有机蒙脱石填充PDMS膜分离水相有机物的渗透汽化研究

以乙醇、乙酸的水溶液为渗透汽化分离对象，将CTAB柱撑蒙脱石作为填充剂，制备了填充型PDMS(聚二甲基硅氧烷)膜，研究填充膜对乙醇／水及乙酸／水体系的渗透汽化分离，结果表明，蒙脱石的吸附特性及其层间柱撑通道可以明显改善PDMS膜的选择性和通量，填充膜分离乙醇或乙酸的分离效果明显不同，对可能存在的渗透汽化分离机理进行了探讨。     

A flow-through passive dosing system for continuously supplying aqueous solutions of hydrophobic chemicals to bioconcentration and aquatic toxicity tests

A continuous supply of water with defined stable concentrations of hydrophobic chemicals is a requirement in a range of laboratory tests such as the OECD 305 protocol for determining the bioconcentration factor in fish. Satisfying this requirement continues to be a challenge, particularly for hydrophobic chemicals. Here we present a novel solution based on equilibrium passive dosing. It employs a commercially available unit consisting of ∼16 000 polydimethylsiloxane (PDMS) tubes connected to two manifolds. The chemicals are loaded into the unit by repeatedly perfusing it with a methanol solution of the substances that is progressively diluted with water. Thereafter the unit is perfused with water and the chemicals partition from the unit into the water. The system was tested with nine chemicals with log K_OW ranging from 4.1 to 6.3. The aqueous concentrations generated were shown to be largely independent of the water flow rate, and the unit to unit reproducibility was within a factor of ∼2. In continuous flow experiments the aqueous concentrations of most of the study chemicals remained constant over 8 d. A model was assembled that allows prediction of the operating characteristics of the system from the log K_OW or PDMS/water partition coefficient of the chemical. The system is a simple, safe, predictable and flexible tool that generates stable aqueous concentrations of hydrophobic chemicals.     

A Review of the Fate and Effects of Silicones in the Environment

Silicones are well-known useful materials varying in structure, reactivity, and chemical and physical properties, but they all contain a covalent bond between the silicon atom and an organic group. Most common of these polymers are those based on polydimethylsiloxane (PDMS) having a siloxane (Si–O–Si) repeat unit and two methyl groups on each silicon atom. All these polymers are manmade, and the organosilicon linkage is not found in nature. It was therefore erroneously assumed that these polymers do not degrade naturally in the environment. It is the purpose of this review to refute this myth and to describe the degradation processes of PDMS in the environment and any potential ecological impact on the terrestrial, aquatic, and atmospheric compartments. Although it was found that minor degradation takes place by hydrolysis of PDMS to dimethylsilandiol followed by oxidation of the methyl group to aldehyde and ultimately to CO₂ by Arthobacter and Fusarium oxysporium schlechtendahl, the major degradation processes are abiotic. High molecular weight PDMS are initially depolymerized by soil hydrolysis of the siloxane bonds to yield organosilanol terminated oligomers. These organosilanols and low molecular weight linear PDMS and cyclics are evaporated into the atmosphere and are oxidized there by hydroxyl radicals to benign silica, water, and CO₂.     

Concentrations and assessment of exposure to siloxanes and synthetic musks in personal care products from China

We investigated the concentrations and profiles of 15 siloxanes (four cyclic siloxanes, D₄-D₇; 11 linear siloxanes, L₄-L₁₄), four synthetic musks (two polycyclic musks, HHCB and AHTN; two nitro musks, MX and MK), and HHCB-lactone, in 158 personal care products marketed in China. Siloxanes were detected in 88% of the samples analyzed, at concentrations as high as 52.6 mg g⁻¹; Linear siloxanes were the predominant compounds. Among synthetic musks, more than 80% of the samples contained at least one of these compounds, and their total concentrations were as high as 1.02 mg g⁻¹. HHCB was the predominant musk in all of the samples analyzed, on average, accounting for 52% of the total musk concentrations. Based on the median concentrations of siloxanes and musks and the average daily usage amounts of consumer products, dermal exposure rates in adults were calculated to be 3.69 and 3.38 mg d⁻¹ for siloxanes and musks, respectively.     

新型吸附搅拌棒被动采样器研制及应用——基于多壁碳纳米管的改性

结合传统被动采样器原理和新发展的吸附搅拌棒技术,研制了以多壁碳纳米管-聚二甲基硅氧烷(MWCTNs/PDMS)作为涂层的新型吸附搅拌棒被动采样器,并以苯酚(PhOH)、己烯雌酚(DES)和铅(Pb)作为目标污染物,考察被动采样器其吸附性能,优化其吸附条件.结果表明,与商业化PDMS涂层吸附搅拌棒被动采样器相比,含MWCTNs/PDMS涂层吸附搅拌棒被动采样器能更快达到吸附平衡时间、具有更大的饱和吸附容量.甲醇是PhOH和DES优良解吸剂,0.6mol/L HNO₃为Pb最优解吸剂.该新型被动采样器重复使用50次以上其解吸效率仍能达到70%以上,具有良好的稳定性和重复利用效果.