电子束辐照降解水中氯霉素的研究

本研究对氯霉素(CAP)在不同条件下的电子束辐照降解进行了研究.结果表明,电子束辐照可有效去除水中CAP,低浓度CAP在酸性条件下的辐照降解更为显著,且降解过程符合准一级动力学模型.通过添加不同的自由基清除剂,发现HO·在CAP降解中起关键作用,此外,CAP分子也会吸收辐照而发生分解.水中共存的阴离子和腐殖酸(HA)对CAP辐照降解均有抑制作用,这跟其与HO·的反应速率常数大小有关,并且反应速率越大,其抑制能力越强.CAP在去离子水中的去除率高于其他实际水体,但辐照剂量为4 k Gy时,污水厂污水过滤水和胶体浓缩液中的CAP也可分别去除89.1%和81.7%.利用GC-MS检测到辐照后溶液中有6种中间产物,主要是通过脱水、不对称中心断键和脱酰胺作用形成.此外,IC检测有Cl-、NO-3和NO-2的产生,并且TOC在一定程度上降低,说明部分CAP被矿化.     

有机酸性腐蚀品生产危险性分析

目前我国化工生产中涉及大量有机酸性腐蚀品,通过对某市化工行业调查及分析,发现有机酸性腐蚀品生产普遍,而且生产原料易燃易爆,生产过程存在火灾爆炸危险,结合具体生产工艺,采用预先危险性分析法和作业条件的危险性评价法分析生产过程危险性,从而揭示并概括有机酸性腐蚀品生产危险性.为更好地促进我国安全生产,在此基础上探讨了一些针对性的安全措施.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

Physicochemical substance properties as indicators for unreliable exposure in microplate-based bioassays

In the last years many efforts were made to transform standardized algal test protocols into low-cost microplate assays. While advantages were pointed out frequently, limitations are not systematically addressed, thus hindering a widespread utilisation. In this study a group of organic substances with a wide distribution of volatility (log K_AW from −6.53 to −2.13) and lipophilicity (log K_OW from 1.26 to 4.92) was investigated with respect to the influence of these physicochemical properties on their algal toxicity in different assays. Therefore the EC₅₀ values were determined with a microplate assay based on ISO 8692 protocol and the results were compared with those of an established algal growth inhibition test conducted in air tight glass vessels. Using the ratio of the EC₅₀ values, a clear connection between biological response and volatility as well as lipophilicity of test substances could be detected. Chemicals with a log K_OW higher than 3 or a Henry coefficient log K_AW higher than −4 were identified as less effective in the microplate assay than in the comparative assay. The loss in nominal concentration due to physicochemical properties could be shown to contribute to this using HPLC analysis. Consequently, when using microplate assay’s one should be aware that lipophilic and volatile chemicals might be underestimated in their toxicity, which could be indicated from evaluating related physicochemical properties modelled from structural information prior to an experimental investigation.     

Effects of humic acids derived from lignite and cattle manure on antioxidant enzymatic activities of barley root

To investigate the effects of humic acids (HAs) on the ability of plants to defend themselves against oxidative stress, barley was hydroponically cultured in the absence and presence of HAs, and the antioxidant enzymatic activities (catalase, superoxide dismutase, ascorbate and glutathione peroxidases) of root tissue were evaluated. Auxin-like structures in HAs, which were extracted from an oxidation product of lignite (LHA) and compost derived from cattle manure (CHA), were identified by pyrolysis-gas chromatography/mass spectrometry (GC/MS) with tetramethylammonium hydroxide. The LHA, which had the lower molecular weight, was more effective in promoting the growth of barley root than CHA. However, the amounts of auxin-like structures in the CHA were much higher than those for LHA. The antioxidant enzymatic activities were initially decreased in the presence of LHA and CHA at the first day after refreshing the culture solution, but were significantly increased on the second day. The CHA sample, which contained relatively high levels of phenolic acids that contained auxin-like structures, was effective in increasing four types of enzymatic activities, while the activities of catalase and ascorbate peroxidase were increased in the presence of LHA, which contains naphthalene derivatives. These results indicate that using HAs as a supplement can be effective in enhancing antioxidation enzymatic activities, while the appearance of the effects is retarded because of the decomposition and release of auxin-like compounds from HAs by organic acids from the plant roots.     

