有机氯农药在南京市郊蔬菜中的生物富集与质量安全

用气相色谱．电子捕获检测器(GC-ECD)测定南京市郊蔬菜中的有机氯农药残留．结果表明，12种有机氯农药在所有的供试蔬菜中均有检出，DDT和HCH在各蔬菜中的含量较高，分别占有机氯农药总残留量的49．5％～75．0％和13．9％～28．2％．Wα-HCH／Wγ-HCH和WDDE／WDDT的比值在各蔬菜体内均小于或等于1，说明这些蔬菜生长的环境中可能有新的有机氯污染物的输入．各种蔬菜对有机氯农药总量的富集因子为0．41～0．78．富集能力最大的为胡萝卜，蒜苗和菠菜．HCH类农药在各种蔬菜体内的生物富集因子(0．70～1．10)要高于DDT类(0．28～0．80)．胡萝卜对HCH和DDT等有机氯农药的富集能力较强，而莴苣、蒜苗和菠菜对六氯苯、狄氏剂，异狄氏剂和硫丹有较高的生物富集能力．虽然各种蔬菜体内有机氯农药的残留量低于国家最大残留限量，但其检出率仍为100％，仍然对农产品质量安全和人类健康造成潜在的威胁．关键词：有机氯农药；蔬菜；残留量；生物富集；人类健康     

膨润土和改性膨润土对电镀污泥中重金属的稳定化处理

采集某电镀厂污泥,以膨润土和改性膨润土为稳定剂,采用TCLP毒性浸出试验分析膨润土和改性膨润土对污泥中重金属Cr、Cd、Zn和Pb的稳定化效果。未加入稳定化剂前,电镀污泥中重金属Cr、Cd、Zn和Pb的浸出毒性分别为154 mg/L、13.5 mg/L、658 mg/L和76 mg/L。稳定化试验结果表明,在膨润土和改性膨润土的投加量与干污泥的质量比分别为1∶5和3∶10,振荡时间为12 h时,浸出液中重金属质量浓度最低,稳定化效果最好。形态分析结果表明,加入膨润土和改性膨润土稳定后重金属以有机结合态和残渣态为主,与未稳定前相比污泥中重金属不稳定态的含量变少。扫描电镜和红外分析结果表明,膨润土和改性膨润土可能通过吸附和离子交换来稳定污泥中的重金属。研究表明,改性膨润土对电镀污泥中高含量重金属的稳定化效果要优于未改性膨润土的稳定化效果。     

近岸水域船舶溢油应急保障能力评估

为了降低溢油事故对近岸水域造成的影响,提高近岸水域船舶溢油事故应急响应系统的能力,采用结构方程模型,评价船舶溢油应急保障能力。在分析近岸水域船舶溢油应急响应系统影响因素的基础上,构建了船舶溢油应急保障能力评价的指标体系,引入结构方程模型,建立船舶溢油应急保障能力分析的路径模型,分析应急保障变量之间的互动关系及其影响程度,研究其算法,并以实例验证模型的可行性。结果表明,人员保障在溢油应急保障能力中起主导作用,其次是物资保障和技术保障。     

低强度超声对短程硝化污泥活性的影响

为提高短程硝化反硝化脱氮效率,采用低强度超声对短程硝化反应进行强化,通过对比氨氧化率和亚硝酸盐生产量,考察低强度超声对短程硝化污泥活性影响。首先,通过对超声能量的优化试验,发现低强度超声能够提升短程硝化污泥反应速率,且超声能量为43.20 kJ时氨氧化率和亚硝酸盐生成量最大;然后考察超声能量与污泥浓度的关系。结果表明:1)在相同超声能量(43.20 kJ)条件下,随着污泥质量浓度(0.34~1.03 g VSS/L)增加,能量密度降低,反应速率不断提高;2)保持污泥浓度恒定,增加超声能量,发现在43.20 kJ时短程硝化污泥活性最好,氨氧化速率比对照组提高25.42%,继续增加能量后去除速率开始下降,原因是适宜的能量会增加微生物细胞壁和细胞膜的通透性,加快基质传递和反应速率,提高微生物活性,但当所施加能量超出其所能承受范围,则会对微生物内部产生损害,降低其活性;3)考察超声能量对胞外聚合物浓度和酶活性影响,在43.20 kJ条件下,多糖、蛋白质和胞外聚合物(EPS)浓度分别提高了18.32%、26.54%和22.05%,氨单加氧酶活性增加19.82%。研究表明,由于低强度超声作用加快胞外聚合物分泌,增加生物酶活性,进而促进了短程硝化污泥反应速率。     

