酚类化合物气相色谱保留指数的定量结构相关性研究

应用偏最小二乘回归技术建立了102种酚类化合物气相色谱保留指数与分子全息结构间的相关模型,在最佳建模条件下得到非交叉验证相关系数(r2)为0.965,交叉验证相关系数(q_LOO2)为0.963. 从102种酚类化合物中随机选出68种作为训练集,其余作为测试集,来验证分子全息QSRR模型的预测能力和稳健性. 在最佳建模条件对训练集进行偏最小二乘回归分析,r2为0.967,q_LOO2为0.927. 用训练集数据所建立的QSRR模型预测测试集中酚类化合物的色谱保留指数,结果表明,基于训练集所建立的QSRR模型具有很高的预测能力和稳健性,可以对测试集酚类化合物的气相色谱保留指数进行很好的预测. 此外,利用最佳全息定量结构保留关系(HQSRR)模型的色码图,探讨酚类化合物中的不同侧链基团对其色谱保留性质的影响,及其在固定相上的色谱保留机理.      

纳米零价铁降解水中多溴联苯醚(PBDEs)及降解途径研究

纳米零价铁(nZVI)法是多溴联苯醚(polybrominated biphenyl ethers,PBDEs)脱溴的有效方法.其反应动力学与途径对阐明PBDEs降解机制具有重要意义.本研究采用液相还原法制备的nZVI,在含有表面活性剂聚乙二醇辛基苯基醚(Triton X-100)的条件下,46 h内完全降解商用八溴联苯醚(octa-BDE)混合物中高溴代物质(7~9个溴代的同系物),其降解过程符合类一级反应动力学(pseudo-first-order)方程,平均降解速率常数(k)为0.106 h-1.本研究利用数量结构保留关系(quantatitivestructure retention relationship,QSRR)模型建立了在缺乏全系标准样品的情况下PBDEs降解产物的有效分析方法.通过混标中39种PBDEs各标准物在气相色谱中的保留时间,再以BDE47和BDE183的平均保留时间归一化后得到每种标准物的相对保留时间(relative retention time,RRT),再将数据库中的相对保留时间指数(relative retention time index,RRTI)与实验测得的相对保留时间拟合,得到QSRR模型.利用该模型对octa-BDE降解产物进行定性分析,推导得出nZVI对octa-BDE的还原降解途径.结果表明,nZVI对PBDEs的逐级脱溴过程中,间位的溴原子最容易被取代.     

镉在土壤中吸持的动力学特征研究

采用间歇法研究了镉在不同土壤中吸持的动力学特征。镉在土壤中的吸持分为快速反应的慢速反应两个阶段，其中快速吸持阶段以化学吸持为主，而慢速吸持以物理吸附为主；在低温下（２９３Ｋ），镉吸持速率与时间符合方程１ｎＶ＝Ａ＋Ｂｔ，高温下３１３Ｋ）为Ｖ＝Ａ＋Ｂ１ｎｔ；不同类型土壤镉吸持的动力学模型以双常数模型较优。     

PAM保水剂对生物反应器填埋场持水性能及生物活性影响研究

填埋垃圾的含水率是生物反应器填埋场中垃圾降解和渗滤液产生的重要影响因素.本文将农业上广泛应用的聚丙烯酰胺(PAM)高分子保水剂用于垃圾填埋场保水持水性能的改善,以提高填埋场微生物活性,促进有机物降解.选取了典型的非水溶性高分子保水剂JB和水溶性高分子保水剂WSN20,通过考察填埋过程中介质含水率、渗滤液产量及水质,填埋气组分和微生物活性的变化,评价保水剂种类及添加量对填埋介质持水性能和垃圾降解过程的影响.结果表明,保水剂的添加量对介质的持水能力和微生物活性具有较大的影响.适量高分子保水剂的添加可有效减少渗滤液的产生并改善其水质.其中非水溶性保水剂JB的效果尤为显著,0.1%的投加比时能使填埋装置内介质的含水率增加12%,提高填埋体系中的微生物活性3.3倍,渗滤液产生量的削减达到75.6%.     

