加速溶剂萃取-凝胶净化色谱-气相色谱质谱法测定农用地土壤中有机氯农药方法研究

通过对加速溶剂萃取、平行蒸发及净化方法等环节的优化实验,建立了加速溶剂萃取-凝胶净化色谱-气相色谱质谱法测定农用地土壤中23种有机氯农药的检测方法。结果表明,方法检出限为0.0034~0.0052 mg/kg;对化合物质量分数为0.25 mg/kg的土壤加标样品进行平行实验,回收率为82.0%~93.7%;测定结果的相对标准偏差（RSD）≤8.7%。对土壤有证标准质控样品进行分析,测定结果均在验收范围之内。该方法准确可靠,灵敏度较高,样品净化效果较好,能够满足农用地土壤中有机氯农药残留痕量分析的要求。     

黄海近岸大气降水中磷溶解度及其影响因素

于2020年6~9月在黄海近岸城市青岛采集31场降水69个样品,分析其中总磷（TP）、溶解态总磷（DTP）及溶解态无机磷（DIP）和有机磷（DOP）,探讨P浓度和溶解度的变化特征及其影响因素.降水中TP浓度为（6.2±1.0）μg/L,DTP浓度为（3.8±0.6）μg/L,P溶解度为（64.8±18.0）%.DTP中以DIP为主,其贡献为（56.5±21.6）%.降水中TP和DTP与降水量呈负幂指数关系,TP清除指数大于DTP.降水量<10mm时,降水对气溶胶P的清除和稀释作用显著影响降水中P浓度,但降水量>40mm时,这种作用对P浓度的影响不大.降水对气溶胶P的清除作用以云下清除为主,占总清除效率的70%~85%.酸化作用显著促进降水中颗粒态P溶解,且无机P溶解效率高于有机P.对降雨量<5mm及>30mm降水,pH值是影响P溶解度的主要因素,降水量和气团来源对P溶解度也有一定影响.当pH值相近时,降水量越大,P溶解度越高;当pH值相近且降水量<5mm时,海洋源贡献越大,P溶解度越高.对降水量5~30mm的降水,P溶解度受到降水量、pH值及气团来源等因素的共同影响.     

城市间PM2.5源的碳成分谱比较

为了解我国不同城市PM_2.5源的碳成分谱特征和地域差异,采集沈阳市、十堰市和乌鲁木齐市的燃煤源、柴油车尾气源、汽油车尾气源和餐饮源样品,使用热光透射法分析PM_2.5中的总碳（TC）、有机碳（OC）和元素碳（EC）,以及细分的8种碳组分（OC1,OC2,OC3,OC4,EC1,EC2,EC3和OPC_T）,构建各类污染源碳成分谱.结果表明：3个城市4类源TC/PM_2.5从高到低分别为：餐饮源（65.1%±8.4%）、柴油车尾气源（46.2%±9.5%）、汽油车尾气源（37.7%±3.5%）和燃煤源（17.3%±8.0%）;OC/TC在餐饮源中最高（98.0%±0.5%）,EC/TC在柴油车尾气源中最高（38.6%±8.5%）.3个城市同类源的碳组分含量受污染源细分后的不同类型影响有一定差异,但归一化处理后总体仍表现为燃煤源中OC2（14%~30%）和OC3（13%~23%）含量最高,柴油车尾气源中EC2（22%~56%）含量最高,汽油车尾气源中OC2（24%~41%）、OC1（16%~42%）和OC3（12%~26%）含量最高,餐饮源中OC2（21%~43%）和OC3（23%~49%）含量最高.不同污染源的OC/EC值为燃煤源在0.4~7.6之间,柴油车尾气源在0.2~5.6之间,汽油车尾气源在1.1~38.5之间,餐饮源在6.4~170.2之间.分歧系数结果显示3个城市不同源的碳成分谱具有差异性,同类源的碳成分谱具有相似性.将3个城市同类源碳成分谱合并后利用化学质量平衡灵敏度矩阵得到OC2,OC3,OC4,EC1和OPC_T可共同作为燃煤源的标识组分;EC2是柴油车尾气源的标识组分;OC1,OC2和OC3可共同作为汽油车尾气源的标识组分;OC2和OC3可共同作为餐饮源的标识组分.沈阳市、十堰市和乌鲁木齐市相同污染源相似的碳成分谱和一致的标识碳组分可为国内其他城市相关研究提供数据参考.     

