Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Sequential Extraction Versus Comprehensive Characterization of Heavy Metal Species in Brownfield Soils

The applicability of sequential extraction as a means to determine species of heavy-metals was examined by a study on soil samples from two Superfund sites: the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data from a standard sequential extraction procedure were compared to those from a comprehensive study that combined optical- and scanning-electron microscopy, X-ray diffraction, and chemical analyses. The study shows that larger particles of contaminants, encapsulated contaminants, and/or man-made materials such as slags, coke, metals, and plastics are subject to incasement, non-selectivity, and redistribution in the sequential extraction process. The results indicate that standard sequential extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for stand-alone determinative evaluations of contaminant species in industrial-site materials. However, if employed as part of a comprehensive, site-specific characterization study, sequential extraction could be a very useful tool.     

Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.     

Is Urban Stream Restoration Worth It?1

Kenney, Melissa A., Peter R. Wilcock, Benjamin F. Hobbs, Nicholas E. Flores, and Daniela C. Martínez, 2012. Is Urban Stream Restoration Worth It? Journal of the American Water Resources Association (JAWRA) 48(3): 603-615. DOI: 10.1111/j.1752-1688.2011.00635.x Abstract: Public investment in urban stream restoration is growing, yet little has been done to quantify whether its benefits outweigh its cost. The most common drivers of urban stream projects are water quality improvement and infrastructure protection, although recreational and aesthetic benefits are often important community goals. We use standard economic methods to show that these contributions of restoration can be quantified and compared to costs. The approach is demonstrated with a case study in Baltimore, Maryland, a city with a legal mandate to reduce its pollutant load. Typical urban stream restoration costs of US$500-1,200 per foot are larger than the cost of the least expensive alternatives for management of nitrogen loads from stormwater (here, detention ponds, equivalent to $30-120 per foot of restored stream) and for protecting infrastructure (rip-rap armoring of streambanks, at $0-120 per foot). However, the higher costs of stream restoration can in some cases be justified by its aesthetic and recreational benefits, valued using a contingent valuation survey at $560-1,100 per foot. We do not intend to provide a definitive answer regarding the worth of stream restoration, but demonstrate that questions of worth can be asked and answered. Broader application of economic analysis would provide a defensible basis for understanding restoration benefits and for making restoration decisions.     

Seawater Intrusion and Sustainable Yield of Basal Aquifers1

Liu, Clark C.K. and John J. Dai, 2012. Seawater Intrusion and Sustainable Yield of Basal Aquifers. Journal of the American Water Resources Association (JAWRA) 48(5): 861‐870. DOI: 10.1111/j.1752‐1688.2012.00659.x Abstract: Basal aquifers, in which freshwater floats on top of saltwater, are the major freshwater supply for the Hawaiian Islands, as well as many other coastal regions around the world. Under unexploited or natural conditions, freshwater and the underlying seawater are separated by a relatively sharp interface located below mean sea level at a depth of about 40 times the hydraulic head. With forced draft, the hydraulic head of a basal aquifer would decline and the sharp interface would move up. It is a serious problem of seawater intrusion as huge amounts of freshwater storage is replaced by saltwater. Also, with forced draft, the sharp interface is replaced by a transition zone in which the salinity increases downward from freshwater to saltwater. As pumping continues, the transition zone expands. The desirable source‐water salinity in Hawaii is about 2% of the seawater salinity. Therefore, the transition zone expansion is another serious problem of seawater intrusion. In this study, a robust analytical groundwater flow and salinity transport model (RAM2) was developed. RAM2 has a simple mathematical structure and its model parameters can be determined satisfactorily with the available field monitoring data. The usefulness of RAM2 as a viable management tool for coastal ground water management is demonstrated by applying it to determine the sustainable yield of the Pearl Harbor aquifer, a principal water supply source in Hawaii.     

Evidence for Acidification-Driven Ecosystem Collapse of Danish Erica tetralix Wet Heathland

We report observations of disappearance of Erica tetralix in wet heathland, which is unlikely to be caused by competition, as E. tetralix is dying before its place is taken up by other species. To investigate the causes, we used both old and new data. Results showed that presence of Molinia caerulea and Calluna vulgaris were substantial in the former E. tetralix dominated areas. Measurements of the C/N ratio in the morlayer were between 21 and 26 under the E. tetralix stands. As the expected C/N ratio in a healthy nutrient poor ecosystem like the E. tetralix wet heathland is around 30, this indicates that the ratio is probably decreasing and, correspondingly, the probability of nitrogen leaching from the ecosystem is increasing. The morlayer pH was extremely low—between 3.03 and 3.78. This represents a pH decline since the 1960s, where pH values generally were above 4. This supports the hypothesis that the decrease in morlayer pH is the major factor explaining the disappearance of E. tetralix and that measures to increase pH should be considered as part of the recommendations for relevant future management.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-012-0251-z) contains supplementary material, which is available to authorized users.     

