Modeling Streamflow and Water Quality Sensitivity to Climate Change and Urban Development in 20 U.S. Watersheds

Watershed modeling in 20 large, United States (U.S.) watersheds addresses gaps in our knowledge of streamflow, nutrient (nitrogen and phosphorus), and sediment loading sensitivity to mid‐21st Century climate change and urban/residential development scenarios. Use of a consistent methodology facilitates regional scale comparisons across the study watersheds. Simulations use the Soil and Water Assessment Tool. Climate change scenarios are from the North American Regional Climate Change Assessment Program dynamically downscaled climate model output. Urban and residential development scenarios are from U.S. Environmental Protection Agency's Integrated Climate and Land Use Scenarios project. Simulations provide a plausible set of streamflow and water quality responses to mid‐21st Century climate change across the U.S. Simulated changes show a general pattern of decreasing streamflow volume in the central Rockies and Southwest, and increases on the East Coast and Northern Plains. Changes in pollutant loads follow a similar pattern but with increased variability. Ensemble mean results suggest that by the mid‐21st Century, statistically significant changes in streamflow and total suspended solids loads (relative to baseline conditions) are possible in roughly 30‐40% of study watersheds. These proportions increase to around 60% for total phosphorus and total nitrogen loads. Projected urban/residential development, and watershed responses to development, are small at the large spatial scale of modeling in this study.     

Evaluation of methylene blue and riboflavin for the photosensitized degradation of ethylene glycol

Degradation rates ranging from 0.22 ± 0.11 to 1.52 ± 0.50 mg/L-h were measured for ethylene glycol in riboflavin solutions exposed to natural sunlight. Significant degradation rates were noted in systems using 6 and 10 mg/L riboflavin at pH values of 4, 7, and 10. No significant degradation was found in systems using methylene blue as the photosensitizing agent. Possible mechanisms for ethylene glycol degradation include a combination hydrogen or electron abstraction by an excited photosensitizer and reaction with singlet oxygen or reaction with superoxide radicals.     

Migration of saline solutions in variably saturated porous media

Migration of concentrated NaNO3 solutions in homogeneous packs of pre-wetted silica sands was investigated using a light transmission system. Solutions of 5 molal NaNO3 were found to migrate downward 24-62% faster than pure water, in an unstable, fingered manner. This behavior was attributed primarily to a surface tension induced, non-zero apparent contact angle between the imbibing and the resident fluids. For saline solutions of similar surface tension to that of pure water (achieved by the addition of 2% methanol), the migration rates and plume shapes were comparable to that of water, demonstrating that density was not the primary source of the observed differences in migration patterns. At depths where resident saturation increased above residual, the migration process appeared to occur via film flow with slight changes in saturation (<4%), rather than in a series of abrupt jumps, as observed at shallower depths. A method for contact angle scaling was used to illustrate the effects of non-zero contact angles on capillary pressure-saturation curves.     

Understanding the sources and composition of the incremental excess of fine particles across multiple sampling locations in one air shed

Well-designed health studies and the development of effective regulatory policies need to rely on an understanding of the incremental differences in particulate matter concentrations and their sources. Although only a limited number of studies have been conducted to examine spatial differences in sources to particulate matter within an air shed, routine monitoring data can be used to better understand these differences. Measurements from the US EPA Chemical Speciation Network （CSN） collected between 2002-2008 were analyzed to demonstrate the utility of regulatory data across three sites located within 100 km of each other. Trends in concentrations, source contribution, and incremental excesses across three sites were investigated using the Positive Matrix Factorization model. Similar yearly trends in chemical composition were observed across all sites, however, excesses of organic matter and elemental carbon were observed in the urban center that originated from local emissions of mobile sources and biomass buming. Secondary sulfate and secondary nitrate constituted over half of the PM2.5 with no spatial differences observed across sites. For these components, the excess of emissions from industrial sources could be directly quantified. This study demonstrates that CSN data from multiple sites can be successfully used to derive consistent source profiles and source contributions for regional pollution, and that CSN data can be used to quantify incremental differences in source contributions of across these sites. The analysis strategy can be used in other regions of the world to take advantage of existing ambient particulate matter monitoring data to better the understanding of spatial differences in source contributions within a given air shed.     

