The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

A study of the total atmospheric sulfur dioxide load using ground-based measurements and the satellite derived Sulfur Dioxide Index

We present characteristics of the sulfur dioxide (SO₂) loading over Thessaloniki, Greece, and seven other selected sites around the world using SO₂ total column measurements from Brewer spectrophotometers together with satellite estimates of the Version 8 TOMS Sulfur Dioxide Index (SOI) over the same locations, retrieved from Nimbus 7 TOMS (1979–1993), Earth Probe TOMS (1996–2003) and OMI/Aura (2004–2006). Traditionally, the SOI has been used to quantify the SO₂ quantities emitted during great volcanic eruptions. Here, we investigate whether the SOI can give an indication of the total SO₂ load for areas and periods away from eruptive volcanic activity by studying its relative changes as a correlative measure to the SO₂ total column. We examined time series from Thessaloniki and another seven urban and non-urban stations, five in the European Union (Arosa, De Bilt, Hohenpeissenberg, Madrid, Rome) and two in India (Kodaikanal, New Delhi). Based on the Brewer data, Thessaloniki shows high SO₂ total columns for a European Union city but values are still low if compared to highly affected regions like those in India. For the time period 1983–2006 the SO₂ levels above Thessaloniki have generally decreased with a rate of 0.028 Dobson Units (DU) per annum, presumably due to the European Union's strict sulfur control policies. The seasonal variability of the SO₂ total column exhibits a double peak structure with two maxima, one during winter and the second during summer. The winter peak can be attributed to central heating while the summer peak is due to synoptic transport from sources west of the city and sources in the north of Greece. A moderate correlation was found between the seasonal levels of Brewer total SO₂ and SOI for Thessaloniki, Greece (R = 0.710–0.763) and Madrid, Spain (R = 0.691) which shows that under specific conditions the SOI might act as an indicator of the SO₂ total load.     

Do earthworms impact metal mobility and availability in soil? - A review

The importance of earthworms to ecosystem functioning has led to many studies on the impacts of metals on earthworms. Far less attention has been paid to the impact that earthworms have on soil metals both in terms of metal mobility and availability. In this review we consider which earthworms have been used in such studies, which soil components have been investigated, which types of soil have been used and what measures of mobility and availability applied. We proceed to review proposed reasons for effects: changes in microbial populations, pH, dissolved organic carbon and metal speciation. The balance of evidence suggests that earthworms increase metal mobility and availability but more studies are required to determine the precise mechanism for this.     

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Predicting bioremediation of hydrocarbons: Laboratory to field scale

There are strong drivers to increasingly adopt bioremediation as an effective technique for risk reduction of hydrocarbon impacted soils. Researchers often rely solely on chemical data to assess bioremediation efficiently, without making use of the numerous biological techniques for assessing microbial performance. Where used, laboratory experiments must be effectively extrapolated to the field scale. The aim of this research was to test laboratory derived data and move to the field scale. In this research, the remediation of over thirty hydrocarbon sites was studied in the laboratory using a range of analytical techniques. At elevated concentrations, the rate of degradation was best described by respiration and the total hydrocarbon concentration in soil. The number of bacterial degraders and heterotrophs as well as quantification of the bioavailable fraction allowed an estimation of how bioremediation would progress. The response of microbial biosensors proved a useful predictor of bioremediation in the absence of other microbial data. Field-scale trials on average took three times as long to reach the same endpoint as the laboratory trial. It is essential that practitioners justify the nature and frequency of sampling when managing remediation projects and estimations can be made using laboratory derived data. The value of bioremediation will be realised when those that practice the technology can offer transparent lines of evidence to explain their decisions.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Examining intra-urban variation in fine particle mass constituents using GIS and constrained factor analysis

