Contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area, Portugal since the 19th century

The main purpose of this study was to evaluate the contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area (Portugal) since the 19th century. The study was based on pre-industrial and recent data series, the results being analyzed according to the atmospheric chemistry. The treatment of ozone and meteorological data was performed by classical statistics and by time-series analysis. It was concluded that in the 19th century the ozone present in the troposphere was not of photochemical origin, being possible to consider the respective concentrations as reference values. For recent data a cycle of 8h for ozone concentrations could be related to traffic. Compared to the 19th century, the current concentrations were 147% higher (252% higher in May) due to the increased photochemical production associated with the increased anthropogenic emissions.     

Perfluorinated chemicals in selected residents of the American continent

Perfluorinated chemicals (PFCs) are used in multiple consumer products. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the most widely studied PFCs, may be potential developmental, reproductive, and systemic toxicants. Although PFCs seem to be ubiquitous contaminants found both in humans and animals, geographic differences may exist in human exposure patterns to PFCs. We measured 11 PFCs in 23 pooled serum samples collected in the United States from 1990 through 2002, and in serum samples collected in 2003 from 44 residents from Trujillo, Peru. PFOS and PFOA were detected in all the pooled samples; perfluorohexane sulfonic acid (PFHxS) was detected in 21. Median concentrations were 31.1 micrograms per liter (mug/l, PFOS), 11.6 microg/l (PFOA), and 2 microg/l (PFHxS). The 90th percentile concentrations of PFCs in the 44 Peruvian residents were 0.7 microg/l (PFOS), 0.1 microg/l (PFOA), and <0.3 microg/l (PFHxS). The frequencies of detection were 20% (PFOS), 25% (PFOA), and 9% (PFHxS). The frequent detection of selected PFCs in the pooled samples from the United States and the lack of clear concentration trends based on a year of collection suggest a sustained widespread exposure to these compounds among US residents, at least since the 1990s. By contrast, the much lower frequency of detection and concentration ranges of PFCs in Peru suggest a lower exposure of Peruvians to PFCs compared with North Americans. Genetic variability, diet, lifestyle, or a combination of all these may contribute to the different patterns of human exposure to PFCs in the United States and Peru.     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

Anthropogenic metal enrichment of snow and soil in north-eastern European Russia

Trace metal composition of winter snowpack, snow-melt filter residues and top-soil samples were determined along three transects through industrial towns in the Usa basin, North-East Russia: Inta, Usinsk and Vorkuta. Snow was analysed for Ag, Al, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn using ICP-MS (Ca and K by F-AAS for Vorkuta only), pH and acidity/alkalinity. Filter residues were analysed for: Al, Ba, Ca, Cd, Cu, K, Mg, Mn, Ni, Pb, Sr and Zn using F-AAS and GF-AAS; top-soil samples were analysed for Ba, Cu, Mg, Mn, Na, Ni, Pb, Sr, Zn using F-AAS. Results indicate elevated concentrations of elements associated with alkaline combustion ash around the coal mining towns of Vorkuta and Inta. There is little evidence of deposition around the gas and oil town of Usinsk. Atmospheric deposition in the vicinity of Vorkuta, and to a lesser extent Inta, added significantly to the soil contaminant loading as a result of ash fallout. Acid deposition was associated with pristine areas whereas alkaline combustion ash near to emission sources more than compensated for the acidity caused by SO2.     

Macrobenthic community in the Douro estuary: relations with trace metals and natural sediment characteristics

The relationship between macrobenthic community structure and natural characteristics of sediment and trace metal contamination were studied in the lower Douro estuary (Portugal, NW, Iberian Peninsula), using an innovative threefold approach (SQG, Sediment Quality Guidelines), metal normalization to Fe, and macrobenthic community structure. This study allowed detection of a clear signature of anthropogenic contamination, in terms of Zn, Cu, Pb, and Cr in the north bank of the estuary, which experiences high urban pressure. Using the SQG approach, metal concentrations above ERM (effects range-median) were observed only at one sampling station, but several stations had levels above ERL (effects range-low). The macrobenthic community had a low diversity, with only 19 species found in the entire estuarine area, dominated by opportunistic species. The granulometric distribution of the sediments (estimated from the combination of organic matter, Fe and Al) seemed to be the major structuring factor for the communities, establishing the natural macrobenthic distribution pattern. The metals (Zn, Cu, Pb, and Cr) seemed to act as a disturbing factor over the natural distribution, with deleterious consequences for the macrobenthic communities.     

Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

AFLP analysis as biomarker of exposure to organic and inorganic genotoxic substances in plants

In recent years several plant species have been in use as bioindicators and several tests have been developed to evaluate the toxicity of environmental pollutants in vegetal organisms. In the present paper Arabidopsis thaliana (L.) Heynh. (ecotype Wassilewskija) was used as bioindicators of two genotoxic substances: potassium dichromate and dihydrophenanthrene. Inhibition of seed germination was observed with both pollutants. AFLP analysis (i) indicated that both substances are genotoxic, (ii) showed that dihydrophenanthrene induces DNA changes in different target sequences than potassium dichromate, (iii) quantified the genotoxic effect using cluster analysis by comparing DNA from treated plants with that of control plants. On the basis of these considerations we suggest that AFLP method is a powerful tool for measuring qualitative and quantitative genotoxic activity due to environmental pollutants. AFLP method can be applied to a wide range of bioindicator organisms and may become a universal methodology to identify target genes for specific genotoxic agents. This could open up possibilities for designing specifically targeted assays and new approaches to risk assessment.     

Source identification of atlanta aerosol by positive matrix factorization

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles < or = 2.5 microm in aerodynamic diameter) samples (PM2.5), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 microm in aerodynamic diameter) samples (PM10-2.5). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO4(2-) -rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO(3-) -rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO4(2-) -rich and NO(3-) -rich secondary aerosols were associated with NH(4+). The SO4(2-) -rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO(3-)-rich secondary aerosol (16%), SO4(2-) -rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

Zingiberene and curcumene in wild tomato

Composition of ginger oil prepared from fresh ginger rhizomes, Zingiber officinale Roscoe (Zingiberaceae) was determined by gas chromatography (GC) and GC-mass spectrometric techniques. The main sesquiterpene hydrocarbons identified were alpha-zingiberene (27-30%), alpha-curcumene (8-9%), beta-sesquiphellandrene (4.8%). and bisabolene (3.2%). The function of zingiberene and curcumene as insecticides, repellents, and insect feeding deterrents has been previously reported. Other plant species having similar constituents might be found. Leaves of six wild tomato accessions of Lycopersicon hirsutum f. glabratum (Mull); three accessions of L. hirsutum f. typicum (Humb & Bonpl.); two accessions of L. pennellii Corr. (D'Arcy); one accession of L. pimpinellifolium; and one commercial tomato L. esculentumm cv. Fabulous were analyzed. Analysis of L. hirsutum f. typicum (Solanaceae) accessions indicated the presence of zingiberene, curcumene, and other lipophilic secondary metabolites in the leaves of two accessions (PI-127826 and PI-127827). An average three month old wild tomato plant of accessions PI-127826 and PI-127827 provided 1.93 and 1.30 kg fresh leaves (averaging about 38,307 and 28,130 cm2 exposed leaf surface area, respectively) and produced 19.3 and 10.1 g of zingiberene and curcumene (PI-127826) and 17.2 and 1.8 g of zingiberene and curcumene (PI-127827), respectively. Leaf extracts of the wild tomato L. hirsutum f. typicum (accessions PI-127826 and PI-127827) can be used as a biorational source of zingiberene and curcumene.