Characterization of atmospheric aerosol (PM10 and PM2.5) from a medium sized city in São Paulo state, Brazil

Air pollution causes deleterious effects on human health with aerosols being among the most polluting agents.The objective of this work is the characterization of the PM_(2.5) and PM_(10) aerosol mass in the atmosphere.The methods of analysis include WD-XRF and EDS.Data were correlated with meteorological information and air mass trajectories(model HYSPLIT)by multivariate analysis.A morphological structural analysis was also carried out to identify the probable sources of atmospheric aerosols in the city of Sao Jose do Rio Preto,Brazil.The mean mass concentration values obtained were 24.54 μg/m~3 for PM_(10),above the WHO annual standard value of 20 μg/m~3 and 10.88 μg/m~3 for PM_(2.5) whose WHO recommended limit is10 μg/m~3.WD-XRF analysis of the samples revealed Si and Al as major components of the coarse fraction.In the fine fraction,the major elements were Al and S.The SEM-FEG characterization allowed identifying the morphology of the particles in agglomerates,ellipsoids and filaments in the PM_(10),besides spherical in the PM_(2.5).The analysis by EDS corroborated WD-XRF results,identifying the crustal elements,aluminosilicates and elements of anthropogenic origin in the coarse fraction.For the fine fraction crustal elements were also identified;aluminosilicates,black carbon and spherical particles(C and O) originating from combustion processes were predominant.The use of multivariate analysis to correlate air mass trajectories with the results of the morpho-structural characterization of the particulate matter allowed confirmation of the complex composition of the particles resulting from the combination of both local and long-distance sources.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

短期干旱胁迫对马尾松排放挥发性有机物的影响

为探究干旱环境对BVOCs排放的影响,应用动态封闭式采样系统和热脱附-气相色谱-飞行质谱仪,对短期干旱胁迫作用下马尾松的BVOCs排放进行了实验室测量,定量分析BVOCs排放速率和排放组成的变化.结果表明,干旱胁迫时异戊二烯的排放受到抑制,排放速率降低约50%;单萜烯和倍半萜烯的排放水平增强,排放速率分别为137.85和0.98μg/（m²·h）,是未受胁迫时的2.9和2.0倍.除反式-α-香柠檬烯外,干旱胁迫促进各单萜烯和倍半萜烯化合物的排放,是未受胁迫时的1.3~42.4倍,其中3-蒈烯排放的响应最敏感,α-葑烯、α-水芹烯和石竹烯的响应最弱.干旱胁迫时单萜烯和倍半萜烯的排放组成有所变化,但主导的化合物种类不变,单萜烯以α-蒎烯、香桧烯和β-蒎烯为主,占比分别为48%、17%和17%;倍半萜烯以石竹烯和长叶烯为主,占比分别为57%和34%.     

Mercury levels in human population from a mining district in Western Colombia

A biomonitoring study was carried out to examine the adverse impacts of total mercury in the blood(HgB), urine(Hg U) and human scalp hair(HgH) on the residents of a mining district in Colombia. Representative biological samples(scalp hair, urine and blood) were collected from volunteered participants(n = 63) to estimate the exposure levels of THg using a Direct mercury analyzer. The geometric mean of THg concentrations in the hair,urine and blood of males were 15.98 μg/g, 23.89 μg/L and 11.29 μg/L respectively, whereas the females presented values of 8.55 μg/g, 5.37 μg/L and 8.80 μg/L. Chronic urinary Hg(HgU)levels observed in male workers(32.53 μg/L) are attributed to their long termed exposures to inorganic and metallic mercury from gold panning activities. On an average, the levels of THg are increasing from blood(10.05 μg/L) to hair(12.27 μg/g) to urine(14.63 μg/L).Significant positive correlation was found between hair and blood urinary levels in both male and female individuals. Thus the present biomonitoring investigation to evaluate the Hg levels and associated health issues would positively form a framework for further developmental plans and policies in building an ecofriendly ecosystem.     

Effect of shore position and environmental metal levels on body metal burdens in the barnacle, Elminius modestus

Body (thorax and prosoma) weight, shell growth, and Zn, Cu, Fe, Mn and Ca levels were measured in artificially settled Elminius modestus over a 14-month period following transfer to high, mid and low tide positions in the uncontaminated Menai Strait and two mid tide sites within a Zn and Cu polluted bay on the North West coast of Anglesey. Barnacles showed higher mortality and slower growth at the upper shore position than at any other site. There was no evidence of Zn and Cu regulation by the bodies or shells, and both seemed to reflect environmental levels. Body metal levels were lowest in early winter and the highest second year values were found in January (Zn), March (Cu, Fe) or May (Ca). Higher shore barnacles contained larger concentrations of Zn than mid or low tide animals. Differences in feeding activity and the amount of testes may account for these variations. Reciprocal transplants between polluted and 'clean' sites indicate that body Cu and Zn accumulation and loss was very rapid. Spatial and temporal changes in shell metal levels closely mirror that of the body.     

