Biodegradation of Hexachlorocyclohexane by two species of Bacillus isolated from contaminated soil

Biodegradation of α, β, γ and δ hexachlorocyclohexane (HCH) isomers was studied in broth medium and soil microcosm by Bacillus circulans and Bacillus brevis isolated from contaminated soil. Degradation of α and γ isomers by both the bacterial isolates was higher than thermodynamically stable β and δ isomers. However, B. circulans was found more effective than B. brevis for β and δ isomers. Maximum rate of degradation was recorded at 150 mg/L followed by 100 and 50 mg/L. Soil microcosm study revealed maximum degradation of HCH isomers in the treatment containing natural soil, pesticide and bacterial inocula than the treatment having sterilised soil, pesticide and bacterial isolates. Chloride release was positively co-related with HCH degradation in broth medium as well as in soil microcosm, suggesting that B. circulans and B. brevis hold promising potential by having efficient enzyme(s) required for dechlorination of HCH from contaminated sites.     

Photodegradation of the antibiotic spiramycin studied by high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry

The degradation of spiramycin induced by ultraviolet (UV) irradiation was studied at pH 3–4, 6–7 and 8–9 using high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry. Furthermore, the influence of hydrogen peroxide and oxygen on the photodegradation was investigated. Three degradation products were observed in the presence of oxygen and four in the absence of oxygen. The degradation kinetics were monitored as mass area-time curves, analyzed and described using subsequent follow-up reaction first-order models. The m/z values of the degradation products were determined to be 160, 322 and 366, the latter representing two separate products, the sugar moieties of spiramycin. Remainders of the macrocycle or the intact lactone ring of spiramycin were not observed, since the conjugated π-electron system was assumed photoexcited and thus undergoing photodegradation and fast destruction of the ring. The kinetic of the degradation of spiramycin itself was described using a first-order model. The degradation was accelerated upon addition of hydrogen peroxide. In contrast, systematic acceleration depending on pH could not be found. The absence of oxygen did not lead to any significant acceleration. The findings are interpreted in terms of the effectiveness of advanced oxidation processes and their potential use as a fourth purification step in wastewater treatment plants.     

Persistence and dissipation of synthetic pyrethroid pesticides in red soils from the Yangtze River Delta area

Laboratory incubation trials were conducted to investigate the effects of several factors on the persistence as well as the dissipation of three synthetic pyrethroid pesticides in red soils obtained from the Yangtze River Delta region in China. The pyrethroids selected for investigation were cypermethrin, fenvalerate, and deltamethrin, which continue to be used extensively to control pests on farmland in the region despite the concern that they are highly toxic to certain vertebrate and mammalian species. Data from this exploratory study showed that the dissipation half-lives (T _1/2) tended to correlate with soil pH and soil organic matter contents, but not with soil cation-exchange capacity. The T _1/2 values were seen to be shorter in soil samples fertilized with glucose than without. The rates of pyrethroid dissipation also tended to increase with increasing initial soil concentration, but were largely unaffected by whether the pesticides were present in the soil separately or as a mixture. Another noteworthy observation is that microbial activity appeared to dominate the degradation process. Findings of this type could offer valuable clues for future research directions in reducing pesticide persistence in soil, which in turn could lead to the ultimate reduction of environmental pollution caused by pyrethroid application to farmland in the region. Project supported by Chinese Academy of Sciences (Project No. KSCX2-YW-N-038) and the National Key Basic Research Support Foundation (973), China (No. 2002CB4108010).     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

欧美农药环境降解动力学评估方法比较

农药在环境中的降解行为是评估农药环境安全性的基础,农药的降解动力学通常以一级动力学模型描述。现有的环境暴露模型也均需要输入一级动力学模型的农药在土壤中50%消失时间(DT50)。但有时一级动力学模型不适用于描述农药在环境中,特别是土壤中的降解。因此欧盟和北美自由贸易区已发布了一系列关于使用非一级动力学模型计算DT50的导则。介绍了欧美降解动力学评估方法,并用多组降解数据比较了2种评估方法的区别。     

