The Southeastern Aerosol Research and Characterization Study: Part II. Filter-based measurements of fine and coarse particulate matter mass and composition

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 (PM2.5) and coarse particulate matter (PM10-2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999-2003) of filter-based PM2.5 and PM10-2.5 data from SEARCH. We find that annual PM2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 microg/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 microg/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 PM2.5 underestimates mass by 3-7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for approximately 60% of PM2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components ("other") account for > or = 80% of PM10-2.5 mass. Limited data suggest that much of the unidentified mass in PM10-2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM2.5 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 PM2.5 and PM10-2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999-2003 period (10-20% in the case of PM2.5, dominated by 14-20% declines in sulfate and 11-26% declines in OM, and 14-25% in the case of PM10-2.5, 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.     

The midlatitude North American background aerosol and global aerosol variation

Protocols for the particulate matter (PM) National Ambient Air Quality Standards (NAAQS), and the Regional Haze Rule (RHR) give two complementary definitions for "natural" background airborne particle concentrations in the United States. The definition for the NAAQS derives largely from reported annual averages, whereas the definition for the RHR takes into account the frequency of occurrence of a range of visibility conditions estimated using fine particle composition. These definitions are simple, static representations of background or "unmanageable" aerosol conditions in the United States. An accumulation of data from rural-remote sites representing global conditions indicates that the airborne particle concentrations are highly variable. Observational campaigns show weather-related variations, including incidents of regional or intercontinental transport of pollution that influence background aerosol levels over midlatitude North America. Defining a background in North America based on long-term observations relies mainly on the remote-rural IMPROVE network in the United States, with a few additional measurements from Canada. Examination of the frequency of occurrence of mass concentrations and particle components provides insight not only about annual median conditions but also the variability of apparent background conditions. The results of this analysis suggest that a more elaborate approach to defining an unmanageable background could improve the present approach taken for information input into the U.S. regulatory process. An approach interpreting the continental gradients in fine PM (PM2.5) concentrations and composition may be warranted.     

Reconciliation and interpretation of Big Bend National Park particulate sulfur source apportionment: results from the Big Bend Regional Aerosol and Visibility Observational Study--part I

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) study was an intensive monitoring study from July through October 1999 followed by extensive assessments to determine the causes and sources of haze in Big Bend National Park, located in Southwestern Texas. Particulate sulfate compounds are the largest contributor of haze at Big Bend, and chemical transport models (CTMs) and receptor models were used to apportion the sulfate concentrations at Big Bend to North American source regions and the Carbón power plants, located 225 km southeast of Big Bend in Mexico. Initial source attribution methods had contributions that varied by a factor of > or =2. The evaluation and comparison of methods identified opposing biases between the CTMs and receptor models, indicating that the ensemble of results bounds the true source attribution results. The reconciliation of these differences led to the development of a hybrid receptor model merging the CTM results and air quality data, which allowed a nearly daily source apportionment of the sulfate at Big Bend during the BRAVO study. The best estimates from the reconciliation process resulted in sulfur dioxide (SO2) emissions from U.S. and Mexican sources contributing approximately 55% and 38%, respectively, of sulfate at Big Bend. The distribution among U.S. source regions was Texas, 16%; the Eastern United States, 30%; and the Western United States, 9%. The Carbón facilities contributed 19%, making them the largest single contributing facility. Sources in Mexico contributed to the sulfate at Big Bend on most days, whereas contributions from Texas and Eastern U.S. sources were episodic, with their largest contributions during Big Bend sulfate episodes. On the 20% of the days with the highest sulfate concentrations, U.S. and Mexican sources contributed approximately 71% and 26% of the sulfate, respectively. However, on the 20% of days with the lowest sulfate concentrations, Mexico contributed 48% compared with 40% for the United States.     

Laboratory evaluation of thermophilic-anaerobic digestion to produce Class A biosolids. 1. Stabilization performance of a continuous-flow reactor at low residence time.

