Kinetics of carbosulfan hydrolysis to carbofuran and the subsequent degradation of this last compound in irrigated rice fields

The objectives of this work were estimate the reaction rates of hydrolysis of carbosulfan to carbofuran and subsequent degradation of this last compound in irrigated rice fields, and the respective half life, in aquatic environment and soil solution, by mean of numerical solution of differential ordinary linear equations system that describes the kinetics of insecticide concentrations. The results indicated that the carbosulfan and carbofuran have low persistence in water and medium persistence in soil solution of tropical irrigated rice fields. However, both compounds can be found in laminar water and soil solution in concentration above environmental and human safety limits.     

Mercury contamination in human hair and fish from Cambodia: levels, specific accumulation and risk assessment

Mercury (Hg) concentrations in human hair and fish samples from Phnom Penh, Kien Svay, Tomnup Rolork and Batrong, Cambodia, collected in November 1999 and December 2000 were determined to understand the status of contamination, and age- and sex-dependent accumulation in humans and to assess the intake of mercury via fish consumption. Mercury concentrations in human hair ranged from 0.54 to 190mug/g dry wt. About 3% of the samples contained Hg levels exceeding the no observed adverse effects level (NOAEL) of WHO (50mug/g) and the levels in some hair samples of women also exceeded the NOAEL (10mug/g) associated with fetus neurotoxicity. A weak but significant positive correlation was observed between age and Hg levels in hair of residents. Mercury concentrations in muscle of marine and freshwater fish from Cambodia ranged from <0.01 to 0.96mug/g wet wt. Mercury intake rates were estimated on the basis of the Hg content in fish and daily fish consumption. Three samples of marine fish including sharp-tooth snapper and obtuse barracuda, and one sample of sharp-tooth snapper exceeded the guidelines by US EPA and by Joint FAO/WHO Expert Committee on Food Additives (JECFA), respectively, which indicates that some fish specimens examined (9% and 3% for US EPA and JECFA guidelines, respectively) were hazardous for consumption at the ingestion rate of Cambodian people (32.6g/day). It is suggested that fish is probably the main source of Hg for Cambodian people. However, extremely high Hg concentrations were observed in some individuals and could not be explained by Hg intake from fish consumption, indicating some other contamination sources of Hg in Cambodia.     

Multivariant statistical analysis of PCDD/FS in sewage sludges from different areas of the Valencian Community (Spain)

The levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in 31 sewage sludges from different wastewater treatment plants corresponding to rural, urban and industrial areas in the Valencian Community (Spain) were analysed. Values of 5.1-346.2 ng I-TEQ kg(-1) (dry weight) were detected for sewage sludge with the highest value in one sample from an industrial area. Therefore the majority of the samples did not exceed the limit proposed (100 ng I-TEQ kg(-1)) by the [EU, 2000. Working document on sludge, 3rd draft. Brussels. Available from: http://europa.eu.int/comm/environment/waste/sludge/sludge_en.pdf] for use in agriculture. The dominant congeners for each family of compounds were 1,2,3,4,6,7,8-HpCDD and OCDD from PCDDs, and 1,2,3,4,6,7,8-HpCDF and OCDF from PCDFs. The total concentrations of PCDD/Fs were evaluated statistically through SPPS 11.0 for Windows. The principal component analysis (PCA) was used to extract two PCs as a linear combination of the original variables, one of them associated to urban+highly industrial areas and the other one to urban+low industrial areas. The linear regression method was applied and an efficient correlation was obtained between the total I-TEQ values for each sample and two of most abundant congeners (OCDF and OCDD). This expression was obtained with the results of the 31 samples analysed and a variety of data from other authors. Furthermore, several bilateral correlations between the different congeners completed the statistical analysis.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Mercury in hair and blood from residents of Phnom Penh (Cambodia) and possible effect on serum hormone levels

High concentration of mercury (Hg) in hair has been reported for Cambodians. To confirm the Hg contamination occurring through intake, Hg concentrations were determined in both hair and blood of residents (n=20) from Phnom Penh, Cambodia. Mercury concentrations in the hair and blood were 0.69-190microg g(-1) dry wt and 5.2-58microg l(-1), respectively, which were lower than those from Hg contaminated or high fish intake regions, but were higher than those from non-contaminated regions. Some female subjects had hair and blood Hg levels exceeding the threshold values for neurotoxic effects. Interestingly, serum estrone and estradiol levels were positively correlated with blood Hg level for both males and females, indicating possible induction of female hormones by Hg exposure in Cambodians.     