Stability studies of cholesterol lowering statin drugs in aqueous samples using HPLC and LC–MS

In this study, stability of statin drugs in different conditions, such as various pH, diverse solvents ratio, presence of UV, and sunlight have been investigated. Results suggest strong dependence of statins upon pH, potential environmental persistence towards sun light, and UV light degradation via singlet excited state obtained by excitation into the π–π* band. In acidic conditions interconversion between lactone and hydroxy acid forms in aqueous solutions at room temperature is retarded, while for the same sun-exposed samples are accelerated. Longer exposures lead to the degradation processes. Statin interconversion in water is much lower than in acetonitrile.     

Dichlorvos degradation studied by 31P-NMR

We studied the hydrolysis and TiO₂ photocatalysis of the pesticide dichlorvos at pH 2.6–9 using phosphorus-31 nuclear magnetic resonance (³¹P NMR). We found that the hydrolysis of dichlorvos led to the formation of dimethyl phosphate at pH 5.6–9. On the other hand, TiO₂ photocatalysis decomposed dichlorvos into dimethyl phosphate, which further reacted to form monomethyl phosphate at pH 2.6 and 9. Monomethylphosphate was hydrolysed into phosphate at pH 2.6. ³¹P NMR is therefore a promising tool to study the degradation of organophosphorus pesticides.     

Wet oxidation of recalcitrant lignin water solutions: experimental and reaction kinetics

The purpose of the research was to study the behavior of lignin degradation under different conditions (T 110–190°C, pO₂ 0.5–1.5 MPa, pH 5, 9 and 12) and to develop a predictive model. Temperature increase improved lignin removal from 75% at 110°C to 100% at 190°C (experimental). Increasing the pH enhanced the lignin removal efficiency from 30 to 97% (experimental). The developed model predicted the lignin degradation and changes in COD, BOD and TOC. The model agreed well with the experimental data (R ² = 0.93 at pH 5 and 12).     

Influence of some abiotic environmental factors on acute toxicity of inorganic lead to Cyprinus carpio var communis (Linn.) and Catla catla (Ham.) in simulated toxic aquatic environment

With the increase of water hardness from 60 to 720?mg/L CaCO₃, total alkalinity from 32 to 376?mg/L CaCO_3, pH from 7.6 to 7.9 and chloride from 28 to 350?mg/L, 96?h LC₅₀ on the basis of total lead increased from 8.2 to 1291?mg/L for Cyprinus carpio and 5.3 to 865?mg/L for Catla catla, when soil sediments were included these values were further raised to 1356 and 874?mg/L, respectively. The dissolved lead LC₅₀ values in all the treatments of soil and water was consistent with fixed amount of dissolved lead (1.04–1.78?mg/L) being needed for median lethal toxicity. Total lead toxicity also decreased with increase in pH from 6.3 to 11.3. 96?h LC₅₀ values increased for common carp 15 to 631?mg/L and for catla, 8 to 355?mg/L. But dissolved lead toxicity was found to increase with the increase of pH from 6.3 to 11.3 for both common carp (LC₅₀, 3.53 to 0.24?mg/L) and catla (LC₅₀, 2.21 to 0.09?mg/L). Removal of dissolved Pb with increasing carbonate content, particulate matter and pH due to adsorption, precipitation or coprecipitation reaction, reduced the dissolved lead concentration and thus the total lead toxicity. Increase in toxicity of lead with increase of exposure time was the biological response of longer contact time and decrease in dissolved lead toxicity with decrease in pH was due to increase H⁺ ion competition.     

