n=32). Uniform delta(13)C TBA values through space and time in this lane suggest that substantial anaerobic biodegradation of TBA did not occur during the experiment. Using the reported range in isotopic enrichment factors for MTBE of -9.2 per thousand to -15.6 per thousand, and values of delta(13)C of MTBE in groundwater samples, MTBE first-order biodegradation rates in the "With ethanol lane" were 12.0 to 20.3 year(-1) (n=18). The isotope-derived rate constants are in good agreement with the previously published rate constant of 16.8 year(-1) calculated using contaminant mass-discharge for the "With ethanol lane".