Quantitative cancer risk assessment and local mortality burden for ambient air pollution in an eastern Mediterranean City

Health risks posed by ambient air pollutants to the urban Lebanese population have not been well characterized. The aim of this study is to assess cancer risk and mortality burden of non-methane hydrocarbons (NMHCs) and particulates (PM) based on two field-sampling campaigns conducted during summer and winter seasons in Beirut. Seventy NMHCs were analyzed by TD-GC-FID. PM_2.5 elemental carbon (EC) components were examined using a Lab OC-EC aerosol Analyzer, and polycyclic aromatic hydrocarbons were analyzed by GC-MS. The US EPA fraction-based approach was used to assess non-cancer hazard and cancer risk for the hydrocarbon mixture, and the UK Committee on Medical Effects of Air Pollutants (COMEAP) guidelines were followed to determine the PM_2.5 attributable mortality burden. The average cumulative cancer risk exceeded the US EPA acceptable level (10⁻⁶) by 40-fold in the summer and 30-fold in the winter. Benzene was found to be the highest contributor to cancer risk (39–43%), followed by 1,3-butadiene (25–29%), both originating from traffic gasoline evaporation and combustion. The EC attributable average mortality fraction was 7.8–10%, while the average attributable number of deaths (AD) and years of life lost (YLL) were found to be 257–327 and 3086–3923, respectively. Our findings provide a baseline for future air monitoring programs, and for interventions aiming at reducing cancer risk in this population.

     

Use of treated bark for the removal of lipids from water

Raw, biologically treated bark and bark impregnated with transition metal ions were used to retain the lipids from synthetic emulsions. Several experimental parameters affecting the lipid removal efficiency (RE) were studied (initial concentration of lipids, temperature, time, pH, carboxylic acid chain length, etc.). Saturated bark was characterized using Fourier transform infrared (FTIR) spectroscopy and light microscopy, and the treated bark wetting index was determined. Results show that lipid removal can exceed 95% of the initial concentration at a pH lower than 7. The uptake of lipids by these sorbents varied from 0.2 to 2.5 g/g of dry bark. Trials for regenerating the sorbent saturated by lipids allowed the recovery of approximately 95% of lipids. The calorific value of the saturated bark was approximately 79% that of domestic fuel and can be considered as an energy source, thus avoiding its waste disposal. These results may upgrade the treatment of wastewater generated by several industrial sectors, such as the food industry, surface treatment, and so on.     

Molecular phylogeny of the American <Emphasis Type="Italic">Callinectes</Emphasis> Stimpson, 1860 (Brachyura: Portunidae), based on two partial mitochondrial genes

The genus Callinectes encompasses 16 species of commercially important swimming crabs. Most (13) occur on the Pacific and Atlantic coasts of the Americas. We compare mtDNA regions corresponding to 964 basepairs of the large (16S) and small (12S) ribosomal subunits among American Callinectes in order to examine phylogenetic relationships. The status of Callinectes affinis Fausto-Filho and Callinectes maracaiboensis Taissoun is questioned, and C. maracaiboensis is concluded to be a junior synonym of Callinectes bocourti A. Milne-Edwards, from which it cannot be consistently distinguished. We find two major lineages, one of which includes C. affinis, C. bocourti, Callinectes rathbunae Contreras, Callinectes sapidus Rathbun, and Callinectes toxotes Ordway. A second lineage is comprised of Callinectes arcuatus Ordway, Callinectes bellicosus (Stimpson), Callinectes danae Smith, Callinectes exasperatus (Gerstaecker), Callinectes larvatus Ordway, Callinectes ornatus Ordway, and Callinectes similis Williams. Definition of these clades is supported by previously described morphological differences in the length of the gonopods and shared physioecological adaptations. A calibrated molecular clock is used to estimate divergence of the two lineages near 13 mybp. Our analyses suggest that C. ornatus is the closest relative of C. arcuatus, and that C. affinis is closest to C. bocourti.     

