Elemental analysis of airborne particulates in Chile

Aerosol samples collected in three characteristic Chilean cities-including urban and remote zones-have been analyzed by the PIXE spectroscopic technique. Elemental composition, total suspended particulate matter (TSP), particle size distribution, and the peculiar geographic and meteorological parameters have been included in this study. Santiago--the polluted capital of Chile--registered high TSP indexes and important amounts of hazardous elements in air such as S, V, Cr, Zn, Br and Pb. The atmosphere of Antofagasta city showed marine and mineral activity influence. Results from Chillán city are similar to those from rural environments. Protons and deuterons-provided by the isochronous cyclotron of the University of Chile-were used to excite X-ray radiation from the sample. Signals were processed by an energy dispersive detection system, including a cryogenic Si(Li) detector, electronic for pulse amplification and an analog to digital converter. The absolute elemental concentration of the particulate matter in air was obtained through a fundamental parameter equation. Samples consist of particulate material collected directly on Nuclepore filters or deposited over Kapton foils. Typical elements analyzed were Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, As, Br and Pb.     

Piezoelectric properties of quartz and cristobalite airborne particulates as a cause of adverse health effects

Inhalation of quartz and cristobalite dusts is commonly linked with health effects although the mechanisms involved are poorly understood. Grinding of these piezoelectric silica polymorphs produces particulates with transient piezoelectric charges. This is likely to cause vigorous reaction with atmospheric gases and, through interaction with surface charges and ‘dangling bonds’, may lead to the formation of highly deleterious ozonide, superoxide and hydroxyl radicals. It is hoped that this study will encourage experimental work to quantify piezoelectric effects in silica dusts and to develop a method for their neutralisation during cutting and grinding processes.     

Trends in airborne particulates in Stuttgart, Germany: 1972-2005

Since 1972, at the University of Hohenheim in Stuttgart, Germany, airborne particulate matter (PM12 and then PM10) was continuously collected on filters and analyzed for environmentally relevant elements by X-ray fluorescence analysis. The resulting long-term time series are suitable for the investigation of trends and of seasonal variation. For the period 1972-2005, monthly and annual concentration mean values of 13 elements (Br, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, S, Ti, V, and Zn) in the air are presented. Trend curves were fitted and the mean yearly variation of the concentration for these elements was calculated and represented graphically. All trend curves show a diminution of the air pollution during this period, but to different extents. Mean trends in percent per year were calculated for each element both for the entire investigation period and for three data subsets of 10-11 years. Possible explanations are discussed in detail.     

Chemical signals of epiphytic lichens in southwestern North America; natural versus man-made sources for airborne particulates

Ambient airborne particulate matter (PM) in southwestern North America consists of naturally derived desert dust, plus anthropogenic inputs from several sources. Epiphytic lichens (Usnea sp.) in this region are a useful biomonitor for the airborne PM because they derive nutrients and moisture largely from incorporated atmospheric aerosols, and not by absorption from the host tree limb from which they are suspended. Using a broad-based sampling strategy from southern Chihuahua, Mexico, to northern New Mexico, USA, we show that select elemental abundance ratios and lead isotopes from epiphytic lichens are useful for distinguishing between sources of airborne PM, and for gauging anthropogenic inputs into desert ecosystems. Abundance patterns of the trace elements La, Nd, and Sm in the lichens suggest origination from continental crust, but rare earth elements display a pronounced enrichment relative to the major element Fe by a factor of about 5. This enrichment appears related to geologic weathering, aeolian transport, and grain-size biases toward trace-element-rich mineral grains in the arid setting. Using the metal Pb as an indicator of human inputs, epiphytic lichens typically show Pb enrichments by a factor of about 25–60 over typical upper crustal values. Regional-scale differences in Pb isotope ratios of these lichens relate to different pollutant sources in southwestern North America.     