饱和多孔介质中胶体运移模拟方法研究进展

阐述了国内外针对胶体在饱和多孔介质中运移模拟方法的研究进展：胶体在多孔介质中由于对流和弥散作用发生运移,而由于表面沉积和筛滤作用滞留在多孔介质中,通常采用含有滞留项的对流弥散方程对胶体的运移行为进行宏观描述,并通过拟合得到胶体运移和滞留的宏观参数,但是对流弥散方程是对试验曲线的宏观描述,无法解释其背后的微观机理;胶体的运移和滞留作用由胶体的微观受力决定,包括胶体在水中的布朗运动和有效重力,胶体-胶体/胶体-固相表面之间的相互作用以及流场作用在胶体上的力3个部分;为了实现从微观受力到宏观参数的升尺度计算,研究者们提出了胶体过滤理论及其后续的修正方法对沉积速率等宏观参数进行预测,然而现有方法通常基于简化的流场,忽略了多孔介质复杂孔隙结构和表面特性的影响;孔隙结构模型是多孔介质孔隙结构的简化模型,基于该模型能够从胶体在多孔介质中的微观力学分析出发,预测胶体的宏观运移行为,然而已有研究中尚未全面的考虑胶体在多孔介质中运移和滞留的多种作用.本文总结了该领域待解决的问题,包括建立考虑微观机理的对流弥散方程,发展考虑多孔介质孔隙结构的胶体过滤理论以及完善基于孔隙结构模型的胶体运移模拟方法.     

DGT富集-乙基化GC-CVAFS测定天然水体中的甲基汞

利用薄膜扩散技术(DGT)原位富集天然水体中的甲基汞,溶剂洗脱后进入水相连行乙基化反应,与气相色谱(GC)联用,冷原子荧光光谱法(CVAFS)测定.实验结果显示,26"(3条件下在超纯水中放置24 h,典型DGT单元的最低检出限为0.014 ng/L;延长放置时闻或者减少扩散层厚度,可以得到更低的检测限.相对标准偏差＜...     

珠江口地区表层水中氯酚化合物污染研究

采用固相微萃取、气-质联用方法,测定分析了珠江口、横门水道及鱼塘表层水中氯酚(CPs)的污染特征。结果显示:USEPA优先控制的四种CPs类化合物在珠江口地区水体中检出率达到98.75%,不同水体氯酚污染程度由高到低的顺序为横门水道>珠江口>鱼塘。参照有关标准,珠江口地区CPs残留水平对环境及人类生活产生危害的风险可能性较低。多元回归分析表明,铁、锰总含量与总CPs和PCP含量存在显著负相关。     

不同布水方式下水平潜流人工湿地的水力效率

通过对4种布水方式(一般水平流式、波流式、对角流式、多点进水式)下水平潜流人工湿地的脉冲示踪剂试验,获得了不同布水方式的水平潜流人工湿地的水力停留时间分布曲线,并计算出水平潜流人工湿地的表观停留时间、平均停留时间、峰值停留时间.同时,根据不同停留时间的对比关系计算不同布水方式的相对水力效率.最后,由停留时间分布函数的对数正态分布拟合模型和连续混合反应器模型分别估算上述停留时间和相对水力效率.结果表明,不同布水方式和不同计算方法得到的水力效率为波流式一般水平流式对角流式多点进水式.     

γ辐照降解水溶液中氯酚的研究

研究了水溶液中氯酚(2-氯酚、3-氯酚、4-氯酚、2,4-二氯酚)的γ辐照降解.通过测定辐照前后氯酚、氯离子浓度以及TOC的变化,考察了不同氯酚、不同初始浓度,以及联合O3、H2O2对辐解效果的影响.结果表明,γ辐照可有效降解水溶液中的氯酚,降解过程符合准一级动力学方程;初始浓度为100mag·L-1,辐照剂量为8kGy时,2-CP、3-CP、4-CP、2,4-DCP的去除率分别为68.0%、97.5%、89.7%和100%,相应的脱氯率分别为60.2%、71.1%、64.3%、78.9%;辐照联合O3或H2O2可有效提高辐照降解氯酚的去除和矿化效率,具有明显"协同效应".     

海水中氯氟烃的气相色谱法测定

应用气相色谱法测定海水中氯氟烃,海水用Niskin采水器采集,将海水转移玻璃注射器中储藏直到分析。把大约30mL海水引入到一个玻璃气提器中,用高纯氮气将溶解在海水中氯氟烃(CFC's)吹扫出来浓缩在冷捕集器中,然后把捕集器加热,用高纯氮气CFC's送入气相色谱分离柱,CFC's由电子捕获检测器(ECD)检测出。结果表明:该方法快速,灵敏度高,分离效果好,适用于分析测定水体中氯氟烃。     

工作场所空气中二乙二醇的测定

建立工作场所空气中二乙二醇的气相色谱测定法。二乙二醇用活性炭采样管采集,丙酮溶液解析后进样,经毛细管色谱柱分离,氢焰离子化检测器检测,以保留时间定性,峰面积定量。该方法灵敏度高,精密度好,准确度好。     

