A comparison of blue crab and bivalve delta15N tissue enrichment in two North Carolina estuaries

Stable isotope analyses (delta(15)N) were used to examine invertebrate tissue enrichment in two North Carolina estuaries with differing amounts of nutrient loading. Bivalves collected from a nutrient sensitive estuary yielded a significant difference in mean nitrogen isotopic composition of tissue (10.4 per thousand+/-0.82; N=66) compared to bivalves collected from a less nutrient sensitive estuary (6.4 per thousand+/-0.63; N=45). Similarly, blue crabs from nutrient sensitive sites had a nitrogen isotopic composition of 11.4 per thousand (+/-1.3, N=77), which was significantly different (P<0.001) than the tissue of less nutrient sensitive blue crabs (9.6 per thousand+/-0.6; N=77). The results showed that an inverse relationship exists between invertebrate tissue enrichment and indicators of water quality across estuarine sites. This study suggests that a relationship may exist between nutrient sources and subsequent energy transfer to estuarine consumers in two North Carolina estuaries.     

Inorganic PM2.5 at a U.S. agricultural site

In this study, we present approximately two years (January 1999-December 2000) of atmospheric NH3, NH4+, HCl, Cl-, HNO3, NO3-, SO2, and SO4= concentrations measured by the annular denuder/filter pack method at an agricultural site in eastern North Carolina. This site is influenced by high NH3 emissions from animal production and fertilizer use in the surrounding area and neighboring counties. The two-year mean NH3 concentration is 5.6 (+/-5.13) microg m(-3). The mean concentration of total inorganic PM2.5, which includes SO4=, NO3-, NH4+, and Cl-, is 8.0 (+/-5.84) microg m(-3). SO4=, NO3-, NH4+, and Cl- represent, respectively, 53, 24, 22, and 1% of measured inorganic PM2.5. NH3 contributes 72% of total NH3 + NH4+, on an average. Equilibrium modeling of the gas+aerosol NH3/H2SO4/HNO3 system shows that inorganic PM2.5 is more sensitive to reductions in gas + aerosol concentrations of sulfate and nitrate relative to NH3.     

Stable isotope determination in wild and farmed gilthead sea bream (Sparus aurata) tissues from the western Mediterranean

Stable isotopes of carbon and nitrogen (delta(13)C and delta(15)N) have been determined in wild and farmed gilthead sea bream (Sparus aurata) samples of white and red muscle, liver, gills and gonads. First, delta(13)C and delta(15)N values were determined in samples with and without lipid removal to check the possible effect of lipid content on the stable isotope values of the different tissues studied. Differences were found for delta(13)C in all tissues studied apart from white muscle of wild fish, the tissue with the lowest lipid content. For delta(15)N values no differences were found in wild fish tissues. Liver from farmed fish showed lower delta(15)N value after lipid removing. Further conclusions were based on results obtained from lipid-free samples. delta(13)C of cultured fish tissues showed a mean depletion of 2.9+/-0.4 per thousand compared to wild specimens, suggesting different sources of carbon in the diet, probably due to the feed used during sea-cage culture. Cultured gilthead sea bream tissues were significantly more enriched in nitrogen than wild specimens by an average of 1.5+/-0.2 per thousand in white muscle, indicating a slight increase in the trophic level. Determination of stable isotope signatures of gilthead sea bream tissues allows clear discrimination between wild and cultured sea bream, and characterisation of differences in diet and feeding conditions in any tissue studied.     

Carbon and nitrogen composition and stable isotope as potential indicators of source and fate of organic matter in the salt marsh of the Changjiang Estuary, China

