Integral assessment of estrogenic potentials in sediment-associated samples

Background, aim, and scope  The enzyme-linked receptor assay (ELRA) detects estrogenic and anti-estrogenic effects at the molecular level of receptor binding and is a useful tool for the integrative assessment of ecotoxicological potentials caused by hormonally active agents (HAA) and endocrine disrupting compounds (EDC). The main advantage of the ELRA is its high sample throughput and its robustness against cytotoxicity and microbial contamination. After a methodological adaptation to salinity of the ELRA, according to the first part of this study, which increased its salinity tolerance and sensitivity for 17-β-estradiol, the optimised ELRA was used to investigate 13 native sediments characterised by different levels of salinity and chemical contamination. The applicability of the ELRA for routine analysis in environmental assessment was evaluated. Salinity is often a critical factor for bioassays in ecotoxicological sediment assessment. Therefore, salinity of the samples was additionally adjusted to different levels to characterise its influence on elution and binding processes of receptor-binding substances. Materials and methods  The ELRA was carried out with the human estrogen receptor α (ER) in a 96-well microplate format using the experimental setup known from the competitive immunoassay based on ligand–protein interaction. It is an important improvement that a physiologically relevant receptor was used as a linking protein instead of an antibody. The microplates were coated with a 17-β-estradiol-BSA conjugate, and dilution series of estradiol and of native sediment samples were added and incubated with the ER. After a washing step, a biotinylated mouse anti-ER antibody was added to each well. Receptor binding to estradiol, agonistic and antagonistic receptor binding, were determined by a streptavidin-POD-biotin complex with subsequent measurement of the peroxidase activity at the wavelength of 450 nm using a commercial ELISA multiplate reader. The sediment elutriates and pore water samples of sediments were tested in a dilution series to evaluate at which dilution step the receptor-binding potential ends. In the elution process (see Section 2.1 to 2.2), a method was developed to adjust the salinity to the levels of the reference testings, which offers an appropriate option to adjust the salinity in both directions. Statistical evaluation was made with a combination of the Mann–Whitney U test and the pT-method. Results  This part of the study characterised the environmental factor ‘salinity’ for prospective applications of the ELRA. Using reference substances such as 17-β-estradiol, the ELRA showed sigmoid concentration-effect relations over a broad range from 0.05 μg/l to 100 μg/l under physiological conditions. After methodological optimisation, both sensitivity and tolerance of the assay against salinity could be significantly raised, and the ELRA became applicable under salinity conditions up to concentrations of 20.5‰. The mean relative inter-test error (n = 3) was around 11% with reference substances and below 5% for single sediments elutriates in three replicates each. For sediment testings, the pore water and different salinity-adjusted elutriates of 13 sediments were used. A clear differentiation of the receptor-binding potential could be reached by application of the pT-method. Thereby, pT-values from one to six could be assigned to the sediments, and the deviation caused by the different salinity conditions was one pT-value. The mean standard deviation in the salinity adaptation procedure of the elutriates was below 5%. Discussion  Although the ELRA has already been used for assessments of wastewater, sludge and soil, its applicability for samples to different salinity levels has not been investigated so far. Even if the ELRA is not as sensitive as the E-screen or the YES-assay, with regard to reference substances like 17-β-estradiol, it is a very useful tool for pre-screening, because it is able to integrate both estrogenic as well as anti-estrogenic receptor-binding effects. According to the results of sediment testing, and given the integrative power to detect different directions of effects, the ELRA shows sufficient sensitivity and salinity tolerance to discriminate receptor-binding potentials in environmental samples. Conclusions  The optimised ELRA assay is a fast, cost-effective, reliable and highly reproducible tool that can be used for high-throughput screening in a microplate format in detecting both estrogenic and anti-estrogenic effects. Additionally, the ELRA is robust against microbial contaminations, and is not susceptible towards cytotoxic interferences like the common cell-culture methods. The general applicability and sufficient sensitivity of the ELRA was shown in freshwater environments. Marine and brackish samples can be measured up to salinity levels of 20.5‰. Recommendations and perspectives  In view of the proven sensitivity, functionality and the fastness of the ELRA, it is recommendable to standardise the test method. At the moment, no adequate in vitro test procedure exists which is standardised to DIN or ISO levels. The E-screen and the yeast estrogen/androgen screens (YES/YAS) sometimes underlie strong cytotoxic effects, as reported in the first part of this study. Further development of an ELRA assay using human androgen receptors appears to be very promising to gain information about androgenic and anti-androgenic effects, too. This would offer a possibility to use the ELRA as a fast and reliable pre-screening tool for the detection of endocrine potentials, thus minimising time and cost-expensive animal experiments.     

