Levels of synthetic musk fragrances in human milk from three cities in the Yangtze River Delta in Eastern China

Synthetic musks are used as additives in many household products. After absorption into the human body, they accumulate and their concentrations in human milk reflect both the mother and her infant’s exposure level. Concentrations of four synthetic musks, musk xylene (1-tert-butyl-2,6-dimethyl-2,4,6-trinitrobenzene, MX), musk ketone (4-tert-butyl-2,6-dimethyl-3,5-dinitroacetophenone, MK), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[ ]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4- tetrahydronaphthalene (AHTN), were determined in human milk samples collected from Shanghai, Wuxi, and Shaoxing in Eastern China. The four synthetic musks were found in most samples analyzed, with HHCB the dominant component followed by MX. The median (mean) values for HHCB, AHTN, MX and MK concentrations were 63 (82), 5 (12), 17 (24) and 4 (9) ng/g lipid weight, respectively. These data suggested the total synthetic musk contamination was low, and the distribution percentage was HHCB > MX > AHTN MK. The relative high ratio of nitro to polycylic musk indicated that nitro musks were still widely used. The musk concentrations in these cities were not significantly different from each other (p > 0.05). Principal components score plots were obtained, which showed similar exposure sources. The amount of total synthetic musks in human milk were not associated with mother’s age, although HHCB was significantly correlated with AHTN (p < 0.05). Daily ingestion of HHCB, AHTN, MX and MK for infants from human milk were estimated as (2526 2926), (370 524), (7391 832), and (277 462) ng/day, respectively. Those doses were 1–2 orders of magnitude below the provisional tolerable daily intakes.     

上海城市污水处理厂中合成麝香的分布与来源解析

于2008年4月、7月、10月在上海12家污水处理厂采集了36个污泥样品,分析了其中合成麝香的浓度水平.结果表明,佳乐麝香(HHCB)和吐纳麝香(AHTN)的浓度变化范围为198~4828μg/kg、89~1455μg/kg,中值为1491,702μg/kg,是其中主要的污染物.分析合成麝香的主要污染来源,发现污泥中HHCB、AHTN主要来源于加香浓度高,使用后又能即刻进入污水的添香类日用品,如洗发水、沐浴露和洗衣粉等,贡献量占90%以上,特别是沐浴露和洗衣粉.利用这些日用品中合成麝香的浓度估算,上海地区居民人均对HHCB、AHTN的贡献量分别为0.33,0.06g/a,是欧洲和美国水平的10%~50%.估算了污水处理厂出水中HHCB、AHTN的最大浓度以及对水生生物的风险系数(RQs),表明目前上海污水处理厂出水中合成麝香对水生生物的风险影响较低.     

人工合成麝香对小麦种子发芽的生态毒性

采用土培实验,研究了佳乐麝香(HHCB)和吐纳麝香(AHTN)对小麦种子发芽的生态毒性,测定了这2种人工合成麝香对小麦种子发芽率、根伸长抑制率和芽伸长抑制率的影响.结果表明,小麦种子的发芽率与这2种人工合成麝香浓度之间剂量-效应关系不明显,低剂量条件下(佳乐麝香≤150 mg·kg-1,吐纳麝香≤200 mg·kg-1...     

再生水灌溉土壤人工合成麝香累积模型模拟

人工合成麝香(HHCB/AHTN)是近几年来受关注较多的药品与个人护理品(PPCPs)类新型污染物之一,再生水灌溉是HHCB/AHTN输入土壤的主要途径.本研究结合再生水灌溉土壤的实地检测结果,采用HYDRUS-1D模型,模拟了长期灌溉再生水条件下土壤中HHCB和AHTN的迁移转化和累积趋势.结果表明,尽管土壤中这两种麝香的含量极低,但是再生水灌溉土壤中的含量是自来水灌溉土壤的5倍;再生水灌溉下HHCB/AHTN累积趋势从lgKoc较低为3.44时的指数型增加,到lgKoc较高为4.12和4.86时的线性增加;半衰期的变化对再生水灌溉途径输入土壤的HHCB/AHTN的表层累积影响并不明显;再生水灌溉下土壤中HHCB/AHTN的垂直迁移能力较小,灌溉40 a以后最大迁移距离只有53 cm,且受Koc变化的影响较大;通过灌溉水途径进入土壤的HHCB和AHTN通过生物降解与植物吸收途径消解的比例较低,最高只占输入总量的7.69%,但是随着lgKoc的减小和灌溉时间增加,通过生物降解和根系吸收的消解率增加.本研究结果能够为准确评估再生水灌溉途径引起的土壤中人工合成麝香HHCB/AHTN的生态风险提供依据.     