Elemental (TOC, TN, C/N) and stable carbon and nitrogen isotopic (delta(13)C, delta(15)N) compositions were measured for surface sediments, three sediment vibrocores, plants, and suspended particulate matter (SPM) collected from salt marsh of the Changjiang Estuary. The purpose of this study is to characterize the sources of organic matter in sediments and to further elucidate the factors influencing the isotope signature in the salt marsh. Our results indicate that organic matter preserved in the sediments is predominantly controlled by the particulate organic matter in the Changjiang Estuary. The in situ contribution of marsh plants carbon to sediment organic matter is clearest in the high marsh, where the low delta(13)C of the plants (-28.1 per thousand) is reflected by a sediment delta(13)C (-24.7 per thousand) lower than values found for the low marsh and bare flat sediments (-23.4 per thousand and -23.0 per thousand, respectively). The effect of grain size on the spatial difference of isotope composition in the marsh sediments is insignificant, based on the observation that similar isotope values are found in different size particles, both for delta(13)C and delta(15)N. Nutrient utilization by plant assimilation, however, shows great impact on the surface sediment delta(15)N composition, due to the isotope fractionation. With extensive plant coverage and the consequent low surface water nitrate concentration, delta(15)N values of the high marsh surface sediments show (15)N enrichment.     

Toxic fluoride and arsenic contaminated groundwater in the Lahore and Kasur districts, Punjab, Pakistan and possible contaminant sources

The present study is the first attempt to put forward possible sources of As, F- and SO4(2-) contaminated groundwater in the Kalalanwala area, Punjab, Pakistan. Five rainwater and 24 groundwater samples from three different depths were analyzed. Shallow groundwater from 24 to 27 m depth contained high F- (2.47-21.1mg/L), while the groundwater samples from the deeper depth were free from fluoride contamination. All groundwater samples contained high As (32-1900 microg/L), in excess of WHO drinking water standards. The SO4(2-) ranges from 110 to 1550 mg/L. Delta34S data indicate three sources for SO4(2-) air pollutants (5.5-5.7 per thousand), fertilizers (4.8 per thousand), and household waste (7.0 per thousand). Our important finding is the presence of SO4(2-), As and F- in rainwater, indicating the contribution of these elements from air pollution. We propose that pollutants originate, in part, from coal combusted at brick factories and were mobilized promotionally by the alkaline nature of the local groundwater.     

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

Evaluation of surface runoff and road dust as sources of nitrogen using nitrate isotopic composition

Stable nitrogen and oxygen isotope ratios of nitrate (δ¹⁵N-NO₃ and δ¹⁸O-NO₃) have recently been used to identify nitrogen sources in water environments. However, there have been no investigations designed to determine nitrate isotopes in non-point sources in urban areas for evaluating the impact of surface deposits on nitrogen in surface runoff. In this study, we collected rainwater, surface runoff and surface deposits (road dust, roof dust and soil) to evaluate the nitrogen sources in surface runoff using nitrate isotopes. There were no large differences in δ¹⁵N-NO₃ among rainwater (−0.3‰ to 1.5‰), surface runoff (−2.7‰ to 0.4‰), leachates from road dust (−5.8‰ to 6.2‰) and soil (−11.5‰ to 0.6‰). In contrast, the δ¹⁸O-NO₃ in surface runoff (28.5-47.9‰) was lower than that in rainwater (62.7-78.6‰), and higher than that in leachates from road dust (6.1-27.6‰) and soil (−1.1‰ to 6.6‰). δ¹⁸O-NO₃ is a useful indicator for evaluating the NO₃-N sources in surface runoff. Using this indicator, NO₃-N from road dust was estimated to account for more than half of the NO₃-N in surface runoff. This is consistent with a result based on a comparison of their loads per unit surface between rainwater and surface runoff, which also showed that most of the nitrogen in surface runoff was derived from surface deposits.     

Particulate matter in California: part 2--Spatial, temporal, and compositional patterns of PM2.5, PM10-2.5, and PM10

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM2.5 and PM10 concentrations range from 3 to 10 microg/m3 and from 5 to 18 microg/m3, respectively. In the urban areas of California, annual-averages for PM2.5 range from 7 to 30 microg/m3, with observed 24-hr peaks reaching levels as high as 160 microg/m3. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM2.5 concentrations that are more prolonged and regional in nature. PM2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO4(2-)) and nitrate (NO3-) components of PM2.5 and PM10) and correlate with reductions in ambient levels of oxides of sulfur (SOx) and oxides of nitrogen (NOx). Annual averages for PM10-2.5 and PM10 exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

Chemical characterization of extractable water soluble matter associated with PM10 from Mexico City during 2000