Aqueous high‐temperature chemistry of arsenic‐containing compounds in water at 300°C

Arsenic compounds, and especially organo‐arsenic derivatives, are highly toxic and many have been manufactured as chemical warfare agents. This study was designed to provide background information relevant to the potential application of aquathermolysis techniques for the detoxification of such potent military warfare agents. Six arsenic‐containing compounds with structural features which mimic known agents were studied in neutral superheated water: 4‐aminophenylarsine oxide, 4‐arsanilic acid, 4‐nitrophenylarsonic acid, 5, 10‐dihydro‐10‐ethylphenarsazine, tetraphenylarsonium chloride hydrate, and (3‐cyanopropyl)dimethyl(2‐phenethyl)arsonium bromide. Most of these compounds were moderately susceptible to hydrolysis for 1h at 300°C. o‐ and p‐Aminosubsituted arsenic compounds were more reactive than compounds with an electron‐withdrawing group substituent. Aromatic C—As bonds were more resistant to cleavage than aliphatic C—As bonds.     

加热移除废弃聚氨酯硬泡中CFC-11的研究

研究了聚氨酯硬泡在不同温度加热过程中的质量损失、生成的气体成分及硬泡结构变化,并对加热聚氨酯硬泡时所释放的发泡剂CFC-11(CCl3F)进行了测定.结果表明,在80~160℃加热聚氨酯硬泡时,CFC-11的释放速率随温度的增加而增加.将破碎后的硬泡颗粒在160℃下加热,既保证硬泡颗粒不发生热解反应,又使包裹和吸附于硬泡中的CFC-11移除速率最快.在160℃下加热过4mm筛硬泡颗粒1,2,4h后,可分别移除的CFC-11占硬泡颗粒中总量的84.5%、95.5%和96.6%,残余CFC-11则需足够长时间才可移除,而加热释放气体中CFC-11占82%~85%.     

飞灰螯合剂中挥发性污染物的释放

采集了4个市售飞灰螯合剂样品，分析其在20，40℃下挥发性污染物的释放规律.结果表明，释放的挥发性污染物主要有甲醛、乙醛、苯、异戊醛/异丙醇、甲硫醇、乙硫醇等；其中3个螯合剂样品甲醛的释放浓度在20℃为748~1325 μg/L-螯合剂，占释放的易挥发污染物的68%~96%（质量比），在40℃为4282~6822 μg/L-螯合剂，占释放的易挥发污染物的87%~95%（质量比）.随着温度升高，释放的挥发性污染物种类变多，部分污染物浓度增加，40℃时，4个螯合剂样品释放的易挥发污染物浓度比20℃时增加了142%~444%.元素分析、拉曼光谱和热重分析结果表明，4个螯合剂的主要有效成分相似，为二硫代氨基甲酸盐类物质.因此，推测这种飞灰螯合剂在稀释和飞灰稳定化过程中，对工作人员的健康可能有潜在的危害风险，应收集释放的气体并进行处理；且在飞灰填埋过程中，可能会导致渗滤液中NH₄⁺-N等物质的浓度升高，增加渗滤液的处理难度.     

FPSO工艺水舱阳极快速消耗原因分析

目的 研究FPSO工艺水舱中铝牺牲阳极消耗过快的原因。方法 参照GB 17848—1999牺牲阳极电化学性能试验方法,对比水舱环境与普通环境下,在役阳极的电化学性能数据,并模拟水舱环境,监测阳极工作时实际的发生电流与工作电位等情况,据此分析牺牲阳极在工艺水舱中消耗过快的原因。结果 在常温（25 ℃）、常温充空气、高温（65 ℃）充空气等条件下,阳极的电化学容量分别是2522.07、2464.29、1943.74 Ah/kg,且高温（65 ℃）充空气环境下阳极的晶间腐蚀较其他两组试验严重许多,说明温度是影响阳极电化学容量的关键因素。在模拟工艺水舱环境下,实测的阳极发生电流最高可达100 mA。将工艺水与海水1:5稀释后,实测的保护电流密度最高达45 mA,说明工艺水中存在大量的去极化剂,是造成阳极快速消耗的又一重要因素。结论 工艺水舱环境下,阳极发生严重的晶间腐蚀,严重影响了阳极的电化学容量,使阳极寿命缩短。工艺水成分中含大量去极化剂,使船舱所需的保护电流密度大大增加,促使阳极发生电流加大,亦缩短了阳极的实际服役寿命。     

