The use of XAD-resins for the detection of mutagenic activity in water: I. Studies with surface water

A study of the effects of different XAD-resins, bed volume, flow rate, pH and type of eluent on the extraction of organic mutagens from surface water is presented. XAD-4/8 is as effective as XAD-2 in concentrating organic mutagens from surface water and dimethylsulfoxide (DMSO) is as efficient as acetone in eluting the adsorbed organic mutagens. The latter allows direct testing up to 0.5 ml of DMSO concentrate in the Ames test. Variation of the pH of the water after passing the XAD-4/8, followed by readsorption, shows that the majority of the mutagenic activity due to dissolved organics is adsorbed at neutral pH. Only a minor fraction is readsorbed at pH 3. Further a XAD-4/8 concentrate and a similar concentrate prepared by freeze drying gives similar mutagenic activity. This indicates that many of the organic mutagens are recovered in the XAD-4/8 concentrate.It is concluded that adsorption on XAD-4/8, followed by direct testing of the DMSO eluates in the Ames test, presents a rapid and relatively simple way to detect low concentrations of organic mutagens in surface water. The general suitability of the method is shown for different types of surface water.     

Dissipation of DDT in a heavily contaminated soil in Mato Grosso, Brazil

After the prohibition of organochlorine-pesticide use in Brazil for controlling insect vector diseases, Mato Grosso State gathered the exceeding DDT and stored it irregularly in an open air area that belongs to the National Health Foundation, causing soil contamination. This study aimed to evaluate the contamination level and dissipation of p,p'-DDT and p,p'-DDE in this area. For that, surface soil samples were collected on 19 September 2000, 15 December 2000, 4 April 2001 and soil samples 30-40 cm; 60-70 cm and 90-100 cm deep were taken from five points in the studied area on 17 July 2001. The contaminants were determined by a small scale method which consists on extraction and clean-up steps combined into one step by transferring soil samples mixed with neutral alumina to a chromatographic column prepacked with neutral alumina and elution with hexane:dichloromethane (7:3 v:v). The eluate was concentrated and the analytes were quantified by gas chromatography with an electron-capture detector. p,p'-DDT at surface soil ranged from 3,800 to 7,300 mg kg(-1). 30-40 cm deep soil sample concentrations varied from 0.036 to 440 mg kg(-1) while 90-100 cm deep samples varied from 0.069 to 180 mg kg(-1). Volatilization is probably the main dissipation process. The p,p'-DDT is moving slowly downward in the soil profile, however, the levels of this contaminant are high enough to present risk to underground waters.     

Modeling lead bioavailability and bioaccumulation by Lumbriculus variegatus using artificial particles. Potential use in chemical remediation processes

Artificial particles, specifically a diverse selection of chromatographical resins, have been recommended and used as a useful experimental model to predict the bioavailability and bioaccumulation of sediment-bound organic chemicals. In this work the same experimental model was adopted to investigate the bioavailability and bioaccumulation of lead by the freshwater oligochaete Lumbriculus variegatus. Particle-water partition coefficients were also determined. Sand particles and the anionic exchange resin promoted a similar uptake and bioaccumulation of lead. Instead, in the presence of the cationic exchanger the metal was not detected in the animals. For neutral particles, the uptake and accumulation depended on the chemistry of the functional groups at the active sites. In addition, a significant negative correlation was found between bioaccumulation and the particle-water partition coefficients. These studies may help to develop alternative methods for chemical remediation of lead-contaminated aquatic systems.     

Effect of chromium on the fatty acid composition of two strains of Euglena gracilis

The effect of hexavalent chromium on fatty acid composition was studied in two strains of Euglena gracilis; UTEX 753 (from the Culture Collection of Algae of Texas University, USA) and MAT (isolated from a highly polluted River). Both were grown in photoauxotrophic and photoheterotrophic conditions and exposed to two metal concentrations, one below and one above IC50. The high malondialdehyde (MDA) levels (3 to 7-fold) obtained with chromium concentration above IC50, suggested the existence of metal-induced lipid peroxidation. Total lipid content increased only with concentration below IC50, whereas it was inhibited by higher metal concentration. Photoheterotrophic control strains exhibited a significantly higher proportion of saturated and polyunsaturated fatty acids. Polyunsaturated acids were most affected by chromium, especially those related to chloroplast structures. Ultra-structure studies showed clear thylakoid disorganization in all treated cells. The results indicate that hexavalent chromium affects levels of fatty acids, especially those related to photosynthetic activity.     

Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Soil temperature effect in calculating attenuation and retardation factors

The effect of annual variation of daily average soil temperature, at different depths, in calculating pesticides ranking indexes retardation factor and attenuation factor is presented. The retardation factor and attenuation factor are two site-specific pesticide numbers, frequently used as screening indicator indexes for pesticide groundwater contamination potential. Generally, in the calculation of these two factors are not included the soil temperature effect on the parameters involved in its calculation. It is well known that the soil temperature affects the pesticide degradation rate, water-air partition coefficient and water-soil partition coefficient. These three parameters are components of the retardation factor and attenuation factor and contribute to determine the pesticide behavior in the environment. The Arrhenius equation, van't Hoff equation and Clausius-Clapeyron equation are used in this work for estimating the soil temperature effect on the pesticide degradation rate, water-air partition coefficient and soil-water partition coefficient, respectively. These dependence relationships, between results of calculating attenuation and retardation factors and the soil temperature at different depths, can aid to understand the potential pesticide groundwater contamination on different weather conditions. Numerical results will be presented with pesticides atrazine and lindane in a soil profile with 20 degrees C constant temperature, minimum and maximum surface temperatures varying and spreading in the soil profile between -5 and 30 degrees C and between 15 and 45 degrees C.     

Risk estimation to human health caused by the mercury content of Sushi and Sashimi sold in Japanese restaurants in Brazil

Although fish is a healthy alternative for meat, it can be a vehicle for mercury (Hg), including in its most toxic organic form, methylmercury (MeHg). The objective of the present study was to estimate the risk to human health caused by the consumption of sushi and sashimi as commercialized by Japanese food restaurants in the city of Campinas (SP, Brazil). The total Hg content was determined by atomic absorption spectrometry with thermal decomposition and amalgamation, and the MeHg content calculated considering that 90% of the total Hg is in the organic form. The health risk was estimated from the values for the provisional tolerable weekly ingestion (PTWI) by both adults and children. The mean concentrations for total Hg were: 147.99, 6.13, and 3.42 µg kg^?1 in the tuna, kani, and salmon sushi samples, respectively, and 589.09, 85.09, and 11.38 µg kg^?1 in the tuna, octopus and salmon sashimi samples, respectively. The tuna samples showed the highest Hg concentrations. One portion of tuna sashimi exceeded the PTWI value for MeHg established for children and adults. The estimate of risk for human health indicated that the level of toxicity depended on the type of fish and size of the portion consumed.     

Pesticide residue removal in classic domestic processing of tomato and its effects on product quality

This study was undertaken to evaluate the effectiveness of several household practices (washing with water or acidic, alkaline, and oxidizing solutions, and peeling) in minimizing pesticide residue contamination of tomatoes, as well as the impact on the quality of the treated fruit. Tests were performed using two systemic fungicides (azoxystrobin and difenoconazole) and one contact fungicide (chlorothalonil). Solid-liquid extraction with low temperature partition (SLE/LTP) and liquid-liquid extraction with low temperature partition (LLE/LTP) were used to prepare the samples for pesticides determination by gas chromatography. Washing the tomatoes with water removed approximately 44% of chlorothalonil, 26% of difenoconazole, and 17% of azoxystrobin. Sodium bicarbonate (5%) and acetic acid (5%) solutions were more efficient, removing between 32 and 83% of the residues, while peeling removed from 68 to 88% of the pesticides. The washing solutions altered some fruit quality parameters, including acidity and chroma, and also caused weight loss. Acetic acid (0.15 and 5%) and hypochlorite (1%) solutions had the greatest effect on these parameters.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Bringing together raptor collections in Europe for contaminant research and monitoring in relation to chemicals regulations

Raptors are good sentinels of environmental contamination and there is good capability for raptor biomonitoring in Europe. Raptor biomonitoring can benefit from natural history museums (NHMs), environmental specimen banks (ESBs) and other collections (e.g. specialist raptor specimen collections). Europe’s NHMs, ESBs and other collections hold large numbers of raptor specimens and samples, covering long periods of time. These collections are potentially a valuable resource for contaminant studies over time and space. There are strong needs to monitor contaminants in the environment to support EU and national chemical management. However, data on raptor specimens in NHMs, ESBs and other collections are dispersed, few are digitised, and they are thus not easy to access. Specimen coverage is patchy in terms of species, space and time. Contaminant research with raptors would be facilitated by creating a framework to link relevant collections, digitising all collections, developing a searchable meta-database covering all existing collections, making them more visible and accessible for contaminant research. This would also help identify gaps in coverage and stimulate specimen collection to fill gaps in support of prioritised contaminant monitoring. Collections can further support raptor biomonitoring by making samples available for analysis on request.