The Influence of Varying Algal Biomass On Contaminant Exposure in Benthic-Planktonic Mesocosms: Copper (Ii)

Abstract

A series of mesocosms was exposed to a suite of light treatments and nutrient enrichment in order to generate algal communities of varying biomass. the influence of this biomass on the speciation of copper (II) was studied. Distribution coefficients ( _Kd,Lkg?1) were relatively high (log _Kd = 5 to 7), indicative of robust trace metal sequestration, and were likely controlled by the particulate organic carbon content (foc). Differences in _Kd over time and among treatments were significant, as was the relationship between _Kd and foc. Fluorescence quenching was used to determine binding capacities ( _Lt , M) and their associated binding constants ( _Kcond ,M^?1) in order to model the solid phase copper speciation. the _Kcond ranged between 2.1 and 5.2 × 10¹²M^?1, indicating a very strong copper-ligand complex, and was higher in mesocosms that received more light. the light _Lt increased over time, dramatically after the nutrient enrichment, but did not vary systematically among light treatments. _Lt ranged from 7.2 × 10? 7 to 4.9 × 10? 5 M. the large magnitudes of _Kd , _Kcond and _Lt ensured that greater than 97% of total copper in the mesocosms was complexed by organic matter. the total copper concentration ([Cu]_T, M) needed to reach a target dissolved copper concentration of 10^?12.5 M (pCu = 12.5) was determined for each mesocosm over time. [Cu]_T was between 8.02 × 10^?5 and 3.41 × 10^?2 M, and increased over time. the [Cu]_T normalized to the target pCu (Effective Dose Ratio, EDR) increased directly with increases in algal biomass, indicating a direct link between system productivity and copper exposure. Approximately 45% of the variance in EDR was explained by variance in total biomass, while the residual variance in EDR was due likely to differences in the strengths of particle associations and magnitude of binding capacities.     

Blockage of saline intrusions in restricted,two-layer exchange flows across a submerged sill obstruction

Results are presented from a series of large-scale experiments investigating the internal and near-bed dynamics of bi-directional stratified flows with a net-barotropic component across a submerged, trapezoidal, sill obstruction. High-resolution velocity and density profiles are obtained in the vicinity of the obstruction to observe internal-flow dynamics under a range of parametric forcing conditions (i.e. variable saline and fresh water volume fluxes; density differences; sill obstruction submergence depths). Detailed synoptic velocity fields are measured across the sill crest using 2D particle image velocimetry, while the density structure of the two-layer exchange flows is measured using micro-conductivity probes at several sill locations. These measurements are designed to aid qualitative and quantitative interpretation of the internal-flow processes associated with the lower saline intrusion layer blockage conditions, and indicate that the primary mechanism for this blockage is mass exchange from the saline intrusion layer due to significant interfacial mixing and entrainment under dominant, net-barotropic, flow conditions in the upper freshwater layer. This interfacial mixing is quantified by considering both the isopycnal separation of vertically-sorted density profiles across the sill, as well as calculation of corresponding Thorpe overturning length scales. Analysis of the synoptic velocity fields and density profiles also indicates that the net exchange flow conditions remain subcritical (G < 1) across the sill for all parametric conditions tested. An analytical two-layer exchange flow model is then developed to include frictional and entrainment effects, both of which are needed to account for turbulent stresses and saline entrainment into the upper freshwater layer. The experimental results are used to validate two key model parameters: (1) the internal-flow head loss associated with boundary friction and interfacial shear; and (2) the mass exchange from the lower saline layer into the upper fresh layer due to entrainment.     

Pharmaceuticals and other organic chemicals in selected north-central and northwestern Arkansas streams

Recently, our attention has focused on the low level detection of many antibiotics, pharmaceuticals, and other organic chemicals in water resources. The limited studies available suggest that urban or rural streams receiving wastewater effluent are more susceptible to contamination. The purpose of this study was to evaluate the occurrence of antibiotics, pharmaceuticals, and other organic chemicals at 18 sites on seven selected streams in Arkansas, USA, during March, April, and August 2004. Water samples were collected upstream and downstream from the influence of effluent discharges in northwestern Arkansas and at one site on a relatively undeveloped stream in north-central Arkansas. At least one antibiotic, pharmaceutical, or other organic chemical was detected at all sites, except at Spavinaw Creek near Mayesville, Arkansas. The greatest number of detections was observed at Mud Creek downstream from an effluent discharge, including 31 pharmaceuticals and other organic chemicals. The detection of these chemicals occurred in higher frequency at sites downstream from effluent discharges compared to those sites upstream from effluent discharges; total chemical concentration was also greater downstream. Wastewater effluent discharge increased the concentrations of detergent metabolites, fire retardants, fragrances and flavors, and steroids in these streams. Antibiotics and associated degradation products were only found at two streams downstream from effluent discharges. Overall, 42 of the 108 chemicals targeted in this study were found in water samples from at least one site, and the most frequently detected organic chemicals included caffeine, phenol, para-cresol, and acetyl hexamethyl tetrahydro naphthalene (AHTN).     

Chemical fractionation of Cu and Zn in stormwater, roadway dust and stormwater pond sediments

This study evaluated the chemical fractionation of Cu and Zn from source to deposition in a stormwater system. Cu and Zn concentrations and chemical fractionation were determined for roadway dust, roadway runoff and pond sediments. Stormwater Cu and Zn concentrations were used to generate cumulative frequency distributions to characterize potential exposure to pond-dwelling organisms. Dissolved stormwater Zn exceeded USEPA acute and chronic water quality criteria in approximately 20% of storm samples and 20% of the storm duration sampled. Dissolved Cu exceeded the previously published chronic criterion in 75% of storm samples and duration and exceeded the acute criterion in 45% of samples and duration. The majority of sediment Cu (92-98%) occurred in the most recalcitrant phase, suggesting low bioavailability; Zn was substantially more available (39-62% recalcitrant). Most sediment concentrations for Cu and Zn exceeded published threshold effect concentrations and Zn often exceeded probable effect concentrations in surface sediments.     

