Study on ambient concentrations of PM10, PM10–2.5, PM2.5 and gaseous pollutants. Trace elements and chemical speciation of atmospheric particulates

This study provides the first comprehensive report on mass concentrations of particulate matter of various sizes, inorganic and organic gas concentrations monitored at three sampling sites in the city of Palermo (Sicily, Italy). It also provides information on the water-soluble species and trace elements. A total of 2054 PM₁₀ (1333) and PM_2.5 (721) daily measurements were collected from November 2006 to February 2008. The highest mass concentrations were observed at the urban stations, average values being about two times higher than those at the suburban (control) site. Time variations in PM₁₀ and also PM_10–2.5 were observed at the urban stations, the highest concentrations being measured in autumn and winter. CO, NOx, NO₂, benzene, toluene and o-xylene concentrations peaked in autumn and winter, a pattern similar to those recorded for PM₁₀ and PM_10–2.5 mass levels, indicating the importance of traffic emissions in urban air pollution. 91% and 51% of the benzene measurements exceeded the limit of 5 μg m^?3 at the two urban monitoring sites. Trace elements (As, Ba, Cr, Cu, Mo, Pb, Sb) suspected of being introduced into the atmosphere mainly by anthropogenic activities, were highly enriched with respect to local soil. Results indicate that a large fraction of PM₁₀ (31–47% in weight) and PM_2.5 (29% in weight) is made up of water-soluble ions. Ammonium sulphate and nitrate particles accounted for 14–29 wt% of particulate matter mass concentrations. Crustal and marine components, combined, account for 41% and 49% in PM_2.5 and PM₁₀, respectively. The calculated deficits in Cl^- and NH₄⁺ ions suggest that a proportion of these ions are lost, via the formation of gaseous NH₄Cl or HCl and NH₃.     

Optimum conditions for microbial carbonate precipitation

The type of bacteria, bacterial cell concentration, initial urea concentration, reaction temperature, the initial Ca(2+) concentration, ionic strength, and the pH of the media are some factors that control the activity of the urease enzyme, and may have a significant impact on microbial carbonate precipitation (MCP). Factorial experiments were designed based on these factors to determine the optimum conditions that take into consideration economic advantage while at the same time giving quality results. Sporosarcina pasteurii strain ATCC 11859 was used at constant temperature (25°C) and ionic strength with varying amounts of urea, Ca(2+), and bacterial cell concentration. The results indicate that the rate of ureolysis (k(urea)) increases with bacterial cell concentration, and the bacterial cell concentration had a greater influence on k(urea) than initial urea concentration. At 25 mM Ca(2+) concentration, increasing bacterial cell concentration from 10(6) to 10(8)cells mL?1 increased the CaCO(3) precipitated and CO(2) sequestrated by over 30%. However, when the Ca(2+) concentration was increased 10-fold to 250 mM Ca(2+), the amount of CaCO(3) precipitated and CO(2) sequestrated increased by over 100% irrespective of initial urea concentration. Consequently, the optimum conditions for MCP under our experimental conditions were 666 mM urea and 250 mM Ca(2+) at 2.3×10? cells mL?1 bacterial cell concentration. However, a greater CaCO(3) deposition is achievable with higher concentrations of urea, Ca(2+), and bacterial cells so long as the respective quantities are within their economic advantage. X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray analyzes confirmed that the precipitate formed was CaCO(3) and composed of predominantly calcite crystals with little vaterite crystals.     

The influence of gill and liver metabolism on the predicted bioconcentration of three pharmaceuticals in fish

The potential for xenobiotic compounds to bioconcentrate is typically expressed through the bioconcentration factor (BCF), which has gained increased regulatory significance over the past decade. Due to the expense of in vivo bioconcentration studies and the growing regulatory need to assess bioconcentration potential, BCF is often calculated via single-compartment models, using K(OW) as the primary input. Recent efforts to refine BCF models have focused on physiological factors, including the ability of the organism to eliminate the compound through metabolic transformation. This study looks at the ability of in vitro biotransformation assays using S9 fractions to provide an indication of metabolic potential. Given the importance of the fish gill and liver in metabolic transformation, the metabolic loss of ibuprofen, norethindrone and propranolol was measured using rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) gill and liver S9 fractions. Metabolic transformation rates (k(M)) were calculated and integrated into a refined BCF model. A significant difference was noted between BCF solely based on K(OW) and BCF including k(M). These studies indicate that the inclusion of k(M) in BCF models can bring predicted bioconcentration estimates closer to in vivo values.     