沈阳市采暖期与非采暖期空气PM2.5污染特征及来源分析

为了研究沈阳市采暖期与非采暖期空气PM_(2.5)污染特征及来源,于2015年1月29日～2016年1月26日在沈阳市采集PM_(2.5)有效样品113组,并分析了其载带的水溶性离子、碳组分及元素组分.结果表明,采样期间沈阳市PM_(2.5)质量浓度均值为66μg·m~(-3),其中31. 0%的样品超过《环境空气质量标准》(GB 3095-2012)日均值二级标准(75μg·m~(-3)),采暖期PM_(2.5)的平均浓度和超标率(90μg·m~(-3)、68. 6%)明显高于非采暖期(51μg·m~(-3)、31. 4%).采样期间21种元素(除了Mg、Ti、Ca、Fe、Si)、水溶性离子(除Ca~(2+)以外)和OC、EC质量浓度均呈现出采暖期高于非采暖期的趋势;[NO_3~-]/[SO_4~(2-)]比值表明非采暖期受移动源影响明显增加,燃煤等固定源仍是采暖期PM_(2.5)的主要来源,PM_(2.5)中水溶性离子是固定源和移动源共同作用的结果;氮氧化率(NOR)和硫氧化率(SOR)分析得到NO_x二次转化程度较弱,SO_2二次转化程度较强,特别是在非采暖期;富集因子结果表明EF值较高的元素主要来自燃煤、交通污染和工业排放. PM_(2.5)组分重构质量与实测质量呈现较好的相关性,采暖期和非采暖期PM_(2.5)中主要组分均为有机物(OM 28. 0%、23. 1%)、矿物尘(MIN 14. 5%、26. 0%)和SO_4~(2-)(15. 1%、19. 9%),PM_(2.5)受二次粒子、燃烧源和扬尘源影响较大.     

成都市夏冬季大气胺颗粒物的单颗粒质谱研究

基于单颗粒气溶胶质谱（SPAMS）对成都市夏冬两季大气胺颗粒进行了综合观测,结合ART-2a算法及人工合并,2个季节大气中的胺颗粒都可分为7类,各类颗粒贡献的季节差异明显,燃烧源颗粒（如EC）在夏季贡献较大,而老化的有机碳颗粒（OCa）贡献在冬季显著升高.两季节平均质谱差减进一步证明夏、冬季分别以燃烧源和老化的胺颗粒为主.因高温分解,夏季胺颗粒占比在正午出现明显的低值,而下午的燃烧活动（如生物质燃烧）对该占比提升作用明显;冬季胺颗粒占比在白天显著高于夜间.随污染加重,胺颗粒数在夏冬两季均快速增加,其中夏季EC颗粒升高最为明显,污染最重时贡献可达47%;冬季升高最明显的是老化程度更高的OCa颗粒,当PM_2.5浓度达到200μg/m³以上时,其贡献比例可达37%.因此,由于污染源和气候条件的差异,成都市大气胺颗粒形成机制和理化特征季节差异巨大.     

哈尔滨市大气细颗粒物污染特征及其毒性效应

为研究哈尔滨市大气细颗粒物的污染特征及其毒效应,分别采集PM_2.5、PM_1.0样品,分析其质量浓度、数浓度的变化分布特征以及对小鼠肺损伤的影响.结果表明：2017年全年PM_2.5、PM_1.0的质量浓度均呈冬高夏低趋势;PM_1.0质量浓度占PM_2.5总质量浓度的62%~85%,PM_1.0数浓度变化趋势为两边高中间低,且其大小与温度呈负相关,与相对湿度无显著相关性;研究大气颗粒物对小鼠肺损伤影响时发现,染毒组小鼠肺组织细胞中LDH、ACP、AKP、ALB增高,说明大气颗粒物PM_2.5和PM_1.0对小鼠肺组织细胞具有毒效应;肺灌洗液中MDA、NO、NOS水平升高,SOD活性下降,说明PM_2.5和PM_1.0都使机体发生氧化损伤,且PM_2.5和PM_1.0质量浓度增加,会使小鼠肺组织细胞毒效应增强,由此引发的机体氧化损伤程度增大.     

Degradation of duloxetine: Identification of transformation products by UHPLC-ESI(+)-HRMS/MS, in silico toxicity and wastewater analysis

Duloxetine (DUL), an antidepressant drug, has been detected in surface water and wastewater effluents, however, there is little information on the formation of its transformation products (TPs). In this work, hydrolysis, photodegradation (UV irradiation) and chlorination experiments were performed on spiked distillated water, under controlled experimental conditions to simulate abiotic processes that can occur in the environment and wastewater treatment plants (WWTPs). Eleven TPs, nine from reaction with UV light and two from chlorine contact, were formed and detected by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry, and nine of them had their chemical structures elucidated upon analyses of their fragmentation patterns in MS/MS spectra. The formation and degradation of the TPs were observed. The parent compound was completely degraded after 30?min in photodegradation and after 24?hr in chlorination. Almost all TPs were completely degraded in the experiments. The ecotoxicity and mutagenicity of the TPs were predicted based on several in silico models and it was found that a few of these products presented more ecotoxicity than DUL itself and six TPs showed positive mutagenicity. Finally, wastewater samples were analyzed and DUL and one TP, possibly formed by chlorination process, were detected in the effluent, which showed that WWTP not only did not remove DUL, but also formed a TP.     

