Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Atmospheric nitrogen deposition in south-east Scotland: Quantification of the organic nitrogen fraction in wet,dry and bulk deposition

Water soluble organic nitrogen (WSON) compounds are ubiquitous in precipitation and in the planetary boundary layer, and therefore are a potential source of bioavailable reactive nitrogen. This paper examines weekly rain data over a period of 22 months from June 2005 to March 2007 collected in 2 types of rain collector (bulk deposition and “dry + wet” deposition) located in a semi-rural area 15 km southwest of Edinburgh, UK (N55°51′44″, W3°12′19″). Bulk deposition collectors are denoted in this paper as “standard rain gauges”, and they are the design used in the UK national network for monitoring precipitation composition. “Dry + wet” deposition collectors are flushing rain gauges and they are equipped with a rain detector (conductivity array), a spray nozzle, a 2-way valve and two independent bottles to collect funnel washings (dry deposition) and true wet deposition. On average, for the 27 weekly samples with 3 valid replicates for the 2 types of collectors, dissolved organic nitrogen (DON) represented 23% of the total dissolved nitrogen (TDN) in bulk deposition. Dry deposition of particles and gas on the funnel surface, rather than rain, contributed over half of all N-containing species (inorganic and organic). Some discrepancies were found between bulk rain gauges and flushing rain gauges, for deposition of both TDN and DON, suggesting biological conversion and loss of inorganic N in the flushing samplers.     

Assessment of heterogeneity of metal composition of fine particulate matter collected from eight U.S. counties using principal component analysis

The main objectives of this study are to (1) characterize chemical constituents of particulate matter (PM) and (2) compare overall differences in PM collected from eight US. counties. This project was undertaken as a part of a larger research program conducted by the Johns Hopkins Particulate Matter Research Center (JHPMRC). The goal of the JHPMRC is to explore the relationship between health effects and exposure to ambient PM of differing composition. The JHPMRC collected weekly filter-based ambient fine particle samples from eight US. counties between January 2008 and January 2010. Each sampling effort consisted of a 5-6-week sampling period. Filters were analyzed for 25 metals using inductively coupled plasma mass spectrometry (ICP-MS). Overall compositional differences were ranked by principal component analysis (PCA). The results showed that weekly concentrations of each element varied 3-40 times between the eight counties. PCA showed that the first five principal components explained 85% of the total variance. The authors found significant overall compositional differences in PM as the average of standardized principal component scores differed between the counties. These findings demonstrate PCA is a useful tool to identify the differences in PM compositional mixtures by county. These differences will be helpful for epidemiological and toxicological studies to help explain why health risks associated with PM exposure are different in locations with similar mass concentrations of PM.     

Effect of diurnal changes in VOC source strengths on performances of receptor models

Introduction

The effect of diurnal changes in strengths of volatile organic compound (VOC) sources on the performances of positive matrix factorization (PMF) and principal component analysis (PCA) was investigated using ambient measurement results that were taken during daytime and nighttime hours between March 24 and May 14, 2011, within Davutpasa Campus of Yildiz Technical University (Istanbul, Turkey).

Methods

Forty-five VOC species, ranging from C₅ to C₁₁ in volatility, were measured in the samples, 40 of which are included in the analyses. Ambient samples were grouped as daytime, nighttime, and all day datasets, and both PMF and PCA were applied to each dataset. A total of six source groups were extracted from each dataset: solvent use, general industrial paint use, gasoline and diesel vehicle exhausts, and biogenic as well as evaporative emissions. Estimated source contributions showed great diurnal variations.

Results

The results suggested that extraction of possible sources by PCA depends greatly on the number of samples and the strength of the sources, while PMF produced stable results regardless of number of samples and source strengths.

Conclusion

Although PMF was unable to resolve gasoline vehicle and evaporative emissions, it was found to be successful in explaining diurnal fluctuations in source strengths, while the performance of PCA depends on the strength of emission source.     

