Sulfuric acid at workplaces--applicability of the new Indicative Occupational Exposure Limit Value (IOELV) to thoracic particles

Until 2009, the limit values for airborne sulfuric acid in Europe were based on the inhalable particle fraction (e.g. MAK (Maximum allowed concentration at workplace) value 0.1 mg m(-3) as the inhalable fraction). With the publication of the Commission Directive 2009/161/EU, an Indicative Occupational Exposure Limit Value (IOELV) of 0.05 mg m(-3) for sulfuric acid aerosols was based for the first time on the thoracic particle fraction. To permit a comparison of the measured values for the inhalable fraction with those of the thoracic fraction and to quantify the thoracic fraction, a cyclone was fabricated out of sulfuric-acid-resistant stainless steel that achieves suitable collection characteristics (PM(10)) at a flow rate of 5.34 L min(-1). 49 measurements were carried out in parallel in 21 companies. At concentrations well below the IOELV, there is little difference between the thoracic and inhalable particle concentrations. At higher concentrations (>0.1 mg m(-3) inhalable aerosol), larger droplets have a marked effect on the measured values and the thoracic fraction accounts for only 32.1 ± 12.5% of the inhalable fraction. The EU's IOELV and the proposal of the MAK Commission therefore provide a comparable level of protection. In the transposition of the IOELV into national law, an air limit of 0.1 mg m(-3) could therefore be implemented for the inhalable fraction.     

Characterisation of occupational exposure to air contaminants in a nitrate fertiliser production plant

The aim of this study was to characterise personal exposures to dust, acid vapours, and gases among workers in a Norwegian nitrate fertiliser production plant, as part of an ongoing epidemiological study. In total, 178 inhalable and 179 thoracic aerosol mass fraction samples were collected from randomly chosen workers (N = 141) from three compound fertiliser departments (A, B and C), a calcium nitrate fertiliser production department, nitric acid- and ammonia-production departments, and a shipping department. The overall median inhalable and thoracic aerosol mass concentrations were generally low (1.1 mg m(-3) (min-max: <0.93-45) and 0.21 mg m(-3) (min-max: <0.085-11), respectively). Workers at the compound fertiliser departments B and C had significantly higher inhalable aerosol mass air concentrations compared to the other departments (p < 0.05), except for compound fertiliser department A; however, the difference between the compound fertiliser department C and calcium nitrate department was slightly above the significant level. Workers at the compound fertiliser department A had significantly higher thoracic aerosol mass air concentrations compared to the other departments (p < 0.05), except for compound fertiliser departments B and C. The results indicate that the extrathoracic aerosol fraction of the aerosol compared to the thoracic fraction dominated in most departments. Measurement of the main constituents Ca, K, Mg, and P in the water-soluble and water-insoluble aerosol mass fractions showed that the air concentrations of these elements were low. There is, however, a shift towards more water-soluble species as the production goes from raw material with phosphate rock towards the final product of fertilisers. Overall, the arithmetic mean of water-soluble Ca in the thoracic mass fraction was 51% (min-max: 1-100). A total of 169 personal samples were analysed for HNO(3) vapour and HF. The highest median concentration of HNO(3) (0.63 mg m(-3)) was in the compound fertiliser departments B, and all measurements but four of the HF concentrations were below the LOD of 190 μg m(-3). Exposures to NH(3), CO and NO(2) were measured using direct-reading electrochemical sensors and the time weighted overall averages were all below the LODs of the respective sensors, NH(3) 2 ppm; CO 2 ppm; and NO(2) 0.2 ppm, but some short-term peaks were detected. Even though our results indicate that the workers may experience peak exposure episodes when performing job tasks such as cleaning or maintenance work, the overall air concentrations are well below what is considered to cause known health risks.     

Manganese air exposure assessment and biological monitoring in the manganese alloy production industry

One hundred workers carried personal air sampling equipment during three days to assess exposure to inhalable and respirable Mn. A novel four-step chemical fractionation procedure developed for the speciation of Mn in workroom aerosols was applied for selected aerosol filters. Blood and urine samples were analysed for Mn. The geometric mean (GM) concentrations of inhalable (n = 265) and respirable (n = 167) Mn determined in all filters were 254 microg m(-3) and 28 microg m(-3) respectively. Only 10.6% (95% CI 8.9-12.5) respirable Mn was found in the inhalable fraction when inhalable and respirable samples collected in parallel were considered (n = 153 pairs). There was a high correlation (Pearson's r = 0.70; p < 0.001) between respirable and inhalable Mn. The largest amounts of Mn in the inhalable aerosol fraction were found as Mn0 and Mn2+ (47.4%), whereas 28% was practically "insoluble". The associations between B-Mn and aerosol concentrations of Mn were weak, but an association was found between U-Mn and respirable Mn; Pearson's r being 0.38 between "soluble" respirable Mn and U-Mn. No significant association was found between the "insoluble" components (probably SiMn) and Mn in biological samples.     

