共价接枝聚季铵盐型杀生剂的制备及工艺优化

研制了一种表面接枝的聚季铵盐型高分子杀生剂,并考察了其对水溶液中的各种菌体的杀生效果,通过对活化剂和硅胶载体的优化,确定了最佳制备方案。结果表明,可以使用价格低廉的-γ氯丙基三甲氧基硅烷代替4-溴丁酰氯作为活化剂,载体硅胶的选择范围广泛,可以采用比表面积大、价格低廉的硅胶作为载体。扫描电镜和红外光谱检测表明杀生功能基团已共价接枝到载体硅胶上。杀生性能检测表明该杀生剂可以在低浓度、短时间内降低水溶液中的大肠杆菌、金黄色葡萄球菌以及真菌的活菌量。显微镜观察发现,杀生剂的灭藻过程是杀生剂表面吸附(藻体)、接触、灭藻。结果表明,新型固定化高分子杀生剂具有较强的抗细菌和抗真菌的能力,对藻类也具有杀灭作用,是一种高效、广普、性质稳定的水处理杀生剂。     

Efficacy of natural biocide on control of microbial induced corrosion in oil pipelines mediated by Desulfovibrio vulgaris and Desulfovibrio gigas

We compared the efficacy of a natural biocide with four chemical tetrakishydroxymethyl phosphonium sulfonate, benzyl trimethyl ammonium chloride, and formaldehyde, glutaraldehyde, to control microbial induced corrosion in oil pipelines. The efficacy of biocides were monitored against Desulfovibrio vulgaris and Desulfovibrio gigas in experimental pipes by measuring cell counts, H2S production, Fe(II) production, production of extracellular polymeric substances and structure of biofilm. The treatment with cow urine had minimum planktonic cell counts of 3 102 CFU/mL as well as biofilm cell counts of 9 101 CFU/mL as compared with tetrakishydroxyl methyl phosphonium sulfonate, benzyl trimethyl ammonium chloride, formaldehyde and glutaraldehyde. Sulfide production was the lowest with cow urine (0.08 mmol/L), followed by tetrakishydroxymethyl phosphonium sulfonate 0.72 mmol/L. On day 90 of treatment, Fe(II) production was also found to be the lowest with cow urine. The scanning electron microscopic studies indicated that the biofilm bacteria were killed by cow urine. These results demonstrate the cow urine mediated control of microbially induced corrosion, and this is indicative of its potential as a viable substitute of toxic biocides. To the best of our knowledge, this seems to be the first report which screens possible biocidal activity by cow urine as compared to the most common biocides which oil industry is currently using.     

海域高温油田1株耐高温耐盐硫酸盐还原菌的筛选与生理特性及活性抑制

油田中硫酸盐还原菌(SRP)的生长代谢能产生大量H_2S,会引起油藏酸化和微生物腐蚀等严重的生产和环境问题,而关于油田环境中SRP微生物多样性与生理活性的研究仍十分缺乏.为了深入了解我国渤海湾海域高温酸化油藏中SRP代谢特点并探究其潜在危害控制方法,本研究采用厌氧纯培养技术从渤海湾某高温油田采出水中分离筛选到1株耐高温、耐盐的SRP菌株BQ1,研究了其生理特性,并评价了不同杀菌剂和代谢抑制剂对其产H_2S活性的影响.结果表明,菌株BQ1的细胞呈短杆状,大小为(1.2~2.5)μm×(0.5~0.8)μm,有运动性.尽管BQ1与普通脱硫弧菌(Desulfovibrio vulgaris Hildenborough)的16S rRNA基因序列相似性达99%,但两者生理特性具有明显差异.BQ1可在温度为14~70℃(最适30℃)、p H 6.0~9.0(最适7.0)、盐度为0%~10%条件下生长代谢.BQ1可利用甲酸钠、乳酸钠、乙酸盐等多种碳源,能以硫酸盐、亚硫酸盐、硫代硫酸盐或单质硫为唯一电子受体产生H_2S.次氯酸钠(600 mg·L~(-1))、苄基三甲基氯化铵(300 mg·L~(-1))或NaNO_3(800 mg·L~(-1))对BQ1产H_2S活性无明显抑制效果.戊二醛(50 mg·L~(-1))、溴硝醇(30 mg·L~(-1))、二氧化氯(50 mg·L~(-1))或NaNO_2(70 mg·L~(-1))可抑制BQ1产H_2S活性达30 d以上,是控制渤海湾高温油田微生物酸化的潜在有效抑制剂.     