Effect of curacron toxicity on the total serum protein content of Cyprinus carpio

An experiment was conducted on freshwater fish Cyprinus carpio to study the effect of the pesticide curacron on total serum protein. Curacron is an organophosphate pesticide and used by the farmers to protect their crops. This pesticide reaches the aquatic ecosystem by direct or indirect means and affects aquatic fauna. LC50 for curacron for C. carpio was calculated by the log-dose/probit regression line method and found to be 0.38?ppm at 96?h. Three sub-lethal concentrations (0.1, 0.01, and 0.001?mL?L^?1) were selected to expose the fish for 1, 7, 14, and 21days. Changes in total serum protein were observed at all pesticide concentrations and exposure periods. Total serum protein was decreased from control. At 1 and 7 days, the decrease was quantitative at all concentrations, while at 14 and 21 days, the fall was significant at all concentrations. Hence, human population may be at risk by consuming these contaminated fish.     

Kinetic studies of the degradation of parabens in aqueous solution by ozone oxidation

Ozone degradation of a mixture containing methylparaben, ethylparaben, propylparaben, butylparaben and benzylparaben was carried out in aqueous solution. The degradation followed the pseudo-first-order kinetic model and occurs with two ozonation stages with the observed rate constants of second stage ozonation, k _obs2, being higher than the observed rate constants in first stage, k _obs1. The k _obs1 of parabens was found to increase exponentially whilst k _obs2 was found to maximize at 35°C. Both k _obs1 and k _obs2 were found to decrease exponentially with respect to the initial concentration of parabens. Both pH and ozone dose showed positive effects on the rate of degradation. It was also observed that an ozone dose of 0.67 g/h resulted in the removal of 99% of parabens in 12 min, and also the removal of 61 and 32% of chemical oxygen demand (COD) and total organic carbon (TOC), respectively, in 3 h of ozonation time for a 500 μM of solution of parabens.     

Biodegradation kinetics of cymoxanil in aquatic system

A potential method to detoxify pesticides in aquatic system is using bioremediation. In this study, four microorganisms (Pseudomonas sp (EB11), Streptomyces sp. (EB12), Aspergillus niger (EB13) and Trichoderma viride (EB14) were isolated from cucumber leaves previously treated with cymoxanil using enrichment technique. These strains were evaluated for their potential to detoxify cymoxanil in aquatic system at the concentration level of 5×10^?4M. The effect of pH and temperature on the growth ability of the tested strains was also investigated by measuring the intracellular protein and mycelia dry weight for bacterial and fungal strains, respectively. Moreover, the remaining toxicity of cymoxanil after 28 days of incubation with tested strains was evaluated to confirm the complete removal of any toxic materials (cymoxanil and its metabolites). The results showed that the optimum pH for the growth of cymoxanil degrading strains (bacteria and fungi) was 7. A temperature of 30°C appears to be the optimum for the growth of either fungal or bacterial strains. Pseudomonas sp. (EB11) was the most effective strain in cymoxanil degradation followed Streptomyces sp (EB12), Trichoderma viride (EB14) and Aspergillus niger (EB13), with half-lives of 4.33, 9.5, 17.3 and 24.7 days, respectively. The degradation of cymoxanil by bacterial strains was much faster than fungal one. There is no remaining toxicity of cymoxanil detected in aqueous media previously treated with Pseudomonas sp. (EB11) for 28 days. The results suggest that bioremediation by Pseudomonas sp. (EB11) are promising for the detoxification of cymoxanil in aqueous media.     

Isolation and characterisation of a carbofuran degrading Burkholderia sp. PCL3 from carbofuran-phytoremediated rhizosphere soil

A bacterial strain capable of degrading carbofuran as the sole carbon source was isolated from carbofuran-phytoremediated rhizosphere soil of rice. A 16S rRNA study identified the strain as Burkholderia sp. (isolate PCL3). Free cells of isolate PCL3 possessed inhibitory-type degradation kinetics with a q _max of 0.087 day^?1 and S _m of 248.76 mg·L^?1. Immobilised PCL3 on corncob and sugarcane bagasse possessed Monod-type degradation kinetics with a q _max of 0.124 and 0.098 day^?1, respectively. The optimal pH and temperature with the highest degradation rate coefficient of carbofuran were pH 7.5 and 35 °C, respectively.     

