Copper transformation, speciation, and detoxification in anoxic and suboxic freshwater sediments.

The complex chemistry of copper (Cu) in freshwater sediments at low concentrations is not well understood. We evaluated the transformation processes of Cu added to freshwater sediments under suboxic and anoxic conditions. Freshwater sediments from three sources in Michigan with different characteristics (Spring Creek, River Raisin, and Maple Lake) were spiked with 30 or 60 mg kg-1 Cu and incubated under a nitrogen atmosphere. After 28-d, each treatment subset was amended with organic matter (OM) to promote anoxic conditions and evaluate its effects on Cu speciation. OM addition triggered a shift from suboxic to anoxic conditions, and sequential extractions showed that Cu accordingly shifted from acid-soluble to oxidizable fractions. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed that Cu sulfides dominated all anoxic samples except for Spring Creek 30 mg kg-1, where Cu(I) was predominantly complexed to thiol groups of OM. Covellite and chalcopyrite (CuFeS2) were the predominant Cu species in nearly all anoxic samples, as determined by Raman spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure (XANES) spectroscopy. Copper reduction also occurred under suboxic conditions: for two of three sediments, around 80% had been reduced to Cu(I), while the remaining 20% persisted as Cu(II) complexed to OM. However, in the third coarsest (i.e., Spring Creek), around 50% of the Cu had been reduced, forming Cu(I)-OM complexes, while the remainder was Cu(II)-OM complexes. Toxicity tests showed that survival of H. azteca and D. magna were significantly lower in suboxic treatments. Anoxic sediments triggered a near-complete transformation of Cu to sulfide minerals, reducing its toxicity.

Can natural levels of Al influence Cu speciation and toxicity to Daphnia magna in a Swedish soft water lake?

It is well known that chemical parameters, such as natural organic matter (NOM), cation content and pH may influence speciation and toxicity of metals in freshwaters. Advanced bioavailability models, e.g. Biotic Ligand Models (BLMs), can use these and other chemical parameters to calculate site specific recommendations for metals in the aquatic environment. However, since Al is not an input parameter in the BLM v.2.2.3, used in this study, there could be a discrepancy between calculated and measured results in Al rich waters. The aim of this study was to evaluate if the presence of Al in a circumneutral (pH ∼6) soft humic freshwater, Lake St. Envättern, will affect the Cu speciation and thereby the toxicity to the cladoceran Daphnia magna. The results show a statistically significant increase in the free Cu(2+) concentration with Al additions and that measured levels of Cu(2+) significantly differed from BLM calculated levels of Cu(2+). Furthermore, there was also a statistically significant elevated acute toxic response to D. magna at low additions of Al (10 µg/L). However, since the large difference between calculated and measured Cu(2+) resulted in a significant but minor (factor of 2.3) difference between calculated and measured toxicity, further studies should be conducted in Al rich soft waters to evaluate the importance of adding Al as an input parameter into the BLM software.

Evaluation of current copper bioavailability tools for soft freshwaters in Sweden.

The Water Framework Directive (WFD) in Europe calls for an improved aquatic ecological status. Biotic ligand models (BLM) have been suggested as a possible tool assisting in the regulatory process. The aim of this study was therefore to investigate the applicability of BLM under the WFD to set environmental quality standards (EQS), in particular regarding copper in Swedish freshwaters of which many are softer than those used for model calibration. Three different BLMs, one acute and two chronic, were applied to water chemistry data from 926 lakes and 51 rivers (1530 data entries) and evaluated with respect to their calibration range for input parameters. In addition, the predicted no-effect concentration (PNEC) for copper was calculated. From the 1530 data entries, 750 ended up outside of the BLM calibration range, when looking at the chemical parameters Ca(2+), alkalinity, pH and DOC, primarily due to low carbonate alkalinity. Furthermore, the calculated Cu PNECs were higher than the suggested Swedish limit for Cu (4µgL(-1)) in surface waters for 98% and 99% of the cases concerning lakes and rivers, respectively. To conclude, our findings show that water chemical characteristics outside of the calibration ranges are quite common in Sweden and that the investigated models differ in how they calculate toxicity concerning Cu under these conditions. As a consequence, additional work is required to validate the BLMs by use of bioassays with representative species of soft waters. Such results will show if these models can be used outside of their calibration ranges and also which of the models that gives the most reliable results.

Environmental assessment of incinerator residue utilisation.

Incineration ashes may be treated either as a waste to be dumped in landfill, or as a resource that is suitable for re-use. In order to choose the best management scenario, knowledge is needed on the potential environmental impact that may be expected, including not only local, but also regional and global impact. In this study, A life cycle assessment (LCA) based approach was outlined for environmental assessment of incinerator residue utilisation, in which leaching of trace elements as well as other emissions to air and water and the use of resources were regarded as constituting the potential environmental impact from the system studied. Case studies were performed for two selected ash types, bottom ash from municipal solid waste incineration (MSWI) and wood fly ash. The MSWI bottom ash was assumed to be suitable for road construction or as drainage material in landfill, whereas the wood fly ash was assumed to be suitable for road construction or as a nutrient resource to be recycled on forest land after biofuel harvesting. Different types of potential environmental impact predominated in the activities of the system and the use of natural resources and the trace element leaching were identified as being relatively important for the scenarios compared. The scenarios differed in use of resources and energy, whereas there is a potential for trace element leaching regardless of how the material is managed. Utilising MSWI bottom ash in road construction and recycling of wood ash on forest land saved more natural resources and energy than when these materials were managed according to the other scenarios investigated, including dumping in landfill.

