Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.     

Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O₃). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O₃, total reactive nitrogen (NO_y) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O₃ and PAN concentration maxima showed a strong correlation (r² = 0.91) in LZ, with a regression slope (PAN/O₃) of 0.091 ppbv ppbv^?1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.     

An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications

The aqueous ozonolysis of α-pinene and β-pinene was conducted under simulated tropospheric conditions at different pHs and temperatures. Three kinds of products, peroxides, carbonyl compounds, and organic acids, were well characterized, and the detection of these products provides effective evidence for understanding the atmospheric aqueous reaction pathway. We have two interesting findings: (1) the unexpected formation of methacrolein (MACR), with a yield of ～40%, in the α-pinene–O₃ aqueous reaction indicates a potentially new SOA formation pathway, because MACR is one of the important precursors of SOA; and (2) the surprisingly high yields of H₂O₂, ～60% for the α-pinene–O₃ reaction and ～100% for the β-pinene–O₃ reaction, indicates that H₂O₂ can be a significant contributor to the origin and transformation of oxidants in the atmosphere, especially in the humid regions. Moreover, we have determined the rate constant for aqueous reaction between MACR and H₂O₂ in pH 2 to 7 and obtained its upper limit as 0.13 M L^?1 s^?1. A mechanism concerning the formation of the species mentioned above is proposed, and it differs from that in the gas-phase reaction. We suggest that water plays a key role in the mechanism, by participating in the reactions as a direct reactant and by removing the excess energy of intermediates formed in the reactions.     

螺、蚌对污水处理厂再生水环境的改善稳定作用

通过选用昆明市第五污水处理厂的一级A标出水和水处理厂外排污泥作为静态实验环境,研究不同混养密度下铜锈环棱螺、椭圆背角无齿蚌对污水处理厂再生水环境的净化性能,筛选出净化效果较好的放养密度。结果表明:放养30 d,铜锈环棱螺、椭圆背角无齿蚌对污水处理厂再生水环境的水质、底质均有一定的净化作用,扣减空白对照影响,水中COD、TP、NH3-N及底泥有机质平均去除率分别为22.26%、26.10%、25.60%和25.69%,底泥厚度平均减少3.8 cm;与对照相比,放养螺蚌45 d内水均能清澈见底,透明度均>70 cm,能明显稳定水体透明度,改善水环境。综合螺蚌生长适应性和净化效果考虑:污水处理厂再生水静态环境中,螺蚌混养密度应≤3 000 g/m3,在2 000～2 500 g/m3为宜,其中铜锈环棱螺的最适放养密度在400 g/m3,椭圆背角无齿蚌为1 600～2 100 g/m3。     

混凝-生物接触氧化处理合成橡胶碱洗废水

对化学合成橡胶碱洗废水进行了有机组分和可生化性分析,废水主要含有氯甲烷、六甲苯、异丁醇、甲醇等污染物质,生化降解实验中废水TOC可在6 d内从60.9 mg/L下降至0.0 mg/L,可生化降解性好,适于生化处理。选择混凝-生物接触氧化组合工艺对废水进行处理,采用优化条件(pH=8、PAC=40 mg/L、PAM=8 mg/L)进行混凝,碱洗废水COD去除率为9.95%~72.94%(平均31.51%);混凝后的碱洗废水与冲洗废水1∶5混合进行接触氧化处理,在HRT为36 h的情况下,COD去除率为65.6%~72.6%(平均70.4%),出水COD为134~331 mg/L,满足企业废水排放市政管网的要求;同时,实验发现COD去除率与COD容积负荷存在指数函数变化关系。     

陶瓷印花废水处理的混凝剂及工艺条件

采用混凝剂聚合氯化铝（PAC）、聚丙烯酰胺（PAM）、聚合硫酸铁（PFS）对陶瓷印花废水进行混凝沉降处理,监测水样的吸光度、浊度、悬浮物,以脱色率、浊度去除率、悬浮物去除率评价混凝处理的效果。结果表明：PAC是陶瓷印花废水沉降处理的理想混凝剂;水样的吸光度、浊度、悬浮物随混凝剂用量增大和沉降时间延长而呈降低趋势,而脱色率、浊度去除率、悬浮物去除率随混凝剂和沉降时间的增大呈增大的趋势;PAC投加量为20mg／L,沉降时间约为24h,水样脱色率达到90．0％,而当PAC投加量达到100mg／L,沉降时间约为4h,陶瓷印花水的脱色率可达到96．0％。证明了药剂用量的增加与沉降时间的延长对混凝过程具有增效作用。     

脂肪酰基氨基酸对矿物润滑油生物降解性的影响研究

通过生物降解试验研究了N-月桂酰基谷氨酸、N-月桂酰基甘氨酸、N-月桂酰基丙氨酸和N-油酰基甘氨酸4种脂肪酰基氨基酸对HVI 350矿物润滑油生物降解性的影响,采用高倍电子显微镜分析了生物降解过程中微生物数量和形态变化。结果表明,在矿物润滑油中添加少量脂肪酰基氨基酸后,矿物润滑油的生物降解性能明显改善,且生物降解过程中微生物数量增多、形态发生变化,这可能是脂肪酰基氨基酸增加了微生物的营养,且具有表面活性,有利于细胞的吸收,从而促进了矿物润滑油生物降解。     

Textural and chemical properties of swine-manure-derived biochar pertinent to its potential use as a soil amendment

Biochars have received increasing attention in recent years because of their properties pertaining to soil fertility and contaminant immobilization as well as serving as carbon sinks. In this work, a series of biochars were produced from dried swine manure waste by slow pyrolysis at different temperatures (i.e., 673-1073 K). The characterization of the resulting biochars was examined for its relevance to its potential use as soil amendment. It was found that the pore properties, ash contents and pH values of all swine-manure-derived biochars basically increased as temperature increased, while the yield and nitrogen/oxygen contents decreased with increasing temperature as a result of pyrolytic volatilization during pyrolysis. From the organic and inorganic elements analyses, the manure-derived biochar was rich in soil nutrients such as N, P, Ca, Mg, and K. Furthermore, the pore, surface and chemical properties were also consistent with the observations of the SEM-EDS, XRD and FTIR. This result suggested that the mesoporous manure-derived biochar could be used as an excellent medium to soil environment.     

高效聚合氯化铝对超滤膜污染影响的中试研究

针对某水厂以超滤为核心的短流程水处理工艺,在通过聚氯乙烯(PVC)超滤膜之前选择不同投加量(5、10、15和20 mg/L)的高效聚合氯化铝(HPAC)对长江下游原水进行混凝处理。通过跨膜压差(TMP)增长趋势、CODMn的去除率以及混凝后的水质,可知HPAC的最优投加量为15 mg/L。在此投加量下,运用体积排阻色谱法分析原水、膜前水、膜后水中各相对分子质量有机物的变化,可以发现混凝去除有机物的效果要优于超滤截留的。继而将HPAC与另外4种常用混凝剂:硫酸铝(分析纯)、氯化铁(化学纯)、聚合氯化铝(PAC)、聚合硫酸铁进行对比,结果表明,在它们各自最优投加量下,HPAC能够更有效地减缓超滤膜TMP的增长率,从而降低膜污染。因此,认为HPAC是与PVC超滤合金膜契合效果最佳的混凝剂。     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.