There is increasing interest in the United States in producing biosolids from municipal wastewater treatment that meet the criteria for Class A designation established by the U.S. Environmental Protection Agency. Class A biosolids are intended to be free of pathogens and also must meet requirements for reduction of the vector-attraction potential associated with untreated sludge. High-temperature processes are considered to produce Class A biosolids if the combination of operating temperature and treatment time exceeds minimum criteria, but this option is not applicable to mixed, continuous-flow reactors. Such reactors, or any combination of reactors that does not meet the holding time requirement at a specific temperature, must be demonstrated to inactivate pathogens to levels consistent with the Class A criteria. This study was designed to evaluate pathogen inactivation by thermophilic anaerobic digestion in a mixed, continuous-flow reactor followed by batch or plug-flow treatment. In this first of a two-part series, we describe the performance of a continuous-flow laboratory reactor with respect to physical and chemical operating parameters; microbial inactivation in the combined continuous-flow and batch treatment system is described in the second part. Sludges from three different sources were treated at 53 degrees C, while sludge from one of the sources was also treated at 55 and 51 degrees C. Relatively short hydraulic retention times (four to six days) were used to represent a conservative operating condition with respect to pathogen inactivation. Treatment of a fermented primary sludge led to an average volatile-solids (VS) destruction efficiency of 45%, while VS destruction for the other two sources was near or below 38%, the Class A criterion for vector attraction reduction. Consistent with other studies on thermophilic anaerobic digestion of sludges at short residence times, effluent concentrations of volatile fatty acids (VFAs) were relatively high. Also consistent with other studies, the most abundant VFA in the effluent was propionate. Gas production ranged from 0.3 to 0.5 m3/kg VS fed and from 0.8 to 1.3 m3/kg VS destroyed.     

Laboratory evaluation of thermophilic-anaerobic digestion to produce Class A biosolids. 2. Inactivation of pathogens and indicator organisms in a continuous-flow reactor followed by batch treatment.

Thermophilic-anaerobic digestion in a single-stage, mixed, continuous-flow reactor is not approved in the United States as a process capable of producing Class A biosolids for land application. This study was designed to evaluate the inactivation of pathogens and indicator organisms in such a reactor followed by batch treatment in a smaller reactor. The combined process was evaluated at 53 degrees C with sludges from three different sources and at 51 and 55 degrees C with sludge from one of the sources. Feed sludge to the continuous-flow reactor was spiked with the pathogen surrogates Ascaris suum and vaccine-strain poliovirus. Feed and effluent were analyzed for these organisms and for indigenous Salmonella spp., fecal coliforms, Clostridium perfringens spores, and somatic and male-specific coliphages. No viable Ascaris eggs were observed in the effluent from the continuous reactor at 53 or 55 degrees C, with greater than 2-log removals across the digester in all cases. Approximately 2-log removal was observed at 51 degrees C, but all samples of effluent biosolids contained at least one viable Ascaris egg at 51 degrees C. No viable poliovirus was found in the digester effluent at any of the operating conditions, and viable Salmonella spp. were measured in the digester effluent in only one sample throughout the study. The ability of the continuous reactor to remove fecal coliforms to below the Class A monitoring limit depended on the concentration in the feed sludge. There was no significant removal of Clostridium perfringens across the continuous reactor under any condition, and there also was limited removal of somatic coliphages. The removal of male-specific coliphages across the continuous reactor appeared to be related to temperature. Overall, at least one of the Class A pathogen criteria or the fecal coliform limit was exceeded in at least one sample in the continuous-reactor effluent at each temperature. Over the range of temperatures evaluated, the maximum time required to meet the Class A criteria by batch treatment of the continuous-reactor effluent was 1 hour for Ascaris suum and Salmonella spp. and 2 hours for fecal coliforms.     