We report the chemical composition of PM10-associated water-soluble species in Mexico City during the second semester of 2000. PM10 samples were collected at four ambient air quality monitoring sites in Mexico City. We determined soluble ions (chloride, nitrate, sulfate, ammonium, sodium, potassium), ionizable transition metals (Zn, Fe, Ti, Pb, Mn, V, Ni, Cr, Cu) and soluble protein. The higher PM(10) levels were observed in Xalostoc (45-174 microg m(-3)) and the lowest in Pedregal (19-54 microg m(-3)). The highest SO2 average concentrations were observed in Tlalnepantla, NO2 in Merced and O3 and NO(x) in Pedregal. The concentration range of soluble sulfate was 6.7-7.9 and 19-25.5 microg m(-3) for ammonium, and 14.8-29.19 for soluble V and 3.2-7.7 ng m(-3) for Ni, suggesting a higher contribution of combustion sources. PM-associated soluble protein levels varied between 0.038 and 0.169 mg m(-3), representing a readily inhalable constituent that could contribute to adverse outcomes. The higher levels for most parameters studied were observed during the cold dry season, particularly in December. A richer content of soluble metals was observed when they were expressed by mass/mass units rather than by air volume units. Significant correlations between Ni-V, Ni-SO4(-2), V-SO4(-2), V-SO2, Ni-SO2 suggest the same type of emission source. The variable soluble metal and ion concentrations were strongly influenced by the seasonal meteoclimatic conditions and the differential contribution of emission sources. Our data support the idea that PM10 mass concentration by itself does not provide a clear understanding of a local PM air pollution problem.     

Quality-assured measurements of animal building emissions: particulate matter concentrations

Federally funded, multistate field studies were initiated in 2002 to measure emissions of particulate matter (PM) < 10 microm (PM10) and total suspended particulate (TSP), ammonia, hydrogen sulfide, carbon dioxide, methane, nonmethane hydrocarbons, and odor from swine and poultry production buildings in the United States. This paper describes the use of a continuous PM analyzer based on the tapered element oscillating microbalance (TEOM). In these studies, the TEOM was used to measure PM emissions at identical locations in paired barns. Measuring PM concentrations in swine and poultry barns, compared with measuring PM in ambient air, required more frequent maintenance of the TEOM. External screens were used to prevent rapid plugging of the insect screen in the PM10 preseparator inlet. Minute means of mass concentrations exhibited a sinusoidal pattern that followed the variation of relative humidity, indicating that mass concentration measurements were affected by water vapor condensation onto and evaporation of moisture from the TEOM filter. Filter loading increased the humidity effect, most likely because of increased water vapor adsorption capacity of added PM. In a single layer barn study, collocated TEOMs, equipped with TSP and PM10 inlets, corresponded well when placed near the inlets of exhaust fans in a layer barn. Initial data showed that average daily mean concentrations of TSP, PM10, and PM2.5 concentrations at a layer barn were 1440 +/- 182 microg/m3 (n = 2), 553 +/- 79 microg/m3 (n = 4), and 33 +/- 75 microg/m3 (n = 1), respectively. The daily mean TSP concentration (n = 1) of a swine barn sprinkled with soybean oil was 67% lower than an untreated swine barn, which had a daily mean TSP concentration of 1143 +/- 619 microg/m3. The daily mean ambient TSP concentration (n = 1) near the swine barns was 25 +/- 8 microg/m3. Concentrations of PM inside the swine barns were correlated to pig activity.     

Quantifying MTBE biodegradation in the Vandenberg Air Force Base ethanol release study using stable carbon isotopes

