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.     

Speciation of Cr and its leachability in coal by-products from spanish coal combustion plants

This study evaluates the behaviour of total Cr and Cr (VI) during coal combustion in two Spanish power stations. The content and distribution of Cr in the feed coal and combustion wastes was determined and the Cr contents were normalized using enrichment factor indexes. The speciation of Cr in the fly ash fractions from the different hoppers of the electrostatic precipitators was established and the possibility that the Cr (VI) might lixiviate when ashes are disposed of at landfill sites was assessed. Differences in the distribution and behavior of Cr in the two power stations were observed. According to European directive 1999/31/CEE, soluble Cr(VI) in the fly ashes studied would be unlikely to pose an environmental or health risk when the ash is disposed of.     

Essential (Cu) and nonessential (Cd and Pb) metals in ichthyofauna from the coasts of Sinaloa state (SE Gulf of California)

With the aim of giving an overview on concentration and distribution of Cd, Cu, and Pb in fish from the coasts of Sinaloa state (SE Gulf of California), specimens with different feeding habits were collected in five locations. Sampling occurred between June 2003 and March 2004. Metal analyses on fish tissues were made by graphite furnace (Cd, Pb) and flame (Cu) atomic absorption spectrophotometry. Metal concentrations in tissues of carnivorous fish were grouped together and compared with corresponding concentrations in non-carnivorous fish; Cu and Pb levels were significantly (p?<?0.05) higher in liver of non-carnivorous species. Though no samples exceeded the maximum level set in international legislation for fish, from the perspective of the public health and considering the legal limits of fishery products for human consumption, Cu concentrations were exceeded (in tissues different from muscle) in four carnivorous and five non-carnivorous species according to the Australian legislation. In the case of Cd, two carnivorous species (Pomadasys leuciscus and Caulolatilus princeps) and one non-carnivorous species (Mugil cephalus), showed concentrations over the maximum level of 2 μg g^???1 dry weight considered in the Mexican legislation. Considering average amounts of fish consumption in Mexico, daily mineral intake (DMI) values for Cu and percentage weekly intake (PWI) of Cd and Pb were estimated; none of the analyzed metals in edible portion of analyzed fish could be detrimental to humans.     

An assessment of heavy metal contamination in surface sediment using statistical analysis

The distribution and accumulation of heavy metals in the sediments, especially those nearest of wastewater discharges of south of Spain, were investigated. Sediment samples from 14 locations were collected and characterised for metal content (e.g. Ni, Cu, Zn, Cr, Pb, Mn, Cd and Hg), organic carbon, total nitrogen, total phosphorous, n-hexane-extractable material, carbonates and grain size. Concentration data were processed using correlation analysis and factor analysis. The correlation analysis of concentrations data showed important positive correlations among organic carbon, total phosphorus, Cu, Zn, Cd and Hg, otherwise weak correlations among Mn, Cr, Ni and CO₃ ^2???, indicating that these metals have complicated geochemical behaviours. The use of statistical factor analysis also confirmed these results. Sediments pollution assessment was carried out using geoaccumulation and metal pollution indexes (MPI₈). The results revealed that sediments of Cádiz bay and Sancti Petri channel were uncontaminated with the studied metals.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.     

Use of microbial activity measurements for monitoring RBC biofilms

Fixed biomass technologies, such as rotating biological contactors or biodiscs, have been applied for wastewater depuration both in large and medium–small-sized agglomerations. Biofilm’s composition and microorganism activity are essential parameters for the successful operation and control of these systems. Biofilm’s thickness and total dry weight have been widely used for biofilm’s characterization but, actually, are not sufficient to describe biofilm activity. In fact, biofilm’s activity is not proportional to the quantity of fixed biomass, but increases with the thickness of biofilm up to a determined level called the “active thickness”. Above this level, the diffusion of nutrients through the film becomes a limiting factor. A stable, thin, and active biofilm thus offers numerous advantages in water and wastewater treatment. Different parameters have been used to evaluate biofilm’s activity. The specific oxygen uptake rate, INT-dehydrogenase activity, and the ratio active/total cells have been applied for that purpose. These methods are not only simple and rapid but also sensitive, precise, and representative. The results obtained confirm the potential of the microbial activity measurements studied for an accurate biofilm’s characterization and biomass activity estimation in fundamental research and for the practical operation and control of fixed biomass depuration systems.     

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.     