吹扫捕集/气联用测定水中25种有机物研究

建立了吹扫捕集/气相色谱-质谱联用测定水中25种挥发性有机物的方法。采用相对经济的氮气作为吹扫气体,优化了吹扫捕集和色谱条件,结果表明,25种挥发性有机物的色谱分离情况较好,在2.0~50.0μg/L范围内线性良好,相关系数均大于0.995,检出限在0.02~0.2μg/L范围内。方法的相对标准偏差(RSD)均小于5%,平均回收率为87.3%~108.3%。该方法前处理简单快速,采用内标法定量准确度高,重复性好,检出限低,适合低浓度水样的分析。     

Highly inhibited transport of dissolved thallium(I) in manganese oxide-coated sand: Chemical condition effects and retention mechanisms

Thallium contamination in water can cause great danger to the environment. In this study, we synthesized manganese oxide-coated sand (MOCS) and investigated the transport and retention behaviors of Tl(I) in MOCS under different conditions. Characterization methods combined with a two-site nonequilibrium transport model were applied to explore the retention mechanisms. The results showed that Tl(I) mobility was strongly inhibited in MOCS media, and the retention capacity calculated from the fitted model was 510.41 mg/g under neutral conditions. The retention process included adsorption and oxidative precipitation by the manganese oxides coated on the sand surface. Cotransport with the same concentration of Mn(II) led to halving Tl(I) retention due to competition for reactive sites. Enhanced Tl(I) retention was observed under alkaline conditions, as increasing pH promoted electronegativity on the media surface. Moreover, the competitive cation Ca²⁺ significantly weakened Tl(I) retention by occupying adsorption sites. These findings provide new insights into understanding Tl(I) transport behavior in water-saturated porous media and suggest that manganese oxide-coated sand can be a cost-effective filter media for treating Tl-contaminated water.     

Effect of sludge retention time on sludge characteristics and membrane fouling of membrane bioreactor

Three identical membrane bioreactors (MBRs) were operated over 2 years at different sludge retention time (SRT) of 10 d, 40 d and no sludge withdrawal (NS), to elucidate and quantify the effect of SRT on the sludge characteristics and membrane fouling. The hydraulic retention times of these MBRs were controlled at 12 h. With increasing SRT, the sludge concentrations in the MBRs increased, whereas the ratio of volatile suspended solid to the total solid decreased, and the size of sludge granule diminished in the meantime. A higher sludge concentration at long SRT could maintain a better organic removal efficiency, and a longer SRT was propitious to the growth of nitrifiers. The performance of these MBRs for the removal of COD and NH₄⁺-N did not change much with different SRTs. However, the bioactivity decreased as SRT increase. The measurement of specific oxygen uptake rates (SOUR) and fluorescence in situ hybridization (FISH) with rRNA-targeted oligonucleotide probes testified that SOUR and the proportion of the bacteria-specific probe EUB338 in all DAPI-stainable bacteria decreased with increasing SRT. The concentrations of total organic carbon, protein, polysaccharides and soluble extracellular polymeric substance (EPS) in the mixed liquor supernatant also decreased with increasing SRT. The membrane fouling rate was higher at shorter SRT, and the highest fouling rate appeared at a SRT of 10 d. Both the sludge cake layer and gel layer had contribution to the fouling resistance, but the relative contribution of the gel layer decreased as SRT increase.     

Hydraulic characteristics of an anaerobic baffled reactor as onsite wastewater treatment system

The feasibility of using anaerobic baffled reactor(ABR)as onsite wastewater treatment system was discussed.The ABR consisted of one sedimentation chamber and three up-flow chambers in series was experimented under different peak flow factors(PFF of 1 to 6),superficial gas velocities(between 0.6 and 3.1 cm/hr)and hydraulic retention times(HRT)(24,36 and 48 hr).Residence time distribution(RTD)analyses were carried out to investigate the hydraulic characteristics of the ABR.It was found that the PFF resulted in hydraulic dead space.The dead space did not exceed 13% at PFF of 1,2 and 4 while there was 2-fold increase(26%)at PFF of 6.Superficial gas velocities did not result in more(biological)dead space.The mixing pattern of ABR tended to be a completelymixed reactor when PFF increased.Superficial gas velocities did not affect mixing pattern.The effects of PFF on mixing pattern could be minimized by higher HRT(48 hr).The tank-in-series(TIS)model(N=4)was suitable to describe the hydraulic behaviour of the studied system.The HRT of 48 hr was able to maintain the mixing pattern under different flow patterns,introducing satisfactory hydraulic efficiency.Chemical oxygen demand(COD)and total suspended solids(TSS)removals under all flow patterns were achieved more than 85% and 90%,respectively.The standard deviation of effluent COD and TSS concentration did not exceed 15 mg/L.     