污水处理厂污泥中多环麝香的初步研究

以几个具有代表性的污水处理厂外排污泥作为研究对象,针对多环麝香的分布特点进行分析.结果表明,各种类型污泥中均检测出了5种多环麝香(佳乐麝香、吐纳麝香、开许梅龙、萨利麝香、粉檀麝香),其中主要是佳乐麝香和吐纳麝香(最高分别可达703.681和169.284 mg·kg-1),这与香精香料行业中多环麝香的使用模式一致.     

城市污泥中合成麝香的分布特征

对上海市15个污水处理厂外排污泥中合成麝香的污染水平及分布特征进行了研究,发现污泥中普遍存在佳乐麝香（HHCB）和吐纳麝香（AHTN）,干污泥中的平均浓度和浓度范围分别为2.92、 0.81～6.39和1.96、 0.35～3.11 mg·kg^-1;萨利麝香（ADBI）、粉檀麝香（AHMI）、酮麝香（MK）则为次要组分;这与日化产品中合成麝香的使用模式一致.污泥中8种合成麝香的总量在1.16～9.57 mg·kg^-1,与国外其它地区相比上海污泥中合成麝香的污染水平较低;污泥中合成麝香的浓度与进水中生活污水的比例、污水处理量以及污水处理工艺等因素有关.HHCB、AHTN和ADBI间存在良好的线性相关性,显示污泥中合成麝香有共同的来源特征.利用污泥中合成麝香的浓度估算了上海地区人均贡献量,并与欧洲的人均使用情况进行了比较;评价了污泥农用后对土壤可能产生的影响.     

Ecotoxicological effects of polycyclic musks and cadmium on seed germination and seedling growth of wheat (Triticum aestivum)

Single and joint toxic e ects of polycyclic musks including 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2- benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronapthalene (AHTN) and cadmium (Cd) on seed germination and seedling growth of wheat (Triticum aestivum) were investigated. The results showed that the toxicity sequence of HHCB toxic to wheat seed germination and seedling growth was similar to that of AHTN, that is, germination rate > shoot elongation > root elongation, while the toxicity of Cd was in the sequence of root elongation > shoot elongation > germination rate, according to the LC50 and EC50 values. It is suggested that polycyclic musks and Cd had di erent toxicological mechanisms. Root and shoot elongation of wheat might be good bioindicators for the contamination of polycyclic musks and Cd in soil. The mixture of polycyclic musks and Cd had synergistic e ects on T. aestivum according to the equi-toxic mixture approach when root elongation was selected as the toxicological endpoint. Thus, the joint toxicity of HHCB and Cd was significantly higher than the single toxicity of HHCB or Cd, which was also confirmed by the EC50 mix value of the mixture (EC50 mix = 0.530 TUmix). The EC50 mix value of the mixture of AHTN and Cd was 0.614 TUmix, which indicated that the mixture toxicity was strengthened when AHTN coexisted with Cd.     

HRT对A2O工艺中典型多环麝香迁移转化的影响

研究了不同水力停留时间(hydraulic retention time,HRT)条件下佳乐麝香(galaxolide,HHCB)与吐纳麝香(tonalide,AHTN)在A2O工艺各池水相和泥相中的变化情况.采用固相萃取与气相质谱联用的方法对水相与泥相中目标物的质量浓度进行检测.结果表明,HRT主要影响HHCB在A2O工艺中的生物降解和随剩余污泥排放的比重,影响AHTN随剩余污泥排放的比重.随着HRT的增大,HHCB、AHTN在厌氧池中的去除率与去除贡献率逐渐减小,而缺氧池与好氧池的去除率与去除贡献率相对增大.2种目标物在4个HRT工况(6、8、10、12 h)下的总去除率分别为73.93%、73.05%、75.14%、76.00%和48.76%、44.27%、57.17%、62.9%.A2O工艺对HHCB的去除效果较好,而对AHTN的去除效果较差.HRT的增大对HHCB的去除影响不大,而对AHTN的去除有促进作用.     