Use of native mosses as biomonitors of heavy metals and nitrogen deposition in the surroundings of two steel works

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was conducted in the surroundings of two steel plants located in the North of Spain. Levels of V, Cr, Ni, Cu, Zn, As, Cd, Hg, Pb and N were determined. Very high concentrations in the areas of study were detected when compared to nearby unaffected regions. Similar trends were observed for all the elements in the differently orientated transects, showing an appreciable influence of the NW prevailing winds of the region in the dispersion of pollutants, as well as a clear decreasing gradient in the concentrations of metals in mosses within a distance of 1500 meters from the facilities. A differentiation between the elements emitted by the chimney as result of the industrial activity (V, Cr, Ni, Cu and As) and those with a high presence in steel slag deposits (Zn, Cd, Hg and Pb) was observed. The range of contamination was also established by means of the Contamination Factor, indicating a category 4 out of 6 categories, which shows the high levels reported in the areas of study. A different dynamic was registered for nitrogen regarding the rest of the heavy metals analysed except for Hg, probably due to the elevated volatility and mobility of both elements, as well as their high persistence in the atmosphere.     

Characteristics of springtime profiles and sources of ozone in the low troposphere over northern Taiwan

To quantify the possible sources of the high ambient ozone concentration in the low troposphere over Taiwan, ozone sounding data from a two-year intensive field measurement program conducted in April and early May of 2004 and 2005 in northern Taiwan has been examined. We found that the vertical ozone distributions and occurrence of enhanced ozone in the lower troposphere (below 6 km) mainly resulted from (1)Type NE: the long-range transport of ozone controlled by the prevailing northeasterly winds below 2 km, (2)Type LO: the local photochemical ozone production process, and (3)Type SW: the strong southwest/westerly winds aloft (2–6 km). In the boundary layer (BL), where Asian continental outflow prevails, the average profile for type NE is characterized by a peak ozone concentration of nearly 65 ppb at about 1500 m altitude. For type LO, high ozone concentration with an average ozone concentration greater than 80 ppb was also found in the BL in the case of stagnant atmospheric and sunny weather conditions dominated. For type SW, significant ozone enhancement with average ozone concentration of 70–85 ppb was found at around 4 km altitude. It is about 10 ppb greater than that of the types NE and LO at the same troposphere layer owing to the contribution of the biomass burning over Indochina. Due to Taiwan's unique geographic location, the complex interaction of these ozone features in the BL and aloft, especially features associated with northeasterly and south/southwesterly winds, have resulted in complex characteristics of ozone distributions in the lower troposphere over northern Taiwan.     

Global scale emission and distribution of sea-spray aerosol: Sea-salt and organic enrichment

The chemical composition of marine aerosols as a function of their size is an important parameter for the evaluation of their impact on the global climate system. In this work we model fine particle organic matter emitted by sea spray processes and its influence on the aerosol chemical properties at the global scale using the off-line global Chemistry-Transport Model TM5. TM5 is coupled to a microphysical aerosol dynamics model providing size resolved information on particle masses and numbers. The mass of the emitted sea spray particles is partitioned between water insoluble organic matter (WIOM) and sea salt components in the accumulation mode using a function that relates the emitted organic fraction to the surface ocean chlorophyll-a concentrations. The global emission in the sub-micron size range of organic matter by sea spray process is 8.2 Tg yr^?1, compared to 24 Tg fine yr^?1 sea-salt emissions. When the marine sources are included, the concentrations of modelled primary particulate organic matter (POM) increase mainly over the oceans. The model predictions of WIOM and sea salt are evaluated against measurements carried out at Mace Head (Northern Hemisphere) and Amsterdam Island (Southern Hemisphere), showing that in clean marine conditions WIOM marine emissions contribute significantly to POM values.     

