Preparation of 2-mercaptobenzothiazole-derivatized mesoporous silica and removal of Hg(ii) from aqueous solution

Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second reaction a multifunctionalized N,S donor compound (2-mercaptobenzothiazol) was incorporated to obtain the functionalized silicas denoted as MBT-SBA-15-Het and MBT-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MBT-SBA-15-Hom or MBT-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions at pH 6 contaminated with Hg(ii) at room temperature. Results obtained indicate that mercury adsorption was higher in the mesoporus silicas prepared by the homogeneous method, and the maximum adsorption value (0.24 +/- 0.02 mmol Hg(ii) g(-1)) was obtained for MBT-SBA-15-Hom. The chemically stability in acid medium of the functionalized silicas, possibility its regeneration washing with concentrate HCl, resulting in the reuse of the adsorbent material for several cycles.     

Status of the Riparian Ecosystem in the Upper San Pedro River, Arizona: Application of an Assessment Model

A portion of Arizona’s San Pedro River is managed as a National Riparian Conservation Area but is potentially affected by ground-water withdrawals beyond the conservation area borders. We applied an assessment model to the Conservation Area as a basis for monitoring long-term changes in riparian ecosystem condition resulting from changes in river water availability, and collected multi-year data on a subset of the most sensitive bioindicators. The assessment model is based on nine vegetation bioindicators that are sensitive to changes in surface water or ground water. Site index scores allow for placement into one of three condition classes, each reflecting particular ranges for site hydrology and vegetation structure. We collected the bioindicator data at 26 sites distributed among 14 reaches that had similar stream flow hydrology (spatial flow intermittency) and geomorphology (channel sinuosity, flood-plain width). Overall, 39% of the riparian corridor fell within condition class 3 (the wettest condition), 55% in condition class 2, and 6% in the driest condition class. Condition class 3 reaches have high cover of herbaceous wetland plants (e.g., Juncus and Schoenoplectus spp.) along the perennial stream channel and dense, multi-aged Populus-Salix woodlands in the flood plain, sustained by shallow ground water in the stream alluvium. In condition class 2, intermittent stream flows result in low cover of streamside wetland herbs, but Populus-Salix remain abundant in the flood plain. Perennial wetland plants are absent from condition class 1, reflecting highly intermittent stream flows; the flood plain is vegetated by Tamarixa small tree that tolerates the deep and fluctuating ground water levels that typify this reach type. Abundance of herbaceous wetland plants and growth rate of Salix gooddingii varied between years with different stream flow rates, indicating utility of these measures for tracking short-term responses to hydrologic change. Repeat measurement of all bioindicators will indicate long-term trends in hydro-vegetational condition.     

SAOZ measurements of NO2 at Aberystwyth

We present in this paper fifteen years' measurements, from March 1991 to September 2005, of stratospheric NO2 vertical columns measured by a SAOZ zenith-sky visible spectrometer. The instrument spent most of its time at Aberystwyth, Wales, with occasional excursions to other locations. The data have been analysed with the WinDOAS analysis program with low-temperature high-resolution NO2 cross-sections and fitting a slit function to each spectrum. Because of a change in detector in May 1998 there is some uncertainty about the relative changes before and after this date, which are partially constrained by the results of an intercomparison exercise. However, the effect of the Mt Pinatubo aerosol cloud is very evident in the data from 1991-94, with a decrease of 10% in NO2 in the summer of 1992 (the SAOZ was located in Lerwick, Scotland during the winter of 1991-92 and observed very low NO2 values but these cannot be directly compared to the Aberystwyth data). To focus more on interannual and long-term variations in NO2, a seasonal variation comprising an annual and semi-annual component was fitted to the morning and evening twilight separately from 1995 to the present. This fit yielded average NO2 columns of 4.08 x 10(15) cm(-2) and 2.68 x 10(15) cm(-2) for the evening and morning twilight, respectively, with a corresponding annual amplitude of +/-2.08 x 10(15) cm(-2) and +/-1.50 x 10(15) cm(-2). Departures from the fitted curve show a trend of 6% per decade, consistent with that reported elsewhere, for the period 1998-2003, but in the past two years a distinct interannual variation of amplitude of approximately 8% has emerged.     

