Lee D. Bryant

Long-term transformation and fate of manufactured ag nanoparticles in a simulated large scale freshwater emergent wetland.

Transformations and long-term fate of engineered nanomaterials must be measured in realistic complex natural systems to accurately assess the risks that they may pose. Here, we determine the long-term behavior of poly(vinylpyrrolidone)-coated silver nanoparticles (AgNPs) in freshwater mesocosms simulating an emergent wetland environment. AgNPs were either applied to the water column or to the terrestrial soils. The distribution of silver among water, solids, and biota, and Ag speciation in soils and sediment was determined 18 months after dosing. Most (70 wt %) of the added Ag resided in the soils and sediments, and largely remained in the compartment in which they were dosed. However, some movement between soil and sediment was observed. Movement of AgNPs from terrestrial soils to sediments was more facile than from sediments to soils, suggesting that erosion and runoff is a potential pathway for AgNPs to enter waterways. The AgNPs in terrestrial soils were transformed to Ag(2)S (~52%), whereas AgNPs in the subaquatic sediment were present as Ag(2)S (55%) and Ag-sulfhydryl compounds (27%). Despite significant sulfidation of the AgNPs, a fraction of the added Ag resided in the terrestrial plant biomass (~3 wt % for the terrestrially dosed mesocosm), and relatively high body burdens of Ag (0.5-3.3 μg Ag/g wet weight) were found in mosquito fish and chironomids in both mesocosms. Thus, Ag from the NPs remained bioavailable even after partial sulfidation and when water column total Ag concentrations are low (<0.002 mg/L).

Hypolimnetic Oxygen Depletion in Eutrophic Lakes

The oxygen-consuming processes in the hypolimnia of freshwater lakes leading to deep-water anoxia are still not well understood, thereby constraining suitable management concepts. This study presents data obtained from 11 eutrophic lakes and suggests a model describing the consumption of dissolved oxygen (O(2)) in the hypolimnia of eutrophic lakes as a result of only two fundamental processes: O(2) is consumed (i) by settled organic material at the sediment surface and (ii) by reduced substances diffusing from the sediment. Apart from a lakes productivity, its benthic O(2) consumption depends on the O(2) concentration in the water overlying the sediment and the molecular O(2) diffusion to the sediment. On the basis of observational evidence of long-term monitoring data from 11 eutrophic lakes, we found that the areal hypolimnetic mineralization rate ranging from 0.47 to 1.31 g of O(2) m(-2) d(-1) (average 0.90 ± 0.30) is a function of (i) a benthic flux of reduced substances (0.37 ± 0.12 g of O(2) m(-2) d(-1)) and (ii) an O(2) consumption which linearly increases with the mean hypolimnion thickness (z(H)) up to ~25 m. This model has important implications for predicting and interpreting the response of lakes and reservoirs to restoration measures.

Controlling soluble iron and manganese in a water-supply reservoir using hypolimnetic oxygenation.

Soluble metals such as iron (Fe) and manganese (Mn) often reach problematic levels in water-supply reservoirs during summer stratification following the onset of hypolimnetic hypoxia. The behavior of soluble and particulate Fe and Mn was studied following the installation of a hypolimnetic oxygenation system in Carvins Cove Reservoir, a water-supply impoundment managed by the Western Virginia Water Authority. During oxygenation, manganese concentrations were very low in the bulk hypolimnion (<0.05 mg l(-1)), but high concentrations (>2.0 mg l(-1)) were still observed in the benthic region close to the sediment, despite near-sediment dissolved oxygen concentrations in excess of 5.0 mg l(-1). Oxygenation appears to affect the location of the oxic/anoxic boundary sufficiently to restrict substantial transport of soluble Mn to the bulk water of the hypolimnion. However, the position of the oxic/anoxic boundary was not uniformly affected along the reservoir bottom, allowing horizontal transport of soluble Mn from higher elevations in contact with hypoxic sediments. During one summer, when the oxygen system was turned off for a month, the soluble Mn in the bulk hypolimnion increased substantially. Oxygen concentrations were quickly restored after the system was turned back on, but elevated levels of soluble Mn persisted until the sedimentation rate of detritus through the hypolimnion increased. When operated without interruption, the oxygenation system was able to reduce the bulk average hypolimnion soluble Mn concentration by up to 97%, indicating that source water control of soluble Mn and Fe can be accomplished with hypolimnetic oxygenation in water-supply reservoirs.