海洋工程用新型牺牲阳极设计与性能研究(Ⅴ)——导管架平台阴极保护设计探讨

目的 针对不同设计使用年限的导管架平台,通过对比新型阳极和常规阳极用量来评价新型阳极的优势和不足。方法 针对设计寿命15年和30年的导管架平台,计算满足不同阶段保护电流需求的新型阳极和常规阳极的需求量。结果 当导管架平台设计年限较短,比如15年,牺牲阳极用量由初期保护电流需求量决定,新型阳极的使用可以达到节约阳极用量的目的。当设计年限较长,比如30年,牺牲阳极用量则由维持电流需求量决定,采用新型阳极并不能节约阳极用量。结论 并非所有设计年限的导管架平台使用新型阳极都能达到节约用量的目的,具体要根据实际计算结果而定。     

温度对镁合金牺牲阳极材料电化学行为的影响研究

目的研究温度对常用镁合金阳极材料MIC、AZ31、AZ63电化学行为的影响。方法根据GB/T 17848—1999,采用四天加速试验法,在25～70℃的人造海水介质中进行阳极电化学性能评价,并观察腐蚀后阳极的宏观腐蚀形貌。采用极化曲线测试技术,研究温度对加速试验前后阳极的极化行为影响。结果随着温度的升高,三种镁阳极的局部腐蚀明显加剧,溶解状态逐渐变得不均匀。随着温度的上升,三种镁阳极的实际电容量和电流效率呈小幅增加趋势,温度的影响不显著。极化曲线显示,镁阳极表现出活化溶解特征,温度升高明显促进了镁阳极的阴极过程,自腐蚀速率逐渐增加。结论在腐蚀初期,温度升高明显促进了镁合金阳极的腐蚀过程,但对镁阳极的电化学性能影响不显著,这可能与后期腐蚀产物生成以及表面状态的变化有关。     

化学工程固沙在塔里木沙漠公路沙害防治中的适宜性

由于天然材料日益紧缺 ,研制适宜于流动性沙漠地区公路沙害防治的人工替代材料势在必行 .结合塔里木沙漠公路沙害环境 ,实验室优选出 L VA、LVP、WBS和 STB 4种抗性较好的固沙剂 ,对其理化性能、粘结体力学性能和抗风蚀性能等测试结果表明 :颗粒粒径 0.2μm～ 0.5μm,粘度 12 Pa·s～ 15Pa·s;10℃～70℃温度下无沉淀 ,不燃烧 ;实验抗压强度 1.0 MPa～12.1 MPa;10℃～-20℃低温下重量损失率 0%～ 1.8%;紫外光照射 300h强度损失率 0%～ 42%;在 5m·s^-1～253m·s^-1实验风速下 ,风蚀量 0g·(106cm²·h)^-1～4.0 g·(106cm²·h)^-1 ;现场试验固结层厚度 0.2 mm～0.5mm,强度高 .化学工程固沙技术适宜于塔里木沙漠公路沙害防治 .     

Toxicity of the nerve agent tabun to Daphnia magna, a new experimental species in military toxicology

Daphnia magna, a freshwater microcrustacean, is currently tested as an alternative experimental species in research dealing with nerve agents poisonings treatment. Because of this, the toxicity of the nerve agent tabun (a cyanide-group containing organophosphate) to Daphnia had to be examined by estimating the EC₅₀ values. The immobilization of daphnids was chosen as the end-point. It was found that D. magna is sensitive to small amounts of tabun, even after 15 min exposure, and tabun toxicity increases with time. The estimated EC₅₀ values for 15, 30, 45, and 60 min exposure were as follows: 67.39, 38.10, 26.95, and 21.9 μg l^-1. In addition, the toxicity of media to which tabun was added 24 h before the start of experiments was examined. The results obtained indicate that daphnids can be used in experiments with nerve-agent intoxication treatment.     

海洋工程用新型牺牲阳极设计与性能研究(Ⅳ)——导管架平台阴极保护应用研究

目的通过构型优化设计了一种新型牺牲阳极,使其在与常规阳极质量相当的前提下,增加初期发生电流,使被保护体较快极化到保护电位,后期发生电流降低,满足平均和末期保护电流需要,达到节约牺牲阳极用量的目的。方法在传统梯形阳极两侧增加两个翼翅,降低接水电阻,增加初期发生电流。翼翅优于本体快速溶解,其表面积迅速减小,发生电流随之降低。结果质量与常规阳极相近的新型阳极,初期发生电流增加30%以上,远高于设计值10%,初期极化完成后,新型阳极发生电流快速降低,达到与常规阳极相当的发生电流。结论据此试验结果对导管架平台水下结构进行阴极保护设计,可达到节约牺牲阳极用量的目的。