The Southeastern Aerosol Research and Characterization Study: Part II. Filter-Based Measurements of Fine and Coarse Particulate Matter Mass and Composition

Abstract

The Southeastern Aerosol Research and Characterization Study (SEARCH) was implemented in 1998–1999 to provide data and analyses for the investigation of the sources, chemical speciation, and long-term trends of fine particulate matter (PM_2.5) and coarse particulate matter (PM_10–2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999–2003) of filter-based PM_2.5 and PM_10–2.5 data from SEARCH. We find that annual PM_2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 µg/m³ annual standard only at monitoring sites in the two largest urban areas (Atlanta, GA, and North Birmingham, AL). Other sites in the network had annual design values below the standard, and no site had daily design values above the NAAQS 65 µg/m³ daily standard. Using a particle composition monitor designed specifically for SEARCH, we found that volatilization losses of nitrate, ammonium, and organic carbon must be accounted for to accurately characterize atmospheric particulate matter. In particular, the federal reference method for PM_2.5 underestimates mass by 3–7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for ≥60% of PM_2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components (“other”) account for ≥80% of PM_10–2.5 mass. Limited data suggest that much of the unidentified mass in PM_10–2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM_2.5 mass are explained, in large part, by higher OM and black carbon at the urban site. For PM₁₀, higher urban concentrations are explained by higher MMO and “other.” Annual means for PM_2.5 and PM_10–2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999–2003 period (10–20% in the case of PM_2.5, dominated by 14–20% declines in sulfate and 11–26% declines in OM, and 14–25% in the case of PM_10–2.5, dominated by 17–30% declines in MMO and 14–31% declines in “ other”). Although declining national emissions of sulfur dioxide and anthropogenic carbon may account for a portion of the observed declines, additional investigation will be necessary to establish a quantitative assessment, especially regarding trends in local and regional emissions, primary carbon emissions, and meteorology.     

Use of sodium decanoate for selective precipitation of metals contained in industrial wastewater

Conventional methods for heavy metal removal from industrial wastewater involve a chemical precipitation. This process leads to sludges without any commercial value which are stored in specialized landfills. This paper describes a study on the possibility to perform selective precipitation of binary mixtures of metal cations using sodium decanoate. First, the solubility product of six metal decanoates is determined. These six compounds were prepared and controlled before determining their solubility in pure water at 20 degrees C. The solubility product K(sp) obtained for Cd, Cu, Mn, Ni, Pb and Zn decanoates are respectively 10(-11.69), 10(-14.65), 10(-10.16), 10(-9.17), 10(-16.05) and 10(-13.05). Additionally, the selective precipitation of binary mixtures was studied. Using pK(sp) values above, the solubility domain of each decanoate was established. The six superimposed curves allow prediction of the feasibility of separation. According to these curves, nine separations seem to be possible. In each case, precipitation was experimentally performed. The obtained results verify the reliability of this prediction tool. The feasibility of the selective precipitation of metal cations using sodium decanoate is clearly shown.     

Characterization of solid-phase microextraction and gas chromatography for the analysis of gasoline tracers in different microenvironments

Gasoline tracers were collected on solid-phase microextraction (SPME) fibers and analyzed by capillary gas chromatography with photoionization detector (GC/PID). This was part of a larger study to quantify personal exposure to motor vehicle gasoline evaporative and combustive emissions in high-end exposure microenvironments (MEs). The SPME fiber selected for this application was a 75-microm carboxen/polydimethylsiloxane. Sequential 10-min samples were collected for measurement of benzene, toluene, ethylbenzene, and ortho-, meta-, and para-xylene in different MEs in Atlanta, GA, in summer 2002 and Reno, NV, in spring 2003. Field calibrations were performed with certified gas standards in 1-L Tedlar bags for varying concentrations and exposure times. SPME detection limits were approximately 0.2 ppbv with a precision of 3-17% and accuracy of 30%. A dynamic system was designed for temperature and relative humidity calibrations, with corrections for the effects of these variables performed when necessary. SPME data compared satisfactorily with integrated canister samples, continuous PID, and field portable mass spectrometer data.     