Concentration and trend of 9,10-phenanthrenequinone in airborne particulates collected in Nagasaki city, Japan

9,10-Phenanthrenequinone (PQ), one of the components of atmospheric pollutants, has potent harmful effects on human health. PQ in airborne particulates collected in Nagasaki city was determined by HPLC with fluorescence derivatization. PQ extracted from airborne particulates using methanol was derivatized with benzaldehyde in the presence of ammonium acetate to give a fluorescent compound. The average concentration (mean+/-SD, n=52) of PQ found in airborne particulates collected from July 1997 to June 1998 was 0.287+/-0.128 ng m-3. Concentrations of PQ in winter were higher than those in summer. In a weekly variation study, PQ concentrations were higher during weekdays and lower at weekend. The levels of PQ were obviously correlated with those of phenanthrene (PH) that is considered as a parent compound of PQ. This observation suggested that PQ was emitted into the atmosphere from the same source as PH, or PQ was converted from PH in the atmosphere.     

Sources of airborne particulates (PM10) in the port city of Rijeka,Croatia

Environmental Science and Pollution Research - The air quality monitoring in Rijeka started in the early 1970s and has been oriented to air pollution caused by the big industrial sources (new...     

Molecular signatures of organic particulates as tracers of emission sources

Chemical signature of airborne particulates and deposition dusts is subject of study since decades. Usually, three complementary composition markers are investigated, namely, (i) specific organic compounds; (ii) concentration ratios between congeners, and (iii) percent distributions of homologs. Due to its intrinsic limits (e.g., variability depending on decomposition and gas/particle equilibrium), the identification of pollution sources based on molecular signatures results overall restricted to qualitative purposes. Nevertheless, chemical fingerprints allow drawing preliminary information, suitable for successfully approaching multivariate analysis and valuing the relative importance of sources. Here, the state-of-the-art is presented about the molecular fingerprints of non-polar aliphatic, polyaromatic (PAHs, nitro-PAHs), and polar (fatty acids, organic halides, polysaccharides) compounds in emissions. Special concern was addressed to alkenes and alkanes with carbon numbers ranging from 12 to 23 and?≥?24, which displayed distinct relative abundances in petrol-derived spills and exhausts, emissions from microorganisms, high vegetation, and sediments. Long-chain alkanes associated with tobacco smoke were characterized by a peculiar iso/anteiso/normal homolog fingerprint and by n-hentriacontane percentages higher than elsewhere. Several concentration ratios of PAHs were identified as diagnostic of the type of emission, and the sources of uncertainty were elucidated. Despite extensive investigations conducted so far, the origin of uncommon molecular fingerprints, e.g., alkane/alkene relationships in deposition dusts and airborne particles, remains quite unclear. Polar organics resulted scarcely investigated for pollution apportioning purposes, though they looked as indicative of the nature of sources. Finally, the role of humans and living organisms as actual emitters of chemicals seems to need concern in the future.

     

Cocaine and other illicit drugs in airborne particulates in urban environments: a reflection of social conduct and population size

Levels of cocaine and other psychoactive substances in atmospheric particulate matter (PM) were determined in urban environments representing distinct social behaviours with regard to drug abuse: night-life, university and residential areas. Three cities (with population >1 million and <0.3 million inhabitants) were selected. Mean daily levels of drugs in PM were 11-336 pg/m³ for cocaine, 23-34 pg/m³ for cannabinoids, and 5-90 pg/m³ for heroin. The highest levels were recorded on weekends, with factors with respect to weekdays of 1-3 for cocaine, 1-2 for cannabinoids and 1.1-1.7 for heroin. Higher levels were detected in the night-life areas, pointing towards consumption and trafficking as major emission sources, and possibly ruling out drug manufacture. The similarities in temporal trends at all sites suggested a city-scale transport of psychoactive substances. Correlations were detected between cocaine and amphetamine consumption (r² = 0.98), and between heroin and cannabinoids (r²>0.82).     

Mutagenic and recombinagenic activity of airborne particulates, PM10 and TSP, organic extracts in the Drosophila wing-spot test

The genotoxicity associated with air pollution in the city of Canoas, Rio Grande do Sul (Brazil), was assessed in November (spring) and January (summer). We applied the somatic mutation and recombination test (SMART) in Drosophila melanogaster in its standard version with normal bioactivation (ST) and in its variant with increased cytochrome P450-dependent biotransformation capacity (HB). The data indicated the genotoxicity of TSP and PM10 collected in November, in both ST and HB crosses. The genotoxic activity of the PM10 material in the spring sample was exclusively associated with the induction of mitotic recombination, whereas the TSP genetic toxicity was due to both recombinational as well as point and/or chromosomal mutation events. Considering PM10 collected in January, a positive response--100% (17.10 m3/ml) concentration--was observed in the HB cross, which was not detected in the ST cross.     