Effect of hypolimnetic oxygenation on oxygen depletion rates in two water-supply reservoirs

Oxygenation systems, such as bubble-plume diffusers, are used to improve water quality by replenishing dissolved oxygen (DO) in the hypolimnia of water-supply reservoirs. The diffusers induce circulation and mixing, which helps distribute DO throughout the hypolimnion. Mixing, however, has also been observed to increase hypolimnetic oxygen demand (HOD) during system operation, thus accelerating oxygen depletion. Two water-supply reservoirs (Spring Hollow Reservoir (SHR) and Carvins Cove Reservoir (CCR)) that employ linear bubble-plume diffusers were studied to quantify diffuser effects on HOD. A recently validated plume model was used to predict oxygen addition rates. The results were used together with observed oxygen accumulation rates to evaluate HOD over a wide range of applied gas flow rates. Plume-induced mixing correlated well with applied gas flow rate and was observed to increase HOD. Linear relationships between applied gas flow rate and HOD were found for both SHR and CCR. HOD was also observed to be independent of bulk hypolimnion oxygen concentration, indicating that HOD is controlled by induced mixing. Despite transient increases in HOD, oxygenation caused an overall decrease in background HOD, as well as a decrease in induced HOD during diffuser operation, over several years. This suggests that the residual or background oxygen demand decreases from one year to the next. Despite diffuser-induced increases in HOD, hypolimnetic oxygenation remains a viable method for replenishing DO in thermally-stratified water-supply reservoirs such as SHR and CCR.

Increased sediment oxygen uptake caused by oxygenation-induced hypolimnetic mixing.

Hypolimnetic oxygenation systems (HOx) are increasingly used in lakes and reservoirs to elevate dissolved oxygen (O(2)) while preserving stratification, thereby decreasing concentrations of reduced chemical species in the hypolimnion. By maintaining an oxic zone in the upper sediment, HOx suppress fluxes of reduced soluble species from the sediment into the overlying water. However, diminished HOx performance has been observed due to HOx-induced increases in sediment O(2) uptake. Based on a series of in situ O(2) microprofile and current velocity measurements, this study evaluates the vertical O(2) distribution at the sediment-water interface as a function of HOx operation. These data were used to determine how sediment O(2) uptake rate (JO2) and sediment oxic-zone depth (z(max)) were affected by applied oxygen-gas flow rate, changes in near-sediment mixing and O(2) concentration, and proximity to the HOx. The vertical sediment-water O(2) distribution was found to be strongly influenced by oxygenation on a reservoir-wide basis. Elevated JO2 and an oxic sediment zone were maintained during continuous HOx operation, with z(max) increasing linearly with HOx flow rate. In contrast, JO2 decreased to zero and the sediment became anoxic as the vertical O(2) distribution at the sediment-water interface collapsed during periods when the HOx was turned off and near-sediment mixing and O(2) concentrations decreased. JO2 and z(max) throughout the reservoir were found to be largely governed by HOx-induced mixing rather than O(2) levels in the water column. By quantifying how JO2 and z(max) vary in response to HOx operations, this work (1) characterizes how hypolimnetic oxygenation affects sediment O(2) dynamics, (2) contributes to the optimization of water quality and management of HOx-equipped lakes and reservoirs, and (3) enhances understanding of the effect of mixing and O(2) concentrations in other systems.

Response of sediment microbial community structure in a freshwater reservoir to manipulations in oxygen availability

Hypolimnetic oxygenation systems (HOx) are being increasingly used in freshwater reservoirs to elevate dissolved oxygen levels in the hypolimnion and suppress sediment-water fluxes of soluble metals (e.g. Fe and Mn) which are often microbially mediated. We assessed changes in sediment microbial community structure and corresponding biogeochemical cycling on a reservoir-wide scale as a function of HOx operations. Sediment microbial biomass as quantified by DNA concentration was increased in regions most influenced by the HOx. Following an initial decrease in biomass in the upper sediment while oxygen concentrations were low, biomass typically increased at all depths as the 4-month-long oxygenation season progressed. A distinct shift in microbial community structure was only observed at the end of the season in the upper sediment near the HOx. While this shift was correlated to HOx-enhanced oxygen availability, increased TOC levels and precipitation of Fe- and Mn-oxides, abiotic controls on Fe and Mn cycling, and/or the adaptability of many bacteria to variations in prevailing electron acceptors may explain the delayed response and the comparatively limited changes at other locations. While the sediment microbial community proved remarkably resistant to relatively short-term changes in HOx operations, HOx-induced variation in microbial structure, biomass, and activity was observed after a full season of oxygenation.

