Single-source impact analysis using three-dimensional air quality models

Isolating the effects of an individual emissions source on secondary air pollutants such as ozone and some components of particulate matter must incorporate complex nonlinear processes, be sensitive to small emissions perturbations, and account for impacts that may occur hundreds of kilometers away. The ability to evaluate these impacts is becoming increasingly important for efficient air quality management. Here, as part of a recent compliance enforcement action for a violation of the Clean Air Act and as an evaluation of ozone response to single-source emissions plumes, two three-dimensional regional photochemical air quality models are used to assess the impact on ozone from approximately 2000 to 3000 excess t/month of nitrogen oxides emitted from a single power plant in Ohio. Periods in May, July, and August are evaluated. Two sensitivity methods are applied: the "brute-force" (B-F) method and the decoupled direct method (DDM). Using DDM, maximum 1-hr averaged ozone concentrations are found to increase by up to 1.8, 1.3, and 2.2 ppbv during May, July, and August episodes, respectively, and concentration increases greater than 0.5 ppbv occur in Ohio, Pennsylvania, Maryland, New York, West Virginia, Virginia, and North and South Carolina. B-F results for the August episode show a maximum 1-hr averaged ozone concentration increase of 2.3 ppbv. Significant localized decreases are also simulated, with a maximum of 3.6 ppbv in Ohio during the August episode and decreases of 0.50 ppbv and greater in Ohio, Pennsylvania, Maryland, West Virginia, and Virginia. Maximum increases are compared with maximum decreases for the August period using second-order DDM and are found, in aggregate, to be greater in magnitude by 42%. When evaluated during hours when ozone concentrations exceed 0.060 ppm, the maximum increases in ozone are higher than decreases by 82%. The spatial extent of ozone increase in both cases is about triple that of reduction.     

Coupled infrared extinction spectra and size distribution measurements for several non-clay components of mineral dust aerosol (quartz, calcite, and dolomite)

Simultaneous size distributions and Fourier transform infrared (FTIR) extinction spectra have been measured for several representative components of mineral dust aerosol (quartz, calcite, and dolomite) in the fine particle size mode (D=0.1–1 μm). Optical constants drawn from the published literature have been used in combination with the experimentally determined size distributions to simulate the extinction spectra. In general, Mie theory does not accurately reproduce the peak position or band shape for the prominent IR resonance features in the 800–1600 cm⁻¹ spectral range. The resonance peaks in the Mie simulation are consistently blue shifted relative to the experimental spectra by 20–50 cm⁻¹. Spectral simulations, derived from a simple Rayleigh-based analytic theory for a “continuous distribution of ellipsoids” particle shape model, better reproduce the experimental spectra, despite the fact that the Rayleigh approximation is not strictly satisfied in these experiments. These results differ from our previous studies of particle shape effects in silicate clay mineral dust aerosols where a disk-shaped model for the particles was found to be more appropriate.     

Assessment of sediment contamination in Casco Bay, Maine, USA

The current status of contaminant concentrations in Casco Bay, decadal trends of these contaminants and changes in their geographical distribution are assessed using sediment samples collected approximately 10 years apart. In general, regulated contaminants appeared to be decreasing in concentration. Total PAH and dioxins/furans concentrations did not significantly change over this period. Total organochlorine pesticides, 4,4-DDE, 4,4-DDD, total DDT, PCB, tributyltin and total butyltin decreased in concentration. Trace element concentrations in sediments decreased at the majority of the sampling sites for chromium, nickel, and selenium while arsenic, cadmium, copper, lead, mercury, silver, and zinc remained relatively constant. None of the contaminants measured has increased by more than a factor of 2. Selected sites located in the Inner Bay, where concentrations are higher and new inputs were more likely, showed increased concentrations of contaminants. Most contaminants were not found at concentrations expected to adversely affect sediment biota based on ERL/ERM guidelines.     