Metal leaching from MSWI bottom ash as affected by salt or dissolved organic matter.

In order to manage municipal solid waste incineration (MSWI) bottom ash safely, risk assessments, including the prediction of leaching under different field conditions, are necessary. In this study, the influence of salt or dissolved organic matter (DOM) in the influent on metal leaching from MSWI bottom ash was investigated in a column experiment. The presence of salt (0.1M NaCl) resulted in a small increase of As leaching, whereas no impact on leachate concentration was found when lakewater DOM (35.1mg/l dissolved organic carbon) was added. Most of the added DOM was retained within the material. Further, X-ray spectroscopy revealed that Cu(II) was the dominating form of Cu and that it probably occurred as a CuO-type mineral. The Cu(2+) activity in the MSWI bottom ash leachate was most likely determined by the dissolution of CuO together with the formation of Cu-DOM complexes and possibly also by adsorption to (hydr)oxide minerals. The addition of lake DOM in the influent resulted in lower saturation indices for CuO in the leachates, which may be due to slow CuO dissolution kinetics in combination with strong Cu-DOM complexation.

Kinetic sorption modelling of Cu, Ni, Zn, Pb and Cr ions to pine bark and blast furnace slag by using batch experiments.

Storm water and landfill leachate can both contain significant amounts of toxic metals such as Zn, Cu, Pb, Cr and Ni. Pine bark and blast furnace slag are both residual waste products that have shown a large potential for metal removal from contaminated water. There are however many variables that must be optimized in order to achieve efficient metal retention. One of these variables is the time of which the solution is in contact with each unit of filter material. Metal sorption was studied in two laboratory experiments to improve the knowledge of the effects of contact time. The results showed that pine bark was generally more efficient than blast furnace slag when the metal concentrations were relatively small, whereas blast furnace slag sorbed most metals to a larger extent at increased metal loads. In addition, sorption to blast furnace slag was found to be faster than metal binding to pine bark. A pseudo-second-order kinetic model was able to describe the data well within 1000 s of reaction time.

Sulphur status in some Swedish podzols as influenced by acidic deposition and extractable organic carbon.

To evaluate the changes in sulphur pools in response to acidic deposition, two studies were made-one in southwest Sweden where podzolic B horizons originally sampled in 1951 were resampled in 1989. At the Norrliden site, northern Sweden, sulphur pools in control plots were compared to plots that had been subjected to H(2)SO(4) application between 1971 and 1976. The results show that in southwest Sweden neither organic S nor extractable SO(4)(2-) increased significantly over the 38-year period, despite a decreasing pH and a high S deposition. At Norrliden, about 37% of the applied S was still remaining in the upper and central parts of the Bs horizon, most of which was inorganic sulphate. These contrasting results are explained by intrinsic differences in the soil organic carbon status between the sites-in southwest Sweden, organic carbon concentrations were high which inhibited SO(4)(2-) adsorption. Low organic carbon concentrations and high extractable Fe/Al concentrations promoted SO(4)(2-) adsorption and caused a low subsequent SO(4)(2-) desorption rate at the Norrliden site. The results suggest that sulphate adsorption may be an important mechanism which delays the response in soil chemistry to H(2)SO(4) deposition, provided that soil organic carbon concentrations are low. Organic S retention was not shown to be an important S retention mechanism in any of the sites studied.

Exposure of newborn infants to plasticizers. Plasma levels of di-(2-ethylhexyl) phthalate and mono-(2-ethylhexyl) phthalate during exchange transfusion.

The exposure of newborn infants to the plasticizer di-(2-ethylhexyl) phthalate (DEHP) and its primary metabolite mono-(2-ethylhexyl) phthalate (MEHP) was studied during exchange transfusions by measuring their contents in the infused blood. Plasma concentrations of DEHP and MEHP in the blood withdrawn from the infants during the transfusions also were determined. The amounts of DEHP and MEHP inadvertently infused varied from 1.7 to 4.2 and 0.2 to 0.7 mg per kg body weight, respectively. Immediately after the transfusions, the plasma levels of DEHP in the individual infants varied between 3.4 and 11.1 micrograms per ml. MEHP in the corresponding samples ranged from 2.4 to 15.1 micrograms per ml. Judging from plasma concentrations of DEHP and MEHP during and after transfusion, there was no gradual accumulation of these substances in the plasma during the course of the transfusion. In the two infants who underwent a second exchange transfusion, significant levels of phthalates were found at 16 and 23 hours, respectively, after the first transfusion. Plasma concentrations of DEHP in these infants declined at a faster rate than those of MEHP, thus pointing to the importance of examining the pharmacokinetics of this potentially toxic metabolite.