Recent studies have used land use regression (LUR) techniques to explain spatial variability in exposures to PM_2.5 and traffic-related pollutants. Factor analysis has been used to determine source contributions to measured concentrations. Few studies have combined these methods, however, to construct and explain latent source effects. In this study, we derive latent source factors using confirmatory factor analysis constrained to non-negative loadings, and develop LUR models to predict the influence of outdoor sources on latent source factors using GIS-based measures of traffic and other local sources, central site monitoring data, and meteorology. We collected 3–4 day samples of nitrogen dioxide (NO₂) and PM_2.5 outside of 44 homes in summer and winter, from 2003 to 2005 in and around Boston, Massachusetts. Reflectance analysis, X-ray fluorescence spectroscopy (XRF), and high-resolution inductively-coupled plasma mass spectrometry (ICP-MS) were performed on particle filters to estimate elemental carbon (EC), trace element, and water-soluble metals concentrations. Within our constrained factor analysis, a five-factor model was optimal, balancing statistical robustness and physical interpretability. This model produced loadings indicating long-range transport, brake wear/traffic exhaust, diesel exhaust, fuel oil combustion, and resuspended road dust. LUR models largely corroborated factor interpretations through covariate significance. For example, ‘long-range transport’ was predicted by central site PM_2.5 and season; ‘brake wear/traffic exhaust’ and ‘resuspended road dust’ by traffic and residential density; ‘diesel exhaust’ by percent diesel traffic on nearest major road; and ‘fuel oil combustion’ by population density. Results suggest that outdoor residential PM_2.5 source contributions can be partially predicted using GIS-based terms, and that LUR techniques can support factor interpretation for source apportionment. Together, LUR and factor analysis facilitate source identification, assessment of spatial and temporal variability, and more refined source exposure assignment for evaluation of source contributions to health outcomes in epidemiological studies.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

High time-resolved measurements of organic air toxics in different source regimes

High time-resolved (HTR) measurements can provide significant insight into sources and exposures of air pollution. In this study, an automated instrument was developed and deployed to measure hourly concentrations of 18 gas-phase organic air toxics and 6 volatile organic compounds (VOCs) at three sites in and around Pittsburgh, Pennsylvania. The sites represent different source regimes: a site with substantial mobile-source emissions; a residential site adjacent to a heavily industrialized zone; and an urban background site. Despite the close proximity of the sites (less than 13 km apart), the temporal characteristic of outdoor concentrations varied widely. Most of the compounds measured were characterized by short periods of elevated concentrations or plume events, but the duration, magnitude and composition of these events varied from site to site. The HTR data underscored the strong role of emissions from local sources on exposure to most air toxics. Plume events contributed more than 50% of the study average concentrations for all pollutants except chloroform, 1,2-dichloroethane, and carbon tetrachloride. Wind directional dependence of air toxic concentrations revealed that emissions from large industrial facilities affected concentrations at all of the sites. Diurnal patterns and weekend/weekday variations indicated the effects of the mixing layer, point source emissions patterns, and mobile source air toxics (MSATs) on concentrations. Concentrations of many air toxics were temporally correlated, especially MSATs, indicating that they are likely co-emitted. It was also shown that correlations of the HTR data were greater than lower time resolution data (24-h measurements). This difference was most pronounced for the chlorinated pollutants. The stronger correlations in HTR measurements underscore their value for source apportionment studies.     

Revised estimates of construction activity and emissions: Effects on ozone and elemental carbon concentrations in southern California

Emissions from diesel-powered construction equipment are an important source of nitrogen oxides (NO_x) and particulate matter (PM). A new emission inventory for construction equipment emissions is developed based on surveys of diesel fuel use; the revised inventory is compared to current emission inventories. California's OFFROAD model estimates are 4.5 and 3.1 times greater, for NO_x and PM respectively, than the fuel-based estimates developed here. The most relevant uncertainties are the overall amount of construction activity/diesel fuel use, exhaust emission factors for PM and NO_x, and the spatial allocation of emissions to county level and finer spatial scales. Construction permit data were used in this study to estimate spatial distributions of emissions; the resulting distribution is well correlated with population growth. An air quality model was used to assess the impacts of revised emission estimates. Increases of up to 15 ppb in predicted peak ozone concentrations were found in southern California. Elemental carbon and fine particle mass concentrations were in better agreement with observations using revised emission estimates, whereas negative bias in predictions of ambient NO_x concentrations increased.