Electrochemical detoxification of four phosphorothioate obsolete pesticides stocks

The phosphorothioate pesticides are widely used for crop production and fruit tree treatment, but their disposal causes serious environmental problems. Four commercial phosphorothioate pesticides (Demeton-S-methyl, Metamidophos, Fenthion and Diazinon) were treated by an electrolysis system using Ti/Pt as anode and stainless steel 304 as cathode. A number of experiments were run in a laboratory scale pilot plant and the results are presented. For Fenthion the achieved reduction was over 60%, while for Demeton-S-methyl, Metamidophos and Diazinon was more than 50%. Diazinon had the lowest energy demand. The COD/BOD5 ratio was improved considerably after electrolysis for all four pesticides examined. As a conclusion, electrochemical oxidation could be used as a pretreatment method of the pesticides detoxification.     

Impact of Effluent Recirculation on Stabilization Pond Performance

This paper presents a test case for the effects of recirculation on stabilization pond performance. The BOD₅, COD, SS and Total Coliform removal at the intermediate treatment stages and the outlet of a stabilization pond treatment line, over a 2-year operational period (January 2000-December 2001), is described in detail and the effluent at different stages of treatment is compared to that of a conventional stabilization pond treatment line operating under similar conditions. The system consisted of four ponds in line—an anaerobic pond, followed by three individual ponds (Pond 1, Pond 2 and Pond 3). The effluent of the last pond (Pond 3) was recirculated back to the inlet of the first pond (Pond 1) at a discharge ratio 2:1 (recirculation:inflow). The overall BOD₅, COD, SS and Total Coliforms total reduction was 89%, 81%, 85% and 99.7%, respectively. The anaerobic pond proved to be the most efficient in removing COD and SS (57% and 68%, respectively) whereas Pond 1 achieved the most significant reduction in BOD₅ and Total Coliforms (69% and 86%, respectively). Although BOD₅ and COD were adequately reduced by the recirculating pond line, the SS concentration was high due to algae presence in the final effluent. Moreover, the Total Coliforms were insufficiently removed due to the reduced hydraulic retention time involved in this type of recirculation.     

Precise sex ratios manifested by several encyrtid parasitoids (Hymenoptera: Encyrtidae) of brown soft scale, <Emphasis Type="Italic">Coccus hesperidum</Emphasis> L. (Hemiptera: Coccidae)

We examined whether several facultatively gregarious encyrtid (Hymenoptera: Encyrtidae) endoparasitoids of brown soft scale, Coccus hesperidum L., manifest precise sex allocation under field conditions. Metaphycus luteolus (Timberlake), Metaphycus angustifrons (Compere), Metaphycus stanleyi (Compere), and Microterys nietneri (Motshulsky) evince brood sex ratios that are female-biased and extremely precise (low variance in the number of sons per host). Typically, this sex allocation pattern is attributed to extreme local mate competition (LMC) in which only one foundress exploits a patch of hosts and mating occurs mostly between her offspring. However, such a pattern of sex allocation was not detected for Metaphycus helvolus (Compere). Also, a large proportion of the broods in all five species contained only daughters; thus, an excess of male-only broods was expected if unmated females (i.e., females that can produce only sons) contribute offspring before mating. All-male broods were rare in our samples. This finding coupled with the life history characteristics of these wasps, such as the exploitation of aggregated hosts and the long life span and mobility of males, suggest that nonlocal mating is frequent. Our empirical work suggests that it is advantageous to allocate precise sex ratios in cases in which mating opportunities for males are not restricted to their natal host and/or when multiple foundresses exploit large patches of hosts. Limited theoretical work also supports this prediction but more detailed studies of this taxon’s mating structure and other life history characteristics are necessary to understand their sex allocation decisions.     