Hydraulic characteristics of an anaerobic ba ed reactor as onsite wastewater treatment system

The feasibility of using anaerobic ba ed reactor (ABR) as onsite wastewater treatment system was discussed. The ABR consisted of one sedimentation chamber and three up-flow chambers in series was experimented under di erent peak flow factors (PFF of 1 to 6), superficial gas velocities (between 0.6 and 3.1 cm/hr) and hydraulic retention times (HRT) (24, 36 and 48 hr). Residence time distribution (RTD) analyses were carried out to investigate the hydraulic characteristics of the ABR. It was found that the PFF resulted in hydraulic dead space. The dead space did not exceed 13% at PFF of 1, 2 and 4 while there was 2-fold increase (26%) at PFF of 6. Superficial gas velocities did not result in more (biological) dead space. The mixing pattern of ABR tended to be a completelymixed reactor when PFF increased. Superficial gas velocities did not a ect mixing pattern. The e ects of PFF on mixing pattern could be minimized by higher HRT (48 hr). The tank-in-series (TIS) model (N = 4) was suitable to describe the hydraulic behaviour of the studied system. The HRT of 48 hr was able to maintain the mixing pattern under di erent flow patterns, introducing satisfactory hydraulic e ciency. Chemical oxygen demand (COD) and total suspended solids (TSS) removals under all flow patterns were achieved more than 85% and 90%, respectively. The standard deviation of e uent COD and TSS concentration did not exceed 15 mg/L.     

基于CFD的内构件强化内循环流化床流场结构分析

针对流化床内部流体结构的复杂性和缺乏有效放大设计理论的问题,以漏斗型导流内构件强化的内循环流化床的气液运动为研究对象,利用欧拉-欧拉双流体模型构建了能描述其复杂流动的CFD数学模型,通过宏观流场、气含率分布、液体速度分布解析内构件对气液混合传质的作用原理.数值模拟结果表明:双流体模型能较好地揭示流化床内气液流场结构,流...     

Determination and discussion hydraulic retention time in membrane bioreactor system

Based on the microorganism kinetic model, the formula for computing hydraulic retention time in a membrane bioreactor system (MBR) is derived. With considering HRT as an evaluation index a combinational approach was used to discuss factors which have an effect on MBR. As a result, the influencing factors were listed in order from strength to weakness as: maximum specific removal rate K, saturation constant Ks, maintenance coefficient m, maximum specific growth rate ,ua and observed yield coefficient Yobs. Moreover, the formula was simplified, whose parameters were experimentally determined in petrochemical wastewater treatment. The simplified formula is θ= 1.1( 1/β -1)(Kｓ S)/KXo , for oetroehemical wastewater treatment K and Ko eaualed 0.185 and 154.2, resoectively.     

纳米Fe0颗粒对三种单氯酚的降解

采用化学还原法制备了纳米Fe0颗粒,研究了不同条件下纳米Fe0对3种单氯酚(2-CP, 3-CP, 4-CP)的去除作用.结果表明,纳米Fe0对单氯酚具有良好的去除效果,主要降解途径为先脱氯后开环,实现氯酚分子与Fe原子间的电子转移,达到还原脱氯的效果.3种单氯酚的脱氯难易程度为2-CP＞3-CP＞4-CP,脱氯反应活性与其分子最低空轨道能量(ELUMO)有关.随着氯酚初始浓度的增大,其相对去除率略有降低, 但绝对降解量有较大提高.温度不仅影响脱氯速率,而且影响氯酚去除的途径,温度较高时,氯酚先脱氯后开环;温度低时,较易产生氧化产物.     

多溴联苯醚定量结构-性质关系的分子表面静电势应用研究

对持久性有机污染物多溴联苯醚(PBDEs)209个分子进行HF/6-31G*水平上的结构优化,并在优化结构基础上进行了分子静电势及其导出参数的计算.应用多元线性回归方法对PBDEs的色谱保留时间(RRT)、正辛醇/空气分配系数(lgKOA)和298K超冷流体蒸气压(lgpL)3种理化性质与分子结构参数进行了关联.结果表明,分子表面静电势参数结合苯环上溴原子取代个数比结合分子体积,可以更好地表达PBDEs的理化性质与其分子结构间的定量关系,所建立的3个QSPR模型的交叉验证相关系数(Rc)分别为0.981 9、0.991 1和0.996 3,标准偏差(SD)分别为0.042 4、0.138 4和0.102 0,说明3个模型均具有较强的稳健性和预测能力,同时也证明了分子静电势参数在PBDE类化合物的QSPR研究中的适用性.