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.     

Lettuce plants as bioaccumulators of trace elements in a community of central Italy

A survey, based on the use of vascular plants to describe the distribution of selected elements (21 in total) was performed in 11 sites in the area of Castelfiorentino (Tuscany, Central Italy) differing for land use, from urban to industrial and rural areas. Lettuce plants grown under standardized conditions were positively used as biodeposimeters of airborne trace elements. Washing was found to be highly significant in reducing concentrations of many elements in the samples, suggesting a general surface contamination of leaves. The typical crustal element Al showed good correlations with Co, Fe, Li and V; on the contrary, Zn and Cd were intercorrelated and showed no connection with crustal indicators. Lead was still a relevant environmental presence, as the experiments were carried out before the ban of leaded gasoline. Source apportionment by factor analysis put in evidence a major contribution of crustal materials, followed by man-related activities; a minor role was ascertained for marine aerosol. A comparison was made between analytical data of lettuce plants grown in our experimental sites and a bulk of commercial lettuce purchased at a local supermarket. It should be stressed how Cu concentrations of commercial material were significantly higher than those found in our plants; this is likely caused by phytosanitary treatments.     

Assessment of long-term wastewater irrigation impacts on the soil geochemical properties and the bioaccumulation of heavy metals to the agricultural products

An extensive field survey was employed for assessing the impacts of long-term wastewater irrigation of forage crops and orange orchards in three suburban agricultural areas in Cyprus (areas I, II, and III), as compared to rainfed agriculture, on the soil geochemical properties and the bioaccumulation of heavy metals (Zn, Ni, Mn, Cu, Co) to the agricultural products. Both ryegrass fields and orange orchards in areas I and II were continuously wastewater irrigated for 10 years, whereas clover fields in area III for 0.5, 4, and 8 years. The results revealed that wastewater reuse for irrigation caused a slight increase in soil salinity and Cl^? content in areas I and II, and a remarkable increase, having strong correlation with the period in which wastewater irrigation was practiced, in area III. Soil salinization in area III was due to the high electrical conductivity (EC) of the wastewater applied for irrigation, attributed to the influx of seawater to the sewage collection network in area III. In addition, the wastewater irrigation practice resulted in a slight decrease of the soil pH values in area III, while a subtle impact was identified regarding the CaCO₃, Fe, and heavy metal content in the three areas surveyed. The heavy metal content quantified in the forage plants’ above-ground parts was below the critical levels of phytotoxicity and the maximum acceptable concentration in dairy feed, whereas heavy metals quantified in orange fruit pulp were below the maximum permissible levels (MPLs). Heavy metal phytoavailability was confined due to soil properties (high pH and clay content), as evidenced by the calculated low transfer factor (TF).     

Epiphyte toxicity bioassay for ecotoxicological and coastal monitoring

Marine epibionts are organisms that grow on submerged surfaces. Those found on seagrass leaves are especially important because of their interactions with the plants, their contribution to primary production in these ecosystems, and their role as food source for heterotrophic fauna. Given the relative lack of ecotoxicological studies on epibionts, the aim of this study is to evaluate the effect of environmental pollution on epiphytes experimentally attached to artificial devices (mimes) consisting of thermally-sealed silicone tubes supported on bamboo sticks that mimic the morphology of seagrasses and serve as an anchor surface for marine epibionts. Mimes were installed on the sea floor in subtidal waters of the Rio San Pedro (Cádiz), collected after 28 days, and incubated in the laboratory with environmental concentrations of atrazine (herbicide), Irgarol (anti-fouling substance), and copper. Tube-dwelling diatoms formed the major component of the epiphyte community. Average surface covering, chlorophyll, and biomass content did not show significant differences between controls and treatments. The glutathione peroxidase activity increased significantly with 4 μg L^?1 of atrazine and 5 μg L^?1 of copper. This enzymatic activity increase seems to be sufficient to prevent oxidative cellular damage by removing reactive oxygen substances produced by oxidative stress; in addition to this enzyme, there might be other antioxidant enzymes which have not been measured in this study, that have also protected the organism from oxidative damage. Thus, the measurement of antioxidant enzymatic activity in epiphytes may be a useful toxicity indicator for coastal biomonitoring.     

