Mild hydrolysis of 2-trifluoromethylphenol: kinetics, mechanism and environmental relevance

2-Trifluoromethylphenol was hydrolysed in a phosphate buffer at neutral pH. At mild temperatures ranging from 34 degrees C to 69 degrees C this compound liberates consecutively fluorine anions to form salicylic acid. This process is energetically driven by the hydration of the fluorine anions. No intermediates have been detected by HPLC and (19)F-NMR and this was confirmed by computer calculations which favor the first step in the whole reaction sequence being rate-limiting. Accordingly, the reaction energy of the first dehalogenation of the trifluoromethyl anion is 28.4 kcal mol(-1) higher than for the second dehalogenation. The pseudo-first-order kinetic was determined and from an Arrhenius diagram an activation energy of E(a)=25.1 kcal mol(-1) has been estimated. At 37 degrees C and a pH of 7.4 the half-life was 6.9 h. The rate of hydrolysis was favored at higher pH and it was not influenced by oxygen, sunlight or trace elements found in natural water. The latter was shown by incubations with lake water instead of distilled water.     

The individual and combined effects of ozone and simulated acid rain on growth, gas exchange rate and water-use efficiency of Pinus armandi Franch

The seedlings of Pinus armandi Franch. were exposed to ozone (O(3)) at 300 ppb for 8 h a day, 6 days a week, and simulated acid rain of pH 3.0 or 2.3, 6 times a week, alone or in combination, for 14 weeks from 15 June to 20 September 1993. The control seedlings were exposed to charcoal-filtered air and simulated rain of pH 6.8 during the same period. Significant interactive effects of O(3) and simulated acid rain on whole plant net photosynthetic rate were observed, but not on other determined parameters. The exposure of the seedlings to O(3) caused the reductions in the dry weight growth, root dry weight relative to the whole plant dry weight, net photosynthetic rate, transpiration rate in light, water-use efficiency and root respiration activity, and increases in shoot/root ratio, and leaf dry weight relative to the whole plant dry weight without an appearance of acute visible foliar injury, but did not affect the dark respiration rate and transpiration rate in the darkness. The decreased net photosynthetic rate was considered to be the major cause for the growth reduction of the seedlings exposed to O(3). On the other hand, the exposure of the seedlings to simulated acid rain reduced the net photosynthetic rate per unit chlorophyll a + b content, but did not induce the significant change in other determined parameters.     

Complete mineralization of benzene by a methanogenic enrichment culture and effect of putative metabolites on the degradation

Microbial degradation of benzene under anaerobic conditions plays an important role in remediation of contaminated sites but the microorganisms and metabolic pathways involved remain poorly understood. In this study, we evaluated degradation of benzene by a methanogenic enrichment culture obtained from non-contaminated lotus field soil, alone and in the presence of several putative metabolic intermediates, that is, toluene, benzoate and phenol. Using stable isotope (¹³C) labeled substrate, benzene was shown to be degraded almost completely to equimolar concentrations of methane and carbon dioxide, without detectable accumulation of extracellular metabolites. Concurrently, toluene, benzoate and phenol were also effectively mineralized, but probably by microorganisms other than the benzene degraders. The latter included Hasda-A, which is putative benzene-degrading deltaproteobacterium present in the culture. While toluene and benzoate did not affect benzene degradation, phenol had a moderate inhibitory effect although it was not a major metabolic intermediate of benzene in our culture. Finally, 4-hydroxycoumarin was detected as a compound formed from phenol but further experiments are required to elucidate its relationship to degradation of phenol.     

A field intercomparison and fundamental characterization of various dust samplers with a reference sampler

The European Economic Community Council Directive 80/779/EEC describes air quality limit values and guide values for sulfur dioxide and suspended particulates. However, article 10, paragraph 1 does not define well enough the reference method required, amongst others, for the gravimetric measurement of suspended particulates. It is explicity stated in article 10, paragraph 5 of the directive, that "the commission shall, in selected locations in the member states and in cooperation with the latter, carry out studies on the sampling...of suspended particulates. These studies shall be designed in particular to promote the harmonization of methods of sampling and analysis of these pollutants." Therefore, in a joint research program the Umweltbundesamt (grant #104 02263), the commission of European Communities (grant #84-B-6642-11-017-11-N) and the U.S. EPA (grant #2-432U-3580) funded the development of a reference dust sampler by the Fraunhofer-Institute of Toxicology and Aerosol Research (FhlTA, in Hannover, Federal Republic of Germany) in order: to study the particle size distribution of ambient air aerosol at a number of selected sites; to compare the results obtained with the reference dust sampler with those of particle samplers operated in Europe and the United States; to verify the applicability of wind tunnel results to sampling behaviour in the free atmosphere.     