Compound-specific isotope analysis (CSIA) was used to assess biodegradation of MTBE and TBA during an ethanol release study at Vandenberg Air Force Base. Two continuous side-by-side field releases were conducted within a preexisting MTBE plume to form two lanes. The first involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene ("No ethanol lane"), while the other involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene and ethanol ("With ethanol lane"). The delta(13)C of MTBE for all wells in the "No ethanol lane" remained constant during the experiment with a mean value of -31.3 +/- 0.5 per thousand (n=40), suggesting the absence of any substantial MTBE biodegradation in this lane. In contrast, substantial enrichment in (13)C of MTBE by 40.6 per thousand, was measured in the "With ethanol lane", consistent with the effects of biodegradation. A substantial amount of TBA (up to 1200 microg/L) was produced by the biodegradation of MTBE in the "With ethanol lane". The mean value of delta(13)C for TBA in groundwater samples in the "With ethanol lane" was -26.0 +/- 1.0 per thousand (n=32). Uniform delta(13)C TBA values through space and time in this lane suggest that substantial anaerobic biodegradation of TBA did not occur during the experiment. Using the reported range in isotopic enrichment factors for MTBE of -9.2 per thousand to -15.6 per thousand, and values of delta(13)C of MTBE in groundwater samples, MTBE first-order biodegradation rates in the "With ethanol lane" were 12.0 to 20.3 year(-1) (n=18). The isotope-derived rate constants are in good agreement with the previously published rate constant of 16.8 year(-1) calculated using contaminant mass-discharge for the "With ethanol lane".     

Measurement and analysis of the relationship between ammonia, acid gases, and fine particles in eastern North Carolina

An annular denuder system, which consisted of a cyclone separator; two diffusion denuders coated with sodium carbonate and citric acid, respectively; and a filter pack consisting of Teflon and nylon filters in series, was used to measure acid gases, ammonia (NH3), and fine particles in the atmosphere from April 1998 to March 1999 in eastern North Carolina (i.e., an NH3-rich environment). The sodium carbonate denuders yielded average acid gas concentrations of 0.23 microg/m3 hydrochloric acid (standard deviation [SD] +/- 0.2 microg/m3); 1.14 microg/m3 nitric acid (SD +/- 0.81 microg/m3), and 1.61 microg/m3 sulfuric acid (SD +/- 1.58 microg/m3). The citric acid denuders yielded an average concentration of 17.89 microg/m3 NH3 (SD +/- 15.03 microg/m3). The filters yielded average fine aerosol concentrations of 1.64 microg/m3 ammonium (NH4+; SD +/- 1.26 microg/m3); 0.26 microg/m3 chloride (SD +/- 0.69 microg/m3), 1.92 microg/m3 nitrate (SD +/- 1.09 microg/m3), and 3.18 microg/m3 sulfate (SO4(2-); SD +/- 3.12 microg/m3). From seasonal variation, the measured particulates (NH4+, SO4(2-), and nitrate) showed larger peak concentrations during summer, suggesting that the gas-to-particle conversion was efficient during summer. The aerosol fraction in this study area indicated the domination of ammonium sulfate particles because of the local abundance of NH3, and the long-range transport of SO4(2-) based on back trajectory analysis. Relative humidity effects on gas-to-particle conversion processes were analyzed by particulate NH4+ concentration originally formed from the neutralization processes with the secondary pollutants in the atmosphere.     

Measured summertime concentrations of particulate components,Hg0, and speciated polycyclic aromatic hydrocarbons at rural sites in New York State

Daily PM2.5 samples, Hg0 and speciated polycyclic aromatic hydrocarbon (PAH) were simultaneously collected at Potsdam and Stockton site in NY during the summers of 2000 and 2001. Samples for determination of the mass concentration and chemical composition of the PM2.5 were obtained with a speciation network PM2.5 sampler. Chemical composition including trace elemental composition, water-soluble ions, and elemental carbon were analyzed. Elemental mercury and PAHs were sampled separately. Daily PM2.5 concentrations ranged from 0.47 to 53.7 microg m(-3) at the Potsdam site, and from 0.82 to 47.23 microg m(-3) at the Stockton site with large daily differences between the two sites. Potsdam consistently had lower mass values than Stockton. The greatest contributors to the PM2.5 mass (generally >0.1 microg/m(3)) were sulfate, nitrate, ammonium, and BC at both sites. Seventeen PAHs were identified at each site in 2000 and the average total concentrations were 3.2 ng/m(3) and 2.9 ng/m(3) at the Potsdam and Stockton sites, respectively. The mean vapor phase mercury concentration at the Potsdam site (2.4 +/-1.2 ng m(-3), n=93) was higher than that at the Stockton site (1.2 +/- 1.0 ng m(-3), n=60) in 2000, whereas in 2001, the average concentrations were 1.1 ng m(-3) and 1.6 ng m(-3) at the Potsdam and Stockton sites, respectively. In general, vapor phase mercury concentrations increased with increasing ambient temperature at the Stockton site in 2000. These differences in values between 2000 and 2001 can be largely explained by distinct differences in the meteorological regimes that dominated in the different years.     

