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.     

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.     

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.     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

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.     

Negative effects of humic acid addition on phytoremediation of pyrene-contaminated sediments by mangrove seedlings

Vegetated (with Kandelia candel seedlings) and non-vegetated mangrove microcosms were employed to remove pyrene from contaminated sediments, and the effects of adding 6.7% humic acid (HA) on such removal were investigated. At the end of 6-month treatment, residual pyrene concentrations in surface sediments (0-2 cm) of the contaminated microcosms reduced from an initial 5.82 to 0.63 microg g(-1) dw, and the reduction was less in HA amended microcosms with the residual pyrene concentration remained at 3.12 microg g(-1) dw. The pyrene removal percentages in microcosms with HA amendment were 29% for surface aerobic sediments and 41% for bottom (anaerobic) sediments, while the respective removal percentages in microcosms without HA amendment were 89% (surface sediments) and 53% (bottom sediments). Microcosms planted with K. candel seedlings had a significantly higher pyrene removal when compared to the non-vegetated ones, and the average removal percentages were 70.9% and 61.4%, respectively. However, when humic acid was added, no significant difference was found between vegetated and non-vegetated microcosms in pyrene removal, both had less than 40% removal, probably because plant growth in humic acid amended contaminated microcosms, in terms of total biomass, was reduced by 50%. Roots of K. candel could accumulate pyrene from contaminated microcosms, and pyrene concentrations in roots harvested from microcosms with and without humic acid addition were 6.01 and 3.46 microg g(-1) dw, respectively. These results suggest that the addition of HA to contaminated sediments decreased the mangrove microcosm's ability to remove pyrene as pyrene was more tightly bound to the organic matter and plant growth was reduced.     

Boreal bog plants: nitrogen sources and uptake of recently deposited nitrogen

The main goals of this study were to determine the delta15N signature of quantitatively important boreal bog plants as basis for discussing their N sources, and to assess the effects of five different 3 year N treatments (i.e. 0, 5, 10, 20 and 40 kg N ha(-1) year(-1)) on the bog plants and surface peat at different depths (i.e. 0, 5, 10, 20 and 40 cm) by using 15N as tracer. Plants and peat were analyzed for N concentration, 15N natural abundance and 15N at.%. From the results we draw three main conclusions: First, the relative importance of different N sources is species-specific among bog plants. Second, an annual addition of 5 kg N ha(-1) year(-1) was sufficient to significantly increase the N concentration in Sphagnum mosses, liverworts and shallow rooted vascular plants, and an annual addition of 40 kg N ha(-1) year(-1) during 3 years was not sufficient to increase the N concentration in deep rooted plants, although the 15N content increased continuously, indicating a possible longer term effect. Third, an annual addition of 40 kg N ha(-1) year(-1) during 3 years increased the N content in surface peat at depths of 5 and 10 cm, but not at depths of 20 and 40 cm, indicating the capacity of the living Sphagnum mosses and the surface peat to take up deposited N, and thereby function as a filter.     

Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.