Adaptation of urine source separation in tropical cities: Process optimization and odor mitigation

Source-separating urine from other domestic wastewaters promotes a more sustainable municipal wastewater treatment system. This study investigated the feasibility and potential issues of applying a urine source-separation system in tropical urban settings. The results showed that source-separated urine underwent rapid urea-hydrolysis (ureolysis) at temperatures between 34–40^oC, stale/fresh urine ratios greater than 40%, and/or with slight fecal cross-contamination. Undiluted (or low-diluted) urine favored ureolysis; this can be monitored by measuring conductivity as a reliable and efficient indicator. The optimized parameters demonstrated that an effective urine source-separation system is achievable in tropical urban areas. On the other hand, the initial release of CO₂ and NH₃ led to an elevated pressure in the headspace of the collection reservoir, which then dropped to a negative value, primarily due to oxygen depletion by the microbial activity in the gradually alkalized urine. Another potential odor source during the ureolysis process was derived from the high production of volatile fatty acids (VFA), which were mainly acetic, propanoic, and butyric acids. Health concerns related to odor issues might limit the application of source separation systems in urban areas; it is therefore vital to systematically monitor and control the odor emissions from a source separation system. As such, an enhanced ureolysis process can attenuate the odor emissions.

Implications: Urine source separation is promising to improve the management of domestic wastewater in a more sustainable way. The work demonstrates the achievability of an effective urine source-separation system in tropical urban areas. The installation of urine-stabilization tanks beneath high-rise buildings lowers the risk of pipe clogging. Conductivity measurement can be utilized as a reliable process indicator for an automated system. However, urine hydrolysis raises a strong potential of odor emission (both inorganic and organic), which might limit the application of source separation systems in urban areas. An enhanced ureolysis process could shorten and attenuate the odor emissions.     

LC–ICP–MS analysis of arsenic compounds in dominant seaweeds from the Thermaikos Gulf (Northern Aegean Sea,Greece)

The content of total arsenic and arsenic compounds in the dominant seaweed species in the Thermaikos Gulf, Northern Aegean Sea was determined in samples collected in different seasons. Total arsenic was determined by acid digestion followed by ICP–MS. Arsenic speciation was analyzed by water extraction followed by LC–ICP–MS. Total arsenic concentrations in the seaweeds ranged from 1.39 to 55.0 mg kg⁻¹. Cystoseira species and Codium fragile showed the highest total As contents, while Ulva species (U. intestinalis, U. rigida,U. fasciata) had the lowest Arsenosugars, the most common arsenic species in seaweeds, were found in all samples, and glycerol-arsenosugar was the most common form; however, phosphate-arsenosugar and sulfate-arsenosugar were also present. Inorganic arsenic was measured in seven algae species and detected in another. Arsenate was the most abundant species in Cystoseira barbata (27.0 mg kg⁻¹). Arsenobetaine was measured in only one sample. Methylated arsenic species were measured at very low concentrations. The information should contribute to further understanding the presence of arsenic compounds in dominant seaweeds from the Thermaikos Gulf.     

Prediction of PAH biodegradation in field contaminated soils using a cyclodextrin extraction technique

Biodegradation has been identified as a major loss process for organic contaminants in soils and, as a result, microbial strategies have been developed for the remediation of contaminated land. Prediction of the biodegradable fraction would be important for determining bioremediation end-points in the clean-up of contaminated land. The aim of this study was to investigate the ability of a cyclodextrin extraction to predict the extent to which polycyclic aromatic hydrocarbons (PAHs) would be degraded microbiologically in field contaminated soils; further testing the robustness and reproducibility of this extraction in chemically complex systems. Dichloromethane and hydroxypropyl-beta-cyclodextrin (HPCD) extractable fractions were measured together with the PAH biodegradable fraction in each of the six field contaminated soils. The amounts of PAHs degraded by the catabolic activity of the indigenous microflora in each of the soils were correlated with HPCD-extractable PAH concentrations. The regressions showed that the amounts of lower molecular weight PAHs extracted by the HPCD were not significantly (P > 0.05) different to the amounts that were degraded. However, higher molecular weight PAHs that were extracted by HPCD did differ significantly (P < 0.05) from the amounts degraded. Although the HPCD extraction did overestimate the microbially degradable fraction of the higher molecular weight PAHs, overall the correlations between the HPCD extractable fraction and the microbially degradable fraction were very close, with mean values of the slope of line for the six soils equalling 1. This study further describes the robust and reproducible nature of the aqueous-based soil extraction technique reliably measuring the extent to which PAHs will be microbially degraded in soil.     

