电化学还原-氧化工艺降解4-氯酚的毒性研究

采用紫外光还原法制备了Pd-Fe/石墨烯催化阴极,并以Ti/IrO_2/RuO_2为阳极,构成三电极体系(双阴极)和两电极体系(单阴极)的电化学还原-氧化降解工艺,分别对4-氯酚进行降解.采用离子色谱、高效液相色谱、TOC仪对4-氯酚降解过程中中间产物及其浓度进行测定.根据公式计算降解过程中理论计算毒性值,应用发光细菌法测定降解过程中的实际毒性值,对理论计算毒性值与实际毒性值进行比较,分析不同体系下降解过程中毒性的变化规律.结果表明,两种工艺体系在最佳降解条件下,阴极室毒性均呈下降的趋势,由于降解过程中在阳极室生成高毒性的苯醌,阳极室毒性均先升高后降低.通过相关性分析得到,两种体系理论计算毒性与实际毒性在P=0.01水平下,相关性系数均为1,显著相关,表明降解过程中实际毒性的测定结果真实可靠.降解至120 min时,三电极体系毒性小于两电极体系,表明三电极体系优于两电极体系.据此提出实际毒性测定方法在电化学还原-氧化工艺降解氯酚类有机废水毒性测试的工业应用中有着广泛的前景.     

锑的表生地球化学行为与环境危害效应

锑(Sb)是一种典型的有毒有害重金属元素。由于自然过程和人为活动的影响,锑及其化合物广泛分布于大气、土壤、水体等表生环境中,锑的环境污染日益严重。Sb不是植物必需元素,但能够被植物体及农作物吸收。Sb对人体和动物体产生慢性毒性及潜在致癌性。本文主要通过分析Sb的主要矿物、锑及其化合物在表生环境中的分布与迁移特性,来阐述人体可能的锑暴露途径及由此产生的环境危害效应。     

Diffusion pollution from livestock and poultry rearing in the Yangtze Delta,China

BACKGROUND: The Yangtze Delta is one of the most developed regions in China and includes Shanghai, eight cities in Jiangsu province and eight cities in Zhejiang province. Meat consumption in this region has increased with economic growth, and most of the consumed meat is produced locally. The water quality of surface waters has deteriorated in recent years. An example was the huge blue-green algae bloom in Tai Lake in late May 2007, which affected millions of people's daily drinking water. However, animal husbandry is considered to be one of the main pollution sources. METHODS: Pollutants (NH3-N, total phosphorus (TP), and total nitrogen (TN)) excreted by livestock and poultry, and the resultant COD (chemical oxygen demand) and BOD (biochemical oxygen demand), were estimated using two different methods based on different data sets. RESULTS: The number of livestock and poultry has remained stable in the Yangtze Delta over the four years from 1999 to 2002, with the average number of pigs, cattle, sheep and poultry being 21.1 M, 0.4 M, 7.7 M and 597.6 M, respectively. Pollutants in livestock and poultry excreta estimated by Method I were: 0.12 Mt NH3-N, 0.11 Mt TP and 0.29 Mt TN, resulting in COD and BOD of 1.34 Mt and 1.30 Mt, respectively, while the estimations based on Method II were: 0.18 Mt NH3-N, 0.15 Mt TP and 0.40 Mt TN, resulting in COD and BOD of 1.95 Mt and 1.80 Mt, respectively. DISCUSSION: Pollutants excreted annually by livestock and poultry in the Yangtze Delta are estimated to be: 0.17 Mt NH3-N, 0.16 Mt TP and 0.42 Mt TN, giving rise to a COD of 1.86 Mt and a BOD of 1.72 Mt. Approximately 25% of this pollution was estimated to enter water bodies, which means that the annual pollutant load is 43,700 t NH3-N, 39,400 tTP, 104,600t TN with a COD of 465,000 tand a BOD of 430,100 t. Pollutants from animal husbandry were similar in magnitude to those from industrial wastewater. Pigs produced the most pollution, followed by poultry, cattle and sheep. The pollution load from animal husbandry in the Yangtze Delta is about twice the average level of the whole of China. CONCLUSIONS: Domestic wastewater was the main pollution source in the Yangtze Delta, followed by pollution from raising livestock and poultry and from industrial wastewater. The pollution load in Shanghai and Jiaxing were the greatest, followed by 7 cities of Jiangsu province (except Suzhou) and other cities of Zhejiang province and Suzhou. Pigs and poultry produced about 90% of the total pollutants from animal husbandry. RECOMMENDATIONS AND PERSPECTIVES: The local governments, especially in Shanghai and Jiaxing, should focus their attention on the pollution produced by livestock and poulrry. Controlling pollution from pigs and poultry will have the greatest impact in this region. Control of pollution will be facilitated by the development of large-scale livestock and poultry farming units and a shift away from small scale husbandry.     

