The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity

To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTE’s) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTE’s only to a limited extent.The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe_ox) and to the reactivity of PTE’s in soils which in fact control the soluble fraction of the contaminants.The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTE’s in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils.     

Organochlorine concentrations in franciscana dolphins, Pontoporia blainvillei, from Brazilian waters

Blubber samples were collected from ten franciscana dolphins either incidentally captured in fishing operations or stranded on São Paulo (SP) and Paraná (PR) states littoral, Southeastern and Southern Brazilian coast, respectively. Determination of PCB, DDT and HCB concentrations were performed by capillary gas chromatograph coupled to electron capture detector (ECD). ΣDDT, ΣPCB and HCB concentrations ranged from 264 ng g⁻¹ to 5811 ng g⁻¹ lipid, from 909 ng g⁻¹ to 5849 ng g⁻¹ lipid and from 10 ng g⁻¹ to 61 ng g⁻¹ lipid, respectively. Regarding DDTs, the distribution of the mean percentages decreased in the following order: p,p′-DDE > p,p′-DDD > p,p′-DDT. The ΣDDT/ΣPCB ratio varied between 0.27 and 0.42 in Northern and Central SP coast, while in Southern SP and PR coast the values were 1.6 and 1.9, respectively. Dissimilarities in ΣDDT/ΣPCB ratios point to different sources of organochlorine compounds to franciscana dolphins in the study area. Considering the endocrine disruptive action of organochlorine compounds, the concentrations found in franciscana dolphins from Brazilian waters may represent an additional obstacle to the conservation of this endangered cetacean species.     

Oxygenated gasoline release in the unsaturated zone - Part 1: Source zone behavior

Oxygenates present in gasoline, such as ethanol and MTBE, are a concern in subsurface contamination related to accidental spills. While gasoline hydrocarbon compounds have low solubility, MTBE and ethanol are more soluble, ethanol being completely miscible with water. Consequently, their fate in the subsurface is likely to differ from that of gasoline. To evaluate the fate of gasoline containing oxygenates following a release in the unsaturated zone shielded from rainfall/recharge, a controlled field test was performed at Canadian Forces Base Borden, in Ontario. 200L of a mixture composed of gasoline with 10% ethanol and 4.5% MTBE was released in the unsaturated zone, into a trench 20cm deep, about 32cm above the water table. Based on soil cores, most of the ethanol was retained in the source, above the capillary fringe, and remained there for more than 100 days. Ethanol partitioned from the gasoline to the unsaturated pore-water and was retained, despite the thin unsaturated zone at the site (~35cm from the top of the capillary fringe to ground surface). Due to its lower solubility, most of the MTBE remained within the NAPL as it infiltrated deeper into the unsaturated zone and accumulated with the gasoline on top of the depressed capillary fringe. Only minor changes in the distribution of ethanol were noted following oscillations in the water table. Two methods to estimate the capacity of the unsaturated zone to retain ethanol are explored. It is clear that conceptual models for sites impacted by ethanol-fuels must consider the unsaturated zone.     

Adsorption and transformation of selected human-used macrolide antibacterial agents with iron(III) and manganese(IV) oxides

The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity.     

Melt Compounded Blends of Short and Medium Chain-Length Poly-3-hydroxyalkanoates

Blends of poly-3-hydroxybutyrate with an elastomeric medium-chain-length poly-3-hydroxyalkanoate (MCL-PHA), containing 98 mol% 3-hydroxyoctanoate and 2 mol% 3-hydroxyhexanoate (referred to as PHO), were prepared by melt compounding. Coarsening of the droplet-matrix morphology of the blends was noted as the PHO content increased beyond 5 wt%; this was attributed to the significant viscosity mismatch between the components. Addition of PHO improved the thermal stability of the blends, reduced their crystallinity and resulted in shifts in their melting and crystallization temperatures. The blends had improved tensile strain at break. The unnotched impact strength showed a threefold increase at 30 wt% PHO content. Cross-linking of PHO using a peroxide initiator increased its viscosity, thus improving the morphology and mechanical properties of the blends.     