Adsorption of Cu(II) ions from aqueous solutions on biochars prepared from agricultural by-products

In this study, the adsorption of Cu(II) from aqueous solutions by agricultural by-products, such as rice husks, olive pomace and orange waste, as well as compost, was evaluated. The aim was to obtain sorbent materials (biochars) through hydrothermal treatment (300?°C) and pyrolysis (300?°C and 600?°C). The effect of adsorbent dose, pH, contact time and initial Cu(II) concentration in batch-mode experiments was investigated. The optimum Cu(II) adsorption conditions was found to occur at 5-12?g/L adsorbent dose, initial pH 5-6, and reaction time 2-4?h. Furthermore, the adsorption kinetics were best described by the pseudo-second order model for all the tested materials, while the adsorption equilibrium best fitted by the linear and Freundlich isotherms. Comparing rice husks and olive pomace, the higher adsorption capacity resulted after pyrolysis at 300?°C. With respect to the orange waste and compost, the highest adsorption capacity was observed using biochars obtained after hydrothermal treatment and pyrolysis at 300?°C.     

Monitoring operational and leachate characteristics of an aerobic simulated landfill bioreactor

Long-term biodegradation of MSW in an aerobic landfill bioreactor was monitored as a function of time during 510 days of operation. Operational characteristics such as air importation, temperature and leachate recirculation were monitored. The oxygen utilization rates and biodegradation of organic matter rates showed that aerobic biodegradation was feasible and appropriate to proceed in aerobic landfill bioreactor. Leachate analyses showed that the aerobic bioreactor could remove above 90% of chemical oxygen demand (COD) and close to 100% of biochemical oxygen demand (BOD5) from leachate. Ammonium (NH4+), nitrate (NO3-) and sulphate (SO4(2-)) concentrations of leachate samples were regularly measured. Results suggest that nitrification and denitrification occurred simultaneously, and the increase in nitrate did not reach the levels predicted stoichiometrically, suggesting that other processes were occurring. Leachate recirculation reduced the concentrations of heavy metals because of the effect of the high pH of the leachate, causing heavy metals to be retained by processes such as sorption on MSW, carbonate precipitation, and hydroxide precipitation. Furthermore, the compost derived from the aerobic biodegradation of the organic matter of MSW may be considered as soil improvement in the agricultural plant production. Bio-essays indicated that the ecotoxicity of leachate from the aerobic bioreactor was not toxic at the end of the experiment. Finally, after 510 days of degradation, waste settlement reached 26% mainly due to the compost of the organic matter.     

Transport of cadmium and assessment of phytotoxicity after electrokinetic remediation

The use of ethylene diamine tetraacetic acid (EDTA) on the electrokinetic removal of cadmium-contaminated soil was evaluated. A total of four different tests were conducted using EDTA as a washing solution as well as a purging solution at the electrode compartments. The efficiency of electrokinetic extraction was significantly influenced by the pH of the soil medium. The results show that EDTA was effective in desorbing cadmium at a high pH, with Cd-EDTA(-) anion complexes migrating toward the anode. At low pH values near the anode area, cadmium existed as Cd(2+), migrating toward the cathode. Such contradicting directions of cadmium have resulted in its detrimental removal from the soil cell. However, accumulation of cadmium near the cathode was observed at the end of the tests due to the dominating low pH in the soil cell. The phytotoxicity after the electrokinetic process was investigated using Sorghum saccharatum, Lepidium sativum and Sinapis alba plants. The germination index was a major endpoint estimated by measuring seed germination and shoot elongation. The results obtained show that the phytotoxicity was increased after electrokinetic extraction. Despite, the extensive cadmium removal from two-thirds of the cell, the low pH of the soil was the principal parameter exhibiting the phytotoxicity.