高效液相色谱-三重四级杆/复合线性离子阱质谱法测定饮用水中22种邻苯二甲酸酯

建立了一种同时测定饮用水中22种邻苯二甲酸酯(PAEs)的高效液相色谱-三重四级杆/复合线性离子阱质谱方法:饮用水样品经针头过滤器过滤,选用Biphenyl液相色谱柱进行分离,以含0.1%甲酸的水溶液和含0.1%甲酸的甲醇溶液为流动相,电离模式为电喷雾正离子,选用多反应监测触发增强子离子扫描模式进行检测。结果表明,22种PAEs的灵敏度良好,定量限为0.001～0.1 μg/L。配制浓度为0.1～100.0 μg/L的混标溶液进行进样分析,分析结果显示,22种PAEs在该范围内的线性关系良好,相关系数均大于0.995,方法的平均回收率为82.9%～108.9%,相对标准偏差为0.9%～11.2%。同时,使用增强子离子扫描谱图进行搜库匹配,定性准确性高。该方法适用于饮用水中PAEs的检测。     

阴角邻面火灾作用下L型钢管混凝土柱耐火极限研究

运用有限元软件ABAQUS计算L形带肋钢管混凝土柱阴角相邻两面受火全过程下的耐火极限,分析了阴角邻面受火方式下构件内部温度场和应力场的变化规律,在此基础上分析荷载比、宽厚比、计算长度、加劲肋纵向间距、荷载偏心率、荷载角等参数对耐火极限的影响规律。数据表明:荷载比、计算长度对构件耐火极限影响较大,随着荷载比和计算长度的增大,耐火极限基本呈线性下降;加劲肋间距对构件耐火性能影响较小;由于L形柱的特殊形式,偏心荷载对耐火极限的影响规律较复杂,荷载作用点偏向低温区可以提高耐火极限。     

Reduced Downward Mobility of Metolachlor and Metribuzin from Surfactant-Modified Clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

有机酸土柱淋洗法修复重金属污染土壤

通过室内模拟实验,采用土柱淋洗方法,研究草酸、柠檬酸、乙酸和酒石酸溶液对某电镀厂附近土壤中重金属的去除效果。探讨了淋洗剂浓度、淋洗次数和淋洗时间等对淋洗效果的影响,研究草酸淋洗前后土壤中重金属形态的变化。结果表明,淋洗过程中铬的去除效果明显滞后于铜、锌和镍3种重金属离子。1 mol/L的草酸在土水比为1∶1,淋洗5h,淋洗4次的条件下可以达到最佳淋洗效果,Cu、Zn、Ni和Cr的去除率分别是99.6%、66.98%、88.7%和18.23%。     

石油污染土壤原位生物修复的强化实验研究

为研究添加营养物质和高效降解石油微生物对油污土壤生物修复的作用,通过分层土柱的方法,连续监测了不同条件下不同土层的含水率、石油烃含量、细菌数量及脱氢酶活性。结果表明:添加营养物质同时接种高效微生物可使降解效果明显改善,降解率比在自然条件下提高近50%,而单纯添加营养物质不接种高效微生物可使降解率比在自然条件下提高约25%。降解初期,上层土壤降解效果较好,而到中后期,中下层降解效果好于上层。微生物数量和脱氢酶活性与石油降解率之间存在良好的相关性,脱氢酶活性比微生物数量更能反映修复过程中微生物的存活状态。添加营养物质和高效降解石油微生物对油污土壤原位生物修复具有强化作用。     

利用钢铁盐酸酸洗废液在填料塔中制备FeCl3

以钢铁盐酸酸洗废液为原料,亚硝酸钠为催化剂,氧气为氧化剂,在填料塔中催化氧化制备三氯化铁。考察了反应温度、催化剂加入量和添加方式、循环流量等对制备三氯化铁的影响。实验结果表明,在优化的工艺条件为料液预热温度为60 ℃、催化剂加入量为钢铁盐酸酸洗废液总质量的0.30%、料液循环流量6.0 m³/h的条件下,反应80~120 min,酸洗废液中的Fe²⁺完全氧化为Fe³⁺。     

Enhanced retention of linuron, alachlor and metalaxyl in sandy soil columns intercalated with wood barriers

A study has been made of the effect a reactive barrier made of pine (softwood) or oak (hardwood) wood intercalated in a sandy soil column has on the retention of linuron, alachlor and metalaxyl (pesticides with contrasting physicochemical characteristics). The leaching of pesticides has been carried out under a saturated flow regime and breakthrough curves (BTCs) have been obtained at flow rates of 1 mL min⁻¹ (all pesticides) and 3 mL min⁻¹ (linuron). The cumulative curves in the unmodified soil indicate a leaching of pesticides >80% of the total amount of compound added. After barrier intercalation, linuron leaching decreases significantly and a modification of the leaching kinetics of alachlor and metalaxyl has been observed. The theoretical R factors increased ∼2.6-3.3, 1.2-1.6-fold, and 1.4-1.7-fold and the concentration of the maximum peak decreased ∼6-12-fold, 2-4-fold and 1.2-2-fold for linuron, alachlor and metalaxyl, respectively. When considering the three pesticides, significant correlations have been found between the theoretical retardation factor (R) and the pore volume corresponding to the maximum peaks of the BTCs (r = 0.77; p < 0.05) or the total volume leached (r = −0.78; p < 0.05). The results reveal the efficacy of reactive wood barriers to decrease the leaching of pesticides from point sources of pollution depends on the type of wood, the hydrophobicity of the pesticide and the adopted water flow rate. Pine was more effective than oak in decreasing the leaching of hydrophobic pesticide linuron or in decreasing the maximum peak concentration of the less hydrophobic pesticides in soils. Efficacy of these wood barriers was limited for the least hydrophobic pesticide metalaxyl.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

硫酸盐还原菌污泥固定化特性

采用玉米芯为碳源,聚乙烯醇(PVA)为包埋载体,饱和硼酸(H3BO3)为交联剂,研究了硫酸盐还原菌污泥(SRBS)、铁屑、麦饭石共固处理合成煤矿酸性废水的最优配比与机理,并分析了固定化过程中小球稳定性及活性的变化规律。实验结果表明,SRBS投加量是影响处理效果的最显著因子,当投加30%SRBS、2%铁屑、3%麦饭石时SO2-4、Mn2+去除率分别为94.13%和84.39%,溶液p H为7.03,未检测出Fe2+;随着交联时间的延长,小球膨胀率及SO2-4还原率分别呈线性与指数下降,从保持小球稳定性与活性角度考虑,可将交联时间设定为4~8 h;该法可为市政污泥的处置以及生物法处理煤矿酸性废水的工程应用提供技术参考。