Research on transesterification parameters for producing plant sterols with supercritical methanol

The supercritical fluid method, regarded as a type of individual production process in the course of preparing plant sterols, has become a promising technology, which possesses advantages of high conversion rate without any pretreatment and need of a catalyst. This study examined the reaction process of the deodorizer distillate (DOD), which mainly included the direct transesterification of DOD to convert into free sterols. The effects of the ratio of methanol to DOD, reaction temperature and time on transesterification were studied. Furthermore, the interactions between different factors were also assessed using the response surface methodology. The optimal conditions obtained were as follows: reaction temperature 553 K, reaction time 80 min, and CH₃OH: DOD = 25:1 (mass ratio). Under these conditions, 36.42% sterol concentration was obtained, which is significantly higher in comparison with the initial sterols’ concentration in raw material (22.45%).     

灾害条件下多层次应急疏散模型的构建方法研究

人们每天都要面对各种造成严重财产和人身安全损失的重大灾害,如何建立灾害条件下中国人口高密度大范围的应急疏散模型,具有重大的意义。该文基于我国灾害条件下高密度人口的集体疏散模式,按照灾害区域的具体情况和人口分布,以道路实时速度和路面损毁程度所决定的道路阻抗性作为评判道路疏散能力的依据,构建从危险区域的多集结点到安全区域的多安置点的多层次应急疏散模型,确定集体疏散人员的疏散路径、人数和车辆,实现在最短的时间内的受灾群众整体最优疏散,并以山东省德州发生地震作为实验区,采用Google Map API和C#搭建多层次应急疏散平台,验证了多层次应急疏散模型的可行性。     

广东某铀废石堆周边土壤中铀污染特征及其环境有效性

铀（U）矿冶过程中产生了大量铀废石。通常认为其放射性核素含量低,大多沿山谷露天自然堆放,一般不对堆场做防渗漏处置,对铀废石可能产生的潜在环境影响尚未引起重视。以广东某花岗岩型铀矿山的一个废石堆周边土壤为研究对象,在废石堆上、下游方向分别采集了2条（即BP1和BP2,视作背景土壤,距离废石堆的距离分别为10和20 m）和3条土壤剖面（即WP1、WP2和WP3,视作潜在U污染土壤,距离废石堆的距离分别为50、100和180 m）。通过对剖面间U分布特征的对比,定量估算了受污染土壤中外源U的输入通量;结合逐级化学提取技术,分析了U在土壤剖面的赋存形态及其环境有效性。结果表明：1）铀废石堆对周边土壤产生了显著的放射性污染,废石堆下游方向由近及远的3条U污染剖面（WP1、WP2和WP3）中U平均质量分数比背景剖面分别富集了634.6、10和3.7倍,其外源U的平均输入通量分别为4840.36、86.72和20.46μg·g-1。距污染源（废石堆）愈近,土壤中外源U的输入通量愈大;2）在近源区,大量的外源U优先在土壤表层聚集,随着远离污染源,逐渐转变为优先在剖面的深部淀积;3）与U 污染剖面相比,背景剖面（BP2）的惰性态 U（晶质铁锰氧化物/氢氧化物结合态+残渣态）所占比例最大,活性态 U（可交换态（包括水溶态）+碳酸盐结合态）所占比例最小,说明U污染土壤的外源U输入更倾向于对活性态U的贡献,这是对植物影响最直接的部分。另外,距污染源由近及远,U污染土壤中活性态U所占比例增大,潜在活性态U（有机质结合态+无定形铁锰氧化物/氢氧化物结合态）所占比例降低;4）3条U污染剖面中,平均90%以上的U（活性态和潜在活性态）对生态系统构成了威胁。因此,铀废石堆对周边环境产生的风险应得到充分重视。本研究为开展铀矿冶地域的放射性环境影响评价和土壤修复提供了有益的参考。     

