Macrobenthic community in the Douro estuary: relations with trace metals and natural sediment characteristics

The relationship between macrobenthic community structure and natural characteristics of sediment and trace metal contamination were studied in the lower Douro estuary (Portugal, NW, Iberian Peninsula), using an innovative threefold approach (SQG, Sediment Quality Guidelines), metal normalization to Fe, and macrobenthic community structure. This study allowed detection of a clear signature of anthropogenic contamination, in terms of Zn, Cu, Pb, and Cr in the north bank of the estuary, which experiences high urban pressure. Using the SQG approach, metal concentrations above ERM (effects range-median) were observed only at one sampling station, but several stations had levels above ERL (effects range-low). The macrobenthic community had a low diversity, with only 19 species found in the entire estuarine area, dominated by opportunistic species. The granulometric distribution of the sediments (estimated from the combination of organic matter, Fe and Al) seemed to be the major structuring factor for the communities, establishing the natural macrobenthic distribution pattern. The metals (Zn, Cu, Pb, and Cr) seemed to act as a disturbing factor over the natural distribution, with deleterious consequences for the macrobenthic communities.     

Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

Boreal bog plants: nitrogen sources and uptake of recently deposited nitrogen

The main goals of this study were to determine the delta15N signature of quantitatively important boreal bog plants as basis for discussing their N sources, and to assess the effects of five different 3 year N treatments (i.e. 0, 5, 10, 20 and 40 kg N ha(-1) year(-1)) on the bog plants and surface peat at different depths (i.e. 0, 5, 10, 20 and 40 cm) by using 15N as tracer. Plants and peat were analyzed for N concentration, 15N natural abundance and 15N at.%. From the results we draw three main conclusions: First, the relative importance of different N sources is species-specific among bog plants. Second, an annual addition of 5 kg N ha(-1) year(-1) was sufficient to significantly increase the N concentration in Sphagnum mosses, liverworts and shallow rooted vascular plants, and an annual addition of 40 kg N ha(-1) year(-1) during 3 years was not sufficient to increase the N concentration in deep rooted plants, although the 15N content increased continuously, indicating a possible longer term effect. Third, an annual addition of 40 kg N ha(-1) year(-1) during 3 years increased the N content in surface peat at depths of 5 and 10 cm, but not at depths of 20 and 40 cm, indicating the capacity of the living Sphagnum mosses and the surface peat to take up deposited N, and thereby function as a filter.     

Removal of heavy metals from a metaliferous water solution by Typha latifolia plants and sewage sludge compost

Typha latifolia plants, commonly known as cattails, were grown in a mixture of mature sewage sludge compost, commercial compost and perlite (2:1:1 by volume). Four Groups (A, B, C and D) were irrigated (once every two weeks) with a solution containing different concentrations of Cu, Ni, and Zn, where in the fifth (group M) tap water was used. At the end of the 10 weeks experimental period substrate and plants were dried, weighed and analysed for heavy metals. The amounts of all three metals removed from the irrigation solution, were substantial. In the roots and leaves/stems of T. latifolia the mean concentration of Zn reached values of 391.7 and 60.8 mg/kg of dry weight (d.w.), respectively. In the substrate of Group D all three metals recorded their highest mean concentrations of 1156.7 mg/kg d.w. for Cu, 296.7 mg/kg d.w. for Ni and 1231.7 mg/kg d.w. for Zn. Linear correlation analyses suggested that there was a linear relationship between the concentration of metals in the solutions and the concentration of metals in the substrates at the end of the experiment. The percentage removal of the metals in the substrate was large, reaching 100% for Cu and Zn in some groups and almost 96% for Ni in group D. The total amount of metals removed by the plants was considerably smaller than that of the substrate, due mainly to the small biomass development. A single factor ANOVA test (5% level) indicated that the build up in the concentration of metals in the roots and the leaves/stems was due to the use of metaliferous water solution and not from the metals pre-existing in the substrate. The contribution of the plants (both roots and leaves/stems) in the removing ability of the system was less than 1%.     