Distribution of the herbicide atrazine in a microcosm with riparian forest plants

Pesticides applied on sugarcane reach the subsoil of riparian forests and probably contaminate the river water. This work was conducted to learn about the phytoremediation of atrazine and subsoil contamination using the common riparian forest species of Cecropia hololeuca Miq. and Trema micranta (L.) Blum. These plants were grown in soil microcosms where (14)C-atrazine at 1/10 of the field-recommended dose was applied at the bottom of the microcosm simulating the movement from contaminated ground water to the upper soil layers and into plants. Residues of (14)C-atrazine were detected in all parts of the microcosm including soil, rhizosphere and the roots in different layers of the microcosm, stem and leaves. Atrazine mineralization was higher (10.2%) in the microcosms with plants than the control microcosms without plants (1.2%). The upward movement of this pesticide from deeper to more superficial soil layers occurred in all the microcosms with plants, powered by evapotranspiration process. From the atrazine applied in this study about 45% was taken up by C. hololeuca and 35% by T. micrantha. The highest amount of radioactivity (%) was found in the fine roots and the specific radioactivity (% g(-1)) showed that thick, fine roots and leaves bioaccumulate atrazine. The enhanced mineralization of atrazine as well the phytostabilization effect of the tree biomass will reduce the bioavailability of these residues and consequently decrease the hazardous effects on the environment.     

Direct measurement of octanol-water partition coefficients of some environmentally relevant brominated diphenyl ether congeners

Octanol-water partition coefficients (K(OW)) of nine environmentally relevant brominated diphenyl ether (BDE) congeners present in two technical mixtures were directly measured using a slow-stir technique. LogK(OW) values of tri- to heptabrominated BDE congeners ranged from 5.74 to 8.27, and were related to bromine content by the equation logK(OW)=0.621(#Br)+4.12(R(2)=0.970). The directly determined K(OW) values were generally lower than those calculated using fragment constant methods, particularly at higher levels of bromine substitution. The quasi-experimental approach of using fragment constants to modify a "backbone" compound of known K(OW) was much more successful than using the fragment constants to "build" the entire molecule. The tri- and tetrabrominated congeners are in the range of optimum bioaccumulation potential.     

新型微生物菌剂对垃圾渗滤液的除臭效果

利用从食材中筛选纯化的特定微生物制成新型复合菌剂,以不同浓度梯度处理垃圾渗滤液,测定其在自然条件下的嗅阈值,监测NH3和H2S即时挥发浓度的变化,评价菌剂的综合除臭效果,设计三因素三水平实验并采用响应面优化法对反应适宜的实验参数进行了优化。研究结果表明,新型复合菌剂的投加会使垃圾渗滤液嗅阈值明显下降;响应面优化模型分析表明,反应时间2.5 d时和0.5%的菌剂投加对抑制NH3的挥发效果最好,而反应时间2.5 d和0.2%的投入量对抑制H2S的挥发效果最好,氧气的供应情况对两者的挥发抑制效果影响不显著。     

Sorption of imazaquin in soils with positive balance of charges

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.     

