Fate and Transport Modeling of Potential Pathogens: The Contribution From Sediments1

Abstract: Escherichia coli was used as a bacterial tracer for the development, calibration, and validation of a watershed scale fate and transport model to be extended to a suite of reference pathogens (Cryptosporidium, Giardia, Campylobacter, E. coli O157:H7). E. coli densities in water and sediments from the Blackstone River Watershed, Massachusetts, were measured at three sites for a total of five wet weather events and three dry weather events covering three seasons. The confirmed E. coli strains were identified by ribotyping for tracking the sources of E. coli and for determining the association of downstream E. coli isolates with isolates from upstream sediments. A large number of downstream samples were associated with upstream sediment sources of E. coli. E. coli densities ranged from 71 to 6,401 MPN/100 ml in water samples and from 2 to 335 MPN/g in sediments. Pearson correlation analysis revealed significant correlations between E. coli and total coliforms in water (r = 0.777, p < 0.01) and sediments (r = 0.728, p < 0.01). In addition, E. coli concentrations in water were weakly correlated with sediment particle size and sediment concentrations (r = 0.298, p < 0.01). A hydrologic model, WATFLOOD/SPL9, was used to predict the temporal and spatial variation of E. coli in the Blackstone River. The rapid rise of stream E. coli densities was more accurately predicted by the model with the inclusion of sediment resuspension, thus demonstrating the importance of the process.     

Nitromusk compounds in San Francisco Bay sediments

Synthetic nitromusk fragrances are used in a wide variety of consumer products and can enter aquatic environments through wastewater effluent. Although nitromusks are known to be hydrophobic, little attention has been paid to their behavior in sediments. A sediment extraction method using sonication was developed and used to analyze samples from San Francisco Bay. Both musk xylene (MX) and musk ketone (MK) were found at low levels, with mean concentrations of 0.034 and 0.038ngg(-1), respectively. The highest concentrations were found in the southernmost region of the Bay. Samples were also analyzed from a nearby tidal channel fed by a wastewater treatment plant outfall. At this location both musk xylene and musk ketone were found at higher concentrations of 0.13-0.24ngg(-1) MX and 1.08-2.74ngg(-1) MK. A metabolite of musk xylene was also found at levels up to 4.08ngg(-1), suggesting that these metabolites may play an important role in the fate of nitromusk compounds. Concentrations of all three compounds were highest at the earliest of four sampling dates, and a geographic survey of sediments along the tidal channel showed that concentrations decreased rapidly with distance from the outfall and were close to background before the channel reached the Bay.     

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than ~0.01 m/day, and a gas phase that covers greater than ~10% of the pool surface area and is located within ~0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.     

Trace contamination with dioxin-like chemicals: evaluation of bioassay-based TEQ determination for hazard assessment and regulatory responses

Many recent dioxin contamination events have been traced back to poisoned animal feed or feed ingredients. Therefore, enforcement authorities placed limits on the levels of dioxins in food and feed or implemented strict monitoring and control programs. The levels in force are generally expressed as TEQ values, which inherently accepts the underlying hypothesis that the effects of dioxin-like chemicals are additive. TEQ determination involves either chemo-analysis, with high-resolution gas chromatography in combination with high-resolution mass spectroscopy, or bio-analysis. Bio-analytical methods, more particularly the reporter gene expression method CALUX, are advantageous due to their high throughput rate and low cost. Moreover, the CALUX methodology detects the overall dioxin-like toxicity, rather than the limited number of compounds investigated by chemo-analysis. Bioanalytical methods such as CALUX also differ from chemo-analysis in that the contribution of antagonistic as well as synergistic effects, which violate the additivity principle, can be detected. The application of bio-analytical methods can facilitate a broader assessment of public health risks by intensifying the current monitoring programs in terms of both sample numbers and types. Bio-analysis provides information on the total dioxin-like activity of the samples under study (hazard assessment); however, chemo-analysis is still needed to identify the predominant contaminants (congener identification) for risk management.     

Quantification of biotransformation of chlorinated hydrocarbons in a biostimulation study: added value via stable carbon isotope analysis