Effects of 2,4-dichlorophenol,pentachlorophenol and vegetation on microbial characteristics in a heavy metal polluted soil

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils.     

Graft Copolymers, for Erodible Resins, from α-Hydroxyacids Oligomers Macromonomers and Acrylic Monomers

Environmental concerns result in a progressive withdrawal of antifouling paints containing organotin derivatives. The nature of the binders is critical with regard to the erosion of the protecting film through factors such as bond cleavage, dissolution, and diffusion of the degradation products. The versatility of acrylic polymers, due to the possibility of varying their chemical structure had conducted, in the first stage, to combine different types of repeating units in the macromolecular backbone. Formulation and evaluation, in natural sites, of these binders, with a well-defined hydrophobic/hydrophilic balance and with hydrolyzable pendant groups, have shown the possibility to prepare new organotin free resins which can be formulated and which are erodible in seawater over a long period (more than 2 years). A further step has been engaged with the development of graft copolymers containing biocompatible and hydrolyzable oligomers of -hydroxyacids. Their preparation requires the synthesis of -methacryloyloxyoligo--hydroxyacid macromonomers. Copolymers prepared from a mixture of the macromonomer and of an alkyl ester of acrylic acid were formulated with a biocide and deposited on a plate. Their ability to release cuprous oxide, as a model molecule, has been checked and quantified by the inductively coupled plasma analytical method. The uptake of water in the paint, which is enhanced by the hydrolysis of -hydroxyacid oligomers, as determined by the enzymatic measurement of liberated L-lactic acid, conducts to the polymer erosion and to a protecting bioactive surface.     

Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

填充新型抗菌PVA小球的固定柱床的应用

通过优化的PVA-H₃BO₃包埋法制备了抗菌PVA小球,并用新制备的小球填充柱床进行水处理研究. 结果表明:抗菌PVA小球具有良好的杀菌性能,在杀生剂添加量为m(杀生剂)∶m(PVA)3∶2时,杀菌率达到(92±2)%;扫描电子显微镜显示,包埋了杀生剂的抗菌PVA凝胶小球是一种多孔性的球形颗粒,结构较密实,并且包埋效果理想. 随着填充高度的升高、处理液与抗菌材料接触时间(停留时间)的延长、处理液出口端流量的减小, 填充柱的杀菌性能逐渐升高;对于30mm×300mm的填充柱,当填充高度≥20cm, 停留时间≥0.5 h,出口端流量为2.7 mL/s时, 杀菌效果较好. 对于50mm×500mm的填充柱,在填充高度为10 cm,停留时间为0.5 h,出口端流量为2.7 mL/s时,其杀菌率为(93±1)%.      

新型杀生剂与阻垢剂组合在城市污水回用中的应用

针对城市污水处理厂二级出水回用作循环冷却水补充水的工艺，采用新型杀生剂与阻垢剂组合进行了动态试验。加入药剂后腐蚀速率为0.00087g/（m^2·h）和0.00116g/（m^2·h），缓蚀率在80%左右，表明该药剂能较好地控制铜管腐蚀。     

石油炼厂循环冷却水中杀生剂的性能评价

选用了氧化型杀生剂二氯异氰尿酸钠来控制循环冷却水中微生物的生长。分别把药剂的投加浓度、温度、接触时间、pH值 4个因素作为变量对杀生效果进行考察 ,总结每个因素及各因素的 3个水平变动对杀生率影响的大小 ,为实际生产提供参数。结果表明 ,浓度因素对杀生率的影响最大 ,其次是时间 ,再次是温度 ,最后是pH值     

二溴次氮基丙酰胺的合成及其在水处理方面应用

二溴次氮基丙酰胺(DBNPA)是一种理想的环保型杀菌灭藻剂和水处理剂。文章通过实验探索了合成DBNPA的最佳方法,并测试了DBNPA在冷却水系统中的杀菌、除粘和缓蚀性能,为DBNPA在我国的应用和推广提供了参考。