南昌市城市空气PM2.5和PM10时空变异特征及其与景观格局的关系

基于2013—2015年南昌市9个空气环境监测点的连续数据,分析了空气PM_(2.5)、PM_(10)质量浓度(以下简称浓度)的时空变异规律,并以景观格局指数为定量指标,研究了监测点的两种颗粒物浓度与其周边500 m半径、1000 m半径缓冲区的土地利用状况的关系.结果表明:(1)南昌市3年来PM_(2.5)和PM_(10)浓度逐年显著降低.(2)通过聚类分析,9个监测站依据颗粒物污染可分为4大类,表现出一致的城乡梯度差异.(3)在斑块类型水平上,PM_(2.5)和PM_(10)浓度与500、1000 m半径缓冲区的C-PLAND(建筑用地覆盖率)、C-SHDI(建筑用地多样性指数)显著正相关,与1000m缓冲区的F-ED(林地边界密度)显著正相关;与F-PLAND(林地覆盖率)、C-Fi(建筑用地分离度指数)、F-MPS(林地平均斑块面积)显著负相关.在景观水平上,PM_(2.5)和PM_(10)浓度在500 m缓冲区与LPI(最大斑块所占景观比例)显著负相关;与1000 m缓冲区的MPS(平均斑块面积)显著负相关.景观格局指数直接反映土地利用状况,它与PM_(2.5)和PM_(10)浓度的相关性,表现出生态学中典型的"源汇景观"关系.     

Aeration optimization through operation at low dissolved oxygen concentrations: Evaluation of oxygen mass transfer dynamics in different activated sludge systems

In wastewater treatment plants(WWTPs)using the activated sludge process,two methods are widely used to improve aeration efficiency — use of high-efficiency aeration devices and optimizing the aeration control strategy. Aeration efficiency is closely linked to sludge characteristics(such as concentrations of mixed liquor suspended solids(MLSS)and microbial communities)and operating conditions(such as air flow rate and operational dissolved oxygen(DO)concentrations). Moreover,operational DO is closely linked to effluent quality. This study,which is in reference to WWTP discharge class A Chinese standard effluent criteria,determined the growth kinetics parameters of nitrifiers at different DO levels in small-scale tests. Results showed that the activated sludge system could meet effluent criteria when DO was as low as 0.3 mg/L,and that nitrifier communities cultivated under low DO conditions had higher oxygen affinity than those cultivated under high DO conditions,as indicated by the oxygen half-saturation constant and nitrification ability. Based on nitrifier growth kinetics and on the oxygen mass transfer dynamic model(determined using different air flow rate(Q′_(air))and mixed liquor volatile suspended solids(MLVSS)values),theoretical analysis indicated limited potential for energy saving by improving aeration diffuser performance when the activated sludge system had low oxygen consumption; however,operating at low DO and low MLVSS could significantly reduce energy consumption. Finally,a control strategy coupling sludge retention time and MLVSS to minimize the DO level was discussed,which is critical to appropriate setting of the oxygen point and to the operation of low DO treatment technology.     

基于SPAMS的太原市典型生活区停暖前后PM2.5来源及组成

为分析太原市采暖期和非采暖期PM_2.5的特征,利用单颗粒气溶胶质谱仪（SPAMS）分析太原市典型生活区采暖期（2016年3月11-18日）和非采暖期（2016年4月1-7日）PM_2.5的来源及组成.结果表明:① 采暖期（停暖前）颗粒物有机碳、硫酸盐和多环芳烃等信号强度大于非采暖期（停暖后）,而元素碳、硝酸盐、铵盐等反之.② 为了尽可能排除气象因素的影响,选取风向（东南风）、风级（二级）相同时段的颗粒物进行分析,停暖前后颗粒物主要化学组分为有机碳、混合碳和元素碳,采暖前有机碳占比（达51.9%）最高,非采暖期元素碳占比（32.6%）最高.采暖期有机碳、高分子有机物和左旋葡聚糖占比明显高于非采暖期,元素碳、矿物质和重金属反之.③ 停暖前后首要的两类污染源为燃煤和机动车尾气,二者贡献率之和分别高达70.1%和67.4%,可见本地主要受这两类源的影响.燃煤在采暖期为首要污染源,并且贡献比例高于非采暖期,而机动车尾气在非采暖期为首要污染源,且比例明显高于采暖期.研究显示,采暖和非采暖期虽然首要污染源有所差异,但在污染过程中,机动车尾气源的贡献比例均高于优良时段,说明无论是采暖期还是非采暖期,除燃煤排放的影响外,机动车尾气的影响也需得到重视,建议加强机动车燃油品质的升级,使用清洁煤,并在重污染时段采取相应的管控措施.