Field and laboratory simulations of storm water pulses: behavioural avoidance by marine epifauna

Epifaunal communities associated with macroalgae were exposed to storm water pulses using a custom made irrigation system. Treatments included Millipore freshwater, freshwater spiked with trace metals and seawater controls to allow for the relative importance of freshwater inundation, trace metals and increased flow to be determined. Experimental pulses created conditions similar to those that occur following real storm water events. Brief storm water pulses reduced the abundance of amphipods and gastropods. Freshwater was the causative agent as there were no additional effects of trace metals on the assemblages. Laboratory assays indicated that neither direct nor latent mortality was likely following experimental pulses and that epifauna readily avoid storm water. Indirect effects upon epifauna through salinity-induced changes to algal habitats were not found in field recolonisation experiments. Results demonstrate the importance of examining the effects of pulsed contaminants under realistic exposure conditions and the need to consider ecologically relevant endpoints.     

Use of principal component analysis to profile temporal and spatial variations of chlorinated solvent concentration in groundwater

This work aims at evaluating spatial distribution patterns of concentration variations for chlorinated solvents in groundwater, based on principal component analysis and geographic information system (GIS) tools. The study investigates long-time series of chlorinated solvent concentrations in groundwater measured for 18 contaminated industrial sites. The characterization of contaminant plumes and delineation of pollutant sources are essential for choosing appropriate monitoring and remediation strategies, as contaminated groundwaters are characterized by complex patterns of spatial and temporal concentration variability, with wide unpredictable fluctuations over time. The present work describes the results of a new exploratory statistical method called the Variability Index Method (VIM) applied to environmental data to assess the performance of using concentration variations as molecular tracers to reveal aquifer dynamics, industrial impacts, and point sources for contamination plumes. The application of this method provides a useful assessment of controls over contaminant concentration variations as well as support for remediation techniques.     

Particle fluxes above forests: observations, methodological considerations and method comparisons

This paper reports a study designed to test, evaluate and compare micro-meteorological methods for determining the particle number flux above forest canopies. Half-hour average particle number fluxes above a representative broad-leaved forest in Denmark derived using eddy covariance range from -7x10(7) m(-2) s(-1) (1st percentile) to 5x10(7) m(-2) s(-1) (99th percentile), and have a median value of -1.6x10(6) m(-2) s(-1). The statistical uncertainties associated with the particle number flux estimates are larger than those for momentum fluxes and imply that in this data set approximately half of the particle number fluxes are not statistically different to zero. Particle number fluxes from relaxed eddy accumulation (REA) and eddy covariance are highly correlated and of almost identical magnitude. Flux estimates from the co-spectral and dissipation methods are also correlated with those from eddy covariance but exhibit higher absolute magnitude of fluxes.     

Sensitivity analysis of a parameterization of the stomatal component of the DO3SE model for Quercus ilex to estimate ozone fluxes

A sensitivity analysis of a proposed parameterization of the stomatal conductance (g(s)) module of the European ozone deposition model (DO(3)SE) for Quercus ilex was performed. The performance of the model was tested against measured g(s) in the field at three sites in Spain. The best fit of the model was found for those sites, or during those periods, facing no or mild stress conditions, but a worse performance was found under severe drought or temperature stress, mostly occurring at continental sites. The best performance was obtained when both f(phen) and f(SWP) were included. A local parameterization accounting for the lower temperatures recorded in winter and the higher water shortage at the continental sites resulted in a better performance of the model. The overall results indicate that two different parameterizations of the model are needed, one for marine-influenced sites and another one for continental sites.     

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region.     

Nitrogen deposition increases the acquisition of phosphorus and potassium by heather Calluna vulgaris

Increased plant productivity due to nitrogen pollution increases the strength of the global carbon sink, but is implicated in plant diversity loss. However, modelling and experimental studies have suggested that these effects are constrained by availability of other nutrients. In a survey of element concentrations in Calluna vulgaris across an N deposition gradient in the UK, shoot concentrations of N and more surprisingly phosphorus and potassium were positively correlated with N deposition; tissue N/P ratio even decreased with N deposition. Elevated P and K concentrations possibly resulted from improved acquisition due to additional enzyme production or mycorrhizal activity. Heather occurs on organic soils where nutrient limitations are likely due to availability constraints rather than small stocks. However, if this effect extends to other plant and soil types, effects of N deposition on C sinks and plant competition may not be as constrained by availability of other nutrients as previously proposed.     

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.