Integrated biomonitoring of air quality with plants and lichens: a case study on ambient ozone from central Italy

A biennial integrated survey, based on the use of vascular plants for the bioindication of the effects of tropospheric ozone together with the use of automatic analysers of ozone, as well as the mapping of lichen biodiversity was performed in the area of Castelfiorentino (Tuscany, central Italy). Photochemically produced ozone proved to be a fundamental presence during the warm season, with maximum hourly means reaching 114 ppb, exceeding the information threshold as fixed by EU: the use of supersensitive tobacco Bel-W3 confirmed the opportunity of carrying out detailed cost-effective monitoring surveys. The potential for didactical and educational implications of this methodology are appealing. Critical levels set up for the protection of vegetation have exceeded considerably. The comparison of biomass productivity in sensitive and resistant individuals (NC-S and NC-R white clover clones, in the framework of an European network) provided evidence that ambient ozone levels are associated with relevant reduction (up to 30%) in the performance of sensitive material; effects on flowering were also pronounced. The economic assessment of such an impact deserves attention. Mapping of epiphytic lichen biodiversity – which has been used to monitor air quality worldwide – was not related to ozone geographical distribution as depicted by tobacco response.     

Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins

The hydrogenation of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, anthracene, and phenanthrene) catalyzed by metalloporphyrins based on cobalt, nickel or iron was studied in aqueous solutions at room temperature and ambient pressure. Nickel porphyrin (P1) activated by nanosized zero-valent iron (nano-ZVI) and cobalt porphyrins (P2) and (P4) activated by titanium(III) citrate as the electron donor were demonstrated to be promising catalysts for the reductive hydrogenation of PAHs. In particular, partially saturated di-, tetra-, and octahydrogenated products were obtained for anthracene or phenanthrene using a nickel porphyrin activated by nano-ZVI, while naphthalene was transformed to tetralin. Systems containing cobalt porphyrins activated by titanium(III) citrate exhibited a high selectivity and activity toward hydrogenation of anthracene, producing 9,10-dihydroanthracene. However, no formation of hydrogenated hydrocarbons was observed from naphthalene or phenanthrene using cobalt porphyrins.     

The use of NTA and EDDS for enhanced phytoextraction of metals from a multiply contaminated soil by Brassica carinata

The potential of nine different species to grow in the presence of metals (As, Cd, Cu, Pb and Zn) and to accumulate them in the shoots was assessed for each metal separately by germination and root length tests, and successively by hydroponic experiments. Of the nine species tested, Brassica carinata was the species that accumulated the highest amounts of metals in shoots without suffering a significant biomass reduction. To further evaluate the potential of B. carinata for chelant-enhanced phytoextraction of a natural, multiply metal-polluted soil (As, Cd, Cu, Pb and Zn), both hydroponic and pot experiments were carried out with nitrilotriacetic acid (NTA) or (S,S)-ethylenediamine disuccinic acid (EDDS) as complexing agents. The hydroponic study with solutions containing the five metals together showed that accumulation of Cd, Cu, Pb and Zn in shoots was higher following EDDS addition compared to NTA. EDDS was more effective than NTA in desorbing Cu, Pb and Zn from the soil, whereas As and Cd were poorly extracted. B. carinata plants were grown for 4 weeks in the multiply metal-contaminated soil and then the soil was amended with 5 mmol kg(-1) NTA or EDDS. All plants were harvested 1 week after amendment. In comparison to NTA, EDDS was more effective in enhancing the concentrations of Cu, Pb and Zn in B. carinata shoots (2- to 4-fold increase compared to the control). One week after chelant addition, the DTPA-extractable metal concentrations in the polluted soil were lower in the EDDS treatment in comparison with the NTA amendment. Even though B. carinata showed a reduced growth and a relatively low metal uptake, it demonstrated the ability to survive and tolerate the presence of more metals simultaneously.     

Suborganismic and organismic effects of aldicarb and its metabolite aldicarb-sulfoxide to the zebrafish embryo (Danio rerio)

The new European chemical regulation (REACH) requires a short-term fish test for chemicals where the level of production exceeds 10tons per year. For ethical reasons (3R-concept), an alternative to the acute fish test should be introduced to decrease the number of animal testing with fish. The zebrafish embryo (Danio rerio) test became a valuable tool in ecotoxicology and already replaces the acute fish test for the evaluation of wastewater in Germany. Recent efforts are targeted to use this and other fish embryo tests for the effect assessment of chemicals. The toxic effects of the carbamate insecticide aldicarb and its metabolite aldicarb-sulfoxide to zebrafish embryos were analysed using two approaches with different endpoints. Organismic tests were conducted with zebrafish embryos exposed to the pesticides for 48h. In addition, suborganismic effects were examined analysing the enzyme inhibition of cholinesterases and carboxylesterases. On the organismic level, the only sublethal effect seen was the increase of heart rate at low and decrease at higher concentration with the use of aldicarb-sulfoxide but not with aldicarb (concentration range 0.2-300microM). In contrast, analysis of enzyme inhibitions showed high to very high effects caused by the two carbamates. The enzyme inhibition analysis of whole homogenates of exposed embryos may be advantageous for toxicant screening (biomarker of exposure) and might be used to bridge the gap of sensitivity of the (48h old) zebrafish embryos to adult fish when exposed to anti-cholinesterase substances (biomarker of prospective effect).     

