Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4^′-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile.

For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h⁻¹ for fast desorption, 0.004 h⁻¹ for slow desorption, and 0.00022 h⁻¹ for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics.

The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.     

Cyanide Removal by Chinese Vegetation. Quantification of the Michaelis-Menten Kinetics (6 pp)

Background Little is known about metabolism rates of environmental chemicals by vegetation. A good model compound to study the variation of rates among plant species is cyanide. Vascular plants possess an enzyme system that detoxifies cyanide by converting it to the amino acid asparagine. Knowledge of the kinetic parameters, the half-saturation constant (Km) and the maximum metabolic capacity (vmax), is very useful for enzyme characterization and biochemical purposes. The goal of this study is to find the enzyme kinetics (KM and vmax) during cyanide metabolism in the presence of Chinese vegetation, to provide quantitative data for engineered phytoremediation, and to investigate the variation of metabolic rates of plants. Methods Detached leaves (1.0 g fresh weight) from 12 species out of 9 families were kept in glass vessels with 100 mL of aqueous solution spiked with potassium cyanide at 23°C for 28 h. Four different treatment concentrations of cyanide were used, ranging from 0.44 to 7.69 mg CN/L. The disappearance of cyanide from the aqueous solution was analyzed spectrophotometrically. Realistic values of the half-saturation constant (KM) and the maximum metabolic capacity (vmax) were estimated by a computer program using non-linear regression treatments. As a comparison, Lineweaver-Burk plots were also used to estimate the kinetic parameters. Results and Discussion The values obtained for KM and vmax varied with plant species. Using non-linear regression treatments, values of vmax and KM were found in a range between 6.68 and 21.91 mg CN/kg/h and 0.90 to 3.15 mg CN/L, respectively. The highest vmax was by Chinese elder (Sambucus chinensis), followed by upright hedge-parsley (Torilis japonica). The lowest vmax was demonstrated by the hybrid willow (Salix matssudana x alba). However, the highest KM was found in the water lily (Nymphea teragona), followed by the poplar (Populus deltoides Marsh). The lowest KM was demonstrated by corn (Zea mays L.). The values of vmax were normally distributed with a mean of 13 mg CN/kg/h. Conclusions Significant removal of cyanide from aqueous solution was observed in the presence of plant materials without phytotoxicity, even at high doses of cyanide. This gives rise to the conclusion that the Chinese plant species used in this study are all able to efficiently metabolize cyanide, although with different maximum metabolic capacities. A second conclusion is that the variation of metabolism rates between species is small. All these plants had a similar KM, indicating the same enzyme is active in all plants. Recommendations and Outlook Detoxification of cyanide with trees seems to be a feasible option for cleaning soils and water contaminated with cyanide. For phytoremediation projects, screening appropriate plant species adapted to local conditions should be seriously considered. More chemicals should be investigated to find common principles of the metabolism of environmental chemicals by plants.     

氧化亚铁硫杆菌对亚铁离子的氧化及其动力学研究

采用9K培养基研究了氧化亚铁硫杆菌氧化Fe^2＋过程中,pH和氧化还原电位的变化规律,并对Fe^2＋的氧化过程进行动力学分析,确定了其反应级数及反应速率常数。结果表明,（1）在温度为30℃,摇床转速为150r／min的条件下,氧化亚铁硫杆菌的最佳接种量为10．0％;（2）Fe^2＋初始质量浓度在11．39～21．72g／L时,随着浓度的增大,Fe^2＋达到100％转化率需要的时间增加;（3）氧化亚铁硫杆菌对Fe^2＋的氧化可近似看作一级反应,反应速率常数为0．0527～0．0788h。     

Fenton降解涂装废水的因素影响及动力学分析

以江苏某电动自行车制造企业的涂装废水为研究对象,采用单因素和响应面优化Fenton氧化处理的反应条件,分析了其动力学过程。结果表明：在pH=3.21、n(H₂O₂/Fe²⁺)=8∶1、m(H₂O₂/COD)=4.17∶1、氧化反应时间为120 min的条件下,COD和TP的去除率均达到最高,分别为81.32%和98%,其降解过程符合一级反应动力学,室温下降解速率常数k为0.014 2 min⁻¹,活化能为4.76 kJ·mol⁻¹。在pH=3.21、n(H₂O₂/Fe²⁺)=8∶1、m(H₂O₂/COD)=0.78∶1、反应时间120 min的条件下,Fenton半氧化体系对COD去除率可达42.5%左右,处理后废水的B/C比由0.12提高至0.35。综合经济因素,认为Fenton半氧化与生物处理工艺耦合处理实际涂装废水更佳。     

微波解吸技术及其应用

通过实验数据对活性炭的升温行为进行了定量描述并对微波解吸动力学模式进行了分析。结果表明,活性炭升温行为可分为2个阶段进行描述,微波解吸再生载乙醇活性炭的速度很快,1 min即可达到80％以上的脱附率,一般3～4 min后脱附率达90％以上,整个解吸过程所用的时间不到6 min.     