Metal availability and soil toxicity after repeated croppings of Thlaspi caerulescens in metal contaminated soils

Metal phytoextraction with hyperaccumulating plants could be a useful method to decontaminate soils, but it is not fully validated yet. In order to quantify the efficiency of Cd and Zn extraction from a calcareous soil with and without Fe amendment and an acidic soil, we performed a pot experiment with three successive croppings of Thlaspi caerulescens followed by 3 months without plant and 7 weeks with lettuce. We used a combined approach to assess total extraction efficiency (2 M HNO3-extractable metals), changes in metal bio/availability (0.1 M NaNO3-extractable metals and lettuce uptake) and toxicity (lettuce biomass and the BIOMET biosensor). The soil solution was monitored over the whole experiment. In the calcareous soil large Cu concentrations were probably responsible for chlorosis symptoms observed on T. caerulescens. When this soil was treated with Fe, the amount of extracted metal by T. caerulescens increased and metal availability and soil toxicity decreased when compared to the untreated soil. In the acidic soil, T. caerulescens was most efficient: Cd and Zn concentrations in plants were in the range of hyperaccumulation and HNO3-extractable Cd and Zn, metal bio/availability, soil toxicity, and Cd and Zn concentrations in the soil solution decreased significantly. However, a reduced Cd concentration measured in the third T. caerulescens cropping indicated a decrease in metal availability below a critical threshold, whereas the increase of dissolved Cd and Zn concentrations after the third cropping may be the early sign of soil re-equilibration. This indicates that phytoextraction efficiency must be assessed by different approaches in order not to overlook any potential hazard and that an efficient phytoextraction scheme will have to take into account the different dynamics of the soil-plant system.     

Occurrence of carbon monoxide during organic waste degradation

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH4) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O2 concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments.     

Discriminating between Copper and Silver Mill Tailings in Silver Bow Creek Overbank Deposits,Butte, Montana,U.S.A.

Mining of the Butte deposit evolved over 100 years from placer mining starting in 1864 through silver mining to copper mining in the 1900s. Tailings resulting from milling during the period 1876-1924 were typically sluiced into the adjacent Silver Bow Creek (SBC) where they were washed downstream. The most significant flood event in 1908, among others, resulted in emplacement of approximately 2.9 m tons of sediment intermixed with tailings as overbank deposits along SBC between Butte and the Warm Springs Ponds. Apportioning the associated costs was contingent in part on discriminating between ownership of liability for the silver and copper tailings, which together formed the most significant portion of the overbank deposits. Samples were collected of tailings end-members and SBC deposits and their characteristic mineralogy (e.g. galena for silver tailings, and enargite for copper tailings) used to ascertain mixing of the tailings along SBC. This analysis identified Pb as a signature element for silver tailings and Cu for copper tailings. Two-hundred and twenty-four Cu and Pb chemical analyses representing 43 transects through the overbank deposits along SBC allowed calculation of the proportional contribution of the end members for each integrated transect. Accumulating the volumes from each transect resulted in an apportionment of 53% copper and 47% silver tailings in the overbank deposits.     

Anaerobic biodegradation of weathered polychlorinated biphenyls (PCBs) in contaminated sediments of Porto Marghera (Venice Lagoon,Italy)

The biodegradation of weathered polychlorinated biphenyls (PCBs) (mono and di-chlorinated biphenyls along with PCBs partially ascribed to Aroclor 1242 and 1254) occurring at 1.5-2.5 mg/kg in three different sediments collected from the Porto Marghera contaminated area of Venice Lagoon (Italy) was reported in this study. Strictly anaerobic, slurry microcosms consisting of sediments suspended (at 25% v/v) in a marine salt medium, lagoon water or lagoon water supplemented with NaHCO3 and Na2S were developed and monitored for PCB transformation, sulfate consumption and methane (CH4) production for 6 months. A marked depletion of highly chlorinated biphenyls along with the accumulation of low-chlorinated, often ortho-substituted biphenyls was observed in the biologically active microcosms, where a remarkable consumption of sulfate and/or a significant production of CH4 were also detected. Notably, a more extensive PCB transformation was observed in the microcosms developed with site water (both without or with NaHCO3 plus Na2S), where both the initial concentration of sulfate and sulfate consumption were five fold-higher than in the corresponding microcosms with salt medium. These data indicate that weathered PCBs of the three contaminated sediments of Porto Marghera utilized in this study can undergo reductive dechlorination, probably mediated by indigenous sulfate-reducing and/or methanogenic bacteria.     