<Emphasis Type="Italic">Mazzaella laminarioides</Emphasis> and <Emphasis Type="Italic">Sarcothalia crispata</Emphasis> as possible bioindicators of heavy metal contamination in the marine coastal zone of Chile

The suitability of Mazzaella laminarioides and Sarcothalia crispata as heavy metal biomonitors of Cd, Cu, Hg, Pb, and Zn was assessed by comparing bioaccumulation of these elements in different life stages and frond sizes in samples from three locations, San Vicente Bay (industrial area), Coliumo, and Quidico (the latter as a reference station), where different degrees of heavy metal pollution are recorded. Bioaccumulation and bioconcentration factors of Cd, Cu, Hg, Pb, and Zn were evaluated. The two macroalgae species showed similar patterns, with higher values of Cu, Hg, Pb, and Zn in polluted areas. M. laminarioides bioaccumulated higher concentrations of all metals assessed than S. crispata, independent of life stage and frond size. The results also showed significantly higher Cu, Hg, Pb, and Zn concentrations (p < 0.05) in water samples from San Vicente Bay than those measured in Coliumo and Quidico. Concentrations of Cd, Hg, Pb, and Zn in San Vicente Bay and Cd, Hg, and Pb in Coliumo and Quidico exceed the mean values considered to represent natural concentrations (Cu = 3.00 μg L^?1; Zn = 5.00 μg L^?1; Pb = 0.03 μg L^?1; Cd = 0.05 μg L^?1; Hg = 0.05 μg L^?1); however, the concentrations recorded do not cause negative effects on the growth and survival of macroalgae. The assessment of heavy metals bioaccumulated in M. laminarioides and S. crispata, particularly Hg, Pb, and Zn, offers a reliable approach for pollution assessment in rocky intertidal environments. Cu and Cd concentrations in seawater samples from San Vicente and Coliumo Bays were significantly higher than in those from Quidico (p value < 0.05); no significant differences in Cd concentrations were observed between San Vicente and Coliumo Bays (p < 0.05). Exceptionally, Cd is bioaccumulated at high levels independent of its availability in the water, thus reaching high concentrations in control areas. High concentrations of metals like Cu and Zn may limit or inhibit Cd uptake in macroalgae, since the transport channels are saturated by some metals, reducing the accumulation of others. These macroalgae species offer good potential for the development of suitable heavy metal pollution survey tools in rocky intertidal environments.     

Potentially toxic elements (PTEs) in soils from the surroundings of the Trans-Amazonian Highway,Brazil

The Trans-Amazonian Highway (TAH) is located in the northern region of Brazil, comprising a border region where agricultural, mining, and logging activities are the main activities responsible for fostering economic development, in addition to large hydroelectric plants. Such activities lead to environmental contamination by potentially toxic elements (PTEs). Environmental monitoring is only possible through the determination of element contents under natural conditions. Many extraction methods have been proposed to determine PTEs’ bioavailability in the soil; however, there is no consensus about which extractor is most suitable. In this study, we determined the contents of PTEs in soils in the surroundings of TAH after mineral extraction with diethylenetriaminepentaacetic acid-triethanolamine (DTPA-TEA), Mehlich I, and Mehlich III solutions. Soil samples were collected in areas of natural vegetation in the vicinity of TAH in the state of Pará, Brazil. Chemical attributes and particle size were determined, besides concentrations of Fe, Al, Mn, and Ti by sulfuric acid digestion, Si after alkaline solution attack, and poorly crystalline Fe, Al, and “free” Fe oxides. Mehlich III solution extracted greater contents from Fe, Al, and Pb as compared to Mehlich I and DTPA-TEA and similar contents from Cd, Mn, Zn, and Cu. Significant correlations were found between concentrations of PTEs and the contents of Fe and Mn oxides as well as organic carbon and soil cation exchange capacity. Contents of Cu, Mn, Fe, and Zn by the three methods were positively correlated.