Modeling contaminant behavior in Lake Superior : a comparison of PCBs, PBDEs, and mercury

A mass‐balance model for Lake Superior was applied to polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and mercury to determine the major routes of entry and the major mechanisms of loss from this ecosystem as well as the time required for each contaminant class to approach steady state. A two‐box model (water column, surface sediments) incorporating seasonally adjusted environmental parameters was used. Both numerical (forward Euler) and analytical solutions were employed and compared. For validation, the model was compared with current and historical concentrations and fluxes in the lake and sediments. Results for PCBs were similar to prior work showing that air‐water exchange is the most rapid input and loss process. The model indicates that mercury behaves similarly to a moderately‐chlorinated PCB, with air‐water exchange being a relatively rapid input and loss process. Modeled accumulation fluxes of PBDEs in sediments agreed with measured values reported in the literature. Wet deposition rates were about three times greater than dry particulate deposition rates for PBDEs. Gas deposition was an important process for tri‐ and tetra‐BDEs (BDEs 28 and 47), but not for higher‐brominated BDEs. Sediment burial was the dominant loss mechanism for most of the PBDE congeners while volatilization was still significant for tri‐ and tetra‐BDEs. Because volatilization is a relatively rapid loss process for both mercury and the most abundant PCBs (tri‐ through penta‐), the model predicts that similar times (from 2 ‐ 10 yr) are required for the compounds to approach steady state in the lake. The model predicts that if inputs of Hg(II) to the lake decrease in the future then concentrations of mercury in the lake will decrease at a rate similar to the historical decline in PCB concentrations following the ban on production and most uses in the U.S. In contrast, PBDEs are likely to respond more slowly if atmospheric concentrations are reduced in the future because loss by volatilization is a much slower process for PBDEs, leading to lesser overall loss rates for PBDEs in comparison to PCBs and mercury. Uncertainties in the chemical degradation rates and partitioning constants of PBDEs are the largest source of uncertainty in the modeled times to steady‐state for this class of chemicals. The modeled organic PBT loading rates are sensitive to uncertainties in scavenging efficiencies by rain and snow, dry deposition velocity, watershed runoff concentrations, and uncertainties in air‐water exchange such as the effect of atmospheric stability.

Modeling particulate organic matter diagenesis with SED2K

Diagenesis of particulate organic matter in lake sediments consumes and produces chemical species that have significant effects on water quality, e.g. oxygen and nitrate depletion and attendant mediation of nutrient and metal recycling. A mechanistic, mass balance model (SED2K) is applied here in quantifying the time course and magnitude of sediment response to reductions in depositional fluxes of organic matter. In applying the model, direct, site-specific measurements of the sedimentation and POM rates in Onondaga Lake are used, leaving only the diagenesis coefficient (solubilization) for estimation by fit to downcore POM profiles. Model calibration is constrained by the dual requirement that both POM profiles and the time series of efflux of the products of diagenesis must be matched. Simulations point to the existence of POM preservation processes at depth, a phenomenon that may enhance the timing and magnitude of lake recovery.

Investigation of surface water/groundwater relationships in a rural watershed in Southern Honduras

Despite failed attempts at obtaining a potable water system, the village of El Caracol in Southern Honduras remains committed to improving access to water resources. To assist in this endeavor, an investigation of the hydrogeological characteristics of the local watershed was conducted. Daily precipitation was recorded to examine the relationship between precipitation and approximated river and spring discharges. A Thornthwaite Mather Water Balance Model was used to predict monthly discharges for comparison with observed values, and to infer the percentage of topographic watersheds contributing to the respective discharges. As aquifer porosity in this region is thought to be primarily secondary (i.e., fractures), field observed lineaments were compared with those interpreted from remote sensing imagery in an attempt to determine the usefulness of these interpretations in locating potential water sources for a future project.