Evaluation of the respicon as a personal inhalable sampler in industrial environments

The Respicon has been introduced as a sampler for health related measurements of airborne contaminants at workplaces. The instrument is aimed at simultaneous collection of three health related aerosol fractions: (a) the coarser inhalable fraction, defining the aerosol fraction that may enter the nose and mouth during breathing; (b) the intermediate thoracic fraction, defining the fraction that may penetrate beyond the larynx and so reach the lung; and (c) the finer respirable fraction, defining the fraction that may penetrate to gas exchange region of the lung. The instrument has a number of features attractive to occupational hygienists: in addition to providing the three aerosol fractions simultaneously, it is light and compact enough to be used as a personal sampler. yet can be a tripod mounted for area sampling, it can provide samples not only for gravimetric analysis but also microscopic and chemical analyses; and it is also available in a photometric direct-reading version. The instrument has previously been evaluated as an area sampler and, in this mode of operation, has shown reasonable accuracy in collecting respirable, thoracic and inhalable particles, the latter up to particle diameters of ca. 80 microm. Except for some scattered unpublished data there exist no systematic investigations in the Respicon's performance when used as a personal sampler in the industrial environment. In this paper, we will report on a study of side by side comparison of the Respicon with the IOM inhalable sampler, regarded as a reference instrument for the inhalable fraction. The main study was performed at six different workplaces in a nickel refinery. Statistical analysis of the gravimetrically-determined concentration data reveals consistently lower aerosol exposure values for the Respicon as compared to the IOM sampler. The data for the nickel workplaces are compared with findings from other studies. The results are interpreted in the light of the overall results and the possibility of introducing a correction factor is discussed.     

Multi-component assessment of worker exposures in a copper refinery. Part 1. Environmental monitoring

The exposure characterisation described in this paper for 135 copper refinery workers (45 females, 90 males) focuses on the concentrations of copper, nickel and other trace elements in the inhalable aerosol fractions, as well as in the water-soluble and water-insoluble subfractions. Some information is also provided on the thoracic and respirable aerosol fractions. Further, results are presented for volatile hydrides of arsenic and selenium released in the copper purification steps of the electrorefining process. For the pyrometallurgical operations, a comparison of the geometric means for the inhalable aerosol fraction indicated that water-soluble copper levels were on average 19-fold higher compared to nickel (p < 0.001) and a significant association was evident between them (r = 0.87, p < 0.001); for the insoluble subfraction, the copper : nickel ratio was 12.5 (p < 0.001) and the inter-element correlation had r = 0.98 and p < 0.001. Although for the electrorefinery workers the relative inhalable concentrations of copper and nickel were not significantly different (p > 0.05), the corresponding inter-element associations were: slope of 7.7, r= 0.54, p < or =0.001 for the water-soluble subfraction and slope of 1.3, r = 0.71 and p < or =0.001 for the water-insoluble subfraction. On average, a good proportion of the inhalable copper and nickel were found in the thoracic (40%) and respirable (20%) aerosol fractions. Cobalt air concentrations were generally low with geometric means and 95% confidence intervals of 3.1 (2.4-4.2)microg m(-3) (pyrometallurgical workers) and 0.3 (0.4-0.5) microg m(-3)(electrorefinery workers). Similarly, the maximum concentrations of cadmium and lead were low, respectively 4 and 25 microg m(-3). Of the hydrides, tellurium and antimony could not be detected, but for the arsenic (arsine) and selenium hydrides measurable exposure occurred for almost all electrorefinery workers, although the levels were generally low at 0.2 microg m(-3).     

