Comparison of Selenium and Sulfur at Remote Sites

Abstract

The Interagency Monitoring of Protected Visual Environments (IMPROVE) particulate monitoring network has been collecting aerosols for visibility apportionment at remote sites in the United States since 1988. The measurements include the major PM_2.5 components, such as sulfur, carbon, and nitrate, and trace elements, such as selenium. This paper will examine the relationship between the sulfurs and selenium concentrations at 61 sites for samples collected in the seasonal year 1993. Maps of mean sulfur and selenium measurements in summer 1993 and winter 1993-1994 indicate that there are well-defined regional patterns for both elements, with concentrations in the Appalachian region that are ten times those in areas of the Pacific Northwest. The S/Se ratios of means are relatively uniform across the United States, at around 2000 in summer and 1000 in winter, indicating a strong sulfur-selenium relationship. The role of conversion of S0₂ to sulfate can also be deduced from the means. For individual samples taken during summer 1993, there is a high correlation between the two variables in the East, especially at sites in the Northeast, where the correlation coefficients (r²) are around 0.9. In the West, the correlation is much lower. This is attributed to fewer sources and differing emission factors.     

Effects of Operating Variables on PAH Emissions and Mutagenicity of Emissions from Woodstoves

As part of the Integrated Air Cancer Project, the U.S. Environmental Protection Agency (EPA) has conducted field emission measurement programs in Raleigh, North Carolina, and Boise, Idaho, to identify the potential mutagenic Impact of residential wood burning and motor vehicles on ambient and indoor air. These studies included the collection of emission samples from chimneys serving wood burning appliances. Parallel projects were undertaken in Instrumented woodstove test laboratories to quantify woodstove emissions during operations typical of in-house usage but under more controlled conditions.

Three woodstoves were operated In test laboratories over a range of burnrates, burning eastern oak, southern yellow pine, or western white pine. Two conventional stoves were tested at an altitude of 90 m. One of the conventional stoves and a catalytic stove were tested at an altitude of 825 m.

Decreasing burnrate increased total paniculate emissions from the conventional stoves while the catalytic stove's total particulate emissions were unaffected. There was no correlation of total particulate emissions with altitude whereas total polynuclear aromatic hydrocarbon (PAH) emissions were higher at the lower altitude. Mutagenicity of the catalytic stove emissions was higher than emissions from the conventional stove. Emissions from burning pine were more mutagenic than emissions from oak.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Sorption Kinetics of Atrazine and Diuron in Soils from Southern Brazil

Abstract

Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0–20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (¹⁴C-atrazine and ¹⁴C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34–42 and 71–79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH 4 ), high CH 4 contents in soil gas near petroleum spills have been reported. While CH 4 is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH 4 accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH 4 and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH 4 associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH 4 associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Contribution of Primary and Secondary Sources to Organic Aerosol and PM2.5 at SEARCH Network Sites

Abstract

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 µm or less in aerodynamic diameter (PM_2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO₄ ^2?], nitrate [NO₃ ^?], ammonium [NH₄ ⁺]), metals, and metal oxides and compared with the measured PM_2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and β-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12–42 µg m^?3. Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM_2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM_2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

Toxicity identification and reduction of wastewaters from a pigment manufacturing factory

In this study, major toxicants in pigment wastewaters (i.e. raw wastewater and effluent) were determined by toxicity identification evaluations (TIEs), and changes in their toxicities due to combined gamma-ray (gamma-ray) and ozone treatments were evaluated. From TIE results using Daphnia magna, Cr(VI) and o-toluidine were identified as major toxicants in the raw wastewater with concentrations of 2.47 and 25.3mg l(-1), respectively. This was confirmed by subsequent spiking and mass balance approaches. For effluent, TIE results suggested that organic anions were likely responsible for the observed toxicities. Toxicity reduction tests showed that gamma-rays with ozone treatment after coagulation was more efficient in reducing toxicities in the raw wastewater (3.9-2.0 TU) than gamma-ray treatment alone (3.9-3.1 TU). For pigment effluent, gamma-ray/O3 treatment resulted in a complete removal of the acute toxicity.     

A 13-Week Comparison of Passive and Continuous Ozone Monitors at Forested Sites in North-Central Pennsylvania

ABSTRACT

Ogawa passive O₃ samplers were used in a 13-week study (June 1-September 1, 1999) involving 11 forested and mountaintop sites in north-central Pennsylvania. Four of the sites were collocated with TECO model 49 O₃ analyzers. A significant correlation (p < 0.0001) was found for 24-hr average weekly O₃ concentrations between the two methodologies at the four sites with collocated monitors. As expected, there were positive relationships between increasing elevation of the sites and increasing O₃ concentrations. No O₃ exposure patterns were found on a west-to-east or south-to-north basis; however, the area known for lower O₃ exposures within a smaller subsection of the study area showed consistently lower O₃ exposures. Preliminary results regarding relationships of symptom responses within O₃-sensitive bioindicators are also presented with black cherry (Prunus serotina, Elirli.) and common milkweed (Asclepias syriaca, L.) showing clear evidence of increasing injury with increasing O₃ exposures. Due to the extremely dry conditions encountered in north-central Pennsylvania during the 1999 growing season, O₃-induced symptoms were sporadic and quite delayed until late-season rains during the latter portion of the observation period.     