Identifying potential receptors and routes of contaminant exposure in the traditional territory of the Ouje-Bougoumou Cree: Land use and a geographical information system

Great concern has been raised with respect to the 13 traplines that constitute the traditional territory of the Ouje-Bougoumou Cree located in the James Bay region of northern Quebec, Canada, with respect to mine wastes originating from three local mines. As a result, an “Integrative Risk Assessment” was initiated consisting of three interrelated components: a comprehensive human health study, an assessment of the existing ecological/environmental database, and a land use/potential sites of concern study. In this paper, we document past and present land use in the traditional territory of the Ouje-Bougoumou Cree for 72 heads of households, including 13 tallymen, and use a Geographic Information System (GIS) to layer harvest/hunting and gathering/collecting data over known mining areas and potential sites of concern. In this way, potential receptors of contamination and routes of human exposure were identified. Areas of overlap with respect to land use activity and mining operations were relatively extensive for certain harvesting activities (e.g., beaver, Castor canadensis and various species of game birds), less so for fish harvesting (all species) and water collection, and relatively restrictive for large mammal harvesting and collection of firewood (and other collection activities). Potential receptors of contaminants associated with mining activity (e.g., fish and small mammals) and potential routes of exposure (e.g., ingestion of contaminated game and drinking of contaminated water) were identified.     

The ‘Storm of the Century’ (December 1999) and the accidental escape of Siberian sturgeons (Acipenser baerii) into the Gironde estuary (Southwest France)

GOAL, SCOPE AND BACKGROUND: The Gironde estuary is considered as a reference ecosystem with a large fish assemblage (75 species) and the presence of eleven diadromous species. However, geochemical studies and biomonitoring using oysters have shown high metal pollution levels. During the December 1999 hurricane, more than 5,000 young Siberian sturgeons (Acipenser baerii) accidentally escaped from a fish farm into the estuary, where this species had not been present until then. METHODS: In 2002/2003, thirteen sturgeons were collected from the estuary and twelve were obtained from the fish farm, from the same initial batch. Analysis of five metals (cadmium, zinc, copper, lead, mercury) measured in the gills, muscle, liver and kidneys, revealed significantly higher levels of cadmium, lead and mercury in the sturgeon collected from the estuary compared with those from the fish farm. RESULTS AND DISCUSSION: Metal analysis of the stomach contents of fish collected from the estuary and artificial food used in the fish farm indicated that dietary exposure might account for the differences observed. Nevertheless, metal concentrations in sturgeons that had spent about three years in the Gironde estuary may be considered low when compared with other species (mullets, eels) or with data in the literature regarding concentrations able to induce structural and functional perturbations in fish. As the introduced Siberian sturgeons live in the same place and feed on the same prey as the juveniles of the endangered A. sturio, our results indicate in the short-term that this strictly protected species does not appear to be much affected by the polymetallic pollution in the Gironde estuary. Marked differences in the concentrations of three metals (Cd, Pb, Hg) were established in four organs (gills, liver, skeletal muscle, kidneys) of Siberian sturgeons between specimens that had accidentally escaped into the Gironde estuary (France) during the December 1999 hurricane and were collected in March/June 2003 and specimens from the same initial batch at the fish farm. RECOMMENDATIONS AND PERSPECTIVES: Based on these results, a programme will be set up, with sampling campaigns carried out in the estuary every two years, with systematic monitoring of age in order to check the origin of individuals, in conjunction with sampling of sturgeon from the fish farm. This programme will complement other studies on several biological species representative of the main trophic levels in the estuary, especially the plankton component, benthic macroinvertebrates and oysters.     