北京市城市污水雌激素活性的研究

采用重组酵母雌激素筛检法(YES法)对北京市3个城市污水处理厂工艺流程污水样品的雌激素活性进行了评价,并采用GC/MS分析了样品中8种内分泌干扰物(EDCs),以进一步阐明城市污水雌激素活性的变化.结果表明,污水处理厂能较好地降低污水雌激素活性,降低率为82.2%～97.0%,但出水仍具有一定的雌激素活性,雌二醇(E2)当量浓度(EEQ)为2.6～16.0 ng/L.GC/MS检测显示,污水处理厂并不能完全去除目标化合物,出水中平均浓度最低的是17α-E2,为13.5 ng/L,最高的是BPA,为106.4 ng/L;出水的雌激素活性主要来自类固醇雌激素.污水厂的出水排放具有潜在的环境风险,在污水处理过程中,应特别关注对类固醇雌激素的去除.     

吹脱捕集GC/MS法测定水中挥发性有机物

采用吹脱捕集GC/MS法对日本环境厅和厚生省规定的水中23项有机污染物进行同时分析测定,该方法在0.1～100μg/L范围内的线性相关系数为0.998以上,相对标准偏差在8%以下,废水加标回收率在92%～102%之间。在实际水样(河水和自来水)分析中,有8种化合物几乎在17个实际水样中都有检出。实验结果表明,吹脱捕集GC/MS法是实现水中挥发性有机物同时分析的最有效的手段之一。      

淀山湖水、沉积物和鱼体中的合成麝香及人体暴露评估

合成麝香是一类"类持久性"有机污染物,研究其在城市近郊湖泊的污染变化,可以更好地了解生活污染源对湖泊水环境的影响特点,为湖泊水环境研究积累更多基础数据.研究了上海近郊淀山湖水体、沉积物和鱼体中合成麝香的污染状况及其人体的暴露状况.结果表明,佳乐麝香(HHCB)是表层水和沉积物中的主要合成麝香类污染物,平均浓度为11.9 ng·L-1和0.98 ng·g-1干重.合成麝香在淀山湖野生鱼体中也有存在,主要污染物HHCB的中值浓度为122 ng·g-1脂重.淀山湖水环境的整体污染水平不高.表层水的合成麝香污染受到采样时间影响较明显,7月丰水期的表层水浓度偏低(Mann-Whitney U检验,p=0.000,p0.05);沉积物浓度随采样时间的变化并不十分明显.淀山湖进水区域采样点的污染程度普遍高于出水区域.淀山湖沉积物的HHCB浓度远小于底栖生物的无观察效应浓度(no observed effect concentration).经食物摄入(饮食、饮水)途径暴露的合成麝香量仅为0.90 ng·d-1·kg-1体重,显著低于因个人护理用品使用产生的皮肤暴露量.淀山湖水环境已受到合成麝香的影响,但污染水平较低,生态风险和健康影响很小.     

Three-stage aged refuse biofilter for the treatment of landfill leachate

A field-scale aged refuse(AR) biofilter constructed in Shanghai Refuse Landfill,containing about 7000 m3 aged refuse inside,was evaluated for its performance in the treatment of landfill leachate. This AR biofilter can be divided into three stages and can manage 50 m3 landfill leachate per day. The physical,chemical,and biological characteristics of AR were analyzed for evaluating the AR biofilter as leachate treatment host. The results revealed that over 87.8%-96.2% of COD and 96.9%-99.4% of ammonia nitrog...     

广州污水厂磺胺和喹诺酮抗生素污染特征研究

采用固相萃取(SPE)-高效液相色谱(HPLC)法分析了广州市3个污水处理厂进出水中磺胺类和喹诺酮类抗生素共10种化合物的含量特征,并探讨其去除效果和环境排放量。结果表明,进水和出水中磺胺类抗生素总含量分别为3591.9～7782.5ng/L和2216.6～3591.9ng/L,喹诺酮类抗生素总含量分别为1539.4～2700.2ng/L和1284.4～5080.1ng/L。单个化合物的检出率在37.5%～97.5%,其中磺胺类抗生素以SMT、SM2和SM1为主,喹诺酮类抗生素以CIP和LOM为主。磺胺类和喹诺酮类抗生素的最高去除率分别为69.2%和27.2%,环境排放量分别为487.7～1512.3g/d和329.3～1117.6g/d。     

Uptake and accumulation of phenanthrene and pyrene in spiked soils by Ryegrass(Lolium perenne L.)