Lead Contamination of Urban Soils and Vegetation by Emissions from Secondary Lead Industries

The degree and extent of lead contamination of urban soils and vegetation in the vicinity of secondary lead industries are provided. These urban industries, a secondary smelter reprocessing lead from used batteries and scrap metal and a manufacturer of new storage batteries, were located near residential communities. Levels as high as 21,000 ppm of lead in the upper 5 cm of soil (based on air dried weight) and 3500 and 2700 ppm in willow foliage (not washed and washed, respectively, based on dry weight) were found adjacent to the secondary smelter, with the levels decreasing exponentially from the sources. The data on lead contamination of soils and vegetation at various distances and directions from the urban secondary lead industries were compared with levels of lead found in control urban and highway locations. In addition, arsenic levels in soil were examined as a tracer for the source of industrial lead emissions. High levels of lead found In both vegetation and soil in the vicinity of the urban industries reflected both historical and current emissions of lead in those areas. These studies were conducted for industrial abatement purposes; to assist medical related epidemiology studies; to define the areas of severe contamination for soil cleanup purposes; and to formulate guidelines for excessive levels of lead in soil and vegetation. Since lead in soil is persistent, concern arises with respect to pica for small children, contamination of edible vegetables grown in high-lead soil, and reentrainment of leaded particulate matter into the air.     

Toxicity of water and sediment from stormwater retarding basins to Hydra hexactinella

Hydra hexactinella was used to assess the toxicity of stormwater and sediment samples from three retarding basins in Melbourne, Australia, using an acute test, a sublethal test, and a pulse test. Stormwater from the Avoca St retarding basins resulted in a LC50 of 613 ml/L, NOEC and LOEC values of 50 ml/L and 100 ml/L, while the 7 h pulse exposure caused a significant increase in the mean population growth rate compared to the control. Water samples from the two other retarding basins were found non-toxic to H. hexactinella. This is the first study to employ sediment tests with Hydra spp. on stormwater sediments and a lower population growth rate was observed for organisms exposed to sediment from the Avoca St retarding basins. The behavioral study showed that H. hexactinella tended to avoid the sediment-water interface when exposed to sediment from all retarding basins, compared to the reference sediment. Further work is needed to determine the long-term effects of stormwater polluted sediments and acute effects due to organism exposure to short-term high concentrations during rain events.     

Sorption and transport of iodine species in sediments from the Savannah River and Hanford Sites

Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at the Savannah River and Hanford Sites, where anthropogenic (129)I from prior nuclear fuel processing activities poses an environmental risk. We conducted integrated column and batch experiments to investigate the interconversion, sorption and transport of iodine species, and the sediments we examined exhibit a wide range in organic matter, clay mineralogy, soil pH, and texture. The results of our experiments illustrate complex behavior with various processes occurring, including iodate reduction, irreversible retention or mass loss of iodide, and rate-limited and nonlinear sorption. There was an appreciable iodate reduction to iodide, presumably mediated by the structural Fe(II) in some clay minerals; therefore, careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. The different iodine species exhibited dramatically different sorption and transport behavior in three sediment samples, possessing different physico-chemical properties, collected from different depths at the Savannah River Site. Our study yielded additional insight into processes and mechanisms affecting the geochemical cycling of iodine in the environment, and provided quantitative estimates of key parameters (e.g., extent and rate of sorption) for risk assessment at these sites.     

Toxicity and biodegradation of diamines

Phytotoxicity and cytotoxicity of 2,4-diaminotoluene (2,4-D), 4,4'-methylenedianiline (4,4-D), and 1,6-hexanediamine (1,6-D) were investigated by observing the germination of young radish seeds and the viability of HeLa cells, respectively. 2,4-D showed the highest, 4,4-D intermediate, and 1,6-D lowest cytotoxicity. However, the phytotoxicity decreased in the order of 4,4-D > 2,4-D > 1,6-D. Contrary to the results previously reported, in the modified Sturm test the activated sludge degraded 2,4-D and 4,4-D as well as 1,6-D without any pre-acclimation. Ochrobacterium antropi was isolated for degradation of 2,4-D and 4,4-D and Pseudomonas citronellolis for 1,6-D degradation. Thielevia sp. was isolated as 2,4-D degrading fungus and Aspergillus sp. as 4,4-D and 1,6-D degrading fungus. The fungi degraded the diamines faster than the bacteria.     