Mesophilic and thermophilic anaerobic biodegradability of water hyacinth pre-treated at 80 °C

Water hyacinth (Eichornia crassipes) is a fast growing aquatic plant which causes environmental problems in continental water bodies. Harvesting and handling this plant becomes an issue, and focus has been put on the research of treatment alternatives. Amongst others, energy production through biomethanation has been proposed. The aim of this study was to assess the anaerobic biodegradability of water hyacinth under mesophilic and thermophilic conditions. The effect of a thermal sludge pre-treatment at 80 °C was also evaluated. To this end, anaerobic biodegradability tests were carried out at 35 °C and 55 °C, with raw and pre-treated water hyacinth. According to the results, the thermal pre-treatment enhanced the solubilisation of water hyacinth (i.e. increase in the soluble to total chemical oxygen demand (COD)) from 4% to 12% after 30 min. However, no significant effect was observed on the methane yields (150–190 L CH₄/kg volatile solids). Initial methane production rates for thermophilic treatments were two fold those of mesophilic ones (6–6.5 L vs. 3–3.5 L CH₄/kg COD·day). Thus, higher methane production rates might be expected from thermophilic reactors working at short retention times. The study of longer low temperature pre-treatments or pre-treatments at elevated temperatures coupled to thermophilic reactors should be considered in the future.     

Soil Phosphorus Concentrations in Dane County,Wisconsin, USA: An Evaluation of the Urban–Rural Gradient Paradigm

Understanding the magnitude and location of soil phosphorus (P) accumulation in watersheds is a critical step toward managing runoff of this pollutant to aquatic ecosystems. Here, I examine the usefulness of urban–rural gradients, an emerging experimental design in urban ecology, for predicting extractable soil P concentrations across a rapidly urbanizing agricultural watershed in southern Wisconsin. I compare several measures of an urban–rural gradient to predictors of soil P such as soil type, slope, topography, land use, land cover, and fertilizer and manure use. Most of the factors that were expected to drive differences in soil P concentrations were found to be poor predictors of Bray-1 (extractable) soil P, which ranged from 4 to 660 ppm; while there were several significant relationships, most explained only a small proportion of the variation. A multiple linear regression model captured approximately 37% of the variation in the data using the urban–rural gradient, topography, land use, land cover, manure use, and soil type as predictors. There was a significant relationship between Bray-1 P concentration and each of the urban–rural gradients, but these relationships explained only between 2.6% and 3.3% of the variation in P concentrations. Extractable P concentration in soils, unlike some other ecosystem properties, is not well predicted by urban–rural gradients.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in River Po sediments

The River Po is the main Italian river draining one of the most populated and industrialised regions in Italy. As part of a monitoring project to assess environmental quality in the River Po, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in bottom sediments collected along the whole course of the river, from the spring to the delta, downstream from the confluence of its main tributaries. The aim was to investigate the level of contamination in the main Italian river and the contribution of contaminant loads from the subbasins. Composite sediment samples were collected in summer and winter surveys in low-flow water conditions and analysed by HRGC-HRMS for PCDD and PCDF homologue groups and for the 2,3,7,8-substituted congeners. The spatial trend observed in the Po River for PCDD and PCDF concentrations varied depending on the load of contaminants received from the tributaries and the processes of sedimentation. The sum of PCDD and PCDF concentrations, and the toxic equivalent content, ranged from 121 to 814 and from 1.3 to 13 ng/kg dry weight sediment, respectively. These levels of contamination seem lower than in the sediments of rivers draining highly industrialised areas. The PCDD and PCDF homologue profiles in all the samples were very similar, suggesting a common source of this contamination in the River Po. Principal component analysis suggested that widespread sources, such as urban runoff and domestic wastewaters, are probably the main cause of these levels of PCDDs and PCDFs.