Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Reusing fly ash in glass fibre reinforced cement: a new generation of high-quality GRC composites

New composite materials based on an alkali-resistant glass-fibre reinforced cement (AR-GRC) system are being developed by using fly ash (FA) produced at coal thermoelectric power plants, and fluid catalytic cracking catalyst residue (FC3R) from the petrol industry as cement replacement materials. These wastes are reactive from the pozzolanic viewpoint, and modify the nature and the microstructure of the cement matrix when a part of the Portland cement is replaced in the formulation of GRC. Several microstructural and mechanical aspects are being studied for AR-GRC systems. The behaviour of composites exposed to ageing shows that the pozzolanic activity of the ground FA added in high amounts and its mixture with the FC3R increase the flexural strength and no evidences of strength decay are observed. Additionally, the fibres due to the high alkalinity of the cementing matrix can be deteriorated. Fibres in the control (only Portland cement) and FC3R containing composites were attacked, whereas composites with FA and their mixture with FC3R show that the fibres have not been attacked, due to the pozzolanic activity of replacing materials that reduce the calcium hydroxide content in the cementing matrix.     

Determination of selenium by GFAAS in slurries of fish feces to estimate the bioavailability of this micronutrient in feed used in pisciculture

This paper presents a simple, fast and sensitive method to determine selenium in samples of feces and of fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of selenium) were 0.31 microg l(-1) and 1.03 microg l(-1), respectively, for the standard feces slurries and 0.35 microg l(-1) and 1.16 microg l(-1), respectively, for the standard feed slurries. The proposed method was applied in studies of bioavailability of selenium in different fish feeds and the results proved consistent with that obtained from samples mineralized by acid digestion using the microwave oven.     

Changes in hematological and serum biochemical values in jundiá Rhamdia quelen due to sub-lethal toxicity of cypermethrin

Jundiá (Rhamdia quelen, Quoy and Gaimard), a South American teleostean fish, was exposed to sub-lethal concentrations of cypermethrin (30% and 45% of the 48-h LC(50) value of 0.265 ppm) for 2, 4 or 8 days. Serum biochemical and hematological values and behavioral changes were studied. The 30% LC(50), 0.08 ppm, produced significant increases in Mg(2+), P, K(+), creatinine, urea, glucose, cholesterol, aspartate aminotransferase and alkaline phosphatase levels, and reduction in total proteins and triglycerides in serum. The 45% LC(50), 0.12 ppm, produced significant increase in Na(+), Mg(2+), P, K(+), creatinine, urea, glucose, cholesterol, and alkaline phosphatase, and reduction in triglycerides and alanine aminotransferase levels in serum. At this concentration, the fish showed behavior changes such as hyper-excitability, asphyxia, and widening of mouth and operculum. The hematological values remained normal, except for hemoglobin concentrations and the mean corpuscular hemoglobin concentration, which increased with exposure to 0.08 ppm and 0.12 ppm cypermethrin. Results of the present work show that biochemical analysis of serum can be useful to detect incipient cypermethrin intoxication of the shoal.     

Biodegradation of catechol (2-hydroxy phenol) bearing wastewater in an UASB reactor

The present study deals with the biodegradation of catechol through co-metabolism with glucose in aqueous solution as primary substrate in an upflow anaerobic sludge blanket (UASB) reactor. Batch studies indicated that the 1000mgl(-1) glucose concentration was sufficient to cometabolize and degrade catechol in an aqueous solution up to a concentration of 1000mgl(-1). The reactor operated at 35+/-2 degrees C, and at a constant hydraulic retention time of 8h with a gradual stepwise increase in catechol concentration from 100 to 1000mgl(-1) along with glucose as a cosubstrate. The results showed that the catechol was successfully mineralized in an UASB reactor in which microbial granulation was achieved with only glucose as the substrate. The reactor showed > or = 95% COD removal efficiency with 500-1000mgl(-1)catechol concentration in the feed and a glucose concentration of 1500mgl(-1) as a cosubstrate. Similar efficiency was obtained at a constant catechol concentration of 1000mgl(-1) with 500-1000mgl(-1) glucose concentration. Once the reactor got acclimatized with catechol, higher concentrations of catechol can be mineralized with a minimum amount of glucose as the cosubstrate without affecting the performance of the UASB reactor.     