Polychlorinated biphenyls and organochlorine pesticides in Baltic Sea sediments and bivalves

Insecticide resistance is an evolutionary response to insecticides and, as such, important for environmental biomonitoring and for pest management. Fitness disadvantage in the absence of insecticide is a frequent assumption in models of insecticide resistance evolution, which was observed in different insect species. Fitness studies are based in demographic performance of isolated populations without direct interaction between insecticide-resistant and -susceptible populations. Here we reported a study of direct competition following a factorial bivariate design between an insecticide-susceptible population of the maize weevil, Sitophilus zeamais Motschulsky (Coleoptera: Curculionidae), and one of two insecticide-resistant populations - one exhibiting fitness disadvantage based on demographic studies (Juiz de Fora) and other not exhibiting it (Jacarezinho). Total number of insects, mortality by insecticide, insect body mass and respiration rate were recorded after three generations of competition. Indeed, fitness disadvantage was observed in the resistant population from Juiz de Fora, but not in the population from Jacarezinho, as expected. The higher body mass and respiration rate of the insecticide-resistant insects from Jacarezinho are probably mitigating the physiological costs associated with the insecticide resistance minimizing their fitness disadvantage, what does not take place with the insecticide-resistant insects from Juiz de Fora. These distinct responses between the insecticide-resistant populations are probably related to the length and intensity of field-selection with insecticides.     

Discriminating between Copper and Silver Mill Tailings in Silver Bow Creek Overbank Deposits,Butte, Montana,U.S.A.

Mining of the Butte deposit evolved over 100 years from placer mining starting in 1864 through silver mining to copper mining in the 1900s. Tailings resulting from milling during the period 1876–1924 were typically sluiced into the adjacent Silver Bow Creek (SBC) where they were washed downstream. The most significant flood event in 1908, among others, resulted in emplacement of approximately 2.9 m tons of sediment intermixed with tailings as overbank deposits along SBC between Butte and the Warm Springs Ponds. Apportioning the associated costs was contingent in part on discriminating between ownership of liability for the silver and copper tailings, which together formed the most significant portion of the overbank deposits. Samples were collected of tailings end-members and SBC deposits and their characteristic mineralogy (e.g. galena for silver tailings, and enargite for copper tailings) used to ascertain mixing of the tailings along SBC. This analysis identified Pb as a signature element for silver tailings and Cu for copper tailings. Two-hundred and twenty-four Cu and Pb chemical analyses representing 43 transects through the overbank deposits along SBC allowed calculation of the proportional contribution of the end members for each integrated transect. Accumulating the volumes from each transect resulted in an apportionment of 53% copper and 47% silver tailings in the overbank deposits.     

Effect of Diffusiophoresis and Thermophoresis on the Overall Particle Collection Efficiency of Spray Droplet Scrubbers

The overall particle collection efficiencies of spray scrubbers using monodisperse droplets of 100,500, and 1000 microns diameter were calculated for the cases of evaporating and condensing droplets. The properties of the gas at the inlet to the spray scrubber were maintained constant at 150°F, 100% relative humidity, and 1 atmosphere pressure. At the liquid entrance to the spray scrubber, the water droplet temperature was 50° F for the condensing case and 180° F for the evaporating case. The liquid to gas flow rate ratio for all the calculations was held constant at 4 gal/1000 acf. The gas velocity in the co-current spray tower was 1 ft/sec in the downwind direction. The calculation results show that for the particles in the 0.01 to 10 Mm diameter range, the overall spray scrubber particle collection efficiency is greater with the cooler 50°F water (condensing case) than with the warmer 180°F water (evaporating case). The effect of diffusiophoresis and thermophoresis is noticeable for all the water droplet sizes considered, but is more significant for the larger water droplets. This greater effect for the larger water droplets compared to the smaller droplets is due to the longer existence of the temperature and water vapor concentration gradients between the water droplets and the surrounding gas.     