Pragmatic estimation of a spatio-temporal air quality model with irregular monitoring data

Statistical analyses of health effects of air pollution have increasingly used GIS-based covariates for prediction of ambient air quality in “land use” regression models. More recently these spatial regression models have accounted for spatial correlation structure in combining monitoring data with land use covariates. We present a flexible spatio-temporal modeling framework and pragmatic, multi-step estimation procedure that accommodates essentially arbitrary patterns of missing data with respect to an ideally complete space by time matrix of observations on a network of monitoring sites. The methodology incorporates a model for smooth temporal trends with coefficients varying in space according to Partial Least Squares regressions on a large set of geographic covariates and nonstationary modeling of spatio-temporal residuals from these regressions. This work was developed to provide spatial point predictions of PM_2.5 concentrations for the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air) using irregular monitoring data derived from the AQS regulatory monitoring network and supplemental short-time scale monitoring campaigns conducted to better predict intra-urban variation in air quality. We demonstrate the interpretation and accuracy of this methodology in modeling data from 2000 through 2006 in six U.S. metropolitan areas and establish a basis for likelihood-based estimation.     

UV–visible light-activated Ag-decorated,monodisperse TiO2 aggregates for treatment of the pharmaceutical oxytetracycline

Noble metal Ag-decorated, monodisperse TiO₂ aggregates were successfully synthesized by an ionic strength-assisted, simple sol–gel method and were used for the photocatalytic degradation of the antibiotic oxytetracycline (OTC) under both UV and visible light (UV–visible light) irradiation. The synthesized samples were characterized by X-ray diffraction analysis (XRD); UV–vis diffuse reflectance spectroscopy; environmental scanning electron microscopy (ESEM); transmission electron microscopy (TEM); high-resolution TEM (HR-TEM); micro-Raman, energy-dispersive X-ray spectroscopy (EDS); and inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that the uniformity of TiO₂ aggregates was finely tuned by the sol–gel method, and Ag was well decorated on the monodisperse TiO₂ aggregates. The absorption of the samples in the visible light region increased with increasing Ag loading that was proportional to the amount of Ag precursor added in the solution over the tested concentration range. The Brunauer, Emmett, and Teller (The BET) surface area slightly decreased with increasing Ag loading on the TiO₂ aggregates. Ag-decorated TiO₂ samples demonstrated enhanced photocatalytic activity for the degradation of OTC under UV–visible light illumination compared to that of pure TiO₂. The sample containing 1.9 wt% Ag showed the highest photocatalytic activity for the degradation of OTC under both UV–visible light and visible light illumination. During the experiments, the detected Ag leaching for the best TiO₂-Ag photocatalyst was much lower than the National Secondary Drinking Water Regulation for Ag limit (0.1 mg L^?1) issued by the US Environmental Protection Agency.     

Biochemical responses in armored catfish (Pterygoplichthys anisitsi) after short-term exposure to diesel oil,pure biodiesel and biodiesel blends

Biodiesel fuel is gradually replacing petroleum-based diesel oil use. Despite the biodiesel being considered friendlier to the environment, little is known about its effects in aquatic organisms. In this work we evaluated whether biodiesel exposure can affect oxidative stress parameters and biotransformation enzymes in armored catfish (Pterygoplichthys anisitsi, Loricariidae), a South American endemic species. Thus, fish were exposed for 2 and 7 d to 0.01 mL L⁻¹ and 0.1 mL L⁻¹ of pure diesel, pure biodiesel (B100) and blends of diesel with 5% (B5) and 20% (B20) biodiesel. Lipid peroxidation (malondialdehyde) levels and the activities of the enzymes glutathione S-transferase, superoxide dismutase, catalase and glutathione peroxidase were measured in liver and gills. Also, DNA damage (8-oxo-7, 8-dihydro-2′-deoxyguanosine) levels in gills and 7-ethoxyresorufin-O-deethylase activity in liver were assessed. Pure diesel, B5 and B20 blends changed most of the enzymes tested and in some cases, B5 and B20 induced a higher enzyme activity than pure diesel. Antioxidant system activation in P. anisitsi was effective to counteract reactive oxygen species effects, since DNA damage and lipid peroxidation levels were maintained at basal levels after all treatments. However, fish gills exposed to B20 and B100 presented increased lipid peroxidation. Despite biodiesel being more biodegradable fuel that emits less greenhouse gases, the increased lipid peroxidation showed that biofuel and its blends also represent hazards to aquatic biota.     

Returning home: resettlement of formerly abducted children in Northern Uganda

This exploratory qualitative study considers the subjective resettlement experiences of children forced into armed conflict in Northern Uganda from the perspectives of 11 former child combatants and 11 adult community members. A thematic analysis was performed on the narrative data. The bioecological model was used to provide a conceptual framework for key themes. Major findings included the overarching impact of ongoing armed conflict on returnees' lives, the important role of the family in supporting children's resettlement, the harassment of former child soldiers by community members, and the community's inability to support systematically the returning children in tangible ways. This study recommends that humanitarian services at all levels strengthen the capacity of families to care for the material and psychoemotional needs of former child soldiers within their communities.