Investigative monitoring within the European Water Framework Directive: a coastal blast furnace slag disposal, as an example

The European Water Framework Directive (WFD) establishes a framework for the protection of estuarine and coastal waters, with the most important objective being to achieve 'good ecological status' for all waters, by 2015. Hence, Member States are establishing programmes for the monitoring of water quality status, through the assessment of ecological and chemical elements. These monitoring programmes can be of three types: surveillance monitoring; operational monitoring (both undertaken on a routine basis); and investigative monitoring (carried out where the reason of any exceedance for ecological and chemical status is unknown). Until now, nothing has been developed in relation to investigative monitoring and no clear guidance exists for this type of monitoring, as it must be tackled on a 'case-by-case' basis. Consequently, the present study uses slag disposal from a blast furnace, into a coastal area, as a case-study in the implementation of investigative monitoring, according to the WFD.In order to investigate the potential threat of such slags, this contribution includes: a geophysical study, to determine the extent of the disposal area; sediment analysis; a chemical metal analysis; and an ecotoxicological study (including a Microtox test and an amphipod bioassay). The results show that metal concentrations are several times above the background concentration. However, only one of the stations showed toxicity after acute toxicological tests, with the benthic communities being in a good status. The approaches used here show that contaminants are not bioavailable and that no management actions are required with the slags.     

Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

Fucus spiralis as monitoring tool of metal contamination in the northwest coast of Portugal under the European Water Framework Directives

Metals (Cd, Cr, Cu, Fe, Mn and Zn) in coastal seawaters and soft tissues of macroalga Fucus spiralis from the northwest coast of Portugal were determined to assess spatial variations of metal bioavailabilities and bioaccumulation factors to compare different ecological quality classifications. Both coastal seawaters and soft tissues of F. spiralis showed significant spatial variations in their metal concentrations along the coast. The macroalgae F. spiralis accumulated more efficiently Cd, Mn and Zn and showed low bioaccumulation factors to Cr, Cu and Fe. Regarding the metal guidelines of the Norwegian Pollution Control Authority, the entire northwest (NW) coast of Portugal in April 2013 should be classified as ‘class I—unpolluted’ for all metals, except in Ave for Cu (‘class II—moderately polluted’) and Cavado for Cd and Cu (‘class II—moderately polluted’), revealing the low metal bioavailabilities of these seawaters. As there were always significant positive correlations between all metals in seawaters and F. spiralis, this macroalga species was considered a suitable monitoring tool of metal contamination in the NW coast of Portugal and a useful aquatic organism to be included in the European Environmental Specimen Banks in order to establish a real-time environmental monitoring network under the European Water Framework Directives.     

Effects of golpar (<Emphasis Type="Italic">Heracleum persicum</Emphasis> Desf.) and probiotics in drinking water on performance,carcass characteristics,organ weights,blood plasma constituents,and immunity of broilers

Increasing levels of Heracleum persicum (golpar) in drinking water were studied in broilers. Two hundred and forty-one-day-old male chickens were allocated to one of six treatments: control, without added phytogenics nor probiotics in drinking water, and probiotics at recommended manufacturer’s level (P) or 1.0, 1.5, 2.0, and 2.5 ml/l of golpar extract solution (G1, G1.5, G2, and G2.5 treatments, respectively) in drinking water. As a result of this study, no linear or quadratic trends in the feed intake (FI) and feed conversion rate (FCR) due to golpar supplementation were found. Body weight gain, final body weight, and relative carcass weight showed a positive linear response with increasing levels of golpar supplementation. Neither golpar nor probiotics had effects on the percentages of edible parts of the carcass. Golpar supplementation levels caused a linear negative response of the albumin content in blood plasma, whereas both abdominal fat as percentage of carcass weight and uric acid levels in blood plasma linearly increased. The effects on Ig responses were only observed at 42 days of age and were similar in probiotics and the highest level of golpar supplementation. Based on our results, both probiotics and golpar supplementation could improve broiler performance and immune function.     

Macrophage activity and histopathology of the lymphohematopoietic organs in male Wistar rats orally exposed to single or mixed pesticides

The noxious effects of low or effective dose exposure to single or mixed pesticides on macrophage activity and the lymphohematopoietic organs were investigated. Male Wistar rats were orally exposed to dichlorvos, dicofol, endosulfan, dieldrin and permethrin, either as single or combined mixtures during a 28-day study containing eight groups: one group received a semipurified diet (non-treated); two groups received a semipurified diet containing low dose mixture (dieldrin 0.025 mg/kg, endosulfan, 0.6 mg/kg, dicofol 0.22 mg/kg, dichlorvos 0.23 mg/kg, permethrin 5 mg/kg) or an effective dose mixture (dichlorvos 2.3 mg/kg, dicofol 2.5 mg/kg, endosulfan 2.9 mg/kg, dieldrin 0.05 mg/kg and permethrin 25.0 mg/kg), respectively; the other five groups received a semipurified diet containing each single pesticide in effective doses. At sacrifice, the thymus, spleen, mesenteric lymph nodes, Payer's patches and bone marrow were removed for histological analysis. Peritoneal macrophages were obtained to determine the phagocytosis and spreading indexes and tumoral necrosis factor alpha (TNF-α), nitric oxide (NO) and H₂O₂ production. Exposure to pesticide mixtures did not alter the percentage of macrophage phagocytosis and spreading, TNF-α production or the NO and H₂O₂ release when compared to the non-treated group. Neither was there any apparent evidence that a pesticide mixture at low or effective doses altered the histological structure of the lymphohematopoietic organs. The findings indicate that short-term treatment with pesticide mixtures did not induce an apparent immunotoxic effect in male Wistar rats.     

Study of the presence of fluorine in the recycled fractions during carbothermal treatment of EAF dust

Carbothermal treatment tests of electric arc furnace dusts (EAFD) using the Waelz kiln process were carried out in pilot-scale for the production of zinc oxide. The association of halides in the EAFD, and the recycled products, such as zinc oxide fumes and high-grade iron contents fractions were examined by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis. XRD reveals the presence of chlorine and fluorine in the dusts in the form of KCl, NaCl and CaF2. An ultra-pure fraction of zinc was obtained after the Double Leaching Waelz Oxide (DLWO) process was performed on the zinc oxide fumes. The halide contents were reduced to approximately 100 ppm Cl and 700 ppm F. The rest of these elements are in the form of CaF2. About 65% F is volatilised as lead and zinc fluorides, 15% is expected in the magnetic fractions and 20% in non-magnetic fractions as CaF2 and MnF2, respectively.