零价铁耦合芬顿氧化法处理TNT红水

采用零价铁耦合芬顿氧化法处理TNT红水,研究了初始pH、零价铁投加量、过氧化氢（H2O2）投加量及温度对红水中总有机碳（TOC）去除效果的影响,同时进行了TOC去除过程中反应动力学的探讨。结果表明,零价铁耦合芬顿氧化体系可有效降解TNT红水中的2,4-二硝基甲苯-3-磺酸钠和2,4-二硝基甲苯-5-磺酸钠。在初始pH为2,温度为20 ℃的条件下,加入1.5 g·L-1零价铁反应1 h后,再加入100 mL·L-1H2O2反应4 h,红水中二硝基甲苯磺酸盐浓度从500 mg·L-1降至0 mg·L-1,去除率为100%,TOC浓度从150 mg·L-1降至30 mg·L-1,去除率达到80%。反应中TOC的降解过程遵循拟二级反应动力学方程。零价铁耦合芬顿氧化法可以作为TNT红水的有效处理途径。     

芒果核壳炭的制备及对水中Cr6+的吸附

以芒果核壳为原料通过H3PO4活化制备了新型的吸附剂H3PO4-C。考察了影响该吸附剂对水体中Cr（VI）的去除效果的因素,并研究了吸附动力学特征和吸附过程控制机理。结果表明,芒果壳生物质炭对Cr（VI）具有良好的吸附能力,在25℃下,较佳的吸附条件为：当投加量为3 g·L-1,Cr（VI）初始浓度为50 mg·L-1,溶液pH值为3时,吸附5 h,去除率为93.8%。准一级、准二级动力学模型用来拟合吸附过程,结果表明,准二级动力学符合该吸附过程,吸附速率常数为0.001 3 g·（mg·min）-1。用Langmuir和Freundlich模型描述吸附等温过程,结果说明,该吸附过程服从Langmuir吸附,饱和吸附量为28.571 mg·g-1,内扩散为该吸附过程的限速步骤,内扩散系数D=4.21×10-9 cm2·s-1。     

一株假单胞菌(Pseudomonas) SYBS01降解石油的特性

从石油污染土壤中筛选得到一株石油降解菌SYBS01,鉴定为假单胞菌（Pseudomonas sp.）。通过单因素实验和正交实验进行石油降解条件优化,结果为35℃、170 r·min-1,酵母浸粉15 g·L-1,KH2PO4 0.5 g·L-1,自然pH值。其中氮源为酵母浸粉时对菌SYBS01降解石油的影响最大。添加酵母浸粉后,4 d石油降解率达到85.6%,分别为（NH4）2SO4、NH4NO3和尿素的6.7、7.8、2.6倍。进一步分析发现酵母浸粉作为氮源的同时也起到外加营养的作用。在最佳条件下,0.5~5 g·L-1的石油的降解均符合一级动力学模型,且石油浓度为3 g·L-1和4 g·L-1的石油降解半衰期仅为26 h。     

高锰酸钾氧化水中二甲基三硫醚的动力学

研究了氧化剂KMnO4氧化水中二甲基三硫醚的效能,探讨了KMnO4投加量、二甲基三硫醚的初始浓度、pH值、腐植酸浓度以及同类臭味物质甲硫醚对氧化反应的影响,并对反应动力学进行了分析。结果表明：不同剂量的高锰酸钾对二甲基三硫醚有较强的氧化能力,基本完全氧化需要一定时间（达2 h）。随着高锰酸钾投量的增加,去除率和反应速率也随之增加,但高锰酸钾投加量不宜过多,建议最佳投加量为2 mg·L-1。实验发现：二甲基三硫醚初始浓度、实际水体pH值以及腐殖酸浓度对氧化反应的影响不明显;但水中同类臭味物质甲硫醚对氧化反应有抑制作用,使反应进程变慢。高锰酸钾氧化二甲基三硫醚的反应符合二级反应动力学模型,二级反应的动力学常数为k=0.006 59 L·（min·mg）-1,理论曲线与实际反应曲线存在一定的差距,但整个反应过程中2条曲线反应的去除率的差距不大,因此理论曲线能较好的指导实践。     

以废塑料为基材的大孔型离子交换树脂的制备、表征和吸附性能

以废旧电视机外壳(WTVS)为原料,通过磺化反应和溶胀-渗透方法来制备大孔型离子交换树脂(SM-D001),并将其作为CO₂吸附材料的载体,采用N₂吸附-脱附、傅里叶变换红外光谱(FT-IR)、热重分析(TGA)、扫描电镜(SEM)、压汞法等手段对大孔型离子交换树脂(SM-D001)进行表征。考察了不同正庚烷的量、不同乙醇/水质量比和不同致孔时间下制备的SM-D001对CO₂吸附能力的影响。结果表明,当致孔剂正庚烷的量为25 g,乙醇/水质量比为90∶10,致孔时间为5 h时,制备的离子交换树脂对CO₂的平衡吸附量达到1.87 mmol·g⁻¹。以SM-D001为载体,五乙烯六胺(PEHA)为改性剂,采用配位法制备的固态胺吸附剂对CO₂的吸附能力达到3.61 mmol·g⁻¹,并对其进行吸附动力学研究。上述研究结果为进一步证明固态胺吸附剂对CO₂吸附过程是物理吸附和化学吸附共同作用的结论提供参考。