A Variance Estimator for Constrained Estimates of Change in Relative Categorical Frequencies

Consistent estimators of change and state becomes an issue when sample data come from a mix of permanent and temporary observation units. A joint maximum likelihood estimator of state and change creates estimates of state that depend on antecedent viz. posterior survey results and may differ from estimates of state derived from a single-date analysis of the sample data. A constrained estimator of change in relative categorical frequencies that eliminates this potential inconsistency is proposed and a model based estimator of their sampling variance is developed. The performance of the constrained estimator is quantified against six criteria and a joint maximum likelihood estimator in simulated sampling from 15 populations with three combinations of permanent and temporary samples, four to six categorical class attributes, and constant size between sampling dates. Bias of the constrained estimators was negligible but larger than for joint maximum likelihood estimators. Mean absolute deviations and variances of constrained estimators were generally at par with the joint estimators. Constrained estimators of root mean square errors and achieved coverage of nominal confidence intervals of constrained estimators were occasionally better. A generalized variance function for the constrained estimates of change is provided as a computational shortcut.     

Seasonal variations in physico-chemical characteristics of River Yamuna in Haryana and its ecological best-designated use

Various physico-chemical characteristics of the River Yamuna flowing in Haryana through Delhi were studied in the summer (April 1998) and winter (Jan.-Feb. 1999). Ecological parameters like dissolved oxygen (DO), pH, nitrate (NO3-), sulfate (SO4(2-)), and phosphate (PO4(3-)), were analyzed and compared with standard permissible limits to assess the best-designated use of the river water for various purposes. The river in Delhi upstream was of better quality whereas the Delhi downstream stretch was polluted as indicated by very low DO and high total dissolved solids (TDS), electric conductivity (EC), total hardness, Na+, K+, Cl-, F- and SO4(2-). The differences in various parameters were statistically significant (p < 0.01) when compared for the Delhi upstream and downstream stretches of the river, particularly in summer. DO and TDS were found to be two important parameters, which showed strong correlation with several other parameters and hence can serve as good indices of river water quality. The river tended to recover from the pollution stress after flowing through a distance of about 80 km downstream of Delhi.     

Impact of automobile emissions on the levels of platinum and lead in Accra,Ghana

Examination of car fleet records in Accra demonstrates an increasing proportion of catalytic converter-equipped cars in the relatively old car fleet (average age 13 years) due to their import from developed countries. However, only leaded petrol is sold in Ghana. Lead anti-knocking additives, which are known to affect catalyst activity and promote thermal sintering and mechanical abrasion, may increase Pt emissions. This possible synergism prompted the concomitant determination of Pb and Pt levels in road dust and roadside soils in Ghana. Both metals followed traffic density with higher concentrations in urban areas compared to remote sites. In urban areas, the range for Pb (365 +/- 93 microg g(-1) for dust and 291 +/- 76 microg g(-1) for soil) reflects precatalyst levels in Europe and the US, while the range for Pt (39 +/- 24 ng g(-1) for dust and 15 +/- 5.3 ng g(-1) for soil) is typical for the same countries. The elevated Pt concentrations were unexpected due to recent introduction of catalysts to Ghana compared to the prolonged use of catalysts in Europe and the US.     

Adenine nucleotides in snail muscles as one of biomarkers of fluoride toxicity

The aim of this work was to determine the extent of bioaccumulation of fluorides in tissues of Helix aspersa maxima. The toxicity of fluorides administered orally on the energy balance of the snail's foot was investigated based on measurements of concentrations of adenine nucleotides and their metabolism degradation products. Quantitation of fluoride levels was done in soft tissues (foot, hepatopancreas) and shells of mature snails. Qualitative and quantitative analysis of purine compounds was performed in slices of foot from mature snails. Fluoride concentrations in pulverized shells were measured using an ion-selective electrode. Gas chromatography was used to determine fluoride concentrations in soft tissues (hepatopancreas and foot). Purines were measured in foot muscle slices with high-performance liquid chromatography (HPLC). Fluoride levels in soft tissues of the snail cannot serve as an indicator for biomonitoring purposes as no significant accumulation was observed during exposure to maximum allowable concentrations of fluoride in drinking water. Contrary to this, levels of fluoride in the shell rose significantly with this concentration of fluoride in drinking water. The effect of fluorides on energy metabolism of foot muscle was evidenced by elevated AMP levels, increased adenine nucleotide pool and reduced conversion of ADP to ATP. Exposure to rising F(-) concentrations was accompanied by decreasing values of the adenylate energy charge AEC. Determination of AMP or AEC in foot muscle of exposed snails seems to be a useful indicator of fluoride effects on metabolic activity.     

Speciation of iron in river water using a specific catalytic determination and size fractionation

A comprehensive speciation scheme was proposed for the speciation of iron in river water (0.45 microm filtrate). The speciation was based on the catalytic determination of reactive iron as Fe3+ and Fe(III)Li/(3 -in)+, where i = 1 or 2 for a unidentate and i = 1 for a bidentate ligand, Ln-. The scheme incudes size fractionation and acid decomposition of the sample and determination of the coexisting species. The proposed scheme was applied to natural and artificial samples and acidified preparations of these. Resulting fractionation patterns of reactive and unreactive iron and of coexisting humic acid were useful for the characterization of iron species in the natural samples. The reactive iron in the molecular weight (Mr) > or = 10(4) fraction was associated with humic iron aggregates and estimated as iron complexed with them. The unreactive iron in this fraction dissociated in 0.1 M HCI and was estimated as iron in the aggregates of iron(III) hydroxide (s) and humic iron. From the fractionation results of the artificial sample, the reactive and unreactive iron in the Mr < 10(3) fraction may be formed by complexing simple anions like F- and C2O4(2-) at their naturally-occurring concentration levels. The fractionation results also suggested that humic acid and Si contributed to the formation of reactive and unreactive iron in the Mr > or = 10(4) fraction.