Combining Logistic Models with Multivariate Methods for the Rapid Biological Assessment of Rivers Using Macroinvertebrates

This work represents an attempt to define a simple method to classify the relative degree of disturbance of sites in lotic systems on the basis of comparison of their faunistic composition with reference sites. Two ecotypes were selected in northern Portugal where benthic invertebrates were sampled in reaches with different levels of contamination. As a first stage, previous Geographic Information System information was used to define reference sites in each ecotype. Afterwards, multivariate techniques and non linear estimation models were combined to assess biological quality. This method allowed us to quantify sites according to increasing levels of contamination, after the probabilities of occurrence of taxa along a gradient of contamination taking into account the reference condition. The results suggest that this method is sensitive to organic pollution, easy to interpret, namely the species tolerance, and could be a good framework to establish regional rankings depending on the ecological impact of river sites.     

The use of bioaccumulation, biomarkers and histopathology diseases in shape Procambarus clarkii to establish bioavailability of Cd and Zn after a mining spill

Individuals of the crayfish Procambarus clarkii (males and females) were exposed simultaneously to cadmium and zinc during 21 days. Exposure concentrations were those determined at the Guadiamar river after the Aznalcóllar mining spill (SW, Spain): 10 and 30 μg L⁻¹ of cadmium and 1000 and 3000 μg L⁻¹ of zinc. Three biomarkers (MT: metallothioneins like proteins, VTG: vitellogenin/vitellin like proteins and histopathology) together with heavy metal bioaccumulation were determined in soft tissues of male and female P. clarkii. At the concentrations tested, increasing cadmium exposure resulted in increasing cadmium bioaccumulation and increasing subletal effects (induction of MT, VTG and histopathological damage in tissues). Nevertheless, although increasing zinc exposure showed increasing VTG induction and histopathological damages, not a positive relationship was determined with MT induction. Concerning to responses determined in male and female crayfishes only differences were found between sexes at the highest cadmium exposure concentration related to bioaccumulation in hepatopancreas tissues. Biomarkers responses to heavy metal contamination in this crayfish, even VTG induction not before tested in heavy metal contamination assessment in crustaceans resulted potential tools for the monitoring of heavy metal environmental contamination.     

Trace Element Concentrations and Bioindicator Responses in Tree Swallows from Northwestern Minnesota

Extremely high concentrations of cadmium (3.5 μg/g dry wgt.) and elevated concentrations of chromium (>10 μg/g dry wgt.) and mercury (1.6 μg/g dry wgt.) were reported in waterbird tissues at Agassiz National Wildlife Refuge in northwestern Minnesota in 1994. Tree swallows (Tachycineta bicolor) were studied during 1998–2001 at three drainages into the Refuge, two pools on the Refuge, and at a nearby reference location to document whether high levels of contaminants were still present, and if so to quantify the source and severity of the contamination. Trace elements were measured in tree swallow eggs, livers, and diet. Reproductive success and bioindicator responses were monitored. In 2000, water was drawn down on Agassiz Pool, one of the main pools on the Refuge. This presented an opportunity to evaluate the response of trace element concentrations in the diet and tissues of tree swallows after reflooding. High concentrations of trace elements were not detected in swallow tissues, nor were there differences among locations. Less than 20% of swallow samples had detectable concentrations of cadmium or chromium. Mercury concentrations were low and averaged <0.25 μg/g dry wgt. in swallow tissues. Trace elements, including mercury, did not increase in tree swallows following the 2000 drawdown at Agassiz Pool. Hatching success and survival of nestlings to 12 days-of-age for tree swallows on the Refuge were similar to the national average and consistent with background trace element concentrations. Bioindicator measurements were within the normal ranges as well.     

Comparative Metal Distribution in Hair of Pakistani and Libyan Population and Source Identification by Multivariate Analysis

Using nitric acid-perchloric acid wet digestion based FAAS method ten selected metals (Cd, Co, Cr, Fe, K, Mn, Na, Ni, Pb and Zn) were determined in the scalp hair of male Pakistani and Libyan donors (n = 62), between 3–54 years age and residing in typical urban areas. The study was taken up to identify sources of metal distribution in two diverse population segments exposed to different environments. Sodium emerged with the highest mean hair concentration of 511.0 μg/g and 496.9 μg/g for Libyan and Pakistani donors respectively, followed by K, at 266.2 μg/g and 242.4 μg/g for the two donor categories. Cadmium showed the lowest mean hair concentration for both Pakistani (0.380 μg/g) and Libyan (0.530 μg/g) donors. Levels of Na, K, Pb, Cr and Cd were higher in hair of Libyan donors compared with Pakistani counterparts which showed higher comparative levels of Zn, Fe, Co, Ni and Mn. Strong metal-to-metal correlations were found between Na–K (r = 0.638) and Cd–Co (r = 0.574) for Pakistani donors, while for Libyan donors, Na–K (r = 0.680) and Fe–Mn (r = 0.624) correlations emerged as strongly significant. Only K was found to have a strong positive correlation (r = 0.611) with age for Pakistani donors while this correlation was significantly negative (r = −0.500) for Libyan donors, probably arising from individual food habits. Other metals showed no viable relationship with age. Principal Component Analysis (PCA) and Cluster Analysis (CA) of the data evidenced food, industrial emissions and automobile emissions as possible sources of metal distribution. The results of the present study are compared with those reported for subjects from other regions of the world.     