Increased sediment oxygen flux in lakes and reservoirs: The impact of hypolimnetic oxygenation

Hypolimnetic oxygenation is an increasingly common lake management strategy for mitigating hypoxia/anoxia and associated deleterious effects on water quality. A common effect of oxygenation is increased oxygen consumption in the hypolimnion and predicting the magnitude of this increase is the crux of effective oxygenation system design. Simultaneous measurements of sediment oxygen flux (JO2) and turbulence in the bottom boundary layer of two oxygenated lakes were used to investigate the impact of oxygenation on JO2. Oxygenation increased JO2 in both lakes by increasing the bulk oxygen concentration, which in turn steepens the diffusive gradient across the diffusive boundary layer. At high flow rates, the diffusive boundary layer thickness decreased as well. A transect along one of the lakes showed JO2 to be spatially quite variable, with near-field and far-field JO2 differing by a factor of 4. Using these in situ measurements, physical models of interfacial flux were compared to microprofile-derived JO2 to determine which models adequately predict JO2 in oxygenated lakes. Models based on friction velocity, turbulence dissipation rate, and the integral scale of turbulence agreed with microprofile-derived JO2 in both lakes. These models could potentially be used to predict oxygenation-induced oxygen flux and improve oxygenation system design methods for a broad range of reservoir systems.

Estimating the microbiological risks associated with inland flood events: Bridging theory and models of pathogen transport

ABSTRACT Flooding is known to facilitate infectious disease transmission, yet quantitative research on microbiological risks associated with floods has been limited. Pathogen fate and transport models provide a framework to examine interactions between landscape characteristics, hydrology, and waterborne disease risks, but have not been widely developed for flood conditions. We critically examine capabilities of current hydrological models to represent unusual flow paths, nonuniform flow depths, and unsteady flow velocities that accompany flooding. We investigate the theoretical linkages between hydrodynamic processes and spatiotemporally variable suspension and deposition of pathogens from soils and sediments; pathogen dispersion in flow; and concentrations of constituents influencing pathogen transport and persistence. Identifying gaps in knowledge and modeling practice, we propose a research agenda to strengthen microbial fate and transport modeling applied to inland floods: (1) development of models incorporating pathogen discharges from flooded sources (e.g., latrines), effects of transported constituents on pathogen persistence, and supply-limited pathogen transport; (2) studies assessing parameter identifiability and comparing model performance under varying degrees of process representation, in a range of settings; (3) development of remotely sensed data sets to support modeling of vulnerable, data-poor regions; and (4) collaboration between modelers and field-based researchers to expand the collection of useful data in situ.

The Panarea natural CO2 seeps: fate and impact of the leaking gas (PaCO2) ; R/V URANIA, Cruise No. U10/2011, 27 July – 01 August 2011, Naples (Italy) – Naples (Italy)

Carbon capture and storage (CCS), both on- and offshore, is expected to be an important technique to mitigate anthropogenic effects on global climate by isolating man-made carbon dioxide (CO2) in deep geological formations. In marine environments, however, the potential impacts of CO2 leakage, appropriate detection methods, and risk and pathways of atmospheric emissions are poorly defined. The natural CO2 gas seeps that occur in the relatively shallow waters off the coast of Panarea Island (Aeolian Islands, Italy) can be studied as a large-scale, real-world analogue of what might occur at a leaking offshore CCS site and what tools can be used to study it. The oceanographic survey PaCO2 was performed aboard R/V Urania from 27 July – 01 August 2011 (Naples – Naples). The project’s ship-time was funded by Eurofleets, with work being performed as a sub-project of the Seventh Framework Programme projects “ECO2” and “RISCS”, which provided subsidiary funding. Large amounts of data and samples were collected during the cruise which will be interpreted in the coming months, with preliminary results detailed here. Of particular importance was the discovery of much larger areas showing gas seepage than previously reported. Interdisciplinary measurements were performed at the Panarea seepage site. The international team of scientists onboard R/V Urania performed complementary sampling and measurements for biological, chemical, and physical parameters throughout the area. Together with the dedication of R/V Urania’s Captain and crew, and the eagerness and cooperation of the scientific crew, we were able to obtain excellent scientific results during this six-day cruise.