Comparison of land-use regression models between Great Britain and the Netherlands

Land-use regression models have increasingly been applied for air pollution mapping at typically the city level. Though models generally predict spatial variability well, the structure of models differs widely between studies. The observed differences in the models may be due to artefacts of data and methodology or underlying differences in source or dispersion characteristics. If the former, more standardised methods using common data sets could be beneficial. We compared land-use regression models for NO₂ and PM_10, developed with a consistent protocol in Great Britain (GB) and the Netherlands (NL).Models were constructed on the basis of 2001 annual mean concentrations from the national air quality networks. Predictor variables used for modelling related to traffic, population, land use and topography. Four sets of models were developed for each country. First, predictor variables derived from data sets common to both countries were used in a pooled analysis, including an indicator for country and interaction terms between country and the identified predictor variables. Second, the common data sets were used to develop individual baseline models for each country. Third, the country-specific baseline models were applied after calibration in the other country to explore transferability. The fourth model was developed using the best possible predictor variables for each country.A common model for GB and NL explained NO₂ concentrations well (adjusted R² 0.64), with no significant differences in intercept and slopes between the two countries. The country-specific model developed on common variables for NL but not GB improved the prediction.The performance of models based upon common data was only slightly worse than models optimised with local data. Models transferred to the other country performed substantially worse than the country-specific models. In conclusion, care is needed both in transferring models across different study areas, and in developing large inter-regional LUR models.     

Establishing ozone flux–response relationships for winter wheat: Analysis of uncertainties based on data for UK and Polish genotypes

The work outlined in this paper had three objectives. The first was to explore the effects of ozone pollution on grain yield and quality of commercially-grown winter wheat cultivars. The second was to derive a stomatal ozone flux model for winter wheat and compare with those already developed for spring wheat. The third was to evaluate exposure- versus flux–response approaches from a risk assessment perspective, and explore the implications of genetic variation in modelled ozone flux.Fifteen winter wheat cultivars were grown in open-top chambers where they were exposed to four levels of ozone. During fumigation, stomatal conductance measurements were made over the lifespan of the flag leaf across a range of environmental conditions. Although significant intra-specific variation in ‘ozone sensitivity’ (in terms of impacts on yield) was identified, yield was inversely related (R² = 0.63, P < 0.001) to the accumulated hourly averaged ozone exposure above 40 ppb during daylight hours (AOT40) across the dataset. The adverse effect of ozone on yield was principally due to a decline in seed weight. Algorithms defining the influence of environmental variables on stomatal uptake were subtly different from those currently in use, based on data for spring wheat, to map ozone impacts on pan-European cereal yield. Considerable intra-specific variation in phenological effects was identified. This meant that an ‘average behaviour’ had to be derived which reduced the predictive capability of the derived stomatal flux model (R² = 0.49, P < 0.001, 15 cultivars included). Indeed, given the intra-specific variability encountered, the flux model that was derived from the full dataset was no better in predicting O₃ impacts on wheat yield than was the AOT40 index. The study highlights the need to use ozone risk assessment tools appropriate to specific vegetation types when modelling and mapping ozone impacts at the regional level.     

A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Characterization of particulate matter concentrations during controlled indoor activities

Indoor sources have been identified as a major contributor to the increase of particle concentration in indoor environments. The work presented here is a study of the characteristics of particulate matter number size distribution and mass concentration under controlled indoor activities in a laboratory room. The objective is to characterize particulate matter concentrations indoors resulted under the influence of specific sources. Measurements were performed in an empty laboratory (period September–October 2006) using a GRIMM SMPS+C system (particle size range between 11.1 and 1083.3 nm), a DustTrak Aerosol Monitor (TSI) and a P-Trak Ultrafine Particle Counter (TSI). The studied indoor activities included candle burning, hot plate heating, water boiling, onion frying, vacuuming, hair drying, hair spraying, smoking and burning of incense stick. The AMANpsd computer algorithm was used to evaluate the modal structure of measured particle number size distribution data. Furthermore, the change of the particle number size distribution shape under the influence of different emission sources was studied versus time. Finally the particle emission rates were computed. High particle number concentrations were observed during smoking, onion frying, candle burning and incense stick burning. The highest particle mass concentrations were measured during smoking and hair spraying. The shift of the particle size distribution to larger diameters suggests the presence of strong coagulation effect during candle burning, incense stick burning, smoking and onion frying. The size distribution was mainly bimodal during onion frying and candle burning, whereas the size distribution remained unimodal during incense stick burning and smoking experiments.