Exploring Chemical Variables in Ligustrum lucidum Ait. F. Tricolor (Rehd.) Rehd. in Relation to Air Pollutants and Environmental Conditions

Ligustrum lucidum Ait. f. tricolor (Rehd.) Rehd. in relation to atmospheric pollutants in Córdoba city, Argentina. The study area receives regional pollutants and was categorized taking into account traffic level, industrial density, type of industry, location of the sample point in relation to the street corner, treeless condition, and topographic level. Dried weight/fresh weight ratio (DW/FW) and specific leaf area (SLA) were calculated, and concentrations of chlorophylls, carotenoids, total sulfur, soluble proteins, malondialdehyde (MDA), and hydroperoxy conjugated dienes (HPCD) were determined in leaf samples. Sulfur content correlates positively with traffic density and SLA correlates negatively with some combinations of the categorical variables; MDA correlates positively with topographic level and total protein concentration correlates negatively with treeless condition. On the basis of our results, traffic, location of trees, type of industry, situation of a tree with respect to others, and topographic level are the environmental variables to bear in mind when selecting analogous sampling points in a passive monitoring program. An approximation to predict tree injury may be obtained by measuring DW/FW ratio, proteins, pigments, HPCD, and MDA as they are responsible for the major variability of data.     

Can Forest-protection carbon projects improve rural livelihoods? Analysis of the Noel Kempff Mercado climate action project,Bolivia

We studied the Noel KempffMercado Climate Action Project (NKMCAP),Bolivia, to assess whether forestprotection carbon (C) projects cansignificantly benefit local people. Wehypothesized that forest protection canonly securely deliver C if significantstakeholders are meaningfully andtransparently involved, traditional orcustomary rights are recognized and theirloss compensated for, and there are directlinkages between conservation anddevelopment objective. Our researchfocused on 53 members of the communities ofFlorida, Porvenir and Piso Firme and 36secondary stakeholders. In each of thevillages we held half-day meetings withcommunity leaders, complemented bysemi-structured one-hour interviews with 5,10, and 7 families, representing 20%, 10%and 8% of each community. The long-termimpact of the NKMCAP on the localcommunities may well be positive. However,in the short run, certain sections of thelocal communities are financially poorer. Forest protection projects clearly have thepotential to sequester C, protectbiodiversity and simultaneously contributeto sustainable rural development, but ifthey really are to improve rurallivelihoods, they must be designed andimplemented carefully and participatively.     

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.     

Effect of chromium on the fatty acid composition of two strains of Euglena gracilis

The effect of hexavalent chromium on fatty acid composition was studied in two strains of Euglena gracilis; UTEX 753 (from the Culture Collection of Algae of Texas University, USA) and MAT (isolated from a highly polluted River). Both were grown in photoauxotrophic and photoheterotrophic conditions and exposed to two metal concentrations, one below and one above IC50. The high malondialdehyde (MDA) levels (3 to 7-fold) obtained with chromium concentration above IC50, suggested the existence of metal-induced lipid peroxidation. Total lipid content increased only with concentration below IC50, whereas it was inhibited by higher metal concentration. Photoheterotrophic control strains exhibited a significantly higher proportion of saturated and polyunsaturated fatty acids. Polyunsaturated acids were most affected by chromium, especially those related to chloroplast structures. Ultra-structure studies showed clear thylakoid disorganization in all treated cells. The results indicate that hexavalent chromium affects levels of fatty acids, especially those related to photosynthetic activity.     

Biofilm responses to marine fish farm wastes

The changes in the biofilm community due to organic matter enrichment, eutrophication and metal contamination derived from fish farming were studied. The biofilm biomass, polysaccharide content, trophic niche and element accumulation were quantified along an environmental gradient of fish farm wastes in two seasons. Biofilm structure and trophic diversity was influenced by seasonality as well as by the fish farm waste load. Fish farming enhanced the accumulation of organic carbon, nutrients, selenium and metals by the biofilm community. The accumulation pattern of these elements was similar regardless of the structure and trophic niche of the community. This suggests that the biofilm communities can be considered a reliable tool for assessing dissolved aquaculture wastes. Due to the ubiquity of biofilms and its wide range of consumers, its role as a sink of dissolved wastes may have important implications for the transfer of aquaculture wastes to higher trophic levels in coastal systems.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Heavy metals effects on proteolytic system in sunflower leaves

Plant proteolytic system includes proteases, mainly localized inside the organelles, and the ubiquitin-proteasome pathway in both, the cytoplasm and the nucleus. It was recently demonstrated that under severe Cd stress sunflower (Helianthus annuus L.) proteasome activity is reduced and this results in accumulation of oxidized proteins. In order to test if under other heavy metal stresses sunflower proteolytic system undergoes similar changes, an hydroponic experiment was carried out. Ten days old sunflower plants were transferred to hydroponic culture solutions devoid (control) or containing 100 microM of AlCl(3), CoCl(2), CuCl(2), CrCl(3), HgCl(2), NiCl(2), PbCl(2) or ZnCl(2) and analyzed for protein oxidative damage and proteolytic activities. After 4 days of metal treatment, only Co(2+), Cu(2+), Hg(2+), and Ni(2+) were found to increase carbonyl groups content. Except for Al(3+) and Zn(2+), all metals tested significantly reduced all proteasome activities (chymotrypsin-like, trypsin-like and PGPH) and acid and neutral proteases activities. The effect on basic proteases was more variable. Abundance of 20S protein after metal treatments was similar to that obtained for control samples. Co(2+), Cu(2+), Hg(2+), Ni(2+), Cr(3+), and Pb(2+) induced accumulation of ubiquitin conjugated proteins. It is concluded that heavy metal effects on proteolytic system cannot be generalized; however, impairment of proteasome functionality and decreased proteases activities seem to be a common feature involved in metal toxicity to plants.     

Adsorption of chloridazon from aqueous solution on modified kerolite-rich materials

The adsorption of chloridazon (5-amine-4-chloro-2-phenylpyridazin-3(2H)-one) on kerolite samples heated at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400), 600 degrees C (K-600) and acid-treated with H(2)SO(4) solutions of two different concentrations (0.25 and 0.5 M) (K-0.25 and K-0.5, respectively) from pure water at 25 degrees C has been studied by using batch and column experiments. The adsorption experimental data points were fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values ranged from 184.7 mg kg(-1) (K-0.5) up to 2253 mg kg(-1) (K-600). This indicated that the heat treatment given to the kerolite greatly increases its adsorption capacity for the herbicide whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) was also calculated; R values ranging from 52.8% (K-0.5) up to 88.3% (K-600). Thus, the results showed that the 600 degrees C heat-treated kerolite was more effective in relation to adsorption of chloridazon and it might be reasonably used in removing this herbicide from water.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Sensitivity analysis of a parameterization of the stomatal component of the DO3SE model for Quercus ilex to estimate ozone fluxes

A sensitivity analysis of a proposed parameterization of the stomatal conductance (g(s)) module of the European ozone deposition model (DO(3)SE) for Quercus ilex was performed. The performance of the model was tested against measured g(s) in the field at three sites in Spain. The best fit of the model was found for those sites, or during those periods, facing no or mild stress conditions, but a worse performance was found under severe drought or temperature stress, mostly occurring at continental sites. The best performance was obtained when both f(phen) and f(SWP) were included. A local parameterization accounting for the lower temperatures recorded in winter and the higher water shortage at the continental sites resulted in a better performance of the model. The overall results indicate that two different parameterizations of the model are needed, one for marine-influenced sites and another one for continental sites.