Phytoremediation has long been recognized as a cost-effective method for the removal of polycyclic aromatic hydrocarbons （PAHs） from soil. A study was conducted to investigate the uptake and accumulation of PAHs in root and shoot of Lolium perenne L. Pot experiments were conducted with series of concentrations of 3.31-378.37 mg/kg for phenanthrene and those of 4.22-365.38 mg/kg for pyrene in a greenhouse. The results showed that both ryegrass roots and shoots did take up PAHs from spiked soils, and generally increased with increasing concentrations of PAH in soil. Bioconcentration factors（BCFs） of phenanthrene by shoots and roots were 0.24- 4.25 and 0.17-2.12 for the same treatment. BCFs of pyrene by shoots were 0.20-1.5, except for 4.06 in 4.32 mg/kg treatment, much lower than BCFs of pyrene by roots （0.58-2.28）. BCFs of phenanthrene and pyrene tended to decrease with increasing concentrations of phenanthrene and pyrene in soil. Direct uptake and accumulation of these compounds by Lolium perenne L. was very low compared with the other loss pathways, which meant that plant-promoted microbial biodegradation might be the main contribution to plant-enhanced removal of phenanthrene and pyrene in soil. However, the presence of Lolium perenne L. significantly enhanced the removal of phenanthrene and pyrene in spiked soil. At the end of 60 d experiment, the extractable concentrations of phenanthrene and pyrene were lower in planted soil than in non-planted soil, about 83.24%-91.98% of phenanthrene and 68.53%-84.10% of pyrene were removed from soils, respectively. The results indicated that the removal of PAHs in contaminated soils was a feasible approach by using Lolium perenne L.     

上海市市政污水中全氟有机酸污染特征

选择上海市9座市政污水处理厂(WWTPs)作为研究对象,检测其进水和出水中全氟有机酸(PFAs)污染水平.结果表明,市政污水中总PFAs浓度为903~4628ng/L,且中短链(C2~C10)全氟羧酸(PFCAs)的检出率一般高于长链(>C10)PFCAs,而对全氟烷基磺酸(PFSAs)而言,全氟辛磺酸(PFOS)的检出率远高于全氟丁磺酸(PFBS)和全氟己磺酸(PFHxS).三氟乙酸(TFA)一般是市政污水中污染水平最高的PFAs,浓度为359~4129ng/L,占总PFAs的20%~93%.尽管全氟辛酸(PFOA)和PFOS的浓度一般低于TFA,甚至在某些情况下还会低于其他PFAs,但在绝大多数情况下它们依然是2种主要的PFAs类污染物,浓度分别为40.6~1571ng/L和21.3~1027ng/L,分别占总PFAs的2%~57%和1%~30%.在污水处理过程中,短链(C2~C5)和长链(>C10)PFCAs浓度的显著下降,而中等链长(C6~C10)PFCAs和PFSAs浓度则显著增加.此外,PFAs浓度和工业废水比例之间并不存在明显的正相关关系.     

典型抗生素类药物在城市污水处理厂中的含量水平及其行为特征

采用固相萃取、液相色谱/串联质谱（LC-MS/MS）法研究了8种常用抗生素（包括喹诺酮类、磺胺类、大环内酯类和氯霉素）在城市污水处理厂中的含量水平、去除特点及其行为特征.结果显示,药物的检出率和含量水平均高于美国及欧洲等国家.氧氟沙星、诺氟沙星、红霉素（脱水）、罗红霉素和磺胺甲唑5种抗生素在4家污水厂(香港2家,广州2家)中都有检出,进水和出水中的含量范围分别在16～1 987 ng·L^-1和16～2 054 ng·L^-1之间.其它3种抗生素仅在某些污水厂中有检出.抗生素在污水处理厂中不能被完全去除,最高去除率为81％.5种高检出率药物在污水厂中每日的环境排放量（包括污水和污泥中含量）在0.5～828 g·d^-1之间.计算结果表明,广州和香港地区的每人日消费量有较大差异,广州地区要明显高于香港地区,特别是大环内酯类药物.     

