Behaviour of different lichen species as biomonitors of air pollution by PAHs in natural ecosystems

Six different species of lichens (Parmelia sulcata Tayl., Evernia prunastri (L.) Ach., Ramalina farinacea, Pseudevernia furfuracea (L.) Zopf., Usnea sp. and Lobaria pulmonaria (Schreb.) Hoffm.) were collected in two mountain valleys in Central Pyrenees: the Aspe and Aragon valleys. Two multivariate techniques have been applied with different purposes, ANOVA and Discriminant Analysis (DA), to evaluate the data. The PAHs spatial distribution was studied in the three more abundant and widespread species in the area: P. sulcata, E. prunastri (L.) Ach. and R. farinacea in terms of total PAHs, PAHs related to the combustion processes and toxicity. Different behaviour of each lichen species to trap PAHs was found, being P. sulcata the best one to monitor the most persistent PAHs of pyrogenic origin and E. prunastri the most appropriate to provide information about pyrogenic and petrogenic PAHs. Traffic was the most relevant influence in PAHs bioaccumulation in lichen species.     

Arbuscular mycorrhizal fungi can decrease the uptake of uranium by subterranean clover grown at high levels of uranium in soil

Subterranean clover inoculated or not with the arbuscular mycorrhizal (AM) fungus Glomus intraradices was grown on soil containing six levels of 238U in the range 0-87 mg kg(-1). Increasing U concentration in soil enhanced the U concentration in roots and shoots of both mycorrhizal and nonmycorrhizal plants but had no significant effects on plant dry matter production or root AM colonization. Mycorrhizas increased the shoot dry matter and P concentration in roots and shoots, while in most cases, it decreased the Ca, Mg and K concentrations in plants. The AM fungus influenced U concentration in plants only in the treatment receiving 87 mg U kg(-1) soil. In this case, U concentration in shoots of nonmycorrhizal plants was 1.7 times that of shoots of mycorrhizal plants. These results suggested that mycorrhizal fungi can limit U accumulation by plants exposed to high levels of U in soil.     

Comparison of metastable atom bombardment and electron capture negative ionization for the analysis of polychloroalkanes

A new method for quantifying C10-C13 polychloroalkanes (PCAs or chloroparaffins, CPs) in environmental samples using metastable atom bombardment ionization (MAB) and high resolution mass spectrometry is presented. Contrary to electron capture negative ionization (ECNI), MAB can produce spectra for molecules having a low number of chlorine atoms. These molecules are present in commercial PCAs and are responsible for a large fraction of the total PCA concentration in water samples analysed. Using ECNI or MAB, no molecular ion can be seen in the spectra. ECNI spectra contain important peaks corresponding to [M-Cl]- and [M-HCl]-* while the base peak in MAB spectra is [M-Cl]+ with no [M-HCl]+* present. The mass range for C10-C13 CPs is very large and scanning the masses for all the compounds involved would lead to a loss of sensitivity. Two chromatographic analysis are thus performed using high resolution selective ion monitoring with only a limited number of masses recorded per run. To reduce analysis time, a short capillary column is used. Application of this method to the analysis of high-volumes water samples (dissolved and particulates portions separately) from the St. Lawrence river near Quebec City using MAB is presented. Contribution of molecules with a low chlorine content in the samples account for between 10% and 46% to the total concentration. Congeners distribution between the different fractions indicates that molecules with a low number of carbon atoms are preferentially retained on the particulates. Within a carbon number group, there is a slight tendency to accumulate molecules with a high number of chlorine atoms in the dissolved fraction.     

The sedimentation capabilities of hexadecyltrimethylammonium-modified montmorillonites

Natural montmorillonite was modified with a quaternary ammonium compound, hexadecyltrimethylammonium (HDTMA). The sedimentation capabilities of unmodified and modified montmorillonites were then investigated. The sedimentation velocity of modified montmorillonites increased if the amounts of adsorbed HDTMA were from 0.3 to 1.0 times the cation exchange capacitity (CEC). It also emerged that the sedimentation capability of modified montmorillonites was improved and that the variously CEC-modified montmorillonites had similar sedimentation capabilities after they had sorbed organic matter from oily wastewater. Thus, modified montmorillonites (especially 0.5 CEC treatment) had good sedimentation capabilities for sorbing organic substance and can act as carriers in wastewater biotreatment.     