Surface ozone-temperature relationships in the eastern US: A monthly climatology for evaluating chemistry-climate models

We use long-term, coincident O₃ and temperature measurements at the regionally representative US Environmental Protection Agency Clean Air Status and Trends Network (CASTNet) over the eastern US from 1988 through 2009 to characterize the surface O₃ response to year-to-year fluctuations in weather, for the purpose of evaluating global chemistry-climate models. We first produce a monthly climatology for each site over all available years, defined as the slope of the best-fit line (m_O3-T) between monthly average values of maximum daily 8-hour average (MDA8) O₃ and monthly average values of daily maximum surface temperature (T_max). Applying two distinct statistical approaches to aggregate the site-specific measurements to the regional scale, we find that summer time m_O3-T is 3–6 ppb K^?1 (r = 0.5–0.8) over the Northeast, 3–4 ppb K^?1 (r = 0.5–0.9) over the Great Lakes, and 3–6 ppb K^?1 (r = 0.2–0.8) over the Mid-Atlantic. The Geophysical Fluid Dynamics Laboratory (GFDL) Atmospheric Model version 3 (AM3) global chemistry-climate model generally captures the seasonal variations in correlation coefficients and m_O3-T despite biases in both monthly mean summertime MDA8 O₃ (up to +10 to +30 ppb) and daily T_max (up to +5 K) over the eastern US. During summer, GFDL AM3 reproduces m_O3-T over the Northeast (m_O3-T = 2–6 ppb K^?1; r = 0.6–0.9), but underestimates m_O3-T by 4 ppb K^?1 over the Mid-Atlantic, in part due to excessively warm temperatures above which O₃ production saturates in the model. Combining T_max biases in GFDL AM3 with an observation-based m_O3-T estimate of 3 ppb K^?1implies that temperature biases could explain up to 5–15 ppb of the MDA8 O₃ bias in August and September though correcting for excessively cool temperatures would worsen the O₃ bias in June. We underscore the need for long-term, coincident measurements of air pollution and meteorological variables to develop process-level constraints for evaluating chemistry-climate models used to project air quality responses to climate change.     

Forecasts of habitat loss and fragmentation due to urban growth are sensitive to source of input data

The conversion of natural habitat to urban settlements is a primary driver of biodiversity loss, and species' persistence is threatened by the extent, location, and spatial pattern of development. Urban growth models are widely used to anticipate future development and to inform conservation management, but the source of spatial input to these models may contribute to uncertainty in their predictions. We compared two sources of historic urban maps, used as input for model calibration, to determine how differences in definition and scale of urban extent affect the resulting spatial predictions from a widely used urban growth model for San Diego County, CA under three conservation scenarios. The results showed that rate, extent, and spatial pattern of predicted urban development, and associated habitat loss, may vary substantially depending on the source of input data, regardless of how much land is excluded from development. Although the datasets we compared both represented urban land, different types of land use/land cover included in the definition of urban land and different minimum mapping units contributed to the discrepancies. Varying temporal resolution of the input datasets also contributed to differences in projected rates of development. Differential predicted impacts to vegetation types illustrate how the choice of spatial input data may lead to different conclusions relative to conservation. Although the study cannot reveal whether one dataset is better than another, modelers should carefully consider that geographical reality can be represented differently, and should carefully choose the definition and scale of their data to fit their research objectives.     

Watershed-based pollution trading development and current trading programs

Watershed-based pollution trading is a very recent water quality management development — preliminary guidance for its use was issued by the EPA in 1996 and final trading guidelines were expected to be published in late 1999. As innovative and flexible methods of maintaining water quality in unique water-sheds, the few existing watershed-based pollution trading programs are extremely distinct in terms of development, implementation, and outcome. The diversity of the existing trading programs exemplifies the flexibility that exists to conform trading programs to manage nearly any site-specific watershed pollution problem. Although the use of watershed-based pollution trading is relatively unproven, observation of the existing trading programs indicates that trading has the potential to improve water quality in heavily impaired watersheds.     

Evaluation of a conceptual model for the subsurface transport of plutonium involving surface mediated reduction of PuV to PuIV

A conceptual model is proposed to explain the transport behavior of plutonium in laboratory columns packed with a sandy coastal soil from the U.S. Department of Energy (DOE)'s Savannah River Site. The column transport experiments involved the introduction of a finite step input of plutonium, predominately in the +5 oxidation state, into the columns followed by elution with a low-carbonate solution of 0.02 M NaClO4 at pH 3, 5, and 8. Total plutonium concentrations were measured in the effluent as a function of time. These elution profiles suggest at least two distinct physical/chemical forms of plutonium, each with a different mobility. To explain the observed behavior, the following conceptual model was evaluated: [1] equilibrium partitioning of plutonium (V) and plutonium (IV) between the aqueous and sorbed phases as defined by pH-dependent, oxidation-state specific distribution coefficients and [2] kinetic reduction of plutonium (V) to plutonium (IV) in the sorbed phase. The conceptual model was applied to the column experiments through a one-dimensional advective/dispersive mathematical model, and predictions of the mathematical model were compared with the experimental data. Overall, the model was successful in predicting some of the major features observed in the experiments. It also yielded quantitative estimates of the rate constant for surface mediated reduction of plutonium (V) to plutonium (IV) that were of the same order (10(-4) to 10(-5) s(-1)) as those calculated from batch data both for this soil and for goethite.