Workplace aerosol mass concentration measurement using optical particle counters

Direct-reading aerosol measurement usually uses the optical properties of airborne particles to detect and measure particle concentration. In the case of occupational hygiene, mass concentration measurement is often required. Two aerosol monitoring methods are based on the principle of light scattering: optical particle counting (OPC) and photometry. The former analyses the light scattered by a single particle, the latter by a cloud of particles. Both methods need calibration to transform the quantity of scattered light detected into particle concentration. Photometers are simpler to use and can be directly calibrated to measure mass concentration. However, their response varies not only with aerosol concentration but also with particle size distribution, which frequently contributes to biased measurement. Optical particle counters directly measure the particle number concentration and particle size that allows assessment of the particle mass provided the particles are spherical and of known density. An integrating algorithm is used to calculate the mass concentration of any conventional health-related aerosol fraction. The concentrations calculated thus have been compared with simultaneous measurements by conventional gravimetric sampling to check the possibility of field OPC calibration with real workplace aerosols with a view to further monitoring particle mass concentration. Aerosol concentrations were measured in the food industry using the OPC GRIMM? 1.108 and the CIP 10-Inhalable and CIP 10-Respirable (ARELCO?) aerosol samplers while meat sausages were being brushed and coated with calcium carbonate. Previously, the original OPC inlet had been adapted to sample inhalable aerosol. A mixed aerosol of calcium carbonate and fungi spores was present in the workplace. The OPC particle-size distribution and an estimated average particle density of both aerosol components were used to calculate the mass concentration. The inhalable and respirable aerosol fractions calculated from the OPC data are closely correlated with the results of the particle size-selective sampling using the CIP 10. Furthermore, the OPC data allow calculation of the thoracic fraction of workplace aerosol (not measured by sampling), which is interesting in the presence of allergenic particles like fungi spores. The results also show that the modified COP inlet adequately samples inhalable aerosol in the range of workplace particle-size distribution.     

A new method for the characterisation and quantitative speciation of base metal smelter stack particulates

Base metal smelters may be a source of particulates containing metals of environmental concern released to the atmosphere. Knowledge of the quantitative chemical speciation of particulate releases from base metal smelters will be of value in smelter emission fingerprinting, site-specific risk assessments, predictions of the behaviour of smelter stack particulates released to the environment and in resolving liability issues related to current and historic releases. Accordingly, we have developed an innovative approach comprising bulk chemical analysis, a leaching procedure, X-ray diffraction analysis and scanning electron microscopy/electron probe microanalysis characterisation in a step-wise apportioning procedure to derive the quantitative speciation of particulate samples from the stacks of three copper smelters designated as A, B and C. For the A smelter stack particulates, the major calculated percentages were 29 CuSO₄, 20 ZnSO₄.H₂O, 13 (Cu_0.94Zn_0.06)₂(AsO₄)(OH), 11 PbSO₄ and four As₂O₃. For the B smelter stack particulates, the primary calculated percentages were 20 ZnSO₄.H₂O, 20 PbSO₄, 12 CuSO₄ and nine As₂O₃. Finally, we calculated that the C smelter stack particulates mostly comprised 34 ZnSO₄.H₂O, 19 (Cu_0.84Zn_0.16)(AsO₃OH), 11 PbSO₄, 10 As₂O₃ and nine Zn₃(AsO₄)₂. Between 56% and 67% by weight of the smelter stack particulates, including the As, was soluble in water. For these and other operations, the data and approach may be useful in estimating metals partitioning among water, soil and sediment, as well as predictions of the effects of the stack particulates released to the environment.     

Characterisation of workers' exposure in a Russian nickel refinery

In support of a feasibility study of reproductive and developmental health among females employed in the Monchegorsk (Russia) nickel refinery, personal exposure and biological monitoring assessments were conducted. The inhalable aerosol fraction was measured and characterised by chemical speciation and particle-size distribution measurements. Unexpected findings were that: (i), pyrometallurgical working environments had significant levels of water-soluble nickel; (ii), significant exposure to cobalt occurred for the nickel workers; (iii), particles of size corresponding to the thoracic and respirable fractions appeared to be virtually absent in most of the areas surveyed. The water-soluble fraction is judged to be primarily responsible for the observed urinary nickel and cobalt concentrations. It is concluded relative to current international occupational-exposure limits for nickel in air, and because of the high nickel concentrations observed in urine, that the Monchegorsk nickel workers are heavily exposed. The implication of this finding for follow-up epidemiological work is alluded to.     

