Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.     

Incidence of organochlorine pesticides in soils of Shenzhen, China

To determine the incidence of organochlorine pesticides (OCPs) in soil in a rapid urbanization region, soil samples from various land use types in Shenzhen were collected in winter, 2007. The concentration of dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) ranged from non-detected to 149 ng g(-1) and 19 to 88 ng g(-1), respectively. The highest levels of OCPs were observed in soil from traffic and industry areas, reflecting that intensive human disturbance make the soil pollution accumulation more disperse. HCHs and DDTs profiles revealed that the sources were associated mainly with lindane and technical DDTs, respectively, while HCHs in the soil of Shenzhen might originate from both recent and historical sources. The loss of OCPs by soil erosion will enter surface runoff and impose impact on the water environment. Non-dietary exposure estimation indicates that children were the most sensitive group. The average daily exposure to OCPs for males was more serious than for females. Non-dietary exposure to DDTs and HCHs in residential blocks of Shenzhen were far below the acceptable daily intake recommended by the Food and Agriculture Organization/World Health Organization.     

Fate estimation of polycyclic aromatic hydrocarbons in soils in a rapid urbanization region, Shenzhen of China

Our previous study indicated that the current level of polycyclic aromatic hydrocarbons (PAHs) in Shenzhen soil is in the low-end of world soil PAH pollution. In this study, the fate of PAHs in the soil of Shenzhen was investigated. The mass inventories of Σ(27)PAHs and Σ(15)PAHs (defined as the sum of the 27 or 15 PAH compounds sought) in topsoil of Shenzhen were ～204 and ～152 metric tons, respectively. Fate estimation of Σ(15)PAHs shows that air-soil gaseous exchange is the primary environmental process with ～10,076 kg/year diffusing from soil to air. Rain washing (～1131 kg/year from air to soil) is the most important input pathway followed by wet (～17 kg/year) and dry deposition (～8 kg/year) to soils in Shenzhen. The transport of Σ(15)PAHs by soil erosion is a crucial loss process for soil PAHs in Shenzhen (1918 kg/year for water runoff and 657 kg/year for solid runoff from soil). Moreover, degradation is not ignorable at present (95 kg/year). Comparison of inventory and residue (defined as Σ(15)PAHs left in topsoils after all environmental loss processes) suggested that input and loss of high molecular weight PAHs for Shenzhen's soil reached apparent equilibrium. Soil PAH pollution in Shenzhen will stay in a quasi-steady state for a long period and the natural environmental processes can not significantly reduce the pollution.     

基于实验模拟的广州市餐饮油烟VOCs排放特征及风险评估

随着城市餐饮行业的快速发展,餐饮源已逐渐成为大气挥发性有机物（VOCs）的主要来源之一。为深入了解广州市餐饮油烟的排放特征,科学制定广州市餐饮源的减排对策,在实验室搭建烹饪平台模拟烹饪过程,探讨不同油温、食用油种类和菜系类型对烹饪油烟排放VOCs组分的影响,并采集广州市典型商圈川菜馆、湘菜馆、粤菜馆、越南菜馆4家餐馆排放的餐饮油烟废气,利用气相色谱质谱仪分析研究4家餐馆油烟废气VOCs组分特征。结果表明：不同食用油、不同油温和不同菜系下所产生的VOCs浓度及组分特征存在较大差异。烹饪油烟VOCs的排放质量浓度与温度呈正相关。东南亚和川菜烹饪方式产生的油烟VOCs均以羰基化合物为主,而油炸类烹饪方式（炸薯条）则以羰基化合物和烷烃类同为主导。炸薯条、东南亚菜和川菜烹饪油烟VOCs的羰基化合物中,乙醛占比突出。乙醛在猪油油烟中占比最高（60.4%）,其次是花生油（53%）。对比环境空气样品,部分醛类物质（丁烯醛、甲基丙烯醛、苯甲醛、戊醛和己醛）在餐饮油烟VOCs中均有检出。结合实验模拟和外场监测结果表明,静电式的油烟净化器可以有效去除乙醛。苯系物在餐饮油烟废气中检出浓度的最小值均高于周边环境样品。4家餐馆中仅湘菜馆的油烟废气中苯的致癌风险＞10^-4,有显著致致癌风险。建议应依据餐饮油烟VOCs关键组分和污染类型,对餐饮行业进行规范科学的管理。     