Total metal levels in crayfish Astacus leptodactylus (Eschscholtz, 1823), and surface sediments in Lake Terkos, Turkey

The aim of this study was to determine the total metal accumulation (aluminium, copper, manganese, lead, cadmium and iron) in different organs and eggs of Astacus leptodactylus (Eschscholtz, 1823) and sediments total metal contents (aluminium, copper, manganese, lead, cadmium, iron, zinc, chromium, nickel) in Lake Terkos. Water and sediment samples were collected from two stations at two different depths (1 and 2 m) of Lake Terkos in May 2008. Crayfish samples were collected by trammel net at the same region. Primary hydrographic conditions, such as temperature (13.6–19.4°C), salinity (0.27–0.34‰), dissolved oxygen (7.04–12.30 mg l^???1) and pH (7.42–8.51), were recorded for each sampling point. Moreover, the total organic carbon (1.65–5.44%) and the total calcium carbonate contents (19.44–41.16%) of sediment samples were determined. According to the Turkish Food Codex (J Zool 26:283–288, 2002), the maximum allowable Pb and Cd levels in crayfish are 0.5 mg/kg wet weight. Accordingly, the Pb and Cd levels determined in A. leptodactylus samples are below this limit. However, when compared with the acceptable metal limits defined by WHO, Australian National Health and Medical Research Council and Ministry of Agriculture in United Kingdom (UK), it is clear that the Cu level is at the limit and the Cd results exceed the limit. When the metal contents in sediment samples from Lake Terkos are examined, it is seen that the Al, Fe, Mn, Ni and Cu contents are lower while Zn, Cr, Cd and Pb contents are higher than the crustal average values. The high values draw attention to the land-based domestic and industrial inputs. Lake Terkos sediments have high enrichment factors (EF) of Zn, Cr, Cd and Pb metals which corroborate this result. The low EFs of Fe, Ni and Cu are due to the natural (terrigeneous) inputs. Additionally, there is no Al, Fe, Ni and Cu metal enrichment in these lake sediments because of the low contamination factor (CF) values. However, it is moderately contaminated by Zn, Cr and Pb, and heavily contaminated by Cd.     

Trace metal concentrations in tissues of two tinamou species in mining areas of Bolivia and their potential as environmental sentinels

Mining has a long history in the Bolivian Andes and has left many tailing piles, from which trace metals may reach surface waters, soils, and biota. The potential of tinamous (Birds: Tinamidae) as sentinels has never been tested before, although their biological and ecological characteristics mean they could well be appropriate bioindicators. We captured 13 and nine individuals of the Ornate Tinamou (Nothoprocta ornata) from two polluted sites (P1 and P2) and 10 and five from control unpolluted sites (NP1 and NP2) and used, for comparative purposes, four specimens bred in captivity. We also captured six specimens of Darwin’s Nothura (Nothura darwinii) from the polluted site, P2. We determined the concentration of As, Cd, Pb, and Sb in feathers, liver, and kidney and conducted histological analyses of liver and kidney. For the Ornate Tinamou, a site effect was found for all trace metals in all tissues, with the highest concentrations at polluted sites. At the P2 site, no differences between the two tinamou species were detected except in some cases where Darwin’s Nothura shows near-double concentrations. In some cases, mean and/or individual values of trace metal concentrations reached toxicity levels at the polluted sites. Thesaurismosis in proximal convoluted renal tubules, probably related to Cd exposure, was observed in 30% of the samples from the P1 site. Significant correlations were observed between all tissues for all trace metals and also for all trace metals in each tissue. Because the species studied are ubiquitous and relatively abundant, we recommend monitoring programs based on feather analysis.     

Pyrolysis of mixtures of sewage sludge and manure: a comparison of the results obtained in the laboratory (semi-pilot) and in a pilot plant

A pilot-scale pyrolysis process was carried out for the treatment of a mixture of two types of waste, sewage sludge and cattle manure, comparing the results with others obtained under laboratory conditions (semi-pilot scale). The aim of this study was to obtain the energetic valorization of the products. Owing to the specific characteristics of the plant, two products were obtained from the process: gas and carbonized solid. As no liquid fraction was obtained, the gas fraction is a greater percentage made up of both condensable and non-condensable compounds, which were obtained separately at the laboratory scale. The pilot plant was designed so that the gases produced by thermolysis were burnt continuously in a combustion chamber, while the carbonized fraction was fed in batches for co-combustion. To determine composition and combustion ability, the gas and solid products from the pilot process were characterized by chromatographic analysis of the gaseous fraction and chemical analysis and programmed-temperature combustion of the carbonized solid. The composition of the combustion gases, rich in light hydrocarbons, and the carbon present in the carbonized fraction enable the energetic valorization of these products. The combustion gases were subjected to a cleaning process and their composition analysed twice: before and after the gas cleaning treatment. The study led to a positive assessment of the possible use of the process products as fuel, provided that the combustion gases are treated. As most of the sulphur and chlorine from the original waste are mainly concentrated in the solid fraction, the use of char as a fuel will depend on the effectiveness of clean-up techniques for combustion gases. During gas cleansing, neutralizing with sodium bicarbonate proved effective, especially for the acidic compounds HCl, HF and SO(2).