预测沉积物-水微宇宙系统中化学品浓度变化的多介质模型

沉积物-水微宇宙系统是经济合作发展组织(Organisation for Economic Co-Operation and Development,OECD)颁布的化学品测试准则中推荐的试验系统之一,可用来测试化学品对底栖生物的慢性毒性。为了在试验前对化学品的浓度变化进行预测,进而确定试验方法,以摇蚊慢性毒性试验系统为例,采用环境多介质模型的建模方法,构建了一种可通过化学品理化性质和试验系统参数,对化学品在沉积物-水试验系统中浓度变化进行预测的模型。结合试验数据和文献资料,给出了模型中试验系统参数的推荐取值,并使用Matlab软件中的Simulink工具对模型进行编程和求解。以此模型为基础,给出了模型在3个方面的应用,即预测蓄积时间、预测平衡时间以及拟合试验数据。对80种已有或假想化学品的蓄积时间和平衡时间进行了计算,得出的范围分别为1~204 d和1~73 d。此外,适当修改模型结构和模型参数,也可将其应用于其他暴露场景中。但使用模型对化学品浓度进行预测时发现,模型仅对沉积物中化学品浓度的预测结果较为准确,而对水中化学品浓度的预测结果与实测值相差1~2个数量级。模型对浓度的预测精度未来仍需进一步提高。上述研究结果完善了沉积物-水微宇宙系统试验方法。     

MIEX~预处理对水源水中藻源DON的去除效能及机理

利用小试试验研究了磁性离子交换树脂预处理(MIEX~)对高藻水源水中的溶解性有机氮(DON)的去除效能,并通过分子量分布测定、双向电泳等手段初步分析了其作用机理.结果表明,MIEX~预处理对DON具有较好地去除效果,并可有效强化混凝工艺的处理效能.投加量为15m L/L时,MIEX~预处理可提升DON去除率20%;以铜绿微囊藻为主要种属的高藻水源水中藻类蛋白种类不低于230种,且大多数处于酸性端,分子量区间主要分布于15~40Ku、65~75Ku,处于MIEX~预处理可去除的分子量区间,从而具有较好的去除效果.综上所述,MIEX~预处理可以作为强化去除高藻水源水中DON的一种方法.     

Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Adsorption and biodegradation of three selected endocrine disrupting chemicals in river-based artificial groundwater recharge with reclaimed municipal wastewater

Endocrine disrupting chemical(EDC) pollution in river-based artificial groundwater recharge using reclaimed municipal wastewater poses a potential threat to groundwater-based drinking water supplies in Beijing, China. Lab-scale leaching column experiments simulating recharge were conducted to study the adsorption, biodegradation, and transport characteristics of three selected EDCs: 17β-estradiol(E2), 17α-ethinylestradiol(EE2) and bisphenol A(BPA). The three recharge columns were operated under the conditions of continual sterilization recharge(CSR), continual recharge(CR), and wetting and drying alternative recharge(WDAR). The results showed that the attenuation effect of the EDCs was in the order of WDAR CR CSR system and E2 EE2 BPA, which followed first-order kinetics. The EDC attenuation rate constants were 0.0783, 0.0505, and 0.0479 m-1 for E2, EE2 and BPA in the CR system, respectively. The removal rates of E2, EE2, and BPA in the CR system were 98%, 96% and 92%, which mainly depended on biodegradation and were affected by water temperature.In the CR system, the concentrations of BPA, EE2, and E2 in soil were 4, 6 and 10 times higher than in the WDAR system, respectively. According to the DGGE fingerprints, the bacterial community in the bottom layer was more diverse than in the upper layer, which was related to the EDC concentrations in the water-soil system. The dominant group was found to be proteobacteria, including Betaproteobacteria and Alphaproteobacteria, suggesting that these microbes might play an important role in EDC degradation.     

