Aquatic toxicity of cartap and cypermethrin to different life stages of Daphnia magna and Oryzias latipes

Cartap and cypermethrin, which are among the most widely used pesticides in many countries, are considered safe because of their low mammalian toxicity and their low persistence in the environment. However, recent findings of endocrine-disrupting effects and developmental neurotoxicity have raised concerns about the potential ecological impacts of these pesticides. We evaluated the aquatic toxicity of cartap [S,S′-(2-dimethylaminotrimethylene) bis(thiocarbamate), unspecified hydrochloride] and cypermethrin [(RS)-alpha-cyano-3-phenoxybenzyl-(1RS,3RS,1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate], both individually and combined, on different life stages of the freshwater cladoceran Daphnia magna and a freshwater teleost, Japanese medaka (Oryzias latipes). The 96-hr Daphnia median effective concentrations (EC50s) for cartap and cypermethrin were 91.0 μ g/L and 0.00061 μ g/L, respectively. Rapid recovery of Daphnia was observed after short-term pulsed exposure to cartap and cypermethrin; there were no adverse effects on reproduction or survival 20 d after a 24 hr exposure to cartap up to 1240 μ g/L and cypermethrin up to 1.9 μ g/L. Chronic continuous exposure (for 21 d) of 7-d-old Daphnia to cypermethrin significantly reduced the intrinsic population growth rate in a concentration-dependent manner. However, because the intrinsic population growth rates were all above zero, populations did not decrease even at the highest experimental concentration of 200 ng/L. Exposure of Daphnia neonates (< 24 hr old) to cypermethrin for 21 d caused significant, sub-lethal reproduction-related problems, such as increased time to first brood, reduced brood size, and reduced total brood number, at 0.0002, 0.002, and 0.2 ng/L cypermethrin, but the intrinsic population growth rate was not significantly affected. Oryzias latipes was relatively more resistant to both pesticides. In particular, embryos appeared to be more resistant than juveniles or adults, which may be partly due to the protective role of the chorion. The incidence of larval fish deformity was significantly higher after a 96 hr exposure to as low as 250 μ g/L of cartap or 40 μ g/L of cypermethrin. The mixture of both compounds showed no synergistic toxicity. The extremely high acute-to-chronic ratio suggests that the standard acute lethal toxicity assessment might not reflect the true environmental hazards of these frequently used pesticides. Ecological hazard assessments of long-term low dose or pulsed exposures to cartap and cypermethrin may reveal more realistic consequences of these compounds in surface water.     

Influence of short-time imidacloprid and acetamiprid application on soil microbial metabolic activity and enzymatic activity

The influence of two neonicotinoids, i.e., imidacloprid (IMI) and acetamiprid (ACE), on soil microbial activities was investigated in a short period of time using a combination of the microcalorimetric approach and enzyme tests. Thermodynamic parameters such as Q _T (J g^?1 soil), ?H _met (kJ mol^?1), J _Q/S (J g^?1 h^?1), k (h^?1), and soil enzymatic activities, dehydrogenase, phosphomonoesterase, arginine deaminase, and urease, were used to evaluate whole metabolic activity changes and acute toxicity following IMI and ACE treatment. Various profiles of thermogenic curves reflect different soil microbial activities. The microbial growth rate constant k, total heat evolution Q _T (expect for IMI), and inhibitory ratio I show linear relationship with the doses of IMI and ACE. Q _T for IMI increases at 0.0–20 μg g^?1 and then decreases at 20–80 μg g^?1, possibly attributing to the presence of tolerant microorganisms. The 50 % inhibitory ratios (IC₅₀) of IMI and ACE are 95.7 and 77.2 μg g^?1, respectively. ACE displays slightly higher toxicity than IMI. Plots of k and Q _T against microbial biomass-C indicate that the k and Q _T are growth yield-dependent. IMI and ACE show 29.6; 40.4 and 23.0; and 23.3, 21.7, and 30.5 % inhibition of dehydrogenase, phosphomonoesterase, and urease activity, respectively. By contrast, the arginine deaminase activity is enhanced by 15.2 and 13.2 % with IMI and ACE, respectively. The parametric indices selected give a quantitative dose-response relationship of both insecticides and indicate that ACE is more toxic than IMI due to their difference in molecular structures.     