Thermal Immobilization of Lead Contaminants in Soils Treated in a Fixed- and Fluidized-Bed Incinerator at Moderate Temperatures

Abstract

Artificially lead-contaminated soils with different lead contents (200, 450, 600, and 900 ppm) were thermally immobilized in both fixed-bed and fluidized-bed modes at moderate treating temperatures (less than 500 °C) for various retention times. Cement powder and brick powder were added to the artificially contaminated soils to enhance lead immobilization. Results indicate that increasing treating temperature and time increases the extent of lead immobilization, as determined by the U.S. Environmental Protection Agency's (U.S. EPA) Toxicity Characteristics Leachability Procedure (TCLP). The percentage of lead leached from the soil/ cement mixtures was in the range of less than 0.251%, compared with the range between 13.6% and 40.7% for the corresponding soil/brick mixtures. As the amount of brick dust added to the Pb-doped soil was increased, the specific Pb immobilization effectiveness increased from 0.0675 to 0.149 mg Pb/g brick (for the 20- and 50-gram brick addition, respectively). An increase in air flow rate from 2 to 40 L/min caused a slight decrease in the Pb leaching percentage from 14.96% to 11.59%. Both the Freundlich and Langmuir isotherms give a satisfactory fit (r = 0.945 ~ 0.998) for the data derived from a TCLP test of the thermally-treated soil samples (105 °C and 500 °C) that contained lead contaminants. Sorption of lead contaminants in soil and sorbent matrices was the primary type of chemisorption. The kinetic results indicated that the Pb-doped soil system was too complicated to be described by a simple calculation.     

Antibiotic Resistance of Enterococcus spp. Isolated from Wastewater and Sludge of Poultry Slaughterhouses

Antibiotimicrobial resistance was investigated in 537 Enterococcus spp. isolates recovered from 22 samples of crude inflow, treated effluent and sludge collected in wastewater treatment plants of eight poultry slaughterhouses of Portugal. No significant differences (P > 0.05) were found in the resistance to each antimicrobial agent with regards to the origin of the sample (inflow, sludge and effluent). Many of the isolates displayed resistance to tetracycline (85.7%), erythromycin (45.7%), nitrofurantoin (34.0%) and rifampicin (17.8%). Resistance was also observed, but to a lesser extent, to ciprofloxacin (10.2%), ampicillin (8.0%), chloramphenicol (4.6%), vancomycin (0.9%) and gentamicin (0.4%). Resistance to three or more antimicrobial classes was present in 37.1% of the isolates. Wastewater treatment resulted in viable enterococci decrease between less than 1 log and 4 log; nevertheless, more than 4.4 × 10⁵ colony forming units (CFU)/100 mL were present in the outflow of the plants and thus resistant enterococci are not prevented from reaching the general environment.     

Contributions of Acid Deposition and Natural Processes to Cation Leaching from Forest Soils: A Review

Methods of quantifying the roles of atmospheric acid inputs and internal acid generation by carbonic, organic, and nitric acids are illustrated by reviewing data sets from several intensively studied sites in North America. Some of the sites (tropical, temperate deciduous, and temperate coniferous) received acid precipitation whereas others (northern and subalpine) did not. Natural leaching by carbonic acid dominated soil leaching in the tropical and temperate coniferous sites, nitric acid (caused by nitrification) dominated leaching In an N-fixing temperate deciduous site, and organic acids dominated surface soil leaching in the subalpine site and contributed to leaching of surface soils in several other sites. Only at the temperate deciduous sites did atmospheric acid input play a major role in soil leaching. In no case, however, are the annual net losses of cations regarded as alarming as compared to soil exchangeable cation capital.

These results were used to illustrate the methods of quantifying the effects of atmospheric inputs and internal processes on soil leaching rates, not to draw broad generalizations as to acid rain effects on soils. However, there are predictable patterns in natural soil leaching processes which relate to climate, soil properties, and vegetation that may help in predicting the relative importances of natural vs. atmospheric acid inputs to soil leaching.     