某酸性矿山排水中溶解性有机物的特征分析

采集安徽某酸性矿山排水（AMD）水库不同离岸距离的表水层水样,结合傅立叶变换离子回旋共振质谱（FT-ICR MS）与三维荧光光谱（EEMs）技术对水样中溶解性有机物（DOM）来源和组分特征进行分析.三维荧光结果表明,样品中内源性色氨酸类荧光峰峰强与离岸距离正相关,且基于三维荧光特征指数（FI,HIX,BIX）分析判断DOM主要来自于内源.FT-ICR MS在分子层面进一步表明,内源性组分（脂类,脂肪族/蛋白类,糖类）在近岸点样品DOM所占比重相对较低（66%）.AMD中DOM的主要成分为CHO（40%~50%）、CHON（25%~30%）、CHOS （22%~36%）等化合物.DOM包含有高比例的CHOS化合物主要与AMD水体高浓度硫酸盐有关.     

Characterization of a new smog chamber for evaluating SAPRC gas-phase chemical mechanism

A new state-of-the-art indoor smog chamber facility (CAPS-ZJU) has been constructed and characterized at Zhejiang University, which is designed for chemical mechanism evaluation under well-controlled conditions. A series of characterization experiments were performed to validate the well-established experimental protocols, including temperature variation pattern, light spectrum and equivalent intensity (J_NO2), injection and mixing performance, as well as gases and particle wall loss. In addition, based on some characterization experiments, the auxiliary wall mechanism has been setup and examined. Fifty chamber experiments were performed across a broad range of experimental scenarios, and we demonstrated the ability to utilize these chamber data for evaluating SAPRC chemical mechanism. It was found that the SAPRC-11 can well predict the O₃ formation and NO oxidation for almost all propene runs, with 6 hr Δ(O₃ – NO) model error of –3% ± 7%, while the final O₃ was underestimated by ~20% for isoprene experiments. As for toluene and p-xylene experiments, it was confirmed that SAPRC-11 has significant improvement on aromatic chemistry than earlier version of SAPRC-07, although the aromatic decay rate was still underestimated to some extent. The model sensitivity test has been carried out, and the most sensitive parameters identified are the initial concentrations of reactants and the light intensity as well as HONO offgasing rate and O₃ wall loss rate. All of which demonstrated that CAPS-ZJU smog chamber could derive high quality experimental data, and could provide insights on chamber studies and chemical mechanism development.     

Surface characterization of metal oxides-supported activated carbon fiber catalysts for simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide

The sol–gel method was used to synthesize a series of metal oxides-supported activated carbon fiber (ACF) and the simultaneous catalytic hydrolysis activity of carbonyl sulfide (COS) and carbon disulfide (CS₂) at relatively low temperatures of 60°C was tested. The effects of preparation conditions on the catalyst properties were investigated, including the kinds and amount of metal oxides and calcination temperatures. The activity tests indicated that catalysts with 5 wt.% Ni after calcining at 400°C (Ni(5)/ACF(400)) had the best performance for the simultaneous catalytic hydrolysis of COS and CS₂. The surface and structure properties of prepared ACF were characterized by scanning electron microscope-energy disperse spectroscopy (SEM-EDS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), carbon dioxide-temperature programmed desorption (CO₂-TPD) and diffuse reflectance Fourier transform infrared reflection (DRFTIR). And the metal cation defects were researched by electron paramagnetic resonance (EPR) method. The characterization results showed that the supporting of Ni on the ACF made the ACF catalyst show alkaline and increased the specific surface area and the number of micropores, then improved catalytic hydrolysis activity. The DRFTIR results revealed that -OH species could facilitate the hydrolysis of COS and CS₂; -COO and -C–O species could facilitate the oxidation of catalytic hydrolysate H₂S. And the EPR results showed that high calcination temperature conditions provide more active reaction center for the COS and CS₂ adsorption.     