A Characterization of Selected Endocrine Disruptor Compounds in a Portuguese Wastewater Treatment Plant

Anthropogenic compounds that are able to disrupt the endocrine system of wildlife species are a major cause for concern and have led to a demand for new screening methods. The identification and quantification of endocrine disruptor compounds at wastewater treatment plant is of major interest to assess the endocrine activity of wastewater treatment plant discharges into the environment. This study consists of a preliminary survey of concentrations of previously selected endocrine disruptor compounds, undertaken to establish environmental concentrations and to support a biological program assay exposing freshwater fish to them. Selected endocrine disrupting chemicals (APEs, bisphenol A and 17 β-estradiol) were measured in samples from a wastewater treatment plant located in Lisbon (Portugal), using recent commercial enzyme-linked immunosorbent assay kits and also LC-MS/MS. The results show that the wastewater treatment plant treatment process is efficient on the removal of target endocrine disruptor compounds. However, environmentally significant concentrations are still present in the treated effluent. The results also show that enzyme-linked immunosorbent assay kit is suitable for routine analysis of the selected compounds. The results are also useful since the wastewater treatment plant is located in a Mediterranean region, which results in an effluent with its own characteristics.     

Little Egrets (Egretta Garzetta) and Trace-Metal Contamination in Wetlands of China

The rapidly developing Asian countries may face threatening environmental contamination, that however remains largely unassessed. We studied persistent trace elements in three wetlands, Poyang Lake, relatively unpolluted, and Tai Lake, and Pearl River Delta, selected as hotspots of pollution in Central China. We adopted as indicator the Little Egret, a widespread colonial waterbird, and during 1999 and 2000 we collected and analysed the same samples as for a parallel study we conducted in Pakistan, e.g. eggs, body feathers of chicks, prey spontaneously regurgitated by the chicks, and sediments at the areas most used by foraging egrets. The levels of trace-metals at our three study areas were similar, or within the range, of those found in the few other studies for East Asia, with few exceptions. The concentrations of the various elements were below the threshold that may affect the survival or reproduction of the birds, and even the highest concentrations relative to background, i.e. Se in eggs, and Hg in feathers at Pearl Delta, do not pose toxic hazards. In sediments, the levels of trace elements were lower than the critical levels assumed for contaminated soil, except for alarming high levels of As at Poyang. These results do not confirm our expectation, that Poyang was relatively uncontaminated, while Tai and Pearl were polluted. Although trace metal concentration differed significantly among the three study areas, these differences were minor and were not consistent among elements and samples. The bioaccumulation ratios from sediments through prey, feather and egg, were consistent with our previous findings for Pakistan. Only Hg exhibited high bioaccumulation, while Se and Zn had low accumulation, and the other elements no accumulation. This reasserts that feathers of predators such as egrets, may be more sensitive indicators of environmental contamination for the elements subject to bioaccumulation, whereas the sediments or the organisms low in the food chain are better indicators for the other elements.     

Fractionation and Sequential Extraction of Heavy Metals in the Soil of Scrapyard of Discarded Vehicles

Chemical and physical size fractionation of heavy metals were carried out on 20 soil samples from the scrap yard area. Tessier method was used in sequential extraction. Cadmium showed the highest levels among the other elements studied in the exchangeable fraction (about 33%), while other elements showed low levels in this fraction (≥1%). Lead and manganese were mostly found in the Fe–Mn oxide fraction, zinc and iron were mostly in residual fraction, while copper was mostly found in the organic fraction of the soil. Soil samples were size-fractionated into four sizes: 1000–500, 500–125, 125–53, and less than 53 μm. The highest levels of Fe, Cu, Pb, Mn, and Cd were found in the medium fraction (500–125 μm), while zinc showed its highest levels in the fine fraction (125–53 μm). The order of heavy metal load in the size fractions was found to be medium > fine > coarse > silt for Fe, Mn, Cu, Pb, and Cd, where it was found as fine > medium > coarse > silt for zinc.