Sediment integrative assessment of the Bay of Cádiz (Spain): An ecotoxicological and chemical approach

This study consisted of the sediment toxicity assessment of the Bay of Cádiz based on two endpoints: growth inhibition for Cylindrotheca closterium (benthic microalgae) and fecundity inhibition for Tisbe battagliai (harpacticoid copepod). A new methodology to eliminate (but not as storage technique) the autochthonous biota present in the sediment samples by immersing them in liquid nitrogen (? 196 °C) was also assessed. Sediment toxicity data showed different toxicity levels for both organisms. In general, T. battagliai was more sensitive; however a good correlation (r = 0.75; p  < 0.05) between sediment toxicity results for both species was found. Data in pore water (pH, redox potential, and toxicity for microalgae and copepod) and sediment (pH, redox potential, organic carbon, and metal concentrations) demonstrated that ultra-freezing did not alter sample characteristics; thus, this technique can be adopted as a pre-treatment in whole-sediment toxicity tests in order to avoid misleading results due to presence of autochthonous biota. Multivariate statistical analysis such as cluster and principal component analysis using chemical and ecotoxicological data were employed. Silt and organic matter percentage and lead concentration were found to be the factors that explain about 77% of sediment toxicity in the Bay of Cádiz. Assay methodology determined in this study for both assayed species is considered adequate to be used in sediment toxicity monitoring programs. Results obtained using both species show that the Bay of Cádiz can be considered a moderately polluted zone.     

Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods

Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a significant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difficulty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specific PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the filters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities.     

Numerical simulations on the influence of matrix diffusion to carbon sequestration in double porosity fissured aquifers

The double porosity model for fissured rocks, such as limestones and dolomites, has some features that may be relevant for carbon sequestration. Numerical simulations were conducted to study the influence of matrix diffusion on the trapping mechanisms relevant for the long-term fate of CO₂ injected in fissured rocks. The simulations show that, due to molecular diffusion of CO₂ into the rock matrix, dissolution trapping and hydrodynamic trapping are more effective in double porosity aquifers than in an equivalent porous media. Mineral trapping, although assessed indirectly, is also probably more relevant in double porosity aquifers due to the larger contact surface and longer contact time between dissolved CO₂ and rock minerals. However, stratigraphic/structural trapping is less efficient in double porosity media, because at short times CO₂ is stored only in the fissures, requiring large aquifer volumes and increasing the risk associated to the occurrence of imperfections in the cap-rock through which leakage can occur. This increased risk is also a reality when considering storage in aquifers with a regional flow gradient, since the CO₂ free-phase will move faster due to the higher flow velocities in fissured media and discharge zones may be reached sooner.     

Anoxic-aerobic treatment of the liquid fraction of cattle manure

Cattle manure from a dairy farm was treated in order to reduce its pollution potential. The manure came from a farm with 120 cows kept in stables in a free stall barn. As pretreatment, the manure is usually filtered on the farm using a screw press separator with a 0.5 mm mesh. Approximately 70% of the total filtered volume passes through the screen, thus constituting the liquid fraction. This fraction, with a composition of around 64,500 mg COD/l, 5770 mg total-N/l and 800 mg total-P/l, was subjected to centrifugation followed by a two-step biological treatment (anoxic-aerobic) to reduce organic matter (COD), nitrogen and phosphorus compounds. Centrifugation led to the following removal efficiencies: 35% total solids, 60% COD, 75% total phosphorus and 20% total nitrogen (mainly organic nitrogen). With the subsequent anoxic-aerobic treatment, average removal efficiencies of 85% for COD, 90% for total phosphorus and 75% for total nitrogen were achieved.     

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.     