Removal of PCBs from wastewater using fly ash

Liquids and sludges containing polychlorinated biphenyls (PCBs) can be treated to concentrate the PCBs in a solid residue. The latter can then be handled to destroy the PCBs. A study on sorption kinetics of PCBs on fly ash was conducted in controlled batch systems. TCB and HeCB are removed at 25 degrees C by adsorption on fly ash up to 97% at pH 7, with an adsorbent dose of 5 g/l. An examination of the thermodynamic parameters shows that the adsorption of TCB and HeCB by fly ash is a process occurring spontaneously at ambient conditions. Activation energies for the sorption process ranged between 5.6 and 49.1 kJ/mol. It was observed that the rate at which TCB and HeCB are adsorbed onto fly ash showed a diffusion limitation. The uptake rate of TCB and HeCB increases with increasing initial concentration and gradually tends to a constant value. A decrease in the adsorption of TCB and HeCB was observed when interfering ions and other PCB congeners were present. Changing the pH in the aqueous solution from 2 to 10 had no effect on the adsorption process. Overall, fly ash can be used for an efficient removal of PCBs from several aqueous solutions.     

Optimizing electron spin resonance detection of hydroxyl radical in water

The parameters affecting the electron spin resonance (ESR) detection of hydroxyl free radical in water are studied and optimized. The hydroxyl radical is generated by the Fenton reaction with iron (II) ammonium sulfate and hydrogen peroxide reacting in a phosphate buffer using N-tert-butyl-alpha-phenylnitron as the spin trap. The concentrations of Fe²⁺, H₂O₂, and phosphate buffer are the parameters studied. The Taguchi method and the orthogonal experiment design were used to evaluate the effects of these parameters on the ESR signal intensity. By the analysis of the signal-to-noise ratio and the analysis of variance, the order of importance of the various parameters on the hydroxyl radical formation is determined for optimal ESR detection of hydroxyl radical. The results will help the development of water purification technologies using hydroxyl free radical as a green oxidant.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.     

Spatial distribution of heavy metals in urban soils of Naples city (Italy)

Concentrations of surface and sub-surface soil Cu, Cr, Pb and Zn in the Naples city urban area were measured in 1999. Contourmaps were constructed to describe the metals spatial distribution. In the most contaminated soil samples, metals were speciated by means of the European Commission sequential extraction procedure. At twelve sites, Cu, Pb and Zn levels in soil were compared with those from a 1974 sampling. Many surface soils from the urban area as well as from the eastern industrial district contained levels of Cu, Pb and Zn that largely exceeded the limits (120, 100 and 150 mg kg(-l) for Cu, Pb and Zn, respectively) set for soils of public, residential and private areas by the Italian Ministry of Environment. Chromium values were never above regulatory limits(120 mg kg(-1)). Copper apparently accumulates in soils contiguous to railway lines and tramway. Cu and Cr existed in soil mainly inorganic forms (-68%), whereas Pb occurs essentially as residual mineral phases (77%). The considerable presence of Zn in the soluble, exchangeable and carbonate bound fraction (23%) suggests this element has high potential bioavailability and leachability through the soil. Concentrations of Cu, Pb and Zn have greatly increased since the 1974 sampling, with higher accumulation in soils from roadside fields.     

Effects of fenoxycarb exposure on complete larval development of the xanthid crab,Rhithropanopeus harrisii

Pest control agents, such as juvenile hormone analogues (JHA), have been developed to limit effects on non-target organisms that co-inhabit insect pest habitats. Rhithropanopeus harrisii, an estuarine xanthid crab, was used to observe the impacts of the JHA, fenoxycarb, on the pattern of complete larval development as well as survival of larvae and successful metamorphosis to first crab stage. Significant mortality occurred in the first of four zoeal stages (after 2-3 days of exposure) at the highest treatment of 240 microg fenoxycarb/l and in megalopae exposed to 48 microg fenoxycarb/l. The time required to metamorphose to the first crab stage was significantly increased for megalopae in all treatments 48 microg/l. This delay in development was sufficient to significantly prolong the entire developmental period from zoea to crabs. Unexposed larvae developed to crabs in an average of 16 days; larvae exposed to >/=48 microg/l required 19-20 days. Reduced survival and extended duration of developing larval stages in the life history of a benthic invertebrate may alter the population dynamics of these organisms in the estuary.