Fluorescence fingerprints and Cu2+-complexing ability of individual molecular size fractions in soil- and waste-borne DOM

Land spreading of organic materials introduces large amounts of dissolved organic matter (DOM) into the soil. DOM has the ability to form stable complexes with heavy metals and can facilitate their transport towards the groundwater. The effects on soil processes are difficult to assess, because different DOM components might react differently towards metal ions. The objective of this study was to investigate the fluorescence signature and the Cu2+-binding capacity of individual molecular size fractions of DOM from various sources. DOM extracted from leaf compost, chicken manure, sugar cane vinasse and a fulvic hypercalcaric cambisol was fractionated by the means of dialysis into four molecular size classes: MW<500, 50012000-14000 Da. Vinasse and leaf compost contained around 80% and 70%, respectively, of the total organic carbon in the fractions with low molecular weight (MW<3500 Da); in chicken manure and soil these fractions accounted for 40% and 50% only. Fluorescence was highest in the fraction MW>12000 Da for leaf compost, chicken manure and soil. The opposite result was obtained for vinasse, where the fractions with low molecular weight showed highest fluorescence intensities, distinguishing it from all other samples. Vinasse showed the greatest ability to bind Cu2+ with a resulting complex concentration of 6.31mgl(-1) while in contact with an excess of Cu2+. Leaf compost, soil and chicken manure followed with 2.69, 1.12, and 0.85mgl(-1), respectively. Within vinasse, the fraction MW<500 Da was able to form the most DOM-Cu complexes, indicating the importance of low molecular weight fractions in metal binding.     

Kinetic and adsorption study of acid dye removal using activated carbon

The adsorption of three acid dyes, Acid Red 97, Acid Orange 61 and Acid Brown 425 onto activated carbon was studied for the removal of acid dyes from aqueous solutions at room temperature (25 degrees C). The adsorption of each dye with respect to contact time was then measured to provide information about the adsorption characteristics of activated carbon. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The experimental isotherms obtained, except for Acid Orange 61 studied in mixture, were of the S-type in terms of the classification of Giles and co-workers. The best fit of the adsorption isotherm data was obtained using the Freundlich model. When a comparative study was made of the results obtained with single and mixed dyes, it can be seen that some of them affect others and modify their behavior in the adsorption process. The results indicate that activated carbon could be employed for the removal of dyes from wastewater.     

Effect of coumaphos on cholinesterase activity, hematology, and biochemical blood parameters of bovines in tropical regions of Mexico

To assess the effect of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] exposure on physiological responses during bovine production, acetylcolinesterase (AChE) and butyrylcholinesterase (BuChE) activities were measured in whole blood, erythrocytes, and plasma of healthy male steers (Bos Taurus x Bos indicus) sprayed with coumaphos at a non-lethal dose of 1 mg kg(- 1) body weight per day once every 14 (in vivo group) or 21 days (southern and central groups). Coumaphos topically administered at 1 mg/kg body weight per day to cattle under normal management practices in tropical areas produced a significant inhibition in erythrocyte (RBC) AChE and BuAChE activities when compared to baseline levels. RBC-AChE activity for the in vivo group decreased 71.3% (P < 0.05) and BuChE activity 59.1% (P < 0.05); RBC-AChE activity decreased 55.1% (P < 0.05) (southern group) and 43.4% (P < 0.05) (central group). Compared to the control specimens, steers from in vivo, southern, and central groups after 150 days of exposure had lower (P < 0.05) leukocyte count, absolute lymphocyte, erythrocyte, and platelet counts. Decreases in RBC-AChE activities correlated with decreased lymphocyte (r = 1.000, p = 0.01), erythrocyte (r = 1.000, p = 0.003), and platelet counts (r = 0.841, p = 0.036). Significantly increased BUN levels (P < 0.05) correlated with the decrease in RBC-AChE activities (r = - 0.997, p = 0.047) and with the decrease in absolute red blood cell (r = - 0.883, p = 0.020) and lymphocyte (r = - 0.825, p = 0.043) counts; increased (P < 0.05) total plasma protein levels correlated with the decrease in RBC-AChE activities (r = -0.998, p = 0.043), absolute red blood cell (r = - 0.998, p = 0.040), lymphocyte (r = - 0.893, p = 0.017), and platelet (r = -0.855, p = 0.030) counts. The physiological responses correlated with the erythrocyte acetylcholinesterase inhibition could be considered as early indicators or warning responses of bovine exposures to organophosphorus pesticides (OPs).     

Acetylcholinesterase-polyaniline biosensor investigation of organophosphate pesticides in selected organic solvents

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved.     

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.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'(W)) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb(T)) in pure water. Experimental breakthrough volumes (Vb(E)) were first determined using purified and deionized water as the matrix for selected compounds having Vb(T) < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4-5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb(E) curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5-6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb(E) in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Use of USLE/GIS Methodology for Predicting Soil Loss in a Semiarid Agricultural Watershed

The Universal Soil Loss Equation (USLE) is an erosion model to estimate average soil loss that would generally result from splash, sheet, and rill erosion from agricultural plots. Recently, use of USLE has been extended as a useful tool predicting soil losses and planning control practices in agricultural watersheds by the effective integration of the GIS-based procedures to estimate the factor values in a grid cell basis. This study was performed in the Kazan Watershed located in the central Anatolia, Turkey, to predict soil erosion risk by the USLE/GIS methodology for planning conservation measures in the site. Rain erosivity (R), soil erodibility (K), and cover management factor (C) values of the model were calculated from erosivity map, soil map, and land use map of Turkey, respectively. R values were site-specifically corrected using DEM and climatic data. The topographical and hydrological effects on the soil loss were characterized by LS factor evaluated by the flow accumulation tool using DEM and watershed delineation techniques. From resulting soil loss map of the watershed, the magnitude of the soil erosion was estimated in terms of the different soil units and land uses and the most erosion-prone areas where irreversible soil losses occurred were reasonably located in the Kazan watershed. This could be very useful for deciding restoration practices to control the soil erosion of the sites to be severely influenced.     

Integrated biomonitoring of air quality with plants and lichens: a case study on ambient ozone from central Italy

A biennial integrated survey, based on the use of vascular plants for the bioindication of the effects of tropospheric ozone together with the use of automatic analysers of ozone, as well as the mapping of lichen biodiversity was performed in the area of Castelfiorentino (Tuscany, central Italy). Photochemically produced ozone proved to be a fundamental presence during the warm season, with maximum hourly means reaching 114 ppb, exceeding the information threshold as fixed by EU: the use of supersensitive tobacco Bel-W3 confirmed the opportunity of carrying out detailed cost-effective monitoring surveys. The potential for didactical and educational implications of this methodology are appealing. Critical levels set up for the protection of vegetation have exceeded considerably. The comparison of biomass productivity in sensitive and resistant individuals (NC-S and NC-R white clover clones, in the framework of an European network) provided evidence that ambient ozone levels are associated with relevant reduction (up to 30%) in the performance of sensitive material; effects on flowering were also pronounced. The economic assessment of such an impact deserves attention. Mapping of epiphytic lichen biodiversity – which has been used to monitor air quality worldwide – was not related to ozone geographical distribution as depicted by tobacco response.     

Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.