Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

Linking stress with macroscopic and microscopic leaf response in trees: new diagnostic perspectives

Visible symptoms in tree foliage can be used for stress diagnosis once validated with microscopical analyses. This paper reviews and illustrates macroscopical and microscopical markers of stress with a biotic (bacteria, fungi, insects) or abiotic (frost, drought, mineral deficiency, heavy metal pollution in the soil, acidic deposition and ozone) origin helpful for the validation of symptoms in broadleaved and conifer trees. Differentiation of changes in the leaf or needle physiology, through ageing, senescence, accelerated cell senescence, programmed cell death and oxidative stress, provides additional clues raising diagnosis efficiency, especially in combination with information about the target of the stress agent at the tree, leaf/needle, tissue, cell and ultrastructural level. Given the increasing stress in a changing environment, this review discusses how integrated diagnostic approaches lead to better causal analysis to be applied for specific monitoring of stress factors affecting forest ecosystems.     

Characterization of gas/particle concentrations and partitioning of polychlorinated biphenyls (PCBs) measured in an urban site of Turkey

Air concentrations of polychlorinated biphenyls (PCBs) in both gas and particle phases were measured in an urban site (BUTAL-Merinos) of the city of Bursa, Turkey between August 2004 and May 2005. The mean of total (particle+gas) PCB concentrations was about 491.8+/-189.4pg/m(3). The main contributors for PCBs in the sampling site were the local sources and long-range atmospheric transport supported by back trajectory analysis. Lower molecular weight PCB congeners generally dominated in the samples. The particle phase of the measured PCBs accounted for 15% of the total PCB concentrations. Gas/particle distribution was investigated using different approaches such as log K(P)-log P(L)(o), log K(P)-log K(OA) and the Junge-Pankow model. Regression analysis among log K(P), log P(L)(o) and log K(OA) exhibited significant correlation at p<0.05. Correlation between PCB homologs and meteorological parameters was formed to investigate the possible relationships.     

Dynamic responses of photosystem II in the Namib Desert shrub, Zygophyllum prismatocarpum, during and after foliar deposition of limestone dust

The effects of limestone dust deposition on vegetation in desert ecosystems have not yet been reported. We investigated these effects in a succulent shrub from the Namib Desert at a limestone quarry near Skorpion Zinc mine (Namibia). Effects of limestone dust were determined in Zygophyllum prismatocarpum (dollar bush) plants with heavy, moderate and no visible foliar dust cover by means of chlorophyll a fluorescence measurements. Limestone dust deposition decreased overall plant performance through loss of chlorophyll content, inhibition of CO(2) assimilation, uncoupling of the oxygen-evolving complex and decreased electron transport. Importantly, dynamic recovery occurred after termination of limestone extraction at the quarry. Recovery was accelerated by rainfall, mainly because of dust removal from leaves and stimulation of new growth. These results indicate that limestone dust has severe effects on photosynthesis in desert shrubs, but that recovery is possible and that, in arid environments, this process is modulated by rainfall.     

Vegetable and synthetic tannins induce hormesis/toxicity in sea urchin early development and in algal growth

Mimosa tannin and phenol-based synthetic tannin (syntan) were tested for toxicity to sea urchin (Paracentrotus lividus and Sphaerechinus granularis) early development and to marine algal growth (Dunaliella tertiolecta). Sea urchin embryogenesis was affected by vegetable tannin and syntan water extracts (VTWE and STWE) at levels >or=1mg/L. Developmental defects were significantly decreased at VTWE and STWE levels of 0.1 and 0.3mg/L when control cultures displayed suboptimal quality, i.e. <70% "viable" (normal or retarded) larvae. Fertilization success of sea urchin sperm was increased up to 0.3 mg/L STWE or VTWE, then was inhibited by increasing tannin levels (1-30 mg/L). Offspring abnormalities, following sperm exposure to VTWE or STWE, showed the same shift from hormesis to toxicity. Cell growth bioassays in D. tertiolecta exposed to VTWE or STWE (0.1-30 mg/L) showed non-linear concentration-related toxicity. Novel criteria are suggested in defining control quality that should reveal hormetic effects.     

Development and application of long-term sublethal whole sediment tests with Arenicola marina and Corophium volutator using Ivermectin as the test compound

Short-term whole sediment tests using the amphipod Corophium volutator and the polychaete Arenicola marina are now routinely used in Europe to assess the acute toxicity of marine sediments. However, there is still a need to develop longer-term assays which measure effects on sublethal endpoints that are more relevant to predicting impacts at the population level. The effect of increasing exposure times and measuring additional endpoints such as growth, on the sensitivity of these assays was investigated. The test compound used was the chemotherapeutant Ivermectin (IVM), used in aquaculture to treat sea lice infestations. IVM was found to be acutely toxic to both test organisms. Extending the lugworm test to 100 days increased sensitivity of survival by a factor of three; a significant reduction in casting rate was observed at concentrations an order of magnitude lower. This assay shows potential for detecting the sublethal effects of low concentrations of sediment contaminants. Increasing the exposure time did not seem to affect the sensitivity of the amphipod, but further method development is required.     

Differential responses of the freshwater wetland species Juncus effusus L. and Caltha palustris L. to iron supply in sulfidic environments

Sulfur pollution can lead to serious problems in freshwater wetlands, including phosphorus eutrophication and sulfide toxicity. We tested the effects of anaerobic iron-rich groundwater discharge in fens, simulated by iron injection, on two characteristic species (Juncus effusus and Caltha palustris) in a sulfidic environment. Biomass production of C. palustris roots showed an optimum response to the combined addition of iron and sulfide, with highest values at intermediate concentrations of both substances. Iron deficiency apparently occurred at low iron concentrations, while at high iron concentrations, growth was decreased. For J. effusus, in contrast, no toxic effects were found of both iron and sulfide. This could be explained by larger radial oxygen loss (ROL) of J. effusus and could not be explained by differences in phosphorous concentrations. The results of our experiments confirm that iron-rich groundwater discharge has the potential to affect vegetation composition through toxicity modification in sulfidic environments.     

Concentrations of cadmium and lead heavy metals in Dardanelles seawater

Cadmium and lead were determined simultaneously in seawater by differential pulse stripping voltammetry (DPSV) preceded by adsoptive collection of complexes with 8-hydroxyquinoline (oxine) on to a hanging mercury drop electrode (HMDE). In preliminary experiments the optimal analytical condition for oxine concentration was found to be 2.10⁻⁵ M, at pH 7.7, the accumulation potential was −1.1 V, and the initial scannig potential was −0.8 V. The peak potentials were found −0.652 V for Cd and −0.463 V for Pb At the 60 s accumalation time. The limit of detection (LOD) and limit of quantitatification (LOQ) were found to be by voltammetry as 0.588 and 1.959 μg l⁻¹ (RSD, 5.50%) for Cd and 0.931 and 3.104 μg l⁻¹ (RSD, 4.10%) for Pb at 60 s stirred accumulation time respectively. In these conditions the most of the seawater samples are amenable for direct voltammetric determination of cadmium and lead using a HMDE. An adsorptive stripping mechanism of the electrode reaction was proposed. For the comparison, seawater samples were also analysed by ICP-atomic emission spectrometry method (ICP-AES). The applied voltammetric technique was validated and good recoveries were obtained.     

Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.