Characterization of chemical species in atmospheric aerosols in a metropolitan basin

Ambient PM10 aerosol samples were collected from Taiwan's Taichung metropolitan basin between October 1997 and January 1998, and their chemical characteristics studied. The average mass concentration of PM10 was 109.0 +/- 54.1 microg/m3. Carbonaceous materials, sulfate, nitrate, and ammonium were the most important contributors to the PM10 component. On average, 64% of the PM10 was made up of fine particles. During PM10 episodes, average wind speed was 0.7 m/s and relative humidity was high, 83% on average, probably giving rise to stagnation of air pollutants and their entrapment close to the surface. With relative humidity < 70%, NO3-, NH4+, SO4(2-), carbonaceous materials, and PM10 mass showed high correlation with maximum hourly average ozone (O3M). Variation in atmospheric humidity may affect the gas-to-particle interactions of S and N species. The most significant contribution to PM10 in the Taichung urban basin was from the photochemical formation of secondary aerosols and carbonaceous materials in the atmospheric environment.     

First assessment of the PM<Subscript>10</Subscript> and PM<Subscript>2.5</Subscript> particulate level in the ambient air of belgrade city

INTENTION, GOAL, SCOPE, BACKGROUND: As the strong negative health effect of exposure to the inhalable particulate matter PM10 in the urban environment has been confirmed, the study of the mass concentrations, physico-chemical characteristics, sources, as well as spatial and temporal variation of atmospheric aerosol particles becomes very important. OBJECTIVE: This work is a pilot study to assess the concentration level of ambient suspended particulate matter, with an aerodynamic diameter of less than 10 microm, in the Belgrade central urban area. Average daily concentrations of PM10 and PM2.5 have been measured at three representative points in the city between June 2002 and December 2002. The influence of meteorological parameters on PM10 and PM2.5 concentrations was analyzed, and possible pollution sources were identified. METHODS: Suspended particles were collected on Pure Teflon filters by using a Mini-Vol low-volume air sampler (Airmetrics Co., Inc.; 5 l min(-1) flow rate). Particle mass was determined gravimetrically after 48 h of conditioning in a desiccator, in a Class 100 clean room at the temperature T = 20 degrees C and at about 50% constant relative humidity (RH). RESULTS AND DISCUSSION: Analysis of the PM10 data indicated a marked difference between season without heating--(summer; mean value 56 microg m(-3)) and heating season--(winter; mean value 96 microg m3); 62% of samples exceeded the level of 50 microg m(-3). The impact of meteorological factors on PM concentrations was not immediately apparent, but there was a significant negative correlation with the wind speed. CONCLUSIONS: The PM10 and PM2.5 mass concentrations in the Belgrade urban area had high average values (77 microg m(-3) and 61 microg m(-3)) in comparison with other European cities. The main sources of particulate matter were traffic emission, road dust resuspension, and individual heating emissions. When the air masses are coming from the SW direction, the contribution from the Obrenovac power plants is evident. During days of exceptionally severe pollution, in both summer and winter periods, high production of secondary aerosols occurred, as can be seen from an increase in PM2.5 in respect to PM10 mass concentration. RECOMMENDATION AND OUTLOOK: The results obtained gave us the first impression of the concentration level of particulate matter, with an aerodynamic diameter of less than 10 microm, in the Belgrade ambient air. Due to measured high PM mass concentrations, it is obvious that it would be very difficult to meet the EU standards (EEC 1999) by 2010. It is necessary to continue with PM10 and PM2.5 sampling; and after comprehensive analysis which includes the results of chemical and physical characterization of particles, we will be able to recommend effective control measures in order to improve air quality in Belgrade.     

Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.     

Ozone measurements in South Carolina using passive samplers

Passive samplers with two different collection substrates were used to obtain an average ozone concentration for 1 month during the summer of 2002 for each South Carolina county. One sampler contained a filter coated with indigo carmine, whose color fades when exposed to ozone. The fading was measured by reflectance spectroscopy. The other sampler contained filters that were coated with nitrite, which is oxidized to nitrate when exposed to ozone. The nitrate was measured by ion chromatography. Calibration curves were developed for the two methods by comparing color fading from indigo carmine and nitrate ion concentration from the nitrite filter with ambient ozone concentration measured by a co-located reference continuous UV ozone analyzer. These curves were used to calculate integrated ozone concentrations for samplers distributed across South Carolina. Using the indigo carmine method, the average ozone concentrations ranged from 21 to 64 ppb (average = 46 +/- 7.9 ppb, n = 58) across the 46 counties in the state during one summer month of 2002. Concentrations for the same time period from the nitrite-coated filters ranged from 23 to 62 ppb (average = 41 +/- 8.1 ppb, n = 58). Also for the same time period, the 23 continuous UV photometric ozone monitors operated by the South Carolina Department of Health and Environmental Control at sites within 10 miles of some of the passive monitors showed ozone concentrations ranging from 28 to 50 ppb (average = 39 +/- 6.3 ppb, n = 22).     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

Historical trends in the mass and chemical species concentrations of coarse particulate matter in the Los Angeles Basin and relation to sources and air quality regulations

To assess the impact of past, current and proposed air quality regulations on coarse particulate matter (CPM), the concentrations of CPM mass and its chemical constituents were examined in the Los Angeles Basin from 1986 to 2009 using PM data acquired from peer-reviewed journals and regulatory agency database. PM10 mass levels decreased by approximately half from 1988 to 2009 at the three sampling sites examined- located in downtown Los Angeles, Long Beach and Riverside. Annual CPM mass concentrations were calculated from the difference between daily PM10 and PM2.5 from 1999 to 2009. High CPM episodes driven by high wind speed/stagnant condition caused year-to-year fluctuations in the 99th/98th percentile CPM levels. The reductions of average CPM levels were lower than those of PM10 in the same period, therefore the decrease of PM10 level was mainly driven by reductions in the emission levels of PM2.5 (or fine) particles, as demonstrated by the higher annual reduction of average PM2.5 (0.92 microg/m3) compared with CPM (0.39 microg/m3) from 1999 to 2009 in downtown Los Angeles despite their comparable concentrations. This is further confirmed by the significant decrease of Ni, Cr, V and EC in the coarse fraction after 1995. On the other hand, the levels of several inorganic ions (sulfate, chloride and to a lesser extent nitrate) remained comparable. From 1995 to 2008, levels of Cu, a tracer of brake wear, either remained similar or decreased at a smaller rate compared with elements of combustion origins. This differential reduction of CPM components suggests that past and current regulations may have been more effective in reducing fugitive dust (Al, Fe and Si) and combustion emissions (Ni, Cr, V, and EC) rather than CPM from vehicular abrasion (Cu) and inorganic ions (NO3(-), SO4(2-) and Cl(-)) in urban areas. Implications: Limited information is currently available to provide the scientific basis for understanding the sources and physical and chemical variations of CPM, and their relations to air quality regulations and adverse health effects. This study investigates the historical trends of CPM mass and its chemical components in the Los Angeles Basin to advance our understanding on the impact of past and current air quality regulations on the coarse fraction of PM. The results of this study will aid policy makers to design more targeted regulations to control CPM sources to ensure substantial protection of public health from CPM exposure. Supplemental Materials: Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for (1) details of the sampling sites and (2) the daily concentrations of high CPM/PM10 episodes.     

Processes influencing secondary aerosol formation in the San Joaquin Valley during winter

Air quality data collected in the California Regional PM10/ PM(2.5) Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM(2.5)) mass concentrations in California (< or = 188 microg/m3 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO(x))-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO(x) and volatile organic compound (VOC) emissions plus background O3 levels are expected to determine NO(x) oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.