The use of potassium dichromate and ethyl alcohol as blood preservatives for analysis of organochlorine contaminants

The "gold standard" for preserving and shipping of human tissue samples for analysis of organochlorine contaminants is freezing. This method can be difficult, costly if using heavy dry ice for shipping, and often unfeasible, especially in less developed countries where electricity and dry ice are frequently rare or absent. Therefore, it is essential that more convenient and practical methods for preservation of blood samples are found. As an alternative to freezing, there have been studies employing potassium dichromate as a preservative for human or cow's milk or ethyl alcohol preservation of blood for dioxin analysis. In this study, four methods were compared to investigate the effectiveness of ethyl alcohol and potassium dichromate as blood preservatives for analysis of dioxins, dibenzofuran, and polychlorinated biphenyl (PCB) congeners. Samples of whole blood from a Dallas, Texas hospital were collected and pooled. Freezing, ethyl alcohol in two concentrations (20% and 40% per volume of sample), and potassium dichromate were used for blood preservation. The blood samples containing potassium dichromate or ethyl alcohol were stored and sent to ERGO laboratory for dioxin analysis and comparison with results from the frozen sample, which was kept frozen at all times until analyzed. This study suggests that potassium dichromate is a suitable alternative to freezing for preservation of whole blood for dioxin, dibenzofuran, and PCB measurements when either lipid or wet weight based results are reported. Potassium dichromate tablets were very easy and convenient to use--two 100 mg tablets (with a dichromate content of about 33 mg each) were added to each bottle containing 65 ml of blood. However, ethyl alcohol at 20% and 40% concentration under the conditions of this pilot study and the analytical method employed did not appear to provide satisfactory preservation when lipid based results are given or when the fat content has to be determined (wet or whole weight). Further research with a larger number of samples, inclusion also of other groups of persistent organic pollutants such as organochlorine pesticides or brominated flame retardants, a longer duration of storage time, and at temperatures greater than US or German room temperature is indicated in order to recommend the routine use of potassium dichromate as preservative for whole blood intended for dioxin, dibenzofuran, and PCB analysis.     

Contaminant transport in a municipal drinking water supply: a steady-state approach to estimate rate and uncertainty

Contaminant transport is generally considered to be a key factor when assessing and classifying the environmental risk of polluted areas. In the study presented here, a steady-state approach was applied to obtain estimates of the transit time and concentration of the pesticide metabolite BAM (2,6-dichlorobenzoamide) at a site where it is contaminating a municipal drinking water supply. A Monte Carlo simulation technique was used to quantify the uncertainty of the results and to evaluate the sensitivity of the used parameters. The adopted approach yielded an estimated median transit time of 10 y for the BAM transport from the polluted site to the water supply. Soil organic carbon content in the unsaturated zone and the hydraulic conductivity in the saturated zone explained 44% and 23% of the uncertainty in the transit time estimate, respectively. The sensitivity analysis showed that the dilution factor due to regional groundwater flow and the soil organic carbon content at the polluted site explained 53% and 31% of the uncertainty of concentration estimates, respectively. In conclusion, the adopted steady-state approach can be used to obtain reliable first estimates of transit time and concentration, but to improve concentration predictions of degrading contaminants, a dynamic model is probably required.     

Adapting a geographical information system-based water resource management to the needs of the Romanian water authorities

Background, aim, and scope

The need for global and integrated approaches to water resources management, both from the quantitative and the qualitative point of view, has long been recognized. Water quality management is a major issue for sustainable development and a mandatory task with respect to the implementation of the European Water Framework Directive as well as the Swiss legislation. However, data modelling to develop relational databases and subsequent geographic information system (GIS)-based water management instruments are a rather recent and not that widespread trend. The publication of overall guidelines for data modelling along with the EU Water Framework Directive is an important milestone in this area. Improving overall water quality requires better and more easily accessible data, but also the possibility to link data to simulation models. Models are to be used to derive indicators that will in turn support decision-making processes. For this whole chain to become effective at a river basin scale, all its components have to become part of the current daily practice of the local water administration. Any system, tool, or instrument that is not designed to meet, first of all, the fundamental needs of its primary end-users has almost no chance to be successful in the longer term.

Materials and methods

Although based on a pre-existing water resources management system developed in Switzerland, the methodological approach applied to develop a GIS-based water quality management system adapted to the Romanian context followed a set of well-defined steps: the first and very important step is the assessment of needs (on the basis of a careful analysis of the various activities and missions of the water administration and other relevant stakeholders in water management related issues). On that basis, a conceptual data model (CDM) can be developed, to be later on turned into a physical database. Finally, the specifically requested additional functionalities (i.e. functionalities not provided by classical commercial GIS software), also identified during the assessment of needs, are developed. This methodology was applied, on an experimental basin, in the Ialomita River basin.