砂砾质地表不同粒径颗粒地球化学特征分析

风沙运动造成地表沉积物组分发生改变,伴随其沉积物地球化学特征发生改变。选取苏宏图洪积扇扇缘戈壁、沙积洼地地表沉积物,基于X射线衍射仪、扫描电镜能谱仪进行其不同组分矿物、地球化学元素测试。结果表明:风沙运动导致不同地表沉积物的风蚀和风积情况不同,但其均处于化学风化的初、中级阶段,具有相似性;该砂砾质地表不同粒径组分以石英、长石、云母、方解石等矿物为主,各沉积物组分矿物衍射峰强具有显著差异性;该区域不同粒径颗粒化学元素组成以SiO_2、Al_2O_3、Fe_2O_3为主,约占总含量的85%左右,沉积物颗粒粒径越大,SiO_2含量越多,Fe_2O_3、MgO、CaO、TiO_2等氧化物表现为在细颗粒组分中富集,而Al_2O_3、K_2O、Na_2O等随颗粒粒径变化无显著差异。     

大靖河径流变化特征及其对气候变化和人类活动的响应

流域径流变化及其影响因素的研究对流域水资源的可持续开发利用以及改善流域的生态环境具有重要意义。以大靖河流域1956—2016年水文气象数据为基础,分析了近61 a来大靖河径流的年内、年际变化特征,并定量评估了气候变化和人类活动对径流变化的影响。结果表明：大靖河径流年内分配不均,主要集中在7—10月,占全年径流的60.98%;1956年以来大靖河径流以1.1×10⁵ m³?a^?1的速率递减,Hurst指数为0.69,表明大靖河径流在未来一段时间将继续呈递减趋势;大靖河径流存在4个震荡周期,分别为2—5 a、8—13 a、17—24 a及35—45 a左右,降水的震荡周期（8—13 a、17—24 a及35—47 a）与径流周期具有较好的一致性;气候变化对大靖河径流减少的贡献率为4.7%,人类活动的贡献率为95.3%,这可能与研究区土地利用方式变化有关。     

生活垃圾焚烧厂周边土壤中PCDD/Fs及重金属含量

为了解城市生活垃圾焚烧发电厂周边表层土壤中二噁英、重金属来源及分布特征,选取成都地区3座典型生活垃圾焚烧厂作为研究对象,开展了周边土壤中17种多氯二苯并对二噁英/呋喃（PCDD/Fs）及11种重金属含量监测.结果显示,土壤样品中的PCDD/Fs和重金属的浓度范围分别为0.25~7.5ng I-TEQ/kg和0.23～580.57mg/kg;3座垃圾焚烧厂周边土壤中多氯二苯并呋喃（PCDFs）的毒性当量浓度贡献率要高于多氯二苯并二噁英（PCDDs）,PCDFs毒性当量浓度平均贡献率达到55%;土壤样品中Cd、Hg、Pb、Cu、Zn之间具有良好的相关性,Hg、Pb、Zn与部分PCDFs具有良好的相关性,相关系数r分别为0.792、0.760、0.788,所对应的p值分别为0.034、0.047、0.035,并被归类为同一聚类,可将这部分重金属元素作为重金属示踪剂来表征PCDFs的来源.