Fugitive Dust Emission Source Profiles and Assessment of Selected Control Strategies for Particulate Matter at Gravel Processing Sites in Taiwan

Abstract

Particles emitted from gravel processing sites are one contributor to worsening air quality in Taiwan. Major pollution sources at gravel processing sites include gravel and sand piles, unpaved roads, material crushers, and bare ground. This study analyzed fugitive dust emission characteristics at each pollution source using several types of particle samplers, including total suspended particulates (TSP), suspended particulate (PM₁₀), fine suspended particulate (PM_2.5), particulate sizer, and dust-fall collectors. Furthermore, silt content and moisture in the gravel were measured to develop particulate emission factors. The results showed that TSP (<100 µm) concentrations at the boundary of gravel sites ranged from 280 to 1290 µg/m³, which clearly exceeds the Taiwan hourly air quality standard of 500 µg/m³. Moreover, PM₁₀ concentrations, ranging from 135 to 550 µg/m³, were also above the daily air quality standard of 125 µg/m³ and approximately 1.2 and 1.5 times the PM_2.5 concentrations, ranging from 105 to 470 µg/m³. The size distribution analysis reveals that mass mean diameter and geometric standard deviation ranged from 3.2 to 5.7 µm and from 2.82 to 5.51, respectively. In this study, spraying surfactant was the most effective control strategy to abate windblown dust from unpaved roads, having a control efficiency of approximately 93%, which is significantly higher than using paved road strategies with a control efficiency of approximately 45%. For paved roads, wet suppression provided the best dust control efficiencies ranging from 50 to 83%. Re-vegetation of disturbed ground had dust control efficiencies ranging from 48 to 64%.     

浙江省船舶修造行业挥发性有机物组分特征及排放系数

基于浙江省29家船舶修造企业的调查数据,研究分析了船舶修造行业挥发性有机物(VOCs)治理情况和VOCs组分特征,并核算了VOCs产生系数和排放系数.结果表明,船舶修造行业VOCs治理设施总体覆盖率为55％,VOCs主要组分为苯系物(BETX)与含氧挥发性有机物(OVOCs).分别以船舶载重量、船舶数量为活动水平时,远...     

Toxicity characterisation of sediment porewaters collected from UK estuaries using a Tisbe battagliai bioassay

The lethal toxicity of sediment porewater isolated from samples collected from six United Kingdom estuaries was tested using a Tisbe battagliai bioassay. A selection of Phase 1 toxicity identification evaluation (TIE) procedures was then used to characterise the substances responsible for the measured toxicity. In samples collected in 2000, cationic metals, ammonia, organic compounds were identified as the cause of toxicity in the most toxic sample collected. Some of the toxicity remained uncharacterised. It was shown that the toxicity in samples collected from the same locations in 2001 was due to ammonia. The successful application of the T. battagliai bioassay demonstrates that it is a suitable assay for marine sediment porewater TIE and that combined with simple characterisation procedures allow an initial assessment to be made on the type of substances responsible for the measured toxicity.     

Toxicity and metal speciation characterisation of waste water from an abandoned gold mine in tropical northern Australia

The decommissioned Mount Todd gold mine, located in the wet-dry tropics of northern Australia, consists of a large waste water inventory and an acid rock drainage problem, which has the potential to impact upon freshwater ecosystems of the Edith River catchment. The toxicity of retention pond 1 (RP1) water was determined using six local freshwater species (duckweed, alga, cladoceran, snail, hydra and a fish). RP1 water was very toxic to all species, with the percentage dilution of RP1 water inhibiting 10% of organism response (IC(10)), or lethal to 5% of individuals (LC(5)), ranging from 0.007 to 0.088%. The percentage dilution of RP1 water inhibiting 50% of organism response (IC(50)), or lethal to 50% of individuals (LC(50)), ranged from 0.051% to 0.58%. Based on chemical analyses and geochemical speciation modelling of the test waters, Cu, Zn and Al were the most likely toxic components at acidic dilutions (i.e. 1%), while Cu and Zn were the most likely toxic components at 0.1% RP1 water, where pH was 6.5. Species sensitivity distributions (SSDs) were used to predict dilutions of RP1 water that would protect or unacceptably affect the downstream aquatic ecosystems. A dilution ratio of 1 part RP1 water to 20000 parts Edith River water (0.005% RP1 water) was calculated to be required for the protection of at least 95% of species. This information can be used in conjunction with field chemical and biological data to better predict the ecological risks of RP1 waste water downstream of the Mount Todd mine.     

Toxicity and detoxification of Swedish detergents and softener products

Detergents and softeners are used in large quantities and some of their ingredients are highly toxic to aquatic organisms. In the present study the acute toxicity to Daphnia magna was determined for 26 detergents and five softener Swedish products. Only one of the detergents had a 48-h EC50 > 100 mg/l. The 48-h EC50 for the other 25 detergents ranged from 4 to 85 mg/l. The 48-h EC50 for the five softeners ranged from 15 to 166 mg/l. Detoxification tests, with and without inoculum of sewage organisms, showed that all tested products were detoxified to some extent after 16 days and that the rate of detoxification was considerably higher with addition of sewage organisms. Toxicity to D. magna of the detergents and softeners, and the biotic detoxification rate was correlated with the concentration of surfactants used in formulating the products (more surfactants increased toxicity and a slower rate of detoxification). These results emphasize the importance of biological purification of domestic wastewater containing detergents and a suggested development of less toxic and more easily degradable surfactants.