2016—2021年四川省地表水体中铀的放射性水平及健康风险评价

为调查四川省地表水体中放射性物质铀（U）的含量,评价居民摄入地表水体中U导致的健康风险,在四川省主要地表水系中共设置23个监测断面,于2016—2021年检测了U的放射性水平,并根据健康风险评价模型对居民的健康风险进行评估。结果表明：四川省地表水体中U的质量浓度为0.16～3.6 μg/L,参照《生活饮用水卫生标准》（GB 5749—2022）,均合格;不同年份、不同地表水体中U的放射性水平间的差异均无统计学意义（P＞0.05）;不同水期U的放射性水平间的差异有统计学意义（P＜0.05）。各年龄组通过饮水、水体浸没途径摄入U所致总年均待积有效剂量均＜0.1mSv;对各年龄段居民的总致癌风险为4.18×10^-9 ～2.24×10^-8 ,均低于世界卫生组织（WHO）和国际放射防护委员会（ICRP）发布的最严格控制限值。全省主要地表水体中U对各年龄组都是安全的。     

某工业城市大气颗粒物中PAHs的粒径分布及人体呼吸系统暴露评估

为研究大气颗粒物中多环芳烃(PAHs)的粒径分布与富集特征,确定不同粒径颗粒物中PAHs在人体呼吸系统各器官内的沉积浓度,以准确评估其人体呼吸暴露风险,选择东北某钢铁工业城市,在采暖期和非采暖期按粒径对大气颗粒物进行分级采样,用高效液相色谱对样品中14种优控PAHs进行分析,并将大气颗粒物粒径分级采样技术与人体呼吸系统内部沉积模型结合进行呼吸暴露评估.结果表明,大气颗粒物中总PAHs浓度变化显著,采暖期(743. 9 ng·m~(-3))高于非采暖期(169. 0ng·m~(-3)),多数PAHs(86. 3%～89. 9%)与大气中粒径≤2. 06μm的细颗粒有关;中低分子量PAHs单体呈双峰型,峰值位于1. 07～2. 06μm和7. 04～9. 99μm.高分子量PAHs呈单峰分布,峰值位于1. 07～2. 06μm; 4环PAHs的含量占主导优势,为总PAHs浓度的40%;在采暖期和非采暖期分别有53. 3%和55. 3%的颗粒态PAHs沉积在人体呼吸系统的不同器官,分别采用人体呼吸系统沉积浓度和在颗粒物上的总浓度计算该地区人群颗粒态PAHs的终身致癌超额风险值(incremental lifetime cancer risk,R值),成人的R值在采暖期为1. 3×10-5和2. 9×10-5,非采暖期为3. 1×10-6和6. 0×10-6,儿童的R值在采暖期为1. 0×10-5和2. 3×10-5,非采暖期为2. 4×10-6和4. 8×10-6.结果表明,颗粒物粒径分布直接影响呼吸系统沉积浓度和致癌风险,将分级采样技术与呼吸系统沉降模型结合方法可有效避免对人体呼吸暴露量的过度评估.     

夏秋季宁波市气态元素汞(GEM)污染特征及潜在源区贡献分析

气态元素汞(gaseous elemental mercury,GEM)是普遍存在于大气中的对生物体有害的重金属元素其化学性质稳定,在大气中停留时间长,可随气团长距离输送属于全球性污染物.本研究于2017年夏秋季对宁波市大气GEM、常规污染物和气象参数进行综合观测,研究沿海地区GEM受人为源和自然源共同作用下的迁移转化规律及潜在源贡献来源.结果表明:①观测期间大气GEM的平均质量浓度为(2.32±0.90) ng·m~(-3),变化范围为0.97～10.95 ng·m~(-3),且夏季低于秋季.②GEM、O_3和GOM在夏季、秋季、晴天和阴雨天的日内浓度变化表明,高浓度的O_3和强烈的光照可加速GEM发生光化学反应,GEM在晴天的光化学氧化强度高于阴雨天.③相关性分析表明,GEM与PM_(2.5)(R=0.65,P0.01)、PM_(10)(R=0.47,P0.01)、NO_2(R=0.46,P0.01)和CO(R=0.57,P0.01)呈显著正相关关系,其来源与化石燃料等物质燃烧有关.④O_3等光化学氧化剂的浓度、GEM在颗粒物上的气粒分配及PM_(2.5)、水汽和NO_2的消光效应,可对GEM光化学氧化速率产生重要影响.⑤潜在源贡献分析(potential source contribution function analysis,PSCF)结果表明夏季浙江省北部(包含宁波市)、西北部,安徽省南部和江西省大部分地区构成一个三角形区域是NBUEORS大气GEM的潜在源贡献区域,且本地源、区域源和长距离源输送对GEM污染均具有重要影响.秋季的潜在源贡献区域主要为浙江省北部区域,范围小于夏季.GEM主要来自本地源和区域源输送影响.因此,针对大气GEM污染的控制,需要跨省的区域联防联控,综合治理,方可有效减轻大气汞的污染.     

