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.     

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.     

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.     

Variability of soil-water quality due to Tsunami-2004 in the coastal belt of Nagapattinam district, Tamilnadu

In this study, the Tsunami-caused deterioration of soil and groundwater quality in the agricultural fields of coastal Nagapattinam district of Tamilnadu state in India is presented by analyzing their salinity and sodicity parameters. To accomplish this, three sets of soil samples up to a depth of 30cm from the land surface were collected for the first six months of the year 2005 from 28 locations and the ground water samples were monitored from seven existing dug wells and hand pumps covering the study region at intervals of 3 months. The EC and pH values of both the soil and ground water samples were estimated and the spatial and temporal variability mappings of these parameters were performed using the geostatistical analysis module of ArcGIS((R)). It was observed that the spherical semivariogram fitted well with the data set of both EC and pH and the generated kriged maps explained the spatial and temporal variability under different ranges of EC and pH values. Further, the recorded EC and pH data of soil and ground water during pre-Tsunami periods were compared with the collected data and generated variability soil maps of EC and pH of the post-Tsunami period. It was revealed from this analysis that the soil quality six months after the Tsunami was nearing the pre-Tsunami scenario (EC< 1.5dSm(-1); pH<8), whereas the quality of ground water remained highly saline and unfit for irrigation and drinking. These observations were compared with the ground scenarios of the study region and possible causes for such changes and the remedial measures for taking up regular agricultural practices are also discussed.     

Analysis of the nitrifying bacterial community in BioCube sponge media using fluorescent in situ hybridization (FISH) and microelectrodes

There is growing interest in the development of more cost-effective and retrofit technologies for the upgrade and expansion of existing wastewater treatment plants with extreme space constraints. A free-floating sponge media (BioCube) process, using a 24L lab scale reactor, was operated to study the nitrification profiles and microbial community. The COD removal efficiencies were maintained, at an average of 95%, with the mixed liquor suspended solids (MLSS) inside the BioCube sponge media maintained at 12,688mg/L. The nitrification removal efficiencies were between 92% and 100%, with an average value of 99%. From the results of microelectrode measurements, the ammonium ion concentration was found to rapidly decrease from the surface of the BioCube sponge media to a depth of 2mm due to chemical reactions carried out by ammonia oxidizing bacteria (AOB) species. Multi-fluorescence in situ hybridization (FISH) has been used to investigate the spatial distributions of various microbial activities within reactors. Microbial communities were targeted using different oligonucleotide probes specific to AOB and nitrite oxidizing bacteria (NOB). There were a large number of AOB populations, but these were not uniformly distributed in the biofilm compared to the NOB populations.     

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

Leaching of cyanogenic glucosides and cyanide from white clover green manure

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5-35 h depending on soil characteristics, a fraction of the applied CGs (0.9-3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50 micrgl(-1) total cyanide for drinking water and 85% exceeded the US threshold of 5 micrgl(-1) for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance.     

Polybrominated diphenyl ethers and HBCD in bird eggs of South Africa

In this paper, the first data on brominated flame retardants (BFRs), in particular polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in eggs of bird species from South Africa are described (N=43). Concentrations of PBDEs were detected in all the studied species and in all the geographic areas. Highest concentrations of PBDEs were measured in bird eggs from the Vaal River, which is situated downstream of the most industrialized area in South Africa. Sum-PBDE concentrations were highest in eggs of one African sacred ibis (396 ng g(-1) lipid weight (lw)), possibly due to foraging on dumping sites. Lowest mean level of sum-PBDEs (2.3 ng g(-1) lw) was measured in cattle egrets (N=11) from Barberspan Sanctuary, a Ramsar site. The PBDE congener pattern showed large differences, reflecting different trophic levels, migratory behavior, distance to the source, and, exposure to different PBDE mixtures, among others. HBCD was detected only in four species, and highest levels were measured in one egg of African sacred ibis (71 ng g(-1) lw). In most species, levels of PBDEs were one to several orders of magnitude lower than levels of DDTs and PCBs. PBDEs correlated strongly with DDTs, PCBs and some other organochlorines (OCs), indicating the same source. The widespread occurrence of PBDEs in the South African avian species showed a strong need for further investigations of PBDEs in the Southern African environment.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.