Rethinking the assessment of photochemical modelin systems in air quality planning applications

The U.S. Environmental Protection Agency provides guidelines for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards on the basis of the application of photochemical modeling systems to simulate the effect of emission reductions. These guidelines also require assessment of the model simulation against observations. In this study, we examined the link between the simulated relative responses to emission reductions and model performance as measured by operational evaluation metrics, a part of the model evaluation required by the guidance, which often is the cornerstone of model evaluation in many practical applications. To this end, summertime O3 concentrations were simulated with two modeling systems for both 2002 and 2009 emission conditions. One of these two modeling systems was applied with two different parameterizations for vertical mixing. Comparison of the simulated base-case 8-hr daily maximum O3 concentrations showed marked model-to-model differences of up to 20 ppb, resulting in significant differences in operational model performance measures. In contrast, only relatively minor differences were detected in the relative response of O3 concentrations to emission reductions, resulting in differences of a few ppb or less in estimated future year design values. These findings imply that operational model evaluation metrics provide little insight into the reliability of the actual model application in the regulatory setting (i.e., the estimation of relative changes). In agreement with the guidance, it is argued that more emphasis should be placed on the diagnostic evaluation of O3-precursor relationships and on the development and application of dynamic and retrospective evaluation approaches in which the response of the model to changes in meteorology and emissions is compared with observed changes. As an example, simulated relative O3 changes between 1995 and 2007 are compared against observed changes. It is suggested that such retrospective studies can serve as the starting point for targeted diagnostic studies in which individual aspects of the modeling system are evaluated and refined to improve the characterization of observed changes.     

Assessment of stream biological responses under multiple-stress conditions

Background, aim and scope  

Due to the numerous anthropogenic stress factors that affect aquatic ecosystems, a better understanding of the adverse consequences on the biological community of combined pressures is needed to attain the objectives of the European Water Framework Directive. In this study we propose an innovative approach to assess the biological impact of toxicants under field conditions on a large spatial scale.     

Geomechanical analysis of the Naylor Field,Otway Basin,Australia: Implications for CO2 injection and storage

A geomechanical assessment of the Naylor Field, Otway Basin, Australia has been undertaken to investigate the possible geomechanical effects of CO₂ injection and storage. The study aims to evaluate the geomechanical behaviour of the caprock/reservoir system and to estimate the risk of fault reactivation. The stress regime in the onshore Victorian Otway Basin is inferred to be strike–slip if the maximum horizontal stress is calculated using frictional limits and DITF (drilling induced tensile fracture) occurrence, or normal if maximum horizontal stress is based on analysis of dipole sonic log data. The NW–SE maximum horizontal stress orientation (142°N) determined from a resistivity image log is broadly consistent with previous estimates and confirms a NW–SE maximum horizontal stress orientation for the Otway Basin.An analytical geomechanical solution is used to describe stress changes in the subsurface of the Naylor Field. The computed reservoir stress path for the Naylor Field is then incorporated into fault reactivation analysis to estimate the minimum pore pressure increase required to cause fault reactivation (ΔP_p).The highest reactivation propensity (for critically-oriented faults) ranges from an estimated pore pressure increase (ΔP_p) of 1 MPa to 15.7 MPa (estimated pore pressure of 18.5–33.2 MPa) depending on assumptions made about maximum horizontal stress magnitude, fault strength, reservoir stress path and Biot's coefficient. The critical pore pressure changes for known faults at Naylor Field range from an estimated pore pressure increase (ΔP_p) of 2 MPa to 17 MPa (estimated pore pressure of 19.5–34.5 MPa).     

Variation of the mixing state of Saharan dust particles with atmospheric transport

Mineral dust is an important aerosol species in the Earth’s atmosphere and has a major source within North Africa, of which the Sahara forms the major part. Aerosol Time of Flight Mass Spectrometry (ATOFMS) is first used to determine the mixing state of dust particles collected from the land surface in the Saharan region, showing low abundance of species such as nitrate and sulphate internally mixed with the dust mineral matrix. These data are then compared with the ATOFMS single particle mass spectra of Saharan dust particles detected in the marine atmosphere in the vicinity of the Cape Verde islands, which are further compared with those from particles with longer atmospheric residence sampled at a coastal station at Mace Head, Ireland. Saharan dust particles collected near the Cape Verde Islands showed increased internally mixed nitrate but no sulphate, whilst Saharan dust particles collected on the coast of Ireland showed a very high degree of internally mixed secondary species including nitrate, sulphate and methanesulphonate. This uptake of secondary species will change the pH and hygroscopic properties of the aerosol dust and thus can influence the budgets of other reactive gases, as well as influencing the radiative properties of the particles and the availability of metals for dissolution.