Linking Climate Trends to Population Dynamics in the Baltic Ringed Seal: Impacts of Historical and Future Winter Temperatures

A global trend of a warming climate may seriously affect species dependent on sea ice. We investigated the impact of climate on the Baltic ringed seals (Phoca hispida botnica), using historical and future climatological time series. Availability of suitable breeding ice is known to affect pup survival. We used detailed information on how winter temperatures affect the extent of breeding ice and a climatological model (RCA3) to project the expected effects on the Baltic ringed seal population. The population comprises of three sub-populations, and our simulations suggest that all of them will experience severely hampered growth rates during the coming 90 years. The projected 30 730 seals at the end of the twenty-first century constitutes only 16 % of the historical population size, and thus reduced ice cover alone will severely limit their growth rate. This adds burden to a species already haunted by other anthropogenic impacts.     

Climate Change and Population Growth in Timor Leste: Implications for Food Security

The climate in Timor Leste (East Timor) is predicted to become about 1.5 °C warmer and about 10 % wetter on average by 2050. By the same year, the population is expected to triple from 1 to 2.5–3 million. This article maps the predicted changes in temperature and rainfall and reviews the implications of climate change and population growth on agricultural systems. Improved cultivars of maize, rice, cassava, sweet potato and peanuts with high yield performance have been introduced, but these will need to be augmented in the future with better adapted cultivars and new crops, such as food and fodder legumes and new management practices. The requirements for fertilizers to boost yields and terracing and/or contour hedgerows to prevent soil erosion of steeply sloping terrain are discussed. Contour hedges can also be used for fodder for improved animal production to provide protein to reduce malnutrition.     

Isolation of mesotrione-degrading bacteria from aquatic environments in Brazil

Mesotrione is a benzoylcyclohexane-1,3-dione herbicide that inhibits 4-hydroxyphenyl pyruvate dioxygenase in target plants. Although it has been used since 2000, only a limited number of degrading microorganisms have been reported. Mesotrione-degrading bacteria were selected among strains isolated from Brazilian aquatic environments, located near corn fields treated with this herbicide. Pantoea ananatis was found to rapidly and completely degrade mesotrione. Mesotrione did not serve as a sole C, N, or S source for growth of P. ananatis, and mesotrione catabolism required glucose supplementation to minimal media. LC-MS/MS analyses indicated that mesotrione degradation produced intermediates other than 2-amino-4-methylsulfonyl benzoic acid or 4-methylsulfonyl-2-nitrobenzoic acid, two metabolites previously identified in a mesotrione-degrading Bacillus strain. Since P. ananatis rapidly degraded mesotrione, this strain might be useful for bioremediation purposes.     

Copper kinetics and internal distribution in the marbled crayfish (Procambarus sp.)

Metal pollution e.g. copper, in water bodies occurs worldwide. Although copper is an essential trace metal, at certain levels it is still considered as pollutant. The aim of this study was to investigate the effect of exposure concentration on copper bioaccumulation in marbled crayfish (Procambarus sp.) by determining uptake and elimination kinetics. Crayfish were exposed to sub-lethal copper concentrations (average measured concentrations of 0.031 and 0.38 mg Cu L⁻¹) for 14 d and transferred to copper-free water for another 14 d. At different time points during the uptake and elimination phases copper concentrations were measured in five organs (exoskeleton, gills, muscle, ovaries and hepatopancreas). At 0.031 mg Cu L⁻¹, copper levels in the crayfish organs were not significantly increased compared to the control animals, suggesting effective regulation. Exposure to 0.38 mg Cu L⁻¹ did lead to not significantly increased copper levels in muscles and ovaries, while the gills and exoskeleton, which are in direct contact with the water, showed significantly higher copper concentrations. In these four organs, copper showed fast uptake kinetics with equilibrium reached within 10 d of exposure. Copper accumulation was highest in the hepatopancreas; uptake in this storage organ steadily increased with time and did not reach equilibrium within the 14-d exposure period. Copper accumulation levels in the marbled crayfish found in this study were hepatopancreas > gills > exoskeleton > muscle.