Multivariate statistical and GIS-based approach to identify heavy metal sources in soils

The knowledge of the regional variability, the background values and the anthropic vs. natural origin for potentially harmful elements in soils is of critical importance to assess human impact and to fix guide values and quality standards. The present study was undertaken as a preliminary survey on soil contamination on a regional scale in Piemonte (NW Italy). The aims of the study were: (1) to determine average regional concentrations of some heavy metals (Cr, Co, Ni, Cu, Zn, Pb); (2) to find out their large-scale variability; (3) to define their natural or artificial origin; and (4) to identify possible non-point sources of contamination. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of three main factors controlling the heavy metal variability in cultivated soils. Geostatistics were used to construct regional distribution maps, to be compared with the geographical, geologic and land use regional database using GIS software. This approach, evidencing spatial relationships, proved very useful to the confirmation and refinement of geochemical interpretations of the statistical output. Cr, Co and Ni were associated with and controlled by parent rocks, whereas Cu together with Zn, and Pb alone were controlled by anthropic activities. The study indicates that background values and realistic mandatory guidelines are impossible to fix without an extensive data collection and without a correct geochemical interpretation of the data.     

Dissipation of DDT in a heavily contaminated soil in Mato Grosso, Brazil

After the prohibition of organochlorine-pesticide use in Brazil for controlling insect vector diseases, Mato Grosso State gathered the exceeding DDT and stored it irregularly in an open air area that belongs to the National Health Foundation, causing soil contamination. This study aimed to evaluate the contamination level and dissipation of p,p'-DDT and p,p'-DDE in this area. For that, surface soil samples were collected on 19 September 2000, 15 December 2000, 4 April 2001 and soil samples 30-40 cm; 60-70 cm and 90-100 cm deep were taken from five points in the studied area on 17 July 2001. The contaminants were determined by a small scale method which consists on extraction and clean-up steps combined into one step by transferring soil samples mixed with neutral alumina to a chromatographic column prepacked with neutral alumina and elution with hexane:dichloromethane (7:3 v:v). The eluate was concentrated and the analytes were quantified by gas chromatography with an electron-capture detector. p,p'-DDT at surface soil ranged from 3,800 to 7,300 mg kg(-1). 30-40 cm deep soil sample concentrations varied from 0.036 to 440 mg kg(-1) while 90-100 cm deep samples varied from 0.069 to 180 mg kg(-1). Volatilization is probably the main dissipation process. The p,p'-DDT is moving slowly downward in the soil profile, however, the levels of this contaminant are high enough to present risk to underground waters.     

Well water contaminated by acidic mine water from the Dabaoshan Mine, south China: chemistry and toxicity

An investigation into well water quality was carried out in a rural area subject to irrigation with acidic mine water from the Guangdong Dabaoshan Mine, southern China. The results of water pH measurements from 112 wells in two different seasons suggest that the well water has been contaminated to varying degrees in the investigated Shangba floodplain (approximately 11km south of the Guangdong Dabaoshan Mine). There is a trend that well water pH increased southwards, suggesting that the impacts of acidic irrigation water on groundwater decreased with increasing distance to the entry point of acidic irrigation water. Water quality monitoring results of the selected wells show that Cu and Cd in the water exceeded the limits set in the Chinese National Standards for Drinking Water (GB 5749-85) for the wells close to the irrigation water source. If the World Health Organization (WHO) standard was considered, Cd in some wells was almost 10 times as high as the WHO guideline value (0.003mg l(-1)). Water collected from the location closest to the acidic irrigation water source was acutely toxic to the test organism (Daphnia carinata) even after 51 time dilution. It is likely that the extremely high mortality rate of the local population reported for the study area is at least partly related to the high levels of heavy metals, particularly Cd in the drinking well water.     

