Copper, zinc and lead speciation in salt marsh sediments colonised by Halimione portulacoides and Spartina maritima

Total concentrations and fractionation of Cu, Zn and Pb in seven operationally defined phases (exchangeable, carbonates, manganese oxides, organic complexes, amorphous iron oxides, crystalline iron oxides and residual) were determined in sediments colonised by the halophyte species Halimione portulacoides and Spartina maritima in a Tagus estuary salt marsh (Portugal). We aimed to determine whether the speciation of these metals was different in areas colonised by each halophyte. Higher concentrations of Cu, Zn and, in particular Pb, were found in the rhizosphere of S. maritima than in the root sediments of H. portulacoides. Geochemical fractionation of Cu, Zn and Pb in sediments of the salt marsh depended upon the metal, and for Zn and Pb clearly varied with depth and with the colonising species. The higher redox potential observed in sediments colonised by H. portulacoides may in part explain the observed differences in the speciation of Cu, Zn and Pb.     

Assessment of a sewage sludge treatment on cadmium, copper and zinc bioavailability in barley, ryegrass and earthworms

The toxicity and bioavailability of metals were assessed to verify the efficiency of a new chemical leaching process (METIX-AC) to minimize the risk of metals found in municipal sewage sludge. For this purpose, sludge samples were spiked with cadmium, copper and/or zinc before being treated using METIX-AC. The sludge decontamination resulted in a removal of spiked metals (79-89%), in a decrease of the more labile fractions, and in a corresponding increase of the residual fraction. The toxicity observed after exposure of two plant species, barley (Hordeum vulgare) and ryegrass (Lolium perenne), and a terrestrial invertebrate, Eisenia andrei, to sludge-soil mixtures, disappeared after treatment, although the adverse effects were minor before treatment. The sludge treatment also significantly decreased the bioaccumulation of cadmium, copper, and zinc in the exposed species. For cadmium, maximum tissue concentrations of 0.45+/-0.08 mg/kg in barley, 0.79+/-0.27 mg/kg in ryegrass, and 21.82+/-1.85 mg/kg in earthworm exposed to sludge before treatment decreased after treatment to values similar to those observed with negative controls.     

Concentration of Organochlorine Pollutants in Surface Waters of the Central European Biosphere Reserve Krivoklatsko (8 pp)

Background, Aim and Scope The article is focused on dioxin, furan, PCB and organochlorine pesticide monitoring in the surface waters of the Central European, protected natural reserve Krivoklatsko, under the UNESCO programme Man and Biosphere. Persistent compounds are presently transported via different means throughout the entire world. This contamination varies significantly between sites. This raises the question of what constitutes the naturally occurring background levels of POPs in natural, unpolluted areas, but which are close to industrialised regions. Information of real background POP contamination can be of high value for risk assessment management of those sites evidently polluted and for the defining of de-contamination limits. Preserved areas should not be seen as isolated regions in which the impacts of human activities and natural factors are either unexpected or overlooked. Every ambient region, even those protected by a law or other means, are still closely connected to neighbouring human developed and impacted areas, and are therefore subject to this anthropogenic contamination. These areas adjacent to natural reserves are sources of diverse substances, via entry of air, water, soil and/or biota. After an extended period of industrial activities, organochlorine pollutants, even those emitted in trace concentrations have reached detectable levels. For future research and for the assessment of environmental changes, present levels of contamination would be of high importance. This work publishes data of the contamination with organochlorine pollutants of this natural region, where biodiversity and ecological functions are of the highest order. Materials and Methods: Semipermeable membrane devices (SPMDs) were utilised as the sampling system. SPMDs were deployed in two small creeks and one water reservoir selected in the central part of the Krivoklatsko Natural Reserve, where it could be expected that any possible contamination by POPs would be lowest. The exposed SPMDs were analysed both for chemical contents of POPs and for toxicity properties. The chemical analyses of dibenzo-dioxins, dibenzo-furans, PCBs and OCPs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Toxicity bioassays were performed on the alga Desmodesmus subspicatus, bacteria Vibrio fischeri and crustacean Daphnia magna. All toxicity data were expressed as the effective volume Vtox. Vtox is a toxicity parameter, the determination of which is independent of SPMD deployment time and pre-treatment dilution (unlike, for example, the EC50 of the SPMD extract). Results: The following chemical parameters were monitored: 1) tetra, penta, hexa and hepta dibenzo-p-dioxins and furans; 2) all those detectable from tri- through deca-polychloriated biphenyls (PCBs) and 3) a group of organochlorine pesticides: hexachlorobenzene and isomers of hexachlorocyclohexane, DDE, DDD and DDT. The concentrations of dioxins and furans on the assessed sites varied from under detection levels up to 7 pg.l-1; PCBs were detected in a sum concentration up to 2.8 ng.l-1; and organochlorine pesticides up to 346 pg.l-1. The responses of bioassays used were very low, with the values obtained for Vtox being under 0.03 l/d. Discussion: Toxicity testing showed no toxicity responses, demonstrating that the system used is in coherence with the ecological status of the assessed sites. Values of Vtox were under the critical value – showing no toxicity. The PCA of chemical analysis data and toxicity responses resulted in no correlations between these two groups of parameters. This demonstrated that the present level of contamination has had no direct adverse effects on the biota. Conclusions: The concentration values of six EPA-listed, toxic dioxins and sums of tetra-hepta dioxins; nine EPA toxic dibenzofurans and the sums of tetra-hepta bibenzofurans are presented together with all tri-deka PCBs and organochlorine pesticides (alfa-, beta-, gama-, delta-HCH, HCB, opDDE, ppDDE, opDDD, ppDDD, opDDT, ppDDT). These values represent possible current regional natural background values of these substances monitored within the Central European region, with no recorded adverse effects on the freshwater ecosystem (up until the present time). Recommendations and Perspectives: Assessment of dioxins, furans and other organochlorine compounds within natural reserves can be important for the monitoring of human-induced impacts on preserved areas. No systematic monitoring of these substances in areas not directly affected by industry has generally been realised. There is a paucity of data of the presence of any of these substances within natural regions. Further monitoring of contamination of both soil and biota by dioxins and furans in preserve regions is needed and can be used for future monitoring of man-made activities and/or accidents. Semipermeable membrane devices proved to be a very good sampling system for the monitoring of trace concentrations of ambient organochlorine compounds. Toxicity evaluation using the Vtox concept demonstrated that those localities assessed expressed no toxicity.     

Effect of reservoir flushing on downstream river water quality

The effect of short-term reservoir flushing on downstream water quality in the Geum River, Korea was studied using field experiments and computer simulations. The reservoir release was increased from 30 to 200 m(3)/s within 6 h for the purpose of this experiment. The flushing discharge decreased the concentrations of soluble nitrogen and phosphorus species considerably, but the experimental results revealed a negative impact on organic forms of nutrients and biochemical oxygen demand (BOD). A dynamic river water quality model was applied to simulate the river hydraulics and water quality variations during the event. The model showed very good performance in predicting the travel time of flushing flow and the variations of dissolved forms of nitrogen and phosphorus constituents. However, it revealed a limited capability in simulating organic forms of nutrients and BOD because it does not consider the re-suspension mechanism of these constituents from sediment during the wave front passage.