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.     

Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.     

Soil subsampling in environmental sciences: the role of granulometry

Uncertainty associated to analytical results is an issue of major interest for the whole analytical community. A large effort has been made to improve analytical techniques and procedures aimed to achieve a well characterized uncertainty associated with analysis. However, it is becoming increasingly recognised that uncertainty deriving from sampling and subsampling can even dominate the global uncertainty budget. A study on subsampling activities on different soil typologies has been performed by granulometry determinations. The differences between sieving methodologies based on both wet and dry mode have been studied. Subsampling is approached by replicated measurements providing a quantitative assessment of the distribution heterogeneity, a suitable method validation scheme and an empirical determination of uncertainty.     

The comparison of heavy metal accumulation ratios of some fish species in Enne Dame Lake (Kütahya/Turkey)

The metal accumulation levels for muscle, skin, gill, liver and intestine tissues of some Cyprinidae species (Carassius carassius, Condrostoma nasus, Leuciscus cephalus and Alburnus alburnus) in Enne Dame Lake (Kütahya/Turkey), which is mostly fed by hot spring waters, were investigated. Analyses were performed for copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), cobalt (Co), magnesium (Mg), nickel (Ni), chrome (Cr) and boron (B) using inductively coupled plasma-optic emission spectroscopy (ICP-OES), and cadmium (Cd) using atomic absorption spectrophotometer (AAS) utilizing microwave digestion techniques. The concentrations of the heavy metals found in the fish varied in the follow ing ranges: Cu: < DL-7.04, Zn: 6.96-357.25, Mn: < DL-20.70, Ni: < DL-6.21, Fe: 9.62-2500.33, Cr: < DL-1.74, Co: < DL-0.54, Cd: 0.01-0.27 and Mg: 197.44-904.90 mg/kg wet weight. While B had the second highest concentration in the water of the lake, it was not encountered in any tissue of the investigated species. In all tissues and the species, While the bioaccumulation factors (BAFs) of Mn, Zn, Fe and Cu were remarkably high, the BAFs of Mg, Cr, Co, and B were also fairly low or none. Although the heavy metal accumulation levels for the muscle were generally lower than other tissues, there were some exceptions. Cd level in the muscle of C. carassius was higher than the permissible limit stated by Turkish legislation, FAO and WHO. The mean metal amounts for all the investigated tissues and species are statistically compared and discussed in this study.     

Analysis of some heavy metals in the riverine water, sediments and fish from river Ganges at Allahabad

The river Ganges has been one of the major recipients of industrial effluents in India. The present paper deals with the study related to occurrence and bioaccumulation of heavy metals (Cu, Cr, Cd, Pb, Zn) in the riverine water, sediment, and the muscles of two cat fish species, Channa punctatus (C. punctatus) and Aorichthys aor (A. aor) procured from the river Ganges at Allahabad. The data obtained after water analysis reflected the order of occurrence of heavy metals to be Zn > Pb > Cu > Cr > Cd, respectively. The analysis of heavy metals in sediment indicated that among the five heavy metals tested; Zn was maximally accumulated followed by Pb, Cr, Cu and Cd. The trend of heavy metals accumulation in fish muscles was found to be similar to that observed in sediment and water such as Zn > Pb > Cu > Cr > Cd. Data indicated that Zn accumulated maximally in the sediment as well as muscles of both of the fish species in comparison to other metals.     

Effects of soil amendments on the bioavailability of heavy metals from zinc mine tailings

A study was conducted to test the effects of soil amendments on the bioavailability of heavy metals in a zinc mine tailings containing soil to plants, using the Indian mustard plant (Brassica juncea) as a test organism. Zinc mine tailing containing soil was amended with humus soil (HS) and phosphatic clay (PC). The zinc mine tailing containing soil (ZMTS) was characterized for heavy metals. It was mixed with PC and HS, and four mixtures were prepared. The first mixture contained ZMTS, and served as a control. The second mixture contained ZMTS and PC in the ratio of 1:1 (w/w). The third mixture contained ZMTS and HS in the ratio of 1:1(w/w). The fourth mixture containing ZMTS, PC and HS in the ratio of (2:1:1) (w/w). A slight increase in the bioavailability of Pb, Cu, Zn and Mn was noticed with increase in the incubation time from 14 to 42 days. The bioavailability of Pb, Cu, Zn and Mn from ZMTS alone in Brassica plant was in the range of 94-99% up to 42 days. Addition of PC and HS to the ZMTS soil reduced the bioavailabilities of Pb by (15%), of Cu by (20%), of Zn by (20%) and of Mn by (25%) in the mustard plant. The data showed that PC in the presence of HS had a high affinity for the heavy metals in the order of Pb, Cu, Zn and Mn.     