Stable carbon isotope analysis of chlorinated aliphatic compounds was performed at an in situ biostimulation pilot test area (PTA) at a site where 1,2-dichloroethane (1,2-DCA) and trichloroethene (TCE) were present in groundwater. Chlorinated products of TCE reductive dechlorination (cis-dichloroethene (cDCE) and vinyl chloride (VC)) were present at concentrations of 17.5 to 126.4 micromol/L. Ethene, a potential degradation product of both 1,2-DCA dihaloelimination and TCE reductive dechlorination was also present in the PTA. Emulsified soybean oil and lactate were added as electron donors to stimulate anaerobic dechlorination in the PTA. Stable carbon isotope analysis provided evidence that dechlorination was occurring in the PTA during biostimulation, and a means of monitoring changes in dechlorination efficiency over the 183 day monitoring period. Stable carbon isotope analysis was also used to determine if ethene production in the PTA was due to dechlorination of TCE, 1,2-DCA, or both. Fractionation factors (alpha) were determined in the laboratory during anaerobic biotransformation of 1,2-DCA via a dihaloelimination reaction in four separate enrichment cultures. These alpha values (as well as the previously published ranges of alpha for the dechlorination of TCE, cDCE and 1,2-DCA) were used, along with isotopic values measured during the pilot test, to derive quantitative estimates of biotransformation during the pilot test. Dechlorination was found to account for 10.7 to 35.9%, 21.9 to 74.9%, and 54.4 to 67.8% of 1,2-DCA, TCE and cDCE concentration loss respectively in the PTA. Stable carbon isotope analysis indicates that dechlorination of 1,2-DCA, TCE and cDCE were all significant processes during the pilot test, while ethene production during the pilot test was dominated by 1,2-DCA dihaloelimination. This study demonstrates how stable carbon isotope analysis can provide more conservative estimates of the extent of biotransformation than do conventional protocols. In addition, in a complex mixed plume such as this, compound specific isotope analysis is shown to be one of the few methods available for clarifying dominant biotransformation pathways where breakdown products are non-exclusive (i.e. ethene).     

Impaired terrestrial and arboreal locomotor performance in the western fence lizard (Sceloporus occidentalis) after exposure to an AChE-inhibiting pesticide

We examined the effects of a commonly used AChE-inhibiting pesticide on terrestrial and arboreal sprint performance, important traits for predator avoidance and prey capture, in the western fence lizard (Sceloporus occidentalis). Lizards were exposed to carbaryl (2.5, 25, and 250 microg/g) and were raced before and 4, 24, and 96 h after dosing. In the terrestrial setting, exposure to low concentrations of carbaryl had stimulatory effects on performance, but exposure to the highest concentration was inhibitory. No stimulatory effects of carbaryl were noted in the arboreal environment and performance in lizards was reduced after exposure to both the medium and highest dose of carbaryl. Our findings suggest that acute exposure to high concentrations of carbaryl can have important sublethal consequences on fitness-related traits in reptiles and that arboreal locomotor performance is a more sensitive indicator of AChE-inhibiting pesticide poisoning than terrestrial locomotor performance.     

Combining Accuracy Assessment of Land-Cover Maps with Environmental Monitoring Programs

A scientifically valid accuracy assessment of a large-area, land-cover map is expensive. Environmental monitoring programs offer a potential source of data to partially defray the cost of accuracy assessment while still maintaining the statistical validity. In this article, three general strategies for combining accuracy assessment and environmental monitoring protocols are described. These strategies range from a fully integrated accuracy assessment and environmental monitoring protocol, to one in which the protocols operate nearly independently. For all three strategies, features critical to using monitoring data for accuracy assessment include compatibility of the land-cover classification schemes, precisely co-registered sample data, and spatial and temporal compatibility of the map and reference data. Two monitoring programs, the National Resources Inventory (NRI) and the Forest Inventory and Monitoring (FIM), are used to illustrate important features for implementing a combined protocol.     

Contaminant Profiles of Two Species of Shorebirds Foraging Together at Two Neighboring Sites in South San Francisco Bay, California

The San Francisco Bay estuary isused by over one million shorebirds during springmigration and is home to several hundred thousandduring the winter. Most shorebird use occurs in thesouthern reach of the estuary (South Bay). Thereduced water circulation and discharge fromindustrial sources in the South Bay are responsiblefor the highest levels of some trace elements in theestuary. Wintering shorebirds have been found to havestrong site fidelity to areas as small as a fewkilometers in the South Bay, which may increase theirexposure to contaminants near local point sources. Inaddition, different shorebird species foraging at thesame site have been shown to have differentcontaminant burdens. Thus, our objectives were totest whether contaminant burdens differed by species,or whether contaminant burdens differed in shorebirdscollected at adjacent sites. We examined thecontaminant profiles of two species of shorebirds,long-billed dowitchers (Limnodromus scolopaceus)and western sandpipers (Calidris mauri) thatforage together at two sites, Hayward and Newark,separated by 8 km in the South Bay. We usedmultivariate analysis of variance tests to compare thecomposition of 14 elemental analytes in their livertissues and estimated their molar ratios of Hg and Se. Composite samples were used for contaminant analysesbecause of the small body size of the shorebirds. Seven elemental analytes (Ag, Ba, Be, Cr, Ni, Pb, V)were below detection limits in a majority of thesamples so statistical analyses were precluded. Inthe measurable analytes (As, Cd, Cu, Hg, Mn, Se, Zn),we found no significant intra-site differences ofcontaminant profiles for the two species. We pooledthe samples to examine inter-site differences andfound significant differences in contaminant profilesbetween shorebirds at the neighboring sites (P = 0.03). Shorebirds at Newark had higher (P < 0.05) concentrations of As, Cd, and Se than those at Hayward. Dowitchers at Newark had concentrations of Hg and Se which were highly correlated (P < 0.003) in a mean molar ratio of 1:19, similar tothat reported in other birds. In the larger dowitcherspecies, we also examined exposure to 20organochlorine compounds. Organic analyses showedthat the dowitchers had been exposed to DDE, PCBs,dieldrin and trans-nonachlor, but with no significantdifferences in concentrations between Hayward andNewark (P > 0.05).     

