Assessing inter-laboratory comparability and limits of determination for the analysis of cyclic volatile methyl siloxanes in whole Rainbow Trout (Oncorhynchus mykiss)

Cyclic volatile methyl siloxanes (cVMS) are high volume production chemicals used in a wide range of industrial and consumer products. Three cVMS compounds (D4, D5, and D6) have and are undergoing environmental risk evaluations in several countries and have been proposed for legal regulation in Canada. As interest in monitoring concentrations of these chemicals in the environment increase, there is a need to evaluate the analytical procedures for cVMS in biological matrices in order to assess the quality of data produced. The purpose of this study was to determine laboratory testing performance for measuring residues of D4, D5, and D6 in a standard set of fish homogenate samples and to estimate limits of determination for each substance. The samples sent to each laboratory consisted of homogenized whole body tissues of hatchery raised rainbow trout which were fed food fortified with D4, D5, and D6 (dosed) and trout that were fed standard food rations (control). The participants analyzed each sample using their analytical method of choice using their own standards and procedures for quantification and quality control. With a few exceptions, participating laboratories generated comparable results for D4, D5, and D6 in both the dosed and control samples having z-scores between 2 and −2. Method detection limits for the whole fish matrix were on average 2.4 ng g⁻¹ ww for D4, 2.3 ng g⁻¹ ww for D5, and 1.8 ng g⁻¹ ww for D6.     

The impact of nitrogen deposition on acid grasslands in the Atlantic region of Europe

A survey of 153 acid grasslands from the Atlantic biogeographic region of Europe indicates that chronic nitrogen deposition is changing plant species composition and soil and plant-tissue chemistry. Across the deposition gradient (2-44 kg N ha⁻¹ yr⁻¹) grass richness as a proportion of total species richness increased whereas forb richness decreased. Soil C:N ratio increased, but soil extractable nitrate and ammonium concentrations did not show any relationship with nitrogen deposition. The above-ground tissue nitrogen contents of three plant species were examined: Agrostis capillaris (grass), Galium saxatile (forb) and Rhytidiadelphus squarrosus (bryophyte). The tissue nitrogen content of neither vascular plant species showed any relationship with nitrogen deposition, but there was a weak positive relationship between R. squarrosus nitrogen content and nitrogen deposition. None of the species showed strong relationships between above-ground tissue N:P or C:N and nitrogen deposition, indicating that they are not good indicators of deposition rate.     

Future landfill emissions and the effect of final cover installation--a case study

Municipal solid waste (MSW) landfills are potential long-term sources of emissions. Hence, they need to be managed after closure until they do not pose a threat to humans or the environment. The case study on the Breitenau MSW landfill was performed to evaluate future emission levels for this site and to illustrate the effect of final cover installation with respect to long-term environmental risks. The methodology was based on a comprehensive assessment of the state of the landfill and included analysis of monitoring data, investigations of landfilled waste, and an evaluation of containment systems. A model to estimate future emission levels was established and site-specific predictions of leachate emissions were presented based on scenario analysis. The results are used to evaluate the future pollution potential of the landfill and to compare different aftercare concepts in view of long-term emissions. As some leachable substances became available for water flow during cover construction due to a change in the water flow pattern of the waste, a substantial increase in leachate concentrations could be observed at the site (e.g. concentrations of chloride increased from 200 to 800 mg/l and of ammonia-nitrogen from 140 to about 500 mg/l). A period of intensive flushing before the final cover installation could have reduced the amount of leachable substances within the landfill body and rapidly decreased the leachate concentrations to 11 mg Cl/l and 79 mg NH₄-N/l within 50 years. Contrarily, the minimization of water infiltration is associated with leachate concentrations in a high range for centuries (above 400 mg Cl/l and 200 mg NH₄-N/l) with low concomitant annual emission loads (below 12 kg/year of Cl or 9 kg/year of NH₄-N, respectively). However, an expected gradual decrease of barrier efficiency over time would be associated with higher emission loads of 50 kg of chloride and 30 kg of ammonia-nitrogen at the maximum, but a faster decrease of leachate concentration levels.     