家用洗衣粉中磷对斜生栅藻生长的影响

以洗衣粉中的有机磷为磷源,通过室内模拟的方法研究在不同磷浓度的水体条件下斜生栅藻的生长情况,以及磷对斜生栅藻的生长是否有毒害作用.通过显微计数测定藻细胞数目来探讨洗衣粉中磷对斜生栅藻生长的影响;同时分析了洗衣粉中磷对斜生栅藻96 h生长期中光合色素的影响.结果表明,洗衣粉中的磷除了促进藻生长外,其浓度过低或过高都会抑制藻的生长.由实验结果可得,磷对藻生长的富营养化作用和毒性作用取决于磷浓度的高低.     

添加不同钝化剂降低污泥堆肥的植物毒性研究

高温堆肥后污泥的土地利用可充分发挥资源化、无害化的优势,污泥土地利用防止重金属污染一直是污泥施用中最重要的问题。通过测验发芽率指数这一代表植物毒性的指标证明,通过在污泥堆肥中加入粉煤灰、磷矿粉和草炭等不同的改性剂或重金属钝化剂可大大降低堆肥的植物毒性,从而降低污泥中重金属的可利用性。     

牛粪厌氧发酵的载体筛选试验研究

为了提高厌氧发酵装置的效率,人们研究了各种各样的方法和措施,其中应用填料或载体使生物菌能够延长驻留期是其中的方法之一,开展载体筛选及其结构设计在厌氧发酵装置中的试验,有助于对此问题的深入研究以及将其成果应用于生产实践。通过静态载体筛选试验选择了玻璃纤维作为载体、PVC塑料管作为载体骨架制成的装置在动态序批式厌氧发酵装置中进行了试验。结果表明：此载体骨架结构对于牛粪动态厌氧发酵具有明显的提高产气效率、改变产气质量和促进有机物转化为挥发性脂肪酸的作用。     

A fluorescence-based bioassay for aquatic macrophytes and its suitability for effect analysis of non-photosystem II inhibitors