Recovery of sulfate saturated soils in the Plynlimon catchments, mid-Wales following reductions in atmospheric S inputs from the 1980s to 2011

Sulfate adsorption capacity of B-horizons of base-poor, predominantly stagnopodzol, soils from the Plynlimon catchments, mid-Wales was determined by combination of laboratory adsorption and desorption isotherms. Results show that sulfate adsorption capacity of a range of stagnopodzol (Histic-stagno-podzol (Leptic), WRB), brown podzolic soil (Histic-umbrisol (Leptic), WRB) and stagnohumic gley (Histic-stagno-gleysol, WRB) B-horizons was positively related to the amounts of extractable (pyrophosphate and oxalate) Fe + Al, with the stagnopodzol and brown podzolic soil Bs horizon having the largest adsorption capacity and stagnohumic gley Bg horizon the smallest adsorption capacity. Results show that dissolved organic carbon (DOC) has a negative but limited effect on sulfate adsorption in these soils. Results obtained from a set of historical soil samples revealed that the grassland brown podzolic soil Bs horizon and afforested stagnopodzol Bs horizon were highly saturated with sulfate in the 1980s, at 63% and 89% respectively, whereas data from some recently sampled soil from two sites revisited in 2010-11 indicates that percentage sulfate adsorption saturation has since fallen substantially, to 41% and 50% respectively. Between 1984 and 2009 the annual rainfall-weighted mean excess SO(4)-S concentration in bulk precipitation declined linearly from 0.37 mg S l(-1) to 0.17 mg S l(-1). Over the same period, flow weighted annual mean stream water SO(4)-S concentrations decreased approximately linearly from 1.47 mg S l(-1) to 0.97 mg S l(-1) in the plantation afforested Hafren catchment compared to a drop from 1.25 to 0.69 mg S l(-1) in the adjacent moorland catchment of the Afon Gwy. In flux terms, the mean decrease in annual stream water SO(4)-S flux has been approximately 0.4 kg S ha(-1) yr(-1), whilst the recovery in stream water quality in the Afon Cyff grassland catchment has been partly offset by loss of SO(4)-S by desorption from the soil sulfur pool of approximately 0.2 kg S ha(-1) yr(-1).     

Spatial and temporal analysis of land cover changes and water quality in the Lake Issaqueena watershed,South Carolina

Monitoring changes in land cover and the subsequent environmental responses are essential for water quality assessment, natural resource planning, management, and policies. Over the last 75 years, the Lake Issaqueena watershed has experienced a drastic shift in land use. This study was conducted to examine the changes in land cover and the implied changes in land use that have occurred and their environmental, water quality impacts. Aerial photography of the watershed (1951, 1956, 1968, 1977, 1989, 1999, 2005, 2006, and 2009) was analyzed and classified using the geographic information system (GIS) software. Seven land cover classes were defined: evergreen, deciduous, bare ground, pasture/grassland, cultivated, and residential/other development. Water quality data, including sampling depth, water temperature, dissolved oxygen content, fecal coliform levels, inorganic nitrogen concentrations, and turbidity, were obtained from the South Carolina (SC) Department of Health and Environmental Control (SCDHEC) for two stations and analyzed for trends as they relate to land cover change. From 1951 to 2009, the watershed experienced an increase of tree cover and bare ground (+17.4 % evergreen, +62.3 % deciduous, +9.8 % bare ground) and a decrease of pasture/grassland and cultivated land (?42.6 % pasture/grassland and ?57.1 % cultivated). From 2005 to 2009, there was an increase of 21.5 % in residential/other development. Sampling depth ranged from 0.1 to 0.3 m. Water temperature fluctuated corresponding to changing air temperatures, and dissolved oxygen content fluctuated as a factor of water temperature. Inorganic nitrogen content was higher from December to April possibly due to application of fertilizers prior to the growing season. Turbidity and fecal coliform bacteria levels remained relatively the same from 1962 to 2005, but a slight decline in pH can be observed at both stations. Prior to 1938, the area consisted of single-crop cotton farms; after 1938, the farms were abandoned, leaving large bare areas with highly eroded soil. Starting in 1938, Clemson reforested almost 30 % of the watershed. Currently, three fourths of the watershed is forestland, with a limited coverage of small farms and residential developments. Monitoring water quality is essential in maintaining adequate freshwater supply. Water quality monitoring focuses mainly on the collection of field data, but current water quality conditions depend on the cumulative impacts of land cover change over time.