Statistical methods to apportion the sources of particles in the industrial region of Estarreja—Portugal

Factor analysis models are very attractive for source apportionment and have been widely applied. They do not require a priori knowledge of the number and composition of the sources, and they can actually uncover previously unsuspected sources and estimate the composition of the sources using only ambient monitoring data.Aerosol particles were collected from an industrial atmosphere and analyses for water soluble and carbon components. Principal components analysis permitted the evaluation of the contribution due to industries, soil fraction, secondary pollutants and sea spray particles of the total suspended aerosol mass.It can be concluded that the atmospheric aerosol in the Industrial Area of Estarreja (Portugal) contains a relative important fraction that is water soluble. Ammonium sulphates and nitrates are the main components of this fraction. Carbon compounds constitute about 30% of the total aerosol mass. These compounds are mainly formed by organic matter emitted by the industries. Due to the mutagenic and carcinogenic characteristics of some organic compounds processed in the Industrial Area (vinyl chloride, benzene, aniline, etc.), the concern exists of negative human health effects as a result of prolonged inhalation. Soil compounds is another important fraction of the aerosol mass, mainly in summer with dry, sunny and windy weather conditions.A more conclusive idea of the sources and effects of aerosol matter can only be obtained with the specific analysis of organic compounds and the determination of trace elements, characteristic of each particular source.     

Aerosol residence times and changes in radioiodine-131I and radiocaesium-137 Cs activity over Central Poland after the Fukushima-Daiichi Nuclear reactor accident

The first detectable activities of radioiodine (131)I, and radiocaesium (134)Cs and (137)Cs in the air over Central Poland were measured in dust samples collected by the ASS-500 station in the period of 21(st) to 24(th) of March, 2011. However, the highest activity of both fission products, (131)I and (137)Cs: 8.3 mBq m(-3) and 0.75 mBq m(-3), respectively, were obtained in the samples collected on 30(th) March, i.e.～18 days after the beginning of the fission products' discharge from the damaged units of the Fukushima Daiichi Nuclear Power Plant. The simultaneously determined corrected aerosol residence time for the same samples by (210)Pb/(210)Bi and (210)Pb/(210)Po methods was equal to 10 days. Additionally, on the basis of the activity ratio of two other natural cosmogenic radionuclides, (7)Be and (22)Na in these aerosol samples, it was possible to estimate the aerosol residence time at ～150 days for the solid particles coming from the stratospheric fallout. These data, as well as the differences in the activity size distribution of (7)Be and (131)I in the air particulate matter, show, in contrast to the Chernobyl discharge, a negligible input of stratospheric transport of Fukushima-released fission products.     

Correlation of urinary nickel excretion with observed 'total' and inhalable aerosol exposures of nickel refinery workers

An investigation of the relationship between observed nickel aerosol exposures and urinary nickel excretion was undertaken at a Scandinavian nickel refinery. The goal of the study was to assess the impact of nickel aerosol speciation, the use of particle size-selective sampling instrumentation and adjustment of urinary levels for creatinine excretion on the usefulness of urinary nickel excretion as a marker for exposure. Urinary nickel measurements and paired 'total' and inhalable aerosol exposure measurements were collected each day for one week from refinery workers in four process areas. The mean observed urinary nickel concentration was 12 micrograms L-1 (11 micrograms of Ni per g of creatinine). The strongest relationships between urinary excretion and aerosol exposure were found when urinary nickel levels were adjusted for creatinine excretion and when exposure to only soluble forms of nickel aerosol was considered. No significant difference was observed between measures of 'total' and inhalable aerosol in the ability to predict urinary excretion patterns. In the light of these results, it is recommended that consideration be given to the chemical species distribution of nickel aerosol in the use of urinary nickel measurements as a screening tool for cancer risk in occupationally-exposed populations.     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

用洁净水体监测大气沉降物污染的新方法研究

使用标本缸做为采样装置盛放去离子水露天连续放置1 a,观测水体受到大气干、湿沉降物和沙尘暴降尘的污染状况。期间每隔5~10 d从缸内抽取一定体积的水样,分析其中的水溶性离子和B、Ba、Be、Cd、Cu、Co、Fe、Mo、Mn、Ni、Pb、Sb、Ti、Tl、V、Zn等16种金属元素,除Be在部分样品中被检出外,其余15种元素的检出率均达到100%。在水体中的浓度总体呈明显富集和逐渐升高趋势。从直观和微观的角度阐述大气干、湿沉降物和沙尘暴降尘对洁净水体的污染过程。     

A Gradient Study of 34 Elements in the Vicinity of a Copper-Nickel Smelter in the Kola Peninsula