The relationship between whole effluent toxicity (WET) and chemical-based effluent quality assessment in Vojvodina (Serbia)

The relationship between whole effluent toxicity (WET) and chemical-based effluent quality assessment across a range of effluent types was examined for the first time in Serbia. WET was determined by Daphnia magna acute tests, while chemical-based toxicity was taken as theoretical for concentrations of priority chemicals and effluent quality assessment based on the valid Serbian regulations. A poor correlation was found between WET and chemical-based effluent quality assessment: positive toxicity tests were found, in general, in cases where samples satisfied the requirements of mandatory effluent monitoring. Statistically insignificant correlation between the predicted and observed toxicity indicated that the presence of priority substances accounted to the overall toxicity only to a certain degree, most probably due to a rather short list of priority pollutants regularly analysed in effluents. Current monitoring requirements neglect hazards that derive from potentially present toxicants and unpredictable toxicity of complex mixtures, which led to poor correlation between the WET and chemical-based results in this study.     

Statistical approaches for hydrogeochemical characterization of groundwater in West Delhi, India

Parametric statistical approaches, correlations and multiple linear regressions were used to develop models for the interpretation of hydrogeochemical parameters in the Western part of Delhi state, India. The hydrogeochemical parameters indicated that the groundwater quality is not safe for consumption. The water is moderately saline and the salinity level is increasing over time. There is also the problem of nitrate pollution. The correlation between electrical conductivity (EC) and other water quality parameters except potassium (K(+)), nitrate (NO(3)(-)) and bicarbonate (HCO(3)(-)) is significantly positive and Ca(++)+ Mg(++)/Na(+)+ K(+) is significantly negative. In predicting EC, the multiple R(2) values of 0.996 and 0.985 indicate that 99.6% and 98.5% variability in the observed EC could be ascribed to the combined effect of Na(+), HCO(3)(-), Cl(-), SO(4)(--), NO(3)(-) and Ca(++)+ Mg(++) for the year of 2005 and 2006 respectively. Out of 99.6% of the variability in EC in 2005, 51.2% was due to Cl(-) alone, and 8.5%, 12.5%, 6.1%, 14.7% and 6.7% were due to Na(+), HCO(3)(-), SO(4)(--), NO(3)(-) and Ca(++) + Mg(++). Similarly in 2006, out of 98.5% of the variability in EC, 48.5% was due to Cl(-) alone, and 10.4%, 12.7%, 5.3%, 17.2% and 4.4% were due to Na(+), HCO(3)(-), SO(4)(--), NO(3)(-) and Ca(++)+ Mg(++). The analysis shows that a good correlation exists between EC, Cl(-) and SO(4)(--) either individually or in combination with other ions and the multiple regression models can predict EC at 5% level of significance.     

Identification and quantification of microcystins from a Nostoc muscorum bloom occurring in Oukaïmeden River (High-Atlas mountains of Marrakech, Morocco)

Atmospheric BTEX [benzene, toluene, ethylbenzene, o-xylene and (m + p)-xylene] concentrations have been determined in the Naples metropolitan area (NMA) and in two suburban areas located on the north within about 25 km, during 2006. The pollutants were collected by passive samplers (24-h samplings), and analysed by GC-MS. In all the areas analysed the average atmospheric benzene concentrations were higher than the limit value fixed by the European Union for 2010 and in NMA the average concentration (9.8 microg m(-3)) also exceeded the limit fixed for 2006. High linear correlation coefficients between the average daily concentrations of the different BTEX are indicative of a single major source, most likely the vehicular traffic. The temporal and spatial distribution of BTEX relative concentrations suggest that massive emissions in NMA negatively affect the quality of the air in northern suburban areas, prevalently during the hottest months of the year, probably due to transport by local seasonal winds. The ratios between BTEX daily concentrations showed a clear dependence on the intensity of solar actinic flow, indicating a major role of photochemical processes in the air cleaning from these volatile organic pollutants.     

Disturbance of Dabao highway construction on plant species and soil nutrients in Longitudinal Range Gorge Region (LRGR) of Southwestern China

The disturbance of highway construction upon surrounding vulnerable ecosystems is a common threat in the Longitudinal Range Gorge Region of southwestern China. We evaluated the disturbance of highway on plant species richness and diversity and soil nutrients from adjacent to the highway to 300 m upslope and 100 m downslope in forests and grasslands by setting 12 belt transects in forests and grasslands (six belt transects and six control belt transects, respectively). The results showed that there were some significant variances in belt transects with respective control belt transects for species richness and diversity in both forests and grasslands. Species richness and diversity of trees were lower within a 50-m distance from the highway and more noticeable on the downslope portion. Species richness and diversity of shrubs and herbs appeared higher near highway edge. Both species richness and diversity of herbs were similar in forests. In addition, exotic species, such as Eupatorium adenophorum, were further from the road and more widely dispersed in grasslands. Soil nutrients except total potassium (TK) were lower in the downslope area adjacent to highway edge and showed a significant increase with increasing distance from the highway in both forests and grasslands. This indicates that grasslands acted as microhabitats for exotic species and are more easily to be invaded than forests, especially if disturbed. Once destroyed, plant species and soil nutrients will require a significant amount of time to be restored to control levels. This work illustrates that the effects extend considerably to distances upslope and downslope from the construction site. Given that these changes occurred relatively quickly, the study suggests that the environmental "footprint" grows far beyond the road and adjacent zone of disruption.