WATER RESOURCES, HEALTH, AND THE SUSTAINABILITY OF INTERVENTIONS TO ACHIEVE WATER AND SANITATION TARGETS OF THE MILLENNIUM DEVELOPMENT GOALS IN A CHANGING WORLD

This dissertation addresses sustainability of rapid provision of safe water and sanitation required to meet the Millennium Development Goals. Review of health-related literature and global statistics demonstrates engineers' role in achieving the MDGs. This review is followed by analyses relating to social, environmental, and health aspects of meeting MDG targets. Analysis of national indicators showed that inadequate investment, poor or nonexistent policies and governance are challenges to global sanitation coverage in addition to lack of financial resources and gender disparity. Although water availability was not found to be a challenge globally, geospatial analysis demonstrated that water availability is a potentially significant barrier for up to 46 million people living in urban areas and relying on already degraded water resources for environmental income. A daily water balance model incorporating the National Resources Conservation Services curve number method in Bolivian watersheds showed that local water stress is linked to climate change because of reduced recharge. Agricultural expansion in the region slightly exacerbates recharge reductions. Although runoff changes will range from -17% to 14%, recharge rates will decrease under all climate scenarios evaluated (-14% to -27%). Increasing sewer coverage may place stress on the readily accessible natural springs, but increased demand can be sustained if other sources of water supply are developed. This analysis provides a method for hydrological analysis in data scarce regions. Data required for the model were either obtained from publicly available data products or by conducting field work using low-cost methods feasible for local participants. Lastly, a methodology was developed to evaluate public health impacts of increased household water access resulting from domestic rainwater harvesting, incorporating knowledge of water requirements of sanitation and hygiene technologies. In 37 West African cities, domestic rainwater harvesting has the potential to reduce diarrheal disease burden by 9%, if implemented alone with 400 L storage. If implemented in conjunction with point of use treatment, this reduction could increase to 16%. The methodology will contribute to cost-effectiveness evaluations of interventions as well as evaluations of potential disease burden resulting from reduced water supply, such as reductions observed in the Bolivian communities.

Using water balance models to approximate the effects of climate change on spring catchment discharge : Mt. Hanang, Tanzania

This project addresses the potential impacts of changing climate on dry-season water storage and discharge from a small, mountain catchment in Tanzania. Villagers and water managers around the catchment have experienced worsening water scarcity and attribute it to increasing population and demand, but very little has been done to understand the physical characteristics and hydrological behavior of the spring catchment. The physical nature of the aquifer was characterized and water balance models were calibrated to discharge observations so as to be able to explore relative changes in aquifer storage resulting from climate changes. To characterize the shallow aquifer supplying water to the Jandu spring, water quality and geochemistry data were analyzed, discharge recession analysis was performed, and two water balance models were developed and tested. Jandu geochemistry suggests a shallow, meteorically-recharged aquifer system with short circulation times. Baseflow recession analysis showed that the catchment behavior could be represented by a linear storage model with an average recession constant of 0.151/month from 2004-2010. Two modified Thornthwaite-Mather Water Balance (TMWB) models were calibrated using historic rainfall and discharge data and shown to reproduce dry-season flows with Nash-Sutcliffe efficiencies between 0.86 and 0.91. The modified TMWB models were then used to examine the impacts of nineteen, perturbed climate scenarios to test the potential impacts of regional climate change on catchment storage during the dry season. Forcing the models with realistic scenarios for average monthly temperature, annual precipitation, and seasonal rainfall distribution demonstrated that even small climate changes might adversely impact aquifer storage conditions at the onset of the dry season. The scale of the change was dependent on the direction (increasing vs. decreasing) and magnitude of climate change (temperature and precipitation). This study demonstrates that small, mountain aquifer characterization is possible using simple water quality parameters, recession analysis can be integrated into modeling aquifer storage parameters, and water balance models can accurately reproduce dry-season discharges and might be useful tools to assess climate change impacts. However, uncertainty in current climate projections and lack of data for testing the predictive capabilities of the model beyond the present data set, make the forecasts of changes in discharge also uncertain. The hydrologic tools used herein offer promise for future research in understanding small, shallow, mountainous aquifers and could potentially be developed and used by water resource professionals to assess climatic influences on local hydrologic systems.