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%).     

基于水域面积法的山区河流水电站下游生态流量定值研究

水电站的大量兴建导致下游河道萎缩退化甚至断流,如何改变水电站运行调度方式,维持下游河道一定的生态流量、保障河流健康成为国内外普遍关注的问题.本文在传统水文学方法的基础上融入生物栖息地法思想,以河流生态系统的生物多样性为功能目标,用河道流量反映河流的水文过程,河道水域面积反映河流生态系统的生物多样性,创新性地提出考虑河道水文生态特性的生态流量定值方法——水域面积法.以北江上游浈江二级支流罗坝水为例进行分析计算.计算结果表明:枯水年罗坝水生态流量为2.26 m3·s-1,占多年平均流量的25.97%;平水年生态流量分月控制,生态流量过程与建站前流量过程基本一致.根据枯水年的生态流量值和平水年各月份的生态流量值,结合水电站的运行调度规则,换算成一定时期内的径流量来确定该时期内水电站需释放的水量,进而对水电站下游河道的生态功能进行保护和修复.     

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.     

东江流域表层土中全氟化合物的空间分布及来源解析

为探究东江流域土壤中全氟化合物(perfluorinated compounds,PFCs)分布特征和潜在来源,2013年8月采集东江流域19份表层土样品,利用高效液相色谱-串联质谱联用(HPLC-MS/MS)技术分析了16种PFCs的含量。结果表明,东江流域表层土总PFCs(∑PFCs)含量范围在2.15~5.49μg/kg dw。所采集的表层土样品中,东江东莞段土壤∑PFCs含量明显高于惠州段,全氟辛烷磺酸(0.65~1.28μg/kg dw)为最主要的污染物。与国内相关研究数据相比,东江流域土壤PFCs含量水平整体较高,这可能与流域产业结构和经济活动有关。主成分分析结果表明,电镀防雾剂、食品包装和全氟羧酸的生产过程、大气沉降、电化学氟化过程为东江流域土壤中PFCs的主要来源。与土壤有机质含量相关性研究表明,PFCs更容易分配到有机质含量高的土壤中,且随着PFCs分子碳链的增加,这种趋势更加显著。     

固相膜萃取-气相色谱法测定地表水中有机氯农药研究

研究了固相膜萃取对地表水中有机氯农药(OCPs)物质的提取效果,并与液液提取法(LLE)进行比较.建立了固相膜萃取/气相色谱法检测地表水中20种有机氯农药的方法.结果表明:当萃取膜为HLB膜,洗脱液溶剂为丙酮和正己烷,萃取效果最理想,20种OCPs的回收率稳定在74.1%~94.3%之间,固相膜萃取法与传统液液提取法相比,既提高了萃取效率同时又减少了有机萃取溶剂的用量.该法检测实际样品时,同时加入2种内标指示剂对方法的性能进行了验证,2种内标示踪剂的回收率分别为71.6%~94.8%和69.9%~109.5%,样品中20种OCPs均未检出.     

HNO_3在气相及SiO_2表面的紫外光解反应

利用紫外及红外吸收光谱等分析手段对365 nm光照下HNO3在气相与SiO2表面的光解反应进行了研究.考察了HNO3浓度、光照时间、相对湿度等条件对反应的影响.结果表明:随着HNO3浓度及光照时间的增加,光解产生的NO2和NO浓度均呈指数增加;无水汽情况下,400 Pa的HNO3光解45 min后,产生NO2及NO浓度比气相光解产生的分别高约3及1.7倍.HNO3光解产生的HONO的浓度随相对湿度的增加而呈线性增加,在SiO2颗粒物表面光解产生的NO2浓度随着相对湿度的增加而减少,而NO浓度则随之增大.400 Pa的HNO3光照45 min后,SiO2表面光解产生的HONO浓度是气相光解的3倍、SiO2表面暗反应的约30倍.     