Improvement of operating conditions in waste incinerators using engineering tools

Operation parameters such as waste feed rate, air supply, and temperature of the gas in incineration plants should be carefully determined for various situations, which include seasonal and annual changes in fuel characteristics, and performance change of the hardware. These changes may cause off-design point operation of the incinerators, which results in many problems in operation of the flue gas treatment system, low-oxygen in the combustion chamber, thermal damage of the incinerator wall, and so on. In this study, an engineering approach using computational tools along with field tests and observation is presented. For computational tools, a 0-dimensional model for heat and mass balance, computational fluid dynamics (CFD), and a global prediction model for dioxin are employed. They play a key role in diagnosing incineration systems and evaluating changes in operating conditions. The typical results of each tool are reported, and examples of improvement in operating performance are described.     

Degradation of atrazine by modified stepwise-Fenton's processes

The removal of atrazine (ATZ) by stepwise Fenton's processes (stepwise-FP) was studied and the system models were developed through the examination of reaction kinetics. The study compared the performance of the removal of ATZ by conventional FP with stepwise-FP, where the total dose of H(2)O(2) was split and inputted into the system at different times and/or quantities. The performance of stepwise-FP was found to be better than that of conventional FP. This was probably due to the minimization of the peak concentration of H(2)O(2) in the solution, which reduced the probability that valuable H(2)O(2) and hydroxyl radicals would be consumed in forming weaker radicals. The reaction kinetics of the decay of ATZ in stepwise-FP was found to be a two-stage process; and in each stage, fast decay followed by stagnant decay was observed. Two characterized constants (the initial decay rate and the oxidative capacity) were introduced and were found to be useful in quantifying the stepwise-FP. The models for predicting stepwise-FP with respect to different dosing times and/or asymmetrical doses were developed, and were found to be very useful for evaluating the system performance and/or for process design.     

Biosorption of reactive black 5 by Corynebacterium glutamicum biomass immobilized in alginate and polysulfone matrices

Corynebacterium glutamicum, a lysine fermentation industry waste, showed promise for the removal of Reactive black 5 (RB5). Due to practical difficulties in solid-liquid separation, the free biomass was immobilized in two polymer matrices: calcium alginate and polysulfone. Initially, the optimization of biomass loading in polymeric beads and bead dosage were examined. Of the different combinations examined, 4% (with bead dosage of 2 g per 40 ml) and 14% (with bead dosage of 1 g per 40 ml) in the case of alginate and polysulfone beads, respectively, were identified as the optimal conditions. According to the Langmuir model, at pH 1, the maximum RB5 uptakes of 352, 282 and 291 mg g(-1) were observed for free, alginate and polysulfone-immobilized biomass, respectively. According to the Weber-Morris model, intraparticle diffusion was found to be the potential rate limiting step for the immobilized beads. Regeneration experiments, with 0.01 M NaOH and Na(2)CO(3) as eluents, revealed that polysulfone beads exhibited invariable RB5 uptake capacity and very high mechanical stability even at the end of twentieth cycle, confirming the technical feasibility of the biosorption process for industrial applications.     