Effects of increased deposition of atmospheric nitrogen on an upland moor: leaching of N species and soil solution chemistry

This study was designed to investigate the leaching response of an upland moorland to long-term (10 yr) ammonium nitrate additions of 40, 80 and 120 kg N ha(-1) yr(-1) and to relate this response to other indications of potential system damage, such as acidification and cation displacement. Results showed increases in nitrate leaching only in response to high rates of N input, in excess of 96 and 136 kg total N input ha(-1) yr(-1) for the organic Oh horizon and mineral Eag horizon, respectively. Individual N additions did not alter ammonium leaching from either horizon and ammonium was completely retained by the mineral horizon. Leaching of dissolved organic nitrogen (DON) from the Oh horizon was increased by the addition of 40 kg N ha(-1) yr(-1), but in spite of increases, retention of total dissolved nitrogen reached a maximum of 92% and 95% of 80 kg added N ha(-1) yr(-1) in the Oh and Eag horizons, respectively. Calcium concentrations and calcium/aluminium ratios were decreased in the Eag horizon solution with significant acidification mainly in the Oh horizon leachate. Nitrate leaching is currently regarded as an early indication of N saturation in forest systems. Litter C:N ratios were significantly lowered but values remained above a threshold predicted to increase leaching of N in forests.     

Metal stress consequences on frost hardiness of plants at northern high latitudes: a review and hypothesis

Since sewage discharges can significantly contribute to the contaminant loadings in coastal areas, it is important to identify sources, pathways and environmental sinks. Sterol and fatty alcohol biomarkers were quantified in source materials, suspended sediments and settling matter from the Ria Formosa Lagoon. Simple ratios between key biomarkers including 5beta-coprostanol, cholesterol and epi-coprostanol were able to identify the sewage sources and effected deposition sites. Multivariate methods (PCA) were used to identify co-varying sites. PLS analysis using the sewage discharge as the signature indicated approximately 25% of the variance in the sites could be predicted by the sewage signature. A new source of sewage derived organic matter was found with a high sewage predictable signature. The suspended sediments had relatively low sewage signatures as the material was diluted with other organic matter from in situ production. From a management viewpoint, PLS provides a useful tool in identifying the pathways and accumulation sites for such contaminants.     

In vitro toxicity of selected pesticides on RTG-2 and RTL-W1 fish cell lines

The rainbow trout fish cell lines RTG-2 and RTL-W1 were used to determine the cytotoxic effects of the pesticides bifenthrin, cypermethrin, cyhalothrin, lambda-cyhalothrin, quinalphos and chlorpyrifos. Cytotoxicity was measured by EROD and beta-Gal enzymatic activities, the neutral red (NR) uptake assay, and the FRAME KB protein (KBP) assay. The beta-Gal activity was unaffected by the pesticide exposure. The EROD activity was induced by cyhalothrin and lambda-cyhalothrin (RTG-2 and RTL-W1) and by bifenthrin (RTL-W1). Dose dependent inhibition responses were observed for EROD activity in cells exposed to quinalphos (RTL-W1) and chlorpyrifos (RTG-2 and RTL-W1). RTL-W1 offered a better response for EROD induction. The EC50 values on EROD endpoint were more sensitive than NR and KBP. The acute fish toxicity of chlorpyrifos and quinalphos depends highly on the species; the species sensitivity distributions cover several orders of magnitude and the values obtained for EROS were within the lowest part of the reported ranges.     

Avoidance behaviour of Enchytraeus albidus: effects of benomyl, carbendazim, phenmedipham and different soil types

Enchytraeids are typical inhabitants of many soils, contributing to vital processes of this environmental compartment. Indirectly they are involved in regulating the degradation of organic matter, as well as improving the pore structure of the soil. Due to their behaviour, they are able to avoid unfavourable environmental conditions. Avoidance tests with enchytraeids, initially developed with earthworms by several authors, are quick and easy to perform. With these tests a first assessment of the toxicity of a (contaminated or spiked) soil is possible in just 48 h by using the reaction of the enchytraeids as measurement endpoint. In this period of time the organisms can choose between the control soil and the other soil (a contaminated or spiked or another soil with different physico-chemical properties). In the tests reported here, the enchytraeids were exposed to control soils spiked with the fungicides Benomyl and Carbendazim and the herbicide Phenmedipham. Several chemical concentrations were tested in order to evaluate the avoidance behaviour to toxic substances. In fact, often these short-term screening tests gave results showing avoidance at concentrations in a range similar to the acute test results but, higher than in chronic tests. Further tests are needed to decide whether the results gained in this study can be extrapolated to other chemicals. It is proposed to standardize the Enchytraeid Avoidance Test as it is currently done for the Earthworm Avoidance Test by the International Standard Organization (ISO).     

An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.