Sources and patterns of polycyclic aromatic hydrocarbons pollution in kitchen air,China

Twelve polycyclic aromatic hydrocarbons, multi-ringed compounds known to be carcinogenic in air of six domestic kitchens and four commercial kitchens of China were measured in 1999-2000. The mean concentration of total PAHs in commercial kitchens was 17 microg/m3, consisting mainly of 3- and 4-ring PAHs, and 7.6 microg/m3 in domestic kitchens, where 2- and 3-ring PAHs were predominant, especially naphthalene. The BaP levels in domestic kitchens were 0.0061-0.024 microg/m3 and 0.15- 0.44 microg/m3 in commercial kitchens. Conventional Chinese cooking methods were responsible for such heavy PAHs pollution. The comparative study for PAH levels in air during three different cooking practices: boiling, broiling and frying were conducted. It was found that boiling produced the least levels of PAHs. For fish, a low-fat food, frying it produced a larger amount of PAHs compared to broiling practice, except pyrene and anthracene. In commercial kitchens, PAHs came from two sources, cooking practice and oil-fumes, however the cooking practice had a more predominant contribution to PAHs in commercial kitchen air. In domestic kitchens, except for cooking practice and oil-fumes, there were other PAHs sources, such as smoking and other human activities in the domestic houses, where 3-4 ring PAHs mainly came from cooking practice. Naphthalene (NA, 2-ring PAHs) was the most predominant kind, mostly resulting from the evaporation of mothball containing a large quantity of NA, used to prevent clothes against moth. A fingerprint of oil-fumes was the abundance of 3-ring PAHs. Heating at the same temperature, the PAHs concentrations in different oil-fumes were lard > soybean oil > rape-seed oil. An increase in cooking temperature increased the levels of PAHs, especially acenaphthene.     

Bioaccumulation kinetics of sediment-associated DE-83 in benthic invertebrates (Nereis succinea, polychaete)

Polychaetes (Nereis succinea) were exposed to DE-83 contaminated sediments to investigate the bioaccumulation and bioavailability of nona- and deca-BDEs in sediment. All the major congeners in DE-83 were bioavailable to the lugworms. The uptake coefficients (K_s) of nona- and deca-BDE congeners in lugworms were in the range of 0.18-0.65 (d⁻¹), with the values of BDE-207 and -208 slightly higher than those of BDE-206 and -209. Elimination of nona- and deca-BDE congeners from lugworms was very fast. The estimated half-lives of nona- and deca-BDE congeners in the lugworms were at 0.7 d. The bioavailability of nona- and deca-BDE congeners was very low, with BSAF of 0.017 for BDE-206 and -209 and 0.054 for BDE-207 and -208. These may be due to the large molecular size and high affinity of PBDEs to sediment particles. The contribution of BDE-206 in the profile of nona-BDEs in lugworm tissue decreased with exposure time while those of BDE-207 and -208 increased, which could be the result of the biotransformation of BDE-209 to BDE-207 and -208.     

Distribution of persistent organic pollutants, polycyclic aromatic hydrocarbons and trace elements in soil and vegetation following a large scale landfill fire in northern Greece

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), including hexaclorocyclohexanes (HCHs) and DDTs, as well as trace elements were determined in soil and vegetation samples collected from the surrounding area of the landfill "Tagarades", the biggest in northern Greece, following a large scale fire involving approximately 50,000 tons of municipal waste. High concentrations of total PAHs, PCBs and heavy metals were found inside the landfill (1475 microg kg(-1) dw, 399 microg kg(-1) dw and 29.8 mg kg(-1) dw, respectively), whereas concentrations in the surrounding soils were by far lower ranging between 11.2-28.1 microg kg(-1) dw for PAHs, 4.02-11.2 microg kg(-1) dw for PCBs and 575-1207 mg kg(-1) dw for heavy metals. The distribution of HCHs and DDTs were quite different since certain soils exhibited equal or higher concentrations than the landfill. In vegetation, the concentrations of PAHs, PCBs, HCHs and DDTs ranged from 14.1-34.7, 3.64-25.9, 1.41-32.1 and 0.61-4.03 microg kg(-1) dw, respectively, while those of heavy metals from 81 to 159 mg kg(-1) dw. The results of the study indicated soil and vegetation pollution levels in the surroundings of the landfill comparable to those reported for other Greek locations. The impact from the landfill fire was not evident partially due to the presence of recent and past inputs from other activities (agriculture, vehicular transport, earlier landfill fires).