区域环境风险评价及其关键科学问题

随着环境中能够检出的有毒污染物种类不断增多,基于制定环境标准来控制有毒污染物的传统方法正在受到挑战,而环境风险评价研究已成为当前环境领域研究的热点.加强风险评价方法研究,认识区域具有潜在风险的有毒污染物环境暴露与环境效应的关系,探讨风险评价中的关键科学问题,为风险管理提供科学依据已显得尤为紧迫.综述和讨论了环境风险评价技术的发展历史和区域生态风险评价存在的科学问题,并对深入开展区域环境风险评价研究提出了建议.     

腐殖酸、细颗粒泥沙对粉末活性炭吸附苯酚特性影响的研究

通过一系列实验,探讨了粉末活性炭吸附水中苯酚时,腐殖酸(HA)浓度和细颗粒泥沙用量对苯酚吸附量和去除率的影响.实验结果表明:在中性条件下,随着HA浓度的增加,粉末活性炭对苯酚的吸附量减少;在不同质量细颗粒泥沙的影响下,苯酚的去除率基本不变;在未加HA时,粉末活性炭对苯酚的吸附行为用Langmuir吸附等温式拟合效果最好,对苯酚的最大吸附量为150.60 mg/g,而在有HA存在时,粉末活性炭对苯酚的吸附行为用Freundlich吸附等温式拟合效果最好,对苯酚的最大吸附量为28.49 mg/g.     

Effect of humic substances on the precipitation of calcium phosphate

For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with synthetic water that contained 20 mg/L phosphate （as P） and 20 mg/L HS （as dissolved organic carbon, DOC） at a constant pH value in the range of 8.0-10.0. The concentration variations of phosphate, calcium （Ca） and HS were measured in the precipitation process; the crystalline state and compositions of the precipitates were analysed by powder X-ray diffraction （XRD） and chemical methods, respectively. It showed that at solution pH 8.0, the precipitation rate and removal efficiency of phosphate were greatly reduced by HS, but at solution pH ≥9.0, the effect of HS was very small. The Ca consumption for the precipitation of phosphate increased when HS was added; HS was also removed from solution with the precipitation of calcium phosphate. At solution pH 8.0 and HS concentrations ≤3.5 mg/L, and at pH ≥ 9.0 and HS concentrations ≤ 10 mg/L, the final precipitates were proved to be hydroxyapatite （HAP） by XRD. The increases of solution pH value and initial Ca/P ratio helped reduce the influence of HS on the precipitation of phosphate.     

聚合物驱采出水中聚丙烯酰胺的微生物联合降解作用研究

通过对2株细菌的培养降解实验研究聚丙烯酰胺(hydrolyzed polyacrylamide,HPAM)降解菌对水环境下聚丙烯酰胺的降解作用,讨论协同降解机理。2株降解聚丙烯酰胺的菌株假单胞菌CJ419、枯草芽孢杆菌FA16在初始30℃废水样品上培养,定期测量细菌生物量和HPAM降解率。培养30 d后CJ419和FA16对聚合物的降解率最大值分别达到30.4%和25%,而以1∶1比例的混合菌降解率最大值达到80.3%。对2株菌胞外各组分研究表明:混合菌降解HPAM的机理主要由胞外降解酶系水解聚合物侧链基团导致HPAM降解为小分子物质,同时生长过程中降解菌还会释放非蛋白还原性物质引发氧化反应共同参与HPAM降解。     

Detection of tritium sorption on four soil materials

In order to measure groundwater age and design nuclear waste disposal sites, it is important to understand the sorption behavior of tritium on soils. In this study, batch tests were carried out using four soils from China: silty clays from An County and Jiangyou County in Sichuan Province, both of which could be considered candidate sites for Very Low Level Waste disposal; silty sand from Beijing; and loess from Yuci County in Shanxi Province, a typical Chinese loess region. The experimental results indicated that in these soil media, the distribution coefficient of tritium is slightly influenced by adsorption time, water/solid ratio, initial tritium specific activity, pH, and the content of humic and fulvic acids. The average distribution coefficient from all of these influencing factors was about 0.1-0.2 mL/g for the four types of soil samples. This relatively modest sorption of tritium in soils needs to be considered in fate and transport studies of tritium in the environment.