Background, Goals and Scope During the last years the miniaturization of toxicity test systems for rapid and parallel measurements of large quantities of samples has often been discussed. For unicellular algae as well as for aquatic macrophytes, fluorescence-based miniaturized test systems have been introduced to analyze photosystem II (PSII) inhibitors. Nevertheless, high-throughput screening should also guarantee the effect detection of a broad range of toxicants in order to ensure routinely applicable, high-throughput measuring device experiments which can cover a broad range of toxicants and modes of action others than PSII inhibition. Thus, the aim of this study was to establish a fast and reproducible measuring system for non-PSII inhibitors for aquatic macrophyte species to overcome major limitations for use. Methods A newly developed imaging pulse-amplitude-modulated chlorophyll fluorometer (I-PAM) was applied as an effect detector in short-term bioassays with the aquatic macrophyte species Lemna minor. This multiwell-plate based measuring device enabled the incubation and measurement of up to 24 samples in parallel. The chemicals paraquat-dichloride, alizarine and triclosan were chosen as representatives for the toxicant groups of non-PSII herbicides, polycyclic aromatic hydrocarbons (PAHs) and pharmaceuticals and personal care products (PPCPs), which are often detected in the aquatic environment. The I-PAM was used (i) to establish and validate the sensitivity of the test system to the three non-PSII inhibitors, (ii) to compare the test systems with standardized and established biotests for aquatic macrophytes, and (iii) to define necessary time scales in aquatic macrophyte testing. For validation of the fluorescence-based assay, the standard growth test with L. minor (ISO/DIS 20079) was performed in parallel for each chemical. Results The results revealed that fluorescence-based measurements with the I-PAM allow rapid and parallel analysis of large amounts of aquatic macrophyte samples. The I-PAM enabled the recording of concentration-effect-curves with L. minor samples on a 24-well plate with single measurements. Fluorescence-based concentration-effect-curves could be detected for all three chemicals after only 1 h of incubation. After 4–5 h incubation time, the maximum inhibition of fluorescence showed an 80–100% effect for the chemicals tested. The EC50 after 24 h incubation were estimated to be 0.06 mg/L, 0.84 mg/L and 1.69 mg/L for paraquatdichloride, alizarine and triclosan, respectively. Discussion The results obtained with the I-PAM after 24 h for the herbicide paraquat-dichloride and the polycyclic aromatic hydrocarbon alizarine were in good accordance with median effective concentrations (EC50s) obtained by the standardized growth test for L. minor after 7 d incubation (0.09 mg/L and 0.79 mg/L for paraquat-dichloride and alizarine, respectively). Those results were in accordance with literature findings for the two chemicals. In contrast, fluorescence-based EC50 of the antimicrobial agent triclosan proved to be two orders of magnitude greater when compared to the standard growth test with 7 d incubation time (0.026 mg/L) as well as with literature findings. Conclusion Typically, aquatic macrophyte testing is very time consuming and relies on laborious experimental set-ups. The I-PAM measuring device enabled fast effect screening for the three chemicals tested. While established test systems for aquatic macrophytes need incubation times of ≥ 7 d, the I-PAM can detect inhibitory effects much earlier (24 h), even if inhibition of chemicals is not specifically associated with PSII. Thus, the fluorescence-based bioassay with the I-PAM offers a promising approach for the miniaturization and high-throughput testing of chemicals with aquatic macrophytes. For the chemical triclosan, however, the short-term effect prediction with the I-PAM has been shown to be less sensitive than with long-term bioassays, which might be due to physicochemical substance properties such as lipophilicity. Recommendations and Perspectives The results of this study show that the I-PAM represents a promising tool for decreasing the incubation times of aquatic macrophyte toxicity testing to about 24 h as a supplement to existing test batteries. The applicability of this I-PAM bioassay on emergent and submerged aquatic macrophyte species should be investigated in further studies. Regarding considerations that physicochemical properties of the tested substances might play an important role in microplate bioassays, the I-PAM bioassay should either be accompanied by evaluating physicochemical properties modeled from structural information prior to an experimental investigation, or by intensified chemical analyses to identify and determine nominal concentrations of the toxicants tested. The chemicals paraquat-dichloride, alizarine and triclosan were chosen as representatives for the toxicant groups of non-PSII herbicides, PAHs and PPCPs which are often detected in the aquatic environment. Nevertheless, in order to ensure a routinely applicable measuring device, experiments with a broader range of toxicants and samples of surface and/or waste waters are necessary. ESS-Submission Editor: Dr. Markus Hecker (MHecker@Entrix.com)     

Growth, photosynthetic and respiratory responses to sub-lethal copper concentrations in Scenedesmus incrassatulus (Chlorophyceae)

In the present paper we investigated the effects of sub-lethal concentrations of Cu²⁺ in the growth and metabolism of Scenedesmus incrassatulus. We found that the effect of Cu²⁺ on growth, photosynthetic pigments (chlorophylls and carotenoids) and metabolism do not follow the same pattern. Photosynthesis was more sensitive than respiration. The analysis of chlorophyll a fluorescence transient shows that the effect of sub-lethal Cu²⁺ concentration in vivo, causes a reduction of the active PSII reaction centers and the primary charge separation, decreasing the quantum yield of PSII, the electron transport rate and the photosynthetic O₂ evolution. The order of sensitivity found was: Growth > photosynthetic pigments content = photosynthetic O₂ evolution > photosynthetic electron transport > respiration. The uncoupled relationship between growth and metabolism is discussed.     

Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater

This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.     

苯酚类化合物对日本长腿蛙蝌蚪的急性毒性与构效关系研究

利用半静态法测定了21种取代苯酚类化合物对日本长腿蛙蝌蚪的24h 急性致死毒性(24h-LC50),并进行了定量结构活性相关研究.研究表明:大部分酚类化合物的毒性表现为极性麻醉作用.影响毒性的因素有化合物的疏水性、电性及离解行为等.