Effects of temperature and dissolved oxygen on Se(IV) removal and Se(0) precipitation by Shewanella sp. HN-41

Facultative anaerobic Shewanella sp. strain HN-41 was able to utilize selenite (Se(IV)) as a sole electron acceptor for respiration in anaerobic condition, resulting in reduction of Se(IV) and then precipitation of elemental Se nano-sized spherical particles, which were identified using energy-dispersive X-ray spectroscopy and X-ray absorption near-edge structure spectroscopy. When the effects on Se(IV) reduction to elemental Se were studied by varying incubation temperatures and dissolved oxygen contents, Se(IV) reduction occurred more actively with higher removal rate of Se(IV) in aqueous phase and well-shaped spherical Se(0) nanoparticles were formed from the incubations under N(2) (100%) or N(2):O(2) (80%:20%) at 30 degrees C with average diameter values of 181+/-40 nm and 164+/-24 nm, respectively, while relatively less amounts of irregular-shaped Se(0) nanoparticles were produced with negligible amount of Se(IV) reduction and removal under 100% of O(2). The Se particle size distributions based on scanning electron microscopy also showed a general tendency towards decreased Se particle size as oxygen content increased, whereas the particle size seemed uncorrelated to the change in the incubation temperature. These results also suggest that the size-controlled biological Se(0) nanospheres production may be achieved simply by changing the culture conditions.     

Estimation Of Selenium Concentration In Shallow Groundwater In Alluvial Fan Area In Tsukui, Central Japan

Total selenium (Se) and water-soluble Se in soil, and Se in a shallow groundwater were hydrogeochemically researched in an alluvial fan area in Tsukui, Central Japan. The water-soluble Se was estimated at average level of 2.6 ± 1.2μg Se kg⁻¹ dry soil (± SD, n = 25), showing less than 1% of the total Se (349–508μg Se kg⁻¹ dry soil) in soil. The monthly Se concentration in groundwater was average 2.2μg,L⁻¹, ranging 1.6–2.4μg,L⁻¹ during 2001–2003. The Se in groundwater significantly decreased with increasing groundwater level after rainfall. This result indicated that Se-bearing water percolated with relatively low Se concentration through the soil layer. According to our prediction model of linear regression curve on the observation data, Se concentration in the groundwater was estimated to be increasing with the very low rate of 4.35 × 10⁻³μg Se L⁻¹,yr⁻¹. The hydrogeochemical research and the result of the prediction model showed that any explosive increase of Se will hardly occur in this groundwater without an anthropogenic Se contamination.     

Desorption Kinetics of Benzene in a Sandy Soil in the Presence of Powdered Activated Carbon

Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption–desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q _irr) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption–desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q _irr) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4–40 times) rate constant for rapid process (k ₁) than that for slow process (k ₂), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.     

PCDD/F and dioxin-like PCB in Hong Kong air in relation to their regional transport in the Pearl River Delta region

PCDD/F and dioxin-like PCB were measured in 142 air samples of Hong Kong. The annual average PCDD/F and dioxin-like PCB concentrations obtained for Hong Kong air at Tap Mun (PCDD/F: 1724+/-1984; dioxin-like PCB: 1572+/-1170 fg m(-3)), Yuen Long (PCDD/F: 2927+/-2695; dioxin-like PCB: 4331+/-1962 fg m(-3)) and Tsuen Wan (PCDD/F: 1875+/-1502; dioxin-like PCB: 2972+/-1510 fg m(-3)) from January 2004 to March 2005 were comparable to other urban centers around the world and were within the Japanese and USA ambient air quality guidelines. A clear seasonal pattern was observed for PCDD/F, generally with a 50-60 times higher air concentration in winter when background northerly wind was weaker and land-sea breeze prevailed, resulting in regional transport; and a lower concentration in summer, due to the inflow of clean oceanic southeasterly wind from the South China Sea. A higher WHO-TEQ value of dioxin-like PCB (mainly attributed to the relatively higher WHO-TEQ value of PCB 126) in Yuen Long during winter, compared with other months, could also be related to the regional transport by the winter monsoon wind and the low mixing height in winter. Spatially, air concentrations of PCDD/F and dioxin-like PCB demonstrated a west-to-east gradient (with Yuen Long>Tsuen Wan>Tap Mun). It is suggested that PCDD/F and dioxin-like PCB were transported into the western airshed of Hong Kong from the Pearl River Delta by land-sea breeze circulation and confined to the northwestern part, due to the blocking effect of the northwestern airshed in Hong Kong.