Concentrations of 34 elements determined by ICP mass spectrometry were studied in surface soil and vegetation along a north–south gradient through the Pechenganickel smelter complex in Kola peninsula, northern Russia. Strong influence from the smelter was evident for Fe, Co, Ni, and Cu, mainly associated with dry deposition of large particles. Also for As, Se, Mo, Sb, Te, Bi, and Pb the smelter or associated sources appeared to be distinct contributors of contamination consisting presumably of smaller particles. Significant but less distinct effects leading to enhanced concentration levels were observed for P, S, V, Cr, Zn, and Tl. In the case of Mn, Rb, Sr, Cs, and Ba the concentrations in vegetation were generally lower near the source, which may be due to cation exchange with protons or heavy metal cations in the soil and subsequent leaching from the root zone. For Li, Be, B, Na, Mg, Al, Ca, Y, Cd, La, Th, and U no particular influence from the smelter complex was observed. Some characteristic differences observed in element concentrations in different plant species and between different years of Pinus sylvestris needles are discussed. The high concentrations observed for many trace elements in the humus horizon indicates that it acts as an active biogeochemical barrier against downward transport of these elements.     

秸秆焚烧对空气质量影响特征及判别方法的研究

利用南京空气自动监测数据及PM_(2.5)组分监测结果,分析了2011年夏收秸秆焚烧期间大气污染特征,并探寻快速判别秸秆焚烧影响的指标及方法。结果表明:秸秆焚烧期间PM_(2.5)污染特征显著,其组分中K~+、EC、OC等浓度相对偏高。基于离子组分及碳元素在线监测数据,可选取K~+作为快速判别指标,并根据K~+与PM_(2.5)的相关性,计算秸秆焚烧对PM_(2.5)的贡献。同时结合OC、EC浓度变化,综合判别秸秆焚烧对空气质量的影响程度。     

Characterisation of PM10, PM2.5 and Benzene Soluble Organic Fraction of Particulate Matter in an Urban Area of Kolkata, India

In this study, the relationship between inhalable particulate (PM₁₀), fine particulate (PM_2.5), coarse particles (PM_{2.5 – 10}) and meteorological parameters such as temperature, relative humidity, solar radiation, wind speed were statistically analyzed and modelled for urban area of Kolkata during winter months of 2003–2004. Ambient air quality was monitored with a sampling frequency of twenty-four hours at three monitoring sites located near traffic intersections and in an industrial area. The monitoring sites were located 3–5 m above ground near highly trafficked and congested areas. The 24 h average PM₁₀ and PM_2.5 samples were collected using Thermo-Andersen high volume samplers and exposed filter papers were extracted and analysed for benzene soluble organic fraction. The ratios between PM_2.5 and PM₁₀ were found to be in the range of 0.6 to 0.92 and the highest ratio was found in the most polluted urban site. Statistical analysis has shown a strong positive correlation between PM₁₀ and PM_2.5 and inverse correlation was observed between particulate matter (PM₁₀ and PM_2.5) and wind speed. Statistical analysis of air quality data shows that PM₁₀ and PM_2.5 are showing poor correlation with temperature, relative humidity and solar radiation. Regression equations for PM₁₀ and PM_2.5 and meteorological parameters were developed. The organic fraction of particulate matter soluble in benzene is an indication of poly aromatic hydrocarbon (PAH) concentration present in particulate matter. The relationship between the benzene soluble organic fraction (BSOF) of inhalable particulate (PM₁₀) and fine particulate (PM_2.5) were analysed for urban area of Kolkata. Significant positive correlation was observed between benzene soluble organic fraction of PM₁₀ (BSM10) and benzene soluble organic fraction of PM_2.5 (BSM2.5). Regression equations for BSM10 and BSM2.5 were developed.     

Experimental photochemical release of organically bound aluminum and iron in three streams in Maine, USA

In the present study, the BCR (Community Bureau of Reference) sequential procedure has been applied to determine the zinc partition in sediments taken from a river situated in the Southwest of Romania, in a region subject of intense mining activities. The sampling was performed during three sampling expeditions, organized in the spring, summer, and autumn, 2007. The zinc concentration in different fractions was normalized, its concentration being related to the concentrations of some metals (such as Al or Fe) that are naturally present in sediments. The zinc-contaminated sediments from the investigated area have been evaluated by means of combining the analysis data from the BCR sequential extraction with the normalization to the Al content. The most important zinc collector in the samples taken during the three sampling expeditions is the easily soluble fraction, next being amorphous iron and manganese hydrated oxides fraction, followed by organic matter fraction.     