Efficiency of a cleanup technology to remove mercury from natural waters by means of rice husk biowaste: ecotoxicological and chemical approach

In the present work, the efficiency of rice husk to remove Hg(II) from river waters spiked with realistic environmental concentrations of this metal (μg L^?1 range) was evaluated. The residual levels of Hg(II) obtained after the remediation process were compared with the guideline values for effluents discharges and water for human consumption, and the ecotoxicological effects using organisms of different trophic levels were assessed. The rice husk sorbent proved to be useful in decreasing Hg(II) contamination in river waters, by reducing the levels of Hg(II) to values of ca. 8.0 and 34 μg L^?1, for an Hg(II) initial concentration of 50 and 500 μg L^?1, respectively. The remediation process with rice husk biowaste was extremely efficient in river waters spiked with lower levels of Hg(II), being able to eliminate the toxicity to the exposed organisms algae Pseudokirchneriella subcapitata and rotifer Brachionus calyciflorus and ensure the total survival of Daphnia magna species. For concentrations of Hg(II) tenfold higher (500 μg L^?1), the remediation process was not adequate in the detoxification process, still, the rice husk material was able to reduce considerably the toxicity to the bacteria Vibrio fischeri, algae P. subcapitata and rotifer B. calyciflorus, whose responses where fully inhibited during its exposure to the non-remediated river water. The use of a battery of bioassays with organisms from different trophic levels and whose sensitivity revealed to be different and dependent on the levels of Hg(II) contamination proved to be much more accurate in predicting the ecotoxicological hazard assessment of the detoxification process by means of rice husk biowaste.     

Decontamination of produced water containing petroleum hydrocarbons by electrochemical methods: a minireview

Produced water (PW) is the largest waste stream generated in oil and gas industries. The drilling and extraction operations that are aimed to maximize the production of oil may be counterbalanced by the huge production of contaminated water (called PW) with pollutants, such as heavy metals, dissolved/suspended solids, and organic compounds. PW is conventionally treated through different physical, chemical, and biological methods. In offshore platforms, because of space constraints, compact physical and chemical systems are used. However, major research efforts are being developed with innovative technologies for treating PW in order to comply with reuse and discharge limits. Among them, electrochemical technologies have been proposed as a promising alternative for the treatment of this kind of wastewaters. Then, this paper presents a minireview of efficient electrochemical technologies used until now for treating PW generated by petrochemical industry.     

Marine sponges with contrasting life histories can be complementary biomonitors of heavy metal pollution in coastal ecosystems

In this study, we compared the usefulness of a long-living sponge (Hymeniacidon heliophila, Class Demospongiae) and a short-living one (Paraleucilla magna, Class Calcarea) as biomonitors of metallic pollution. The concentrations of 16 heavy metals were analyzed in both species along a gradient of decreasing pollution from the heavily polluted Guanabara Bay to the less impacted coastal islands in Rio de Janeiro, SE Brazil (SW Atlantic). The levels of most elements analyzed were higher in H. heliophila (Al, Co, Cr, Cu, Fe, Mn, Ni, Hg, Ni, and Sn) and P. magna (Ni, Cu, Mn, Al, Ti, Fe, Pb, Co, Cr, Zn, and V) collected from the heavily polluted bay when compared with the cleanest sites. Hymeniacidon heliophila accumulates 11 elements more efficiently than P. magna. This difference may be related to their skeleton composition, histological organization, symbiont bacteria and especially to their life cycle. Both species can be used as a biomonitors of metallic pollution, but while Hymeniacidon heliophila was more effective in concentrating most metals, Paraleucilla magna is more indicated to detect recent pollutant discharges due to its shorter life cycle. We suggest that the complementary use of species with contrasting life histories can be an effective monitoring strategy of heavy metals in coastal environments.