Biochemical responses in Salmo salar muscle following exposure to ethynylestradiol and tributyltin

This study investigated the effects of nominal concentrations of two endocrine-disrupting chemicals (EDCs) on fish physiology. The effects of the synthetic pharmaceutical estrogen ethynylestradiol (EE(2)) and the antifoulant tributyltin (TBT) were investigated in exposure studies with immature Atlantic salmon, Salmo salar. Fish were exposed for 7 days to waterborne EE(2), TBT, or a combination of both. The activities of lactate dehydrogenase (LDH), acetylcholinesterase (AchE) and glutathione S-transferase (GST), and lactate and glycogen content were determined in samples of fish muscle. Fish exposed to EE(2) for 3 days responded rapidly with increasing AchE and GST activities and increasing lactate content. These responses were limited to the first 3 days of exposure and had disappeared by day 7, indicating that the fish had adapted to EE(2) exposure. Compared to the controls, TBT increased AchE and LDH activity, inhibited GST activity and had no effect on lactate content. When mixed, the highest concentration of EE(2) increased the effect of TBT on lactate content. However, fish exposed to a lower concentration of EE(2) in combination with TBT had the lowest lactate content. Effects on AchE and LDH activities were smaller when TBT was combined with EE(2) compared to TBT alone. This suggests that TBT and EE(2) influence biochemical processes in fish muscle, acting on different organizational levels, by antagonistic and synergistic mechanisms.     

Promoting the O3 flux concept for European forest trees

Tropospheric ozone (O3) levels are predicted to stay high, being a factor within "global change" with potential effects on the carbon sink strength of forest trees. Hence, new approaches to O3 risk assessment and their validation are required, although appropriate databases for adult trees are scant. Approaches based on external O3 exposure are presently being evaluated against the ones on O3 flux into leaves, as the cumulative uptake has the capacity for deriving O3 risk from cause-effect relationships. The effective dose, however, needs to account for the trees' O3 defence and tolerance in addition to O3 uptake. The current status of promoting the preferable mechanistic O3 flux concept is highlighted for major regions of Europe, addressing refinements and simplifications needed for routine use. At the pan-European scale, however, the flux-based concept is ready for use in O3 risk assessment and has the potential of meso-scale application at the forest ecosystem level.     

Non-aromatic hydrocarbons in surface sediments near the Pearl River estuary in the South China Sea

Surface sediment samples at 4 sites along an offshore transect from outer continental shelf off the Pearl River estuary to the shelf slope region of the northern South China Sea, have been analyzed for total organic carbon (TOC), total nitrogen (TN), solvent extractable organic matter (EOM) and non-aromatic hydrocarbons. TOC, TN and EOM show distinct spatial variations. Their highest values are all recorded at the shelf slope region. EOM varies from 18.70-38.58 microgg(-1) dry sediment and accounts for 0.20-0.72% of the TOC contents. The non-aromatic hydrocarbons are an important fraction of EOM. Their contents range from 3.43-7.06 microgg(-1) dry sediment. n-Alkanes with carbon number ranging from 15-38 are identified. They derive from both biogenic and petrogenic sources in different proportions. Results of isoprenoid hydrocarbons, hopanes and steranes also suggest possible petroleum contamination.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Comparison between the accumulation capacity of four lichen species transplanted to a urban site

The capacity to accumulate trace elements from the atmosphere of the lichens Hypogymnia physodes, Parmelia sulcata, Pseudevernia furfuracea and Usnea gr. hirta transplanted to an urban site of N Italy was compared. Twenty-nine elements (Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, I, K, La, Mg, Mn, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Zn) were analyzed by Instrumental Neutron Activation Analysis (INAA) and Electro-Thermal Atomic Absorption Spectroscopy (ET-AAS). The ratio between the concentrations of each element in exposed samples to that of control samples (exposed-to-control ratio and EC ratio) was used to investigate the accumulation rates of lichen thalli. The results showed that in general elements did not exhibit well defined trends, but rather showed fluctuations, and indicated that H. physodes, P. furfuracea and U. gr. hirta have a similar accumulation capacity, while that of P. sulcata is lower.