Probabilistic Flood Inundation Forecasting Using Rating Curve Libraries

One approach for performing uncertainty assessment in flood inundation modeling is to use an ensemble of models with different conceptualizations, parameters, and initial and boundary conditions that capture the factors contributing to uncertainty. However, the high computational expense of many hydraulic models renders their use impractical for ensemble forecasting. To address this challenge, we developed a rating curve library method for flood inundation forecasting. This method involves pre‐running a hydraulic model using multiple inflows and extracting rating curves, which prescribe a relation between streamflow and stage at various cross sections along a river reach. For a given streamflow, flood stage at each cross section is interpolated from the pre‐computed rating curve library to delineate flood inundation depths and extents at a lower computational cost. In this article, we describe the workflow for our rating curve library method and the Rating Curve based Automatic Flood Forecasting (RCAFF) software that automates this workflow. We also investigate the feasibility of using this method to transform ensemble streamflow forecasts into local, probabilistic flood inundation delineations for the Onion and Shoal Creeks in Austin, Texas. While our results show water surface elevations from RCAFF are comparable to those from the hydraulic models, the ensemble streamflow forecasts used as inputs to RCAFF are the largest source of uncertainty in predicting observed floods.     

Mercury flows in a zinc smelting facility in South Korea

To prepare for the international mercury convention, the characteristics of mercury emissions from a zinc smelting facility in South Korea have been reviewed and a material flow analysis (MFA) has been conducted in this research. As inputs into the mercury MFA study, zinc ores and sulfuric acid were examined, whereas wastewater sludge, effluence water, spent catalyst, and emissions from the casting and roasting processes were examined as outputs. Mercury concentrations extracted from end products like zinc ingots, cadmium ingots, and sulfuric acid were then analyzed. Our results showed that the wastewater sludge discharged from the zinc smelting process had a relatively higher concentration of mercury, indicating that the concentration of mercury was further enriched in the wastewater sludge. The wastes discharged through the zinc smelting process should be thoroughly controlled, as results of the MFA showed that approximately 89 % of the mercury contained in the original input was later found in the waste. According to this study, the higher the concentration of mercury within zinc ores at the input stage, the higher is the mercury concentration found in the wastewater sludge at the output stage.     

How to Constrain Multi‐Objective Calibrations of the SWAT Model Using Water Balance Components

Accurate discharge simulation is one of the most common objectives of hydrological modeling studies. However, a good simulation of discharge is not necessarily the result of a realistic simulation of hydrological processes within the catchment. We propose an evaluation framework that considers both discharge and water balance components as evaluation criteria for calibration of the Soil and Water Assessment Tool (SWAT). In this study, we integrated average annual values of surface runoff, groundwater flow, and evapotranspiration in the model evaluation procedure to constrain the selection of good model runs for the Little River Experimental Watershed in Georgia, United States. For evaluating water balance and discharge dynamics, the Nash‐Sutcliffe efficiency (NSE) and percent bias (PBIAS) were used. In addition, the ratio of root mean square error and standard deviation of measured data (RSR) was calculated for individual segments of the flow duration curve to identify the best model runs in terms of discharge magnitude. Our results indicate that good statistics for discharge do not guarantee realistic simulations of individual water balance components. Therefore, we recommend constraining the ranges of water balance components to achieve a more realistic simulation of the entire hydrological system, even if tradeoffs between good statistics for discharge simulations and reasonable amounts of the water balance components are unavoidable. Editor's note : This paper is part of the featured series on SWAT Applications for Emerging Hydrologic and Water Quality Challenges. See the February 2017 issue for the introduction and background to the series.     

Designing and Implementing a Network for Sensing Water Quality and Hydrology across Mountain to Urban Transitions

Water resources are increasingly impacted by growing human populations, land use, and climate changes, and complex interactions among biophysical processes. In an effort to better understand these factors in semiarid northern Utah, United States, we created a real‐time observatory consisting of sensors deployed at aquatic and terrestrial stations to monitor water quality, water inputs, and outputs along mountain to urban gradients. The Gradients Along Mountain to Urban Transitions (GAMUT) monitoring network spans three watersheds with similar climates and streams fed by mountain winter‐derived precipitation, but that differ in urbanization level, land use, and biophysical characteristics. The aquatic monitoring stations in the GAMUT network include sensors to measure chemical (dissolved oxygen, specific conductance, pH, nitrate, and dissolved organic matter), physical (stage, temperature, and turbidity), and biological components (chlorophyll‐a and phycocyanin). We present the logistics of designing, implementing, and maintaining the network; quality assurance and control of numerous, large datasets; and data acquisition, dissemination, and visualization. Data from GAMUT reveal spatial differences in water quality due to urbanization and built infrastructure; capture rapid temporal changes in water quality due to anthropogenic activity; and identify changes in biological structure, each of which are demonstrated via case study datasets.     

Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.