Results

The results obtained from this action-research project consist of a set of tangible elements, among which (1) a conceptual data model adapted to the Romanian specificities regarding water resources management (needs, data availability, etc.), (2) a related spatial relational database (objects and attributes in tables, links, etc.), that can be used to store the data collected, among others, by the water administration, and later on exploited with geographical information systems, (3) a toolbar (in the ESRI environment) offering the requested data processing and visualizing functionalities. Lessons learned from this whole process can be considered as additional, although less tangible, results.

Discussion

The applied methodology is fairly classical and did not come up with revolutionary results. Actually, the interesting aspects of this work are, on the one hand, and obviously, the fact that it produced tools matching the needs of the local (if not national) water administration (i.e. with a good chance of being effectively used in the day-to-day practice), and, on the other hand, the adaptations and adjustments that were needed both at the staff level and in technical terms.

Conclusions

This research showed that a GIS-based water management system needs to be backed by some basic data management tools that form the necessary support upon which a GIS can be deployed. The main lesson gained is that technology transfer has to pay much attention to the differences in existing situations and backgrounds in general, and therefore must be able to show much flexibility. The fact that the original objectives could be adapted to meet the real needs of the local end-users is considered as a major aspect in achieving a successful adaptation and development of water resources management tools. Time needed to setup things in real life was probably the most underestimated aspect in this technology transfer process.

Recommendations and perspectives

The whole material produced (conceptual data model, database and GIS tools) was disseminated among all river basin authorities in Romania on the behalf of the national water administration (ANAR). The fact that further developments, for example, to address water quantity issues more precisely, as envisaged by ANAR, can be seen as an indication that this project succeeded in providing an appropriate input to improve water quality in Romania on the long term.

     

Stress biomarkers and alkali-labile phosphate level in mussels (Mytilus galloprovincialis) collected in the urban area of Venice (Venice Lagoon, Italy)

In this study, a spatial and temporal survey at three sites located in the "canals" of the Venice historic centre (Italy) and at a reference site was undertaken to evaluate stress effects on mussels sampled in the Venice urban area, where raw sewage is discharged without treatment directly into the water. A battery of biomarkers (metallothionein, micronuclei, condition index and survival in air) was used to evaluate the stress condition of the animals. At the same time the alkali-labile phosphate assay (ALP) was performed in mussel' hemolymph with the aim to find an estrogenic effect biomarker in this mussel species. Biomarker results showed an impairment of the general health condition in the mussels coming from the urban area, in agreement with the chemical analysis. Significantly higher level of the ALP was found in male mussels sampled in April in the urban area, in comparison with the ones from the reference site (P<0.001). Finally, the PCA proved an easy and useful tool to summarize the obtained results, also able to classify the data to indicate a pollution gradient in the Venice urban area.     

Spectroscopic Raman study of sulphate precipitation sequence in Rio Tinto mining district (SW Spain)

Acidic waters and sulphate-rich precipitates are typical by-products of mining activity such as in Rio Tinto (Huelva, SW Spain). This river drains pyrite mines situated in the Iberian Pyrite Belt which have been in operation since the Bronze Age and probably constitutes the oldest continuously operating mining activity over the world. In the present work, we have used Raman spectroscopy to study a wide range of natural mineral samples collected at Rio Tinto which origin is related to evaporation and mineral transformation processes in a wet and extreme acidic environment. In addition, we simulated the phenomenon of mineral precipitation in controlled conditions by using a simulator developed at the laboratory evaporating natural water collected at Rio Tinto. Also, a series of experiments using the same waters as small droplets have been carried out using micro-Raman technique. The droplets were placed on substrates with different chemical composition and reactivity. The results reveal that the precipitation sequence occurred in Rio Tinto mainly comprises copiapite and coquimbite group minerals followed by several other low hydrated iron sulphates. The experiments carried out on droplets allow estimating with higher accuracy the precipitation sequence.