绿狐尾藻对铜绿微囊藻和羊角月牙藻的抑藻效应

分别将不同起始浓度(10~5、10~6、10~7、10~8和10~9ind.·L~(-1))的铜绿微囊藻和羊角月牙藻分组与绿狐尾藻进行共培养,连续10 d,每天测定各组铜绿微囊藻或羊角月牙藻的光密度值,用以确定绿狐尾藻对两种藻类不同浓度的生长抑制情况.结果表明,2. 5 g·(200 m L)~(-1)的绿狐尾藻对起始浓度为10~7ind.·L~(-1)和10~8ind.·L~(-1)的铜绿微囊藻具有明显的抑制作用;而对实验所设的所有起始浓度的羊角月牙藻生长均没有显著的抑制作用.并且,采用溶剂浸提与气相色谱-质谱联用(GC-MS)测定的方法,分析了绿狐尾藻粉末浸提液和绿狐尾藻生长液中可能存在的化感物质,通过分析,确定棕榈酸是绿狐尾藻分泌的化感物质之一,并且发现了3种可能是绿狐尾藻分泌的新型化感物质:3-乙基-3-甲基庚烷、磷酸三乙酯和酞酸二丁酯.     

包埋反硝化填料强化二级出水深度脱氮性能研究及中试应用

利用包埋广谱性高效反硝化填料处理城市污水厂二级出水,可有效降低出水总氮(TN)浓度,本研究共分为两部分,D1阶段研究了包埋反硝化填料对污水厂二级出水的适应性、TN去除效果、稳定运行及填料反冲洗的工况条件; D2阶段研究了填料在中试条件下稳定运行1 a脱氮性能的变化,并通过高通量测序和荧光定量分析(q PCR)手段,研究对比了包埋填料运行前后微生物种群的变化规律.通过研究发现,包埋反硝化填料在水温为(24±1)℃、pH为7. 1、HRT为1 h和填充率为10%,投加乙酸钠保证碳源充足的条件下稳定运行7 d,即可适应二级出水水质,实现出水总氮5 mg·L~(-1).通过对比研究不同水力停留时间(HRT)对填料TN去除效果的影响,得出适宜的HRT为30 min,填充率为10%的运行条件,在7. 2 m~3·d~(-1)的进水条件下经过1 a的稳定运行,TN去除率最高可达到90. 42%,出水总氮可稳定在5 mg·L~(-1)以下.通过对比反冲洗效果,确定了反冲洗强度为5. 2 L·(m~2·s)~(-1),周期为每3 d进行一次.高通量测序和荧光实时定量PCR分析结果表明,运行前后填料上反硝化功能菌属的丰度及拷贝数都有了明显增长,这说明细菌在包埋条件下可实现良好的自我生长.     

不同粒径纳米TiO2对大型溞的毒性效应及腐殖酸的调控作用

为评估纳米TiO₂在环境水体中的暴露风险,选用大型溞作为模式生物,研究了不同粒径纳米TiO₂（20、40、60和100 nm）对大型溞毒性效应的影响,并探究了腐殖酸对不同粒径纳米TiO₂毒性效应的调控作用.结果表明,粒径是影响纳米TiO₂颗粒毒性效应的重要因素,以大型溞半数致死时间（LT₅₀）为指标,不同粒径纳米TiO₂对大型溞的毒性作用强弱顺序依次为：20 nm颗粒 > 40 nm颗粒 > 60 nm颗粒 > 100 nm颗粒（p<0.05）.腐殖酸的存在可以显著降低纳米TiO₂颗粒对大型溞的毒性作用,腐殖酸对小尺寸纳米TiO₂颗粒的毒性抑制作用更为明显（p<0.05）.大型溞体内ROS水平与抗氧化系统相关酶活分析表明,纳米TiO₂导致大型溞体内活性氧自由基（ROS）浓度升高是其产生毒性作用的重要原因,腐殖酸的存在可以显著降低大型溞体内由于纳米TiO₂暴露而引起的ROS浓度上升（p<0.05）,进而减轻纳米TiO₂对大型溞的毒性作用.此外,腐殖酸可以减小不同粒径纳米TiO₂之间的毒性差异.本研究结果可为纳米TiO₂在环境水体中的暴露风险评估提供参考依据.