Assessment of pesticide residues in freshwater areas affected by rice paddy effluents in Southern Japan

Pesticide residues in five freshwater areas that are directly affected by rice paddy effluents in southern Japan were measured to determine their maximum concentrations and temporal variations. Water samples were collected every week during the 2005 rice planting season in Kagoshima Prefecture and stations were established in Amori River, Sudo River, Nagaida River (that drains into the bigger Kotsuki River), rice paddy drainage canal, and wastewater reservoir (that collects effluents from rice paddy fields). Of the 14 target pesticides examined, a total of 11 were detected in all stations. Mefenacet, fenobucarb, and flutolanil were the three pesticides with the highest maximum concentrations and were also detected frequently. Analysis of temporal variations of pesticides showed that herbicides had relatively higher concentrations in the earlier stages of the rice planting season, while insecticides and fungicides had relatively higher concentrations at the later stages. There was no significant difference among stations with regards to the temporal patterns of the top three pesticides. The calculated toxic units were less than 1 in all stations, implying low or negligible environmental risk of pesticides detected to freshwater organisms.     

Mullet and gudgeon liver histopathology and macroinvertebrate indexes and metrics upstream and downstream from a wastewater treatment plant (Febros River—Portugal)

The increased pollution in ecosystems reinforces the importance of both chemical monitoring and biological monitoring of streams and rivers, as an effective water quality-based approach to assess aquatic ecosystem health. In this study, gudgeon (Gobio gobio) and mullet (Mugil cephalus) liver histopathology (biomarker) and some macroinvertebrate community indexes and metrics (bioindicator) were used to evaluate the effect of the wastewater treatment plant (WWTP) of Febros (Avintes) in Febros River water quality and ecosystem health. Regarding macroinvertebrate communities, the Belgian Biotic Index (BBI) and Iberian Biological Monitoring Working Party (IBMWP) indexes suggested that Febros water was slightly polluted, even though the worst situation was found downstream the WWTP discharge. Concerning community metrics, upstream percent of individuals in five numerically dominant taxa (80%) was slightly more superior than the downstream (78%). The presence of intolerant or sensible individuals, determined by percent of Ephemeroptera, Plecoptera, and Trichoptera individuals and number of Ephemeroptera, Plecoptera, and Trichoptera families metrics, was higher upstream WWTP, reflecting a better water quality. The histopathology shows the presence of hepatic lesions in gudgeon and mullet. The statistical analysis of the lesion gradation showed that only necrosis was significantly higher in gudgeon captured downstream the WWTP, while differences were not observed for mullet. The multivariate analysis of data confirmed the existence of differences in hepatic lesions between gudgeon and mullet and between sampling sites. Regarding macroinvertebrate community, this analysis showed that the organic contamination reflected by the BBI and IBMWP indexes values was a determinant factor in the spatial distribution of macroinvertebrates. This work showed that the study of different biological organization levels can be used for a better assessment of ecosystem ecological integrity and can be used as a tool to reveal anthropogenic activity effects in macroinvertebrate diversity and in fish liver pathology from Febros River.     

Management of MSW in Spain and recovery of packaging steel scrap

Packaging steel is more advantageously recovered and recycled than other packaging material due to its magnetic properties. The steel used for packaging is of high quality, and post-consumer waste therefore produces high-grade ferrous scrap. Recycling is thus an important issue for reducing raw material consumption, including iron ore, coal and energy. Household refuse management consists of collection/disposal, transport, and processing and treatment - incineration and composting being the most widely used methods in Spain. Total Spanish MSW production exceeds 21 million tons per year, of which 28.1% and 6.2% are treated in compost and incineration plants, respectively. This paper presents a comprehensive study of incineration and compost plants in Spain, including a review of the different processes and technologies employed and the characteristics and quality of the recovered ferrous scrap. Of the total amount of packaging steel scrap recovered from MSW, 38% comes from compost plants and 14% from incineration plants. Ferrous scrap from incineration plants presents a high degree of chemical alteration as a consequence of the thermal process to which the MSW is subjected, particularly the conditions in which the slag is cooled, and accordingly its quality diminishes. Fragmentation and magnetic separation processes produce an enhancement of the scrap quality. Ferrous scrap from compost plants has a high tin content, which negatively affects its recycling. Cleaning and detinning processes are required prior to recycling.