Activated carbon coated palygorskite as adsorbent by activation and its adsorption for methylene blue

An activation process for developing the surface and porous structure of palygorskite/carbon(PG/C) nanocomposite using ZnC l2 as activating agent was investigated. The obtained activated PG/C was characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), field-emission scanning electron microscopy(SEM), and Brunauer–Emmett–Teller analysis(BET) techniques. The effects of activation conditions were examined,including activation temperature and impregnation ratio. With increased temperature and impregnation ratio, the collapse of the palygorskite crystal structure was found to accelerate and the carbon coated on the surface underwent further carbonization. XRD and SEM data confirmed that the palygorskite structure was destroyed and the carbon structure was developed during activation. The presence of the characteristic absorption peaks of C_C and C–H vibrations in the FTIR spectra suggested the occurrence of aromatization. The BET surface area improved by more than 11-fold(1201 m2/g for activated PG/C vs. 106 m2/g for PG/C) after activation, and the material appeared to be mainly microporous. The maximum adsorption capacity of methylene blue onto the activated PG/C reached 351 mg/g. The activated PG/C demonstrated better compressive strength than activated carbon without palygorskite clay.     

Mercury levels and estimated total daily intakes for children and adults from an electronic waste recycling area in Taizhou, China: Key role of rice and fish consumption

In order to assess the potential health risks of Hg pollution, total mercury (T–Hg) and methyl mercury (MeHg) concentrations were determined in air, dust, surface soil, crops, poultry, fish and human hair samples from an electronic waste (e-waste) recycling area in Taizhou, China. High concentrations of T–Hg and MeHg were found in these multiple matrices, and the mean concentration was 30.7 ng/m³ of T–Hg for atmosphere samples, 3.1 μg/g of T–Hg for soil, 37.6 μg/g of T–Hg for dust, 20.3 ng/g of MeHg for rice and 178.1 ng/g of MeHg for fish, suggesting that the e-waste recycling facility was a significant source of Hg. The inorganic Hg (I–Hg) levels (0.84 μg/g) in hair samples of e-waste workers were much higher than that in the reference samples. Pearson''s correlation coefficients showed that strong positive correlations (p < 0.01) between hair I–Hg and time staying in industrial area (r = 0.81) and between MeHg and fish consumption frequency (r = 0.91), imply that workers were mainly exposed to Hg vapor through long-time inhalation of contaminated air and dust, while other population mainly exposed to MeHg through high-frequency fish consumption. The estimated daily intakes of Hg showed that dietary intake was the major Hg exposure source, and Hg intakes from rice and fish were significantly higher than from any other foods. The estimated total daily intakes (TDIs) of MeHg for both children (696.8 ng/(kg·day)) and adults (381.3 ng/(kg·day)) greatly exceeded the dietary reference dose (RfD) of 230 ng/(kg·day), implying greater health risk for humans from Hg exposures around e-waste recycling facilities.     

Environmental behaviors of phoxim with two formulations in bamboo forest under soil surface mulching

Phoxim (emulsifiable concentrate (EC) and granules (G)) has been widely used in bamboo forests. The persistence and magnitude of phoxim residues in the crop and soil must be investigated to ensure human and environmental safety. The environmental behaviors of the two formulations were investigated in a bamboo forest under soil surface mulching conditions (CP) and non-covered cultivation conditions (NCP). The half-lives of phoxim in soil under the two conditions in soil were 4.1–6.2 days (EC) and 31.5–49.5 days (G), respectively. Phoxim in EC could be leached from the topsoil into the subsoil. A minimized leaching effect was observed for G under NCP. Inversely, an enhanced leaching effect was observed for G under CP. The G formulation resulted in more parent compound (in bamboo shoots) and metabolite (in soil) residues of phoxim than in the case of EC, especially under CP conditions. In addition, the intensity and duration of the formulation effect on soil pH adjustment from G were more obvious than that from EC. Results showed that the environmental behaviors (distribution, degradation, residue) of phoxim in the bamboo forest were significantly influenced by the type of formulation. The prolongation effect from phoxim G might cause persistence and long-term environmental risk. However, bamboo shoot consumption could be considered relatively safe after applying the recommended dose of the two phoxim formulations.