Comparison of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons in airborne particulates collected in downtown and suburban Kanazawa,Japan

In this study, airborne particulates were collected at three sites, two in a downtown area and the other in a suburban area of Kanazawa, Japan in each season for 7 years. Two polycyclic aromatic hydrocarbons (PAHs), pyrene (Py) and benzo[a]pyrene (BaP) and four nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (NP) and 1,3-, 1,6-, and 1,8-dinitropyrenes (DNP) were determined by high-performance liquid chromatography with fluorescence and chemiluminescence detection. At the downtown sites, the mean concentration of each DNP was about two orders of magnitude lower than that of 1-NP and more than three orders of magnitude lower than those of Py and BaP. This tendency reflected the composition of PAHs and NPAHs in diesel-engine exhaust particulates. Concentrations of these PAHs and NPAHs were higher at the downtown sites than at the suburban site, suggesting the dilution of these compounds during the transportation from the downtown to the suburban area. The concentration ratios of NPAHs to PAHs were larger at the downtown sites than at the suburban site. Studies using UV light and sunlight showed that degradation of NPAHs was faster than that of PAHs. Thus, the lower concentrations of NPAHs in the suburban sites may be due to their being photodegraded faster than PAHs during the atmospheric transportation from the downtown area to the suburban area.     

Native plant species suitable as bioindicators and biomonitors for airborne fluoride

For 30-40 years airborne fluoride, usually in the form of HF or SiF4, was one of the most important and damaging air pollutants affecting forests, crops and natural vegetation. It is much more toxic than most other air pollutants such as O3 or SO2 because injury to the most sensitive species begins when they are exposed to a concentration below 1 ppb (ca. 0.8 microg m(-3)) for a 1- to 3-day period. The long-term threshold concentration is around 0.25-0.30 microg m(-3). Higher concentrations and longer durations of exposure induce much more rapid and extensive injury. However, there is a difference in sensitivity between the most and least sensitive species of around 2-3 orders of magnitude and most species possess a degree of resistance. Dramatic improvements in engineering technology have greatly reduced emissions but because of the high toxicity, cases of vegetation injury are still common, even in developed countries, and cases involving litigation still occur. Therefore there is a continuing need for bioindicators and biomonitoring of fluorides, so this paper reviews the subject, drawing attention to the strengths and limitations of the techniques. Visible symptoms are described and illustrated and tables of relative sensitivity are given and their limitations discussed. Finally, examples of biomonitoring in Europe and the USA are presented.     

Photolysis of nitroaromatics in aquatic systems. I. 2,4,6-trinitrotoluene

Photolysis of 2,4,6-trinitrotoluene (TNT) occurs rapidly in pure and natural waters irradiated with sunlight, with half-lives of less than a half-hour in some natural waters. Experiments to study the TNT photolysis products and to obtain evidence for complexation of TNT with natural substances are discussed.     

Source apportionment of airborne particulate matter using organic compounds as tracers

A chemical mass balance receptor model based on organic compounds has been developed that relates source contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.     

Adsorption of aluminium by stream particulates

An experimental study was made of the adsorption of aluminium by fine particulates from Whitray Beck, a hill stream in NW England. Adsorption increased with Al(3) activity, pH and concentration of particles, and could be quantitatively described by the empirical equation: [Formula: see text] [particles] where square brackets indicate concentrations, curly brackets, activities, and alpha, beta and gamma are constants with values of 5.14x10(-10) (mol litre(-1))(2.015) (g particles litre(-1))(-1), 0.457, and 1.472, respectively. For the experimental data, the equation gave a correlation ratio of 0.99. The equation accounts reasonably well for the adsorption of Al by particulates from seven other streams. In applying the equation, it must be borne in mind that the desorption kinetics of Al depend on pH, and rapid reversibility (<15min) can only be assumed for pHor=10%) of total monomeric Al.