Characterization of airborne particles at a high-btu coal-gasification pilot plant

Airborne particles in fugitive emissions have been measured at a slagging fixed-bed coal-gasification pilot plant using lignite. Sampling was conducted during shutdown operations and opening of the gasifier following an aborted startup. Aerosol collected with a Sierra high-volume impactor was subjected to analysis by gas chromatography, mass spectrometry, and scanning electron microscopy; aerosol collected with an Andersen low-volume impactor was subjected to flameless atomic absorption analysis. The data show that the bulk of the trace organic material is associated with small particles: these data are similar to data on ambient air reported in the literature. Particle morphologies resemble those of fly ash from coal combustion, including smooth spheres, vesicular spheres, and crystalline material. Trace element size distributions are bimodal and resemble data for ambient air. Pb-containing particles are generally submicron, while particles containing Al, Fe, and other crustal species are mostly of supermicron size. Aluminum-based aerosol enrichment factors calculated from the lignite composition show that the composition of the aerosol resembles that of the coal, with the exception of modest enrichments of Mg, Na, As, and Pb in the submicron size range. Aerosol enrichment factors based on the earth's crustal composition are somewhat greater than those based on coal composition for several elements, suggesting potential errors in using crustal enrichment data to investigate chemical fractionation during aerosol formation.     

Littoral diatoms as indicators of recent water and sediment contamination by metals in lakes

We studied the response of benthic diatoms to recent metal contamination in littoral cores collected at 25 sites in 11 lakes situated at different distances from a smelter in the Rouyn-Noranda mining region (Quebec). Diatom response was described in terms of density, diversity, and taxonomic composition of the entire assemblages and as abundance of individual indicator taxa. Metal concentrations were measured in sediment and in the overlying water (as total dissolved and as free-ions). Sediment metal contamination was significantly higher in lakes located <10 km from the smelters than in lakes farther away. Such difference was not significant when metal concentrations in the overlying water were considered. Metal contamination did not affect diatom density, which indeed was highest in the most contaminated lake. Diversity (either measured as number of taxa or as Shannon and evenness indices) was instead significantly higher in lakes close to the smelter than elsewhere. Redundancy analysis indicated that diatom composition changed along a gradient in alkalinity (CO?) and one in sediment metal contamination (Cd, Hg, Cu). We identified three diatom taxa (Fragilaria construens var. venter, F. construens var. pumila, and Brachysira vitrea) that increased in relative and absolute abundance with metal contamination. Benthic diatom responses at the community (density, diversity, assemblage composition) and population levels (abundance of selected benthic taxa) were stronger to the sediment metal contamination than to the contamination of overlying water. Comparisons with available literature indicated that, for monitoring recent sediment contamination, diatoms in littoral sediments are preferable to invertebrates that mostly respond to overlying water. Diatoms in littoral cores are therefore unique as tools for monitoring recent contamination of lake sediments.     

Vehicular particulate matter emissions in road tunnels in Sao Paulo, Brazil

In the metropolitan area of S?o Paulo, Brazil, ozone and particulate matter (PM) are the air pollutants that pose the greatest threat to air quality, since the PM and the ozone precursors (nitrogen oxides and volatile organic compounds) are the main source of air pollution from vehicular emissions. Vehicular emissions can be measured inside road tunnels, and those measurements can provide information about emission factors of in-use vehicles. Emission factors are used to estimate vehicular emissions and are described as the amount of species emitted per vehicle distance driven or per volume of fuel consumed. This study presents emission factor data for fine particles, coarse particles, inhalable particulate matter and black carbon, as well as size distribution data for inhalable particulate matter, as measured in March and May of 2004, respectively, in the Janio Quadros and Maria Maluf road tunnels, both located in S?o Paulo. The Janio Quadros tunnel carries mainly light-duty vehicles, whereas the Maria Maluf tunnel carries light-duty and heavy-duty vehicles. In the Janio Quadros tunnel, the estimated light-duty vehicle emission factors for the trace elements copper and bromine were 261 and 220 microg km(-1), respectively, and 16, 197, 127 and 92 mg km(-1), respectively, for black carbon, inhalable particulate matter, coarse particles and fine particles. The mean contribution of heavy-duty vehicles to the emissions of black carbon, inhalable particulate matter, coarse particles and fine particles was, respectively 29, 4, 6 and 6 times higher than that of light-duty vehicles. The inhalable particulate matter emission factor for heavy-duty vehicles was 1.2 times higher than that found during dynamometer testing. In general, the particle emissions in S?o Paulo tunnels are higher than those found in other cities of the world.