Variations in PCB concentrations between genders of six warmwater fish species in Lake Logan Martin, Alabama, USA

We collected and analyzed 955 individual fish (six species) for sexual differences in PCB bioaccumulations from a southeastern, USA reservoir. Using 2-way ANCOVAs, we found significant differences in fillet PCB concentrations between sexes for channel catfish (Ictalurus punctatus), largemouth bass (Micropterus salmoides) and spotted bass (Micropterus punctulatus). Striped bass (Morone saxatilus), black crappie (Pomoxis nigromaculatus) and freshwater drum (Aplodinotus grunniens) did not display differences between sexes in PCB concentrations. We suspect that sexual differences may be due to biological differences in reproduction, relative motility and lipid deposition. For one species (striped bass), sexual differences in PCB concentrations were inconsistent with a study in the Hudson River suggesting that sexual differences in bioaccumulations can change across ecosystems. Two species which did show sexual differences, largemouth bass and channel catfish, are often chosen as representative species (e.g., "piscivore" and "benthivore") in contaminant monitoring in many USA states indicating human consumption and risk management decisions would be improved if an equal number of male and female fish were included in composite PCBs analysis. This could reduce variability in fish PCBs data from which consumption advisories are based.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco, Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-alpha,alpha,alpha -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g(-1); short-term experiment) to 200 days (initial concentration = 689 ng g(-1); long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Mobility of dimethoate residues from spring broccoli field

Dimethoate [O, O-dimethyl-S-(N-methylcarbamoyl-methyl) phosphorodithioate] is a broad-spectrum systemic insecticide currently used worldwide and on many vegetables in Kentucky. Dimethoate is a hydrophilic compound (log KOW = 0.7) and has the potential of offsite movement from the application site into runoff and infiltration water. The dissipation patterns of dimethoate residues were studied on spring broccoli leaves and heads under field conditions. Following foliar application of Dimethoate 4E on broccoli foliage at the rate of 0.47 L acre(-1), dimethoate residues were monitored in soil, runoff water collected down the land slope, and in infiltration water collected from the vadose zone. The study was conducted on a Lowell silty loam soil (pH 6.9) planted with broccoli under three soil management practices: (i) soil mixed with municipal sewage sludge, (ii) soil mixed with yard waste compost, and (iii) no-mulch rototilled bare soil. The main objective of this investigation was to study the effect of mixing native soil with municipal sewage sludge or yard waste compost, having considerable amounts of organic matter, on off-site movement of dimethoate residues into runoff and infiltration water following spring rainfall. The initial deposits of dimethoate were 6.2 and 21.4 micro g g(-1) on broccoli heads and leaves, respectively. These residues dissipated rapidly and fell below the maximum residue limit of 2 micro g g(-1) on the heads and leaves after 10 and 14 d, respectively, with half-lives of 5.7 d on broccoli heads and 3.9 d on the leaves. Dimethoate residues detected in top 15 cm of soil (due to droplet drift and wash off residues from broccoli foliage) one day (d) following spraying, were 30.5 ng g(-1) dry soil in the sewage sludge treatment, and 46.1 and 134.5 ng g(-1) dry soil in the yard waste and no mulch treatments, respectively. Water infiltration was greater from yard waste compost treatment than from no mulch treatment, however concentrations of dimethoate in the vadose zone of the three soil treatments did not differ.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State-Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, alpha and beta endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino-Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6% leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (alpha-endosulfan), 1.47E-162 (beta-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.