Effect of particle size on CO adsorption and thermodynamic analysis

The liquid nitrogen adsorption method was used to characterize the pore structure of non-cohesive coal in the 061,404 working face of the Lingxin coal mine. The amount of specific surface area of micropores in the sample continuously rose as particle sizes reduced. The volumetric method was used to measure the CO isothermal adsorption curves of three samples (sample I, 0.425–0.25 mm, sample II, 0.18–0.25 mm, and sample III, 0.15–0.18 mm). The experimental results were fitted by the Langmuir model. According to the experimental results, it was conducive to CO adsorption with the conditions of high pressure and low-temperature. The decrease in grain diameter increased the number and volume of micropores in the sample, which improved the adsorption capacity of the sample. In addition, according to the adsorption data, the CO adsorption thermodynamics of three samples were analyzed, including surface potential (Ω), Gibbs free energy change (ΔG) and entropy change (ΔS). The results demonstrated that CO adsorption by coal was a spontaneous process. Sample III has the most substantial adsorption capacity, whereas the sample I has the weakest adsorption capacity.     

通过屋顶暴露方法模拟聚碳酸酯微塑料在长江水样的长期老化行为

由于较低的自然老化速率,微塑料在实际水体长期户外暴露过程中老化行为的数据仍较缺乏.通过聚碳酸酯（Polycarbonate,PC）微塑料在长江表层水样的18个月户外暴露试验以揭示自然老化过程对微塑料表面特征及对金属离子(Cr⁶⁺和Co²⁺)吸附行为的重要影响.结果显示,户外暴露改变了PC微塑料的理化性质,包括表面开裂、粒径降低、亲水性和熔点增加以及表面氧化（产生羰基和羟基）.同时,户外老化过程明显影响微塑料对金属离子的吸附行为.原始和低老化程度PC对金属离子的吸附主要通过物理作用控制,而高老化程度微塑料由于产生含氧功能团对金属离子的吸附主要由化学过程如络合和共价键等作用控制.并且,不同老化程度PC微塑料对Cr⁶⁺和Co²⁺的吸附性能不同.对于Cr⁶⁺,PC的吸附性能随其老化程度增加呈先升高后降低的趋势,然而对于Co²⁺,平衡吸附性能随老化程度增加呈增加的趋势.户外老化过程产生含氧官能团、破碎和开裂以及生物膜可能是影响吸附性能的主要因素.本研究证实了长期户外...     

未来RCP4.5情景下黄海DMS浓度变化模拟与分析

使用CORDEX-EA过去气候态(2000-2009年)与RCP4.5情景下近未来气候态(2041-2050年)大气强迫结果驱动中国东部陆架海域耦合DMS模块生态模型,模拟了黄海过去及近未来表层DMS浓度(C_DMS),探究了黄海近未来C_DMS时空分布的变化及其影响因素.结果表明:近未来黄海C_DMS的年循环发生变化,北黄海C_DMS极高值出现月份由5、9月转变为4、10月,南黄海由4、9月转变为4、8月;局部C_DMS高值区也发生变化,春季山东半岛附近海域、夏季苏北浅滩、南黄海中东部、秋季南黄海东部C_DMS高值区加强,夏季山东半岛附近C_DMS高值区减弱.近未来热通量、风应力对山东半岛、南黄海中东部海域C_DMS影响较大;降水量、云量对西朝鲜湾C_DMS的影响占优;苏北浅滩C_DMS受多个气候因子共同作用.     

正渗透去除地表水中DOM的效能研究

采用经砂滤处理后的滆湖水作为原料液,氯化钠溶液作为汲取液,在不同影响因素条件下进行正渗透试验,并对试验后的膜片进行清洗,探究膜污染的可逆性.结果表明:提高汲取液浓度、运行温度及膜面流速均可有效增加膜通量;正渗透对滆湖水体中的溶解性微生物代谢产物、类色氨酸、类富里酸和腐殖酸四种主要DOM成分均有较好的去除效果,DOC、UV₂₅₄截留率均在96%以上;短期运行通过水力清洗几乎可以完全恢复膜通量,而长期运行通过超声清洗可以基本恢复全部膜通量,通过分析膜清洗液可知造成膜污染的主要物质为类色氨酸类和类富里酸类物质.