A laboratory experiment for determining both the hydraulic and diffusive properties and the initial pore-water composition of an argillaceous rock sample: a test with the Opalinus clay (Mont Terri, Switzerland)

Argillaceous formations are thought to be suitable natural barriers to the release of radionuclides from a radioactive waste repository. However, the safety assessment of a waste repository hosted by an argillaceous rock requires knowledge of several properties of the host rock such as the hydraulic conductivity, diffusion properties and the pore water composition. This paper presents an experimental design that allows the determination of these three types of parameters on the same cylindrical rock sample. The reliability of this method was evaluated using a core sample from a well-investigated indurated argillaceous formation, the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL) (Switzerland). In this test, deuterium- and oxygen-18-depleted water, bromide and caesium were injected as tracer pulses in a reservoir drilled in the centre of a cylindrical core sample. The evolution of these tracers was monitored by means of samplers included in a circulation circuit for a period of 204 days. Then, a hydraulic test (pulse-test type) was performed. Finally, the core sample was dismantled and analysed to determine tracer profiles. Diffusion parameters determined for the four tracers are consistent with those previously obtained from laboratory through-diffusion and in-situ diffusion experiments. The reconstructed initial pore-water composition (chloride and water stable-isotope concentrations) was also consistent with those previously reported. In addition, the hydraulic test led to an estimate of hydraulic conductivity in good agreement with that obtained from in-situ tests.     

Optimization of photo-Fenton process parameters on carbofuran degradation using central composite design

Carbofuran, one of the most toxic and biorefractory carbamate compounds, is widely used in insecticides in Taiwan (9-18% of total insecticides production per year). In the present study, a central composite design experiment was used to study the effect of photo-Fenton treatment on carbofuran solution and to optimize the process variables such as carbofuran concentration (1-100 mg L(-1)), H(2)O(2) dosage rate (0.25-6 mg L(-1) min(-1)) and Fe(3+) dosage (1-50 mg L(-1)), which influenced the efficiency of carbofuran degradation and mineralization. The results indicated that all the variables investigated in this study had significant roles in the degradation and mineralization of carbofuran in solution. The carbofuran degradation and mineralization efficiencies were increased with increase in H(2)O(2) dosage rate and Fe(3+) dosage, and with decrease in carbofuran concentration. Furthermore, optimum values of both H(2)O(2) dosage rate and Fe(3+) dosage were found to shift to higher values as carbofuran concentration increased. Based on the model obtained in this study, optimum H(2)O(2) dosage rate and Fe(3+) dosage were found to be 4 mg L(-1) min(-1) and 20 mg L(-1), respectively, for 51 mg L(-1) of carbofuran concentration. Under these conditions, carbofuran was completely removed within 30 min and coupled with 78% mineralization at the end of experiment.     

Comparison of methods for evaluation of activity of photocatalytic films

Objective

This work aims to investigate the correlation between the photocatalytic activity determined by methylene blue bleaching (DIN 52980), stearic acid degradation, and degradation of acetone in gas phase.

Method

The photocatalytic TiO₂ coatings included in this investigation ranged from thin commercially available coatings (Activ^TM and BioClean^TM) and ready to use suspensions (Nano-X PK1245) to lab-produced PVD and sol?Cgel coatings. XRD analysis of the photocatalytic coatings showed that all the coatings consisted of nanocrystalline anatase, although the thickness and porosity varied considerably.

Results

The study showed that the reproducibility of the activity measurements was good. However, more importantly, the investigation showed that there is a good correlation between the activities determined by the different methods even though the characteristics of the photocatalytic coatings and the organic probe molecules varied considerably.

Conclusion

The overall findings of this work suggest that there is a good correlation between the investigated methods. These results are promising for the future work concerning standardization of methods for determination of the activity of photocatalytic films.     

Influences of natural emission sources (wildfires and Saharan dust) on the urban organic aerosol in Barcelona (Western Mediterranean Basis) during a PM event

The urban air quality in Barcelona in the Western Mediterranean Basin is characterized by overall high particulate matter (PM) concentrations, due to intensive local anthropogenic emissions and specific meteorological conditions. Moreover, on several days, especially in summer, natural PM sources, such as long-range transported Saharan dust from Northern Africa or wildfires on the Iberian Peninsula and around the Mediterranean Basin, may influence the levels and composition of the organic aerosol. In the second half of July 2009, daily collected PM₁₀ filter samples in an urban background site in Barcelona were analyzed on organic tracer compounds representing several emission sources. During this period, an important PM peak event was observed. Individual organic compound concentrations increased two to five times during this event. Although highest increase was observed for the organic tracer of biomass burning, the contribution to the organic aerosol was estimated to be around 6?%. Organic tracers that could be related to Saharan dust showed no correlation with the PM and OC levels, while this was the case for those related to fossil fuel combustion from traffic emissions. Moreover, a change in the meteorological conditions gave way to an overall increase of the urban background contamination. Long-range atmospheric transport of organic compounds from primary emissions sources (i.e., wildfires and Saharan dust) has a relatively moderate impact on the organic aerosol in an urban area where the local emissions are dominating.