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.     

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.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

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.     

Using Spatial Pattern to Quantify Relationship Between Samples, Surroundings, and Populations

The need for accurate carbon budgeting, climate change modelling, and sustainable resource management has lead to an increase in the number of large area forest monitoring programs. Large area forest monitoring programs often utilize field and remotely sensed data sources. Sampling, via field or photo plots, enables the collection of data with the desired level of categorical detail in a timely and efficient manner. When sampling, the aim is to collect representative detailed data enabling the statistical reporting upon the characteristics of larger areas. As a consequence, approaches for investigating how well sample data represent larger areas (i.e., the sample neighbourhood and the population) are desired. Presented in this communication is a quantitative approach for assessing the nature of sampled areas in relation to surrounding areas and the overall population of interest. Classified Landsat data is converted to forest/non-forest categories to provide a consistent and uniform data set over a 130,000 km² study region in central British Columbia, Canada. From this larger study area 322 2 × 2 km photo plots on a 20 × 20 km systematic grid are populated with composition and configuration information for comparison to non-sampled areas. Results indicate that typically, within the study area, the spatial pattern of forest within a photo plot is representative of the forest patterns found within primary and secondary neighbourhoods and over the entire population of the study. These methods have implications for understanding the nature of data used in monitoring programs worldwide. The ability to audit photo and field plot information promotes an increased understanding of the results developed from sampling and provides tools identifying locations of possible bias.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Effect of pre-treatment and supporting media on Ni(II), Cu(II), Al(III) and Fe(III) sorption by plant root material

In this work Paspalum notatum root material was used to elucidate the influence of acid leaching pre-treatment and of sorption medium on metal adsorption. Ground P. notatum root was leached with 0.14M HNO(3). Leached root material (LRM) and non-leached root material (NLRM) were employed to flow sorption of Ni(II), Cu(II), Al(III) and Fe(III) in 0.5M CH(3)COONH(4) medium at pH 6.5. For LRM the sorption was also studied in 0.5M KNO(3) medium. The acid pre-treatment increased the sorption capacity (SC) for all ions studied. For the KNO(3) medium, Cu(II) and Fe(III) sorption was higher than in CH(3)COONH(4) and the type of the Ni(II) isotherm's model changed. The Freundlich model was the most representative isotherm model to describe metallic ions sorption. The (1)H NMR spectra showed differences between LRM and NLRM and the acid-basic potentiometric titration elucidated that acid-leaching procedure affected the root material sorption sites once only two predominant sorption sites were found for LRM (phenolic and amine, both able cations sorption) and five sorption sites (two carboxylic, amine and two phenolic) were founded for NLRM.     

Future climate scenarios and rainfall--runoff modelling in the Upper Gallego catchment (Spain)

Global climate change may have large impacts on water supplies, drought or flood frequencies and magnitudes in local and regional hydrologic systems. Water authorities therefore rely on computer models for quantitative impact prediction. In this study we present kernel-based learning machine river flow models for the Upper Gallego catchment of the Ebro basin. Different learning machines were calibrated using daily gauge data. The models posed two major challenges: (1) estimation of the rainfall-runoff transfer function from the available time series is complicated by anthropogenic regulation and mountainous terrain and (2) the river flow model is weak when only climate data are used, but additional antecedent flow data seemed to lead to delayed peak flow estimation. These types of models, together with the presented downscaled climate scenarios, can be used for climate change impact assessment in the Gallego, which is important for the future management of the system.     

Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Northern Idaho House Dust and Soil Lead Levels Compared to the Bunker Hill Superfund Site

House dust has been identified as a major exposure medium for lead (Pb) in children. High levels of Pb in soil and house dust have been recorded at the Bunker Hill Superfund Site (BHSS) in northern Idaho, an historic mining and smelting district. Soil and dust remediation at the site was required; however, regional background soil and dust Pb levels had not been well characterized. The objective of this survey was to determine background house dust Pb levels and to compare those levels with concentrations, and dust and Pb loading rates measured at the BHSS. Soil and house dust samples were collected in five towns demographically similar to the BHSS but unaffected by the mining industry. The background concentrations and loading rates were significantly lower than those observed at the site. House age was a significant factor affecting background soil and house dust Pb concentrations and loading rates.