Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

Nitrogen evolution during the co-combustion of hydrothermally treated municipal solid waste and coal in a bubbling fluidized bed

Nitrogen evolution was studied during the co-combustion of hydrothermally treated municipal solid wastes (HT MSW) and coal in a bubbling fluidized bed (BFB). HT MSW blending ratios as 10%, 20% and 30% (wt.%) were selected and tested at 700, 800, 900 °C. Emissions of NO and N₂O from blends were measured and compared with the results of mono-combustion trials. Moreover, concentrations of precursors like NH₃ and HCN were also quantified. The results are summarized as follows: NO emissions were predominant in all the cases, which rose with increasing temperature. The blending of HT MSW contributed to the NO reduction. N₂O emissions decreased with temperature rising and the blending of HT MSW also presented positive effects. At 30% HT MSW addition, both NO and N₂O emissions showed the lowest values (391.85 ppm and 55.33 ppm, respectively at 900 °C). For the precursors, more HCN was detected than NH₃ and both played important roles on the gas side nitrogen evolution.     

Hazard property classification of waste according to the recent propositions of the EC using different methods

Hazard classification of waste is a necessity, but the hazard properties (named “H” and soon “HP”) are still not all defined in a practical and operational manner at EU level. Following discussion of subsequent draft proposals from the Commission there is still no final decision. Methods to implement the proposals have recently been proposed: tests methods for physical risks, test batteries for aquatic and terrestrial ecotoxicity, an analytical package for exhaustive determination of organic substances and mineral elements, surrogate methods for the speciation of mineral elements in mineral substances in waste, and calculation methods for human toxicity and ecotoxicity with M factors.In this paper the different proposed methods have been applied to a large assortment of solid and liquid wastes (>1 0 0).Data for 45 wastes – documented with extensive chemical analysis and flammability test – were assessed in terms of the different HP criteria and results were compared to LoW for lack of an independent classification. For most waste streams the classification matches with the designation provided in the LoW. This indicates that the criteria used by LoW are similar to the HP limit values.This data set showed HP 14 ‘Ecotoxic chronic’ is the most discriminating HP. All wastes classified as acute ecotoxic are also chronic ecotoxic and the assessment of acute ecotoxicity separately is therefore not needed. The high number of HP 14 classified wastes is due to the very low limit values when stringent M factors are applied to total concentrations (worst case method). With M factor set to 1 the classification method is not sufficiently discriminating between hazardous and non-hazardous materials. The second most frequent hazard is HP 7 ‘Carcinogenic’. The third most frequent hazard is