Profiles and removal efficiency of polycyclic aromatic hydrocarbons by two different types of sewage treatment plants in Hong Kong

Sewage discharge could be a major source of polycyclic aromatic hydrocarbons(PAHs) in the coastal waters. Stonecutters Island and Shatin Sewage Treatment Works(SCISTW and STSTW)in Hong Kong, adopted chemically enhanced primary treatment and biological treatment,respectively. This study aimed at(1) determining the removal efficiencies of PAHs,(2) comparing the capabilities in removing PAHs, and(3) characterizing the profile of each individual PAHs, in the two sewage treatment plants(STPs). Quantification of 16 PAHs was conducted by a Gas Chromatography. The concentrations of total PAHs decreased gradually along the treatment processes(from 301 ± 255 and 307 ± 217 ng/L to 14.9 ± 12.1 and 63.3 ± 54.1 ng/L in STSTW and SCISTW, respectively). It was noted that STSTW was more capable in removing total PAHs than SCISTW with average total removal efficiency 94.4% ± 4.12% vs. 79.2% ± 7.48%(p 0.05). The removal of PAHs was probably due to sorption in particular matter, confirmed by the higher distribution coefficient of individual and total PAHs in solid samples(dewatered sludge contained92.5% and 74.7% of total PAHs in SCISTW and STSTW, respectively) than liquid samples(final effluent-total contained 7.53% and 25.3% of total PAHs in STSTW and SCISTW, respectively).Despite the impressive capability of STSTW and SCISTW in removing PAHs, there was still a considerable amount of total PAHs(1.85 and 39.3 kg/year, respectively for the two STPs) being discharged into Hong Kong coastal waters, which would be an environmental concern.     

A SPE-HPLC-MS/MS method for the simultaneous determination of prioritised pharmaceuticals and EDCs with high environmental risk potential in freshwater

This work describes the development, optimisation and validation of an analytical method for the rapid determination of 17 priority pharmaceutical compounds and endocrine disrupting chemicals (EDCs). Rather than studying compounds from the same therapeutic class, the analyses aimed to determine target compounds with the highest risk potential (with particular regard to Scotland), providing a tool for further monitoring in different water matrices. Prioritisation was based on a systematic environmental risk assessment approach, using consumption data; wastewater treatment removal efficiency; environmental occurrence; toxicological effects; and pre-existing regulatory indicators. This process highlighted 17 compounds across various therapeutic classes, which were then quantified, at environmentally relevant concentrations, by a single analytical methodology. Analytical determination was achieved using a single-step solid phase extraction (SPE) procedure followed by high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The fully optimised method performed well for the majority of target compounds, with recoveries >71% for 15 of 17 analytes. The limits of quantification for most target analytes (14 of 17) ranged from 0.07 ng/L to 1.88 ng/L in river waters. The utility of this method was then demonstrated using real water samples associated with a rural hospital/setting. Eight compounds were targeted and detected, with the highest levels found for the analgesic, paracetamol (at up to 105,910 ng/L in the hospital discharge). This method offers a robust tool to monitor high priority pharmaceutical and EDC levels in various aqueous sample matrices.     

吐纳麝香对东海原甲藻的毒性作用机制

为研究吐纳麝香(AHTN)对海洋微藻的毒性作用机制,以东海原甲藻(Prorocentrum donghaiense)为受试对象,测定5种浓度的AHTN(1,10,50,200和400μg/L)对微藻的生长、光合色素含量、细胞形态结构、细胞膜通透性、抗氧化系统和光合系统的影响.结果表明,AHTN显著抑制东海原甲藻的生长,...     

典型医药活性物质在污水处理厂中的归趋及其风险评估

采用固相萃取、高效液相色谱/串联质谱法 (污泥样品先采用超声波萃取预处理方法提取) 检测分析了包括磺胺类、喹诺酮类、大环类酯类抗生素、心血管类、止痛剂类等8类医药活性物质在重庆某污水厂中的含量水平及其行为归趋.采用 EC/PNEC 综合评价体系评估环境中目标医药活性物质的生态风险,利用质量平衡分析的方法分析了其在水相及污泥相中的分布.结果表明,目标物质在水相中均可检出,其检出浓度在ng/L~μg/L,在污泥样品中可检测出18种目标物质,其浓度在ng/g (干重,下同).仅仅1.1%的目标物质被污泥吸附去除.污水处理厂初级处理及氯化消毒阶段对目标物质无明显去除效果,目标物质的去除主要发生在生物处理阶段,生物的降解或转化作用是目标物质的主要去除机制.EC/PNEC分析表明,磺胺嘧啶、磺胺甲恶唑、氧氟沙星与脱水红霉素在污水处理厂出水及其污泥中综合评价因子均大于1,它们的存在可能对环境产生不同程度的危害.本研究结果表明,污水处理厂并不能完全去除水相中微量的医药物质,为防止排放导致的潜在生态风险,出水及污泥中活性医药物质需采取措施进行进一步的处理.