A microinjection technique using a pH-sensitive dye to determine the gut pH of Calanus helgolandicus

By applying a microinjection technique previously used in cell biology, a pH-sensitive dye, 2,7-bis(2-carboxyethyl)-5,6-carboxyfluorescein) (BCECF), was injected into the gut of the copepod Calanus helgolandicus to determine pH under a range of feeding conditions. The median gut pH of the fore- and hindguts of starved individuals was 6.86 and 7.19, respectively. This was a consistently lower pH than that observed in copepods feeding on either the diatom Thalassiosira weissflogii, the dinoflagellate Prorocentrum micans, or the coccolithophorid Emiliania huxleyi (Strain 92D), all of which had a median gut pH>7.0. In all treatments, the median pH of the foregut was more acidic than the median of the hindgut, implying that the foregut is the site of acid secretion. The results, which demonstrate pH values down to 6.11, are discussed in terms of coccolith dissolution, pigment degradation and digestive enzyme activity.     

极性有机物整合采样技术在监测水环境中农药的应用

明确水环境中农残的污染状况对研究其环境行为和生态风险至关重要。传统主动采样法耗能、耗力且单次采样仅获得瞬时浓度值。被动采样节能、方便且为时间加权平均浓度,利于大规模采样。极性有机物整合采样技术(polar organic chemical integrative sampler,POCIS)是针对极性有机物的被动采样技术,近年来在水环境中农药监测的运用越来越广泛。本文概述了POCIS结构、原理和校正方法,探讨了环境因素(如水流速率、温度、p H、溶解性有机质、盐度和膜污染)、化合物性质及POCIS结构对农药采样速率(Rs)的影响。此外,综述了POCIS在监测水环境中农药的应用,展望了POCIS在该领域中的问题、解决方式及前景。     

Response of sea urchin pluteus larvae (Echinodermata: Echinoidea) to reduced seawater pH: a comparison among a tropical, temperate, and a polar species

Ocean acidification, as a result of increased atmospheric CO₂, is predicted to lower the pH of seawater to between pH 7.6 and 7.8 over the next 100 years. The greatest changes are expected in polar waters. Our research aimed to examine how echinoid larvae are affected by lower pH, and if effects are more pronounced in polar species. We examined the effects of lowered pH on larvae from tropical (Tripneustes gratilla), temperate (Pseudechinus huttoni, Evechinus chloroticus), and a polar species (Sterechinus neumayeri) in a series of laboratory experiments. Larvae were reared in a range of lower pH seawater (pH 6.0, 6.5, 7.0, 7.5, 7.7, 7.8 and ambient), adjusted by bubbling CO₂ gas. The effect of pH on somatic and skeletal growth, calcification index, development and survival were quantified, while SEM examination of the larval skeleton provided information on the effects of seawater pH on the fine-scale skeletal morphology. Lowering pH resulted in a decrease in survival in all species, but only below pH 7.0. The size of larvae were reduced at lowered pH, but the external morphology (shape) was unaffected. Calcification of the larval skeleton was significantly reduced (13.8–36.9% lower) under lowered pH, with the exception of the Antarctic species, which showed no significant difference. SEM examination revealed a degradation of the larval skeletons of Pseudechinus and Evechinus when grown in reduced pH. Sterechinus and Tripneustes showed no apparent difference in the skeletal fine structure under lowered pH. The study confirms the need to look beyond mortality as a single endpoint when considering the effects of ocean acidification that may occur through the 21st century, and instead, look for a suite of more subtle changes, which may indirectly affect the functioning of larval stages.     

Impact of deltamethrin on the endophytic fungal community of a Chinese cabbage,Brassica chinensis

Endophytic fungi, being closely associated with their host plants, are an important part of the ecosystem and food web. In modern agriculture, pesticides are widely used. The impact of pesticides on the endophytic fungal community of crops remains poorly understood. In this paper, Chinese cabbage Brassica chinensis, a popular leafy vegetable consumed worldwide, was selected for evaluating the potential effects of a pesticide, deltamethrin, on the endophytic fungal community. By culture method, 195 endophytic fungal strains classified into 39 taxa and 186 strains classified into 30 taxa, respectively, were isolated from the pesticide-treated and untreated B. chinensis samples. Sirodesmium spp. were the predominant endophytic fungi from both samples. The colonisation rates of endophytic fungi of the treated and the untreated samples were not significantly different, as determined by one-way analysis of variance (p?>?.05). The Shannon diversity indexes (H′) were close, being 2.216 and 2.152, respectively. However, the endophyte compositions of the treated and the untreated samples were significantly different (p?B. chinensis.     

The use of algae to control heavy metals in the environment

Aqueous effluents from a lead mining and milling operation located in southeastern Missouri, USA, caused a degradation of stream quality despite treatment by a large tailings pond. The receiving stream was choked with algal mats which accumulated unexpectedly large amounts of manganese, lead and zinc. A wastewater treatment system was designed to utilize algae and benthic macrophytes to remove metals from the tailings pond effluent. The system has proved successful and water quality in the receiving stream has been improved to drinking water standards.Experiments were conducted to understand more fully the phenomenon of heavy metal accumulation by algae. Radionuclides (²¹⁰Pb,²⁰³Hg,⁶⁵Zn,¹⁰⁹Cd) were used in conjunction with commercially available microculture apparatus to screen several species of algae for heavy metal accumulation. It was found that all species of algae studied concentrated mercury, green algae were more efficient accumulators of cadmium than blue-green algae, one alga (Chlamydomonas) proved best at removing lead from solution and no alga studied removed zinc.     

Effect of carbon dioxide concentration on calcification in the red coralline alga Bossiella orbigniana

The relationship between various experimental concentrations of CO₂ and calcification in Bossiella orbigniana (Decaisne) was studied by measuring Ca-45 incorporation into the crystalline matrix. Air containing CO₂ at partial pressures (P_{CO 2}) of 0.04 to 5.5% was bubbled through synthetic seawater in incubation vessels. The resultant pH values in the presence of plants ranged from 6.5 to 8.7. The maximum calcification rate appears to lie between 0.11 and 1.05% P_{CO 2}. The data suggest that calcification is controlled by a biological process that may be sensitive to pH and/or to the relative bicarbonate concentration. The data also suggest that a severalfold increase in CO₂ over the present atmospheric level might lead to increased calcification in this marine alga.     

Ionic dye adsorption by zinc oxide nanoparticles

The adsorption behaviour of Basic Red 12, Acid Orange 7 and Acid Blue 1 on zinc oxide nanoparticles (ZNP) has been investigated to understand the physicochemical process involved and to explore the possible use of nanoparticles in the treatment and management of textile waste matter. The dye removal capacity of ZNP towards Basic Red 12, Acid Orange 7 and Acid Blue 1 was found to be 15.64, 6.78 and 6.38 mg g^?1, respectively. The adsorption process was pH dependent and optimum pH values of 9.0, 2.0 and 4.0 were obtained for Basic Red 12, Acid Orange 7 and Acid Blue 1, respectively. Equilibrium was established after 1.0 h for all dyes. Langmuir, Freundlich and Temkin isotherm models were applied to the system. The adsorbent ZNP was characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) and Fourier transform infrared (FTIR) techniques. SEM analysis revealed the noticeable nanoporous morphology of the material. The results of FTIR spectroscopy showed that the process is driven by an electrostatic complexation mechanism. XRD studies revealed the nanocrystalline structure of ZNP. BET surface area measurement suggested a high pore volume and large surface area for the adsorbent. The kinetic measurements suggested pseudo-second-order kinetic processes with high regression coefficients and smaller standard error of estimate values and lower residual sum of squares. The thermodynamic measurements suggested that all processes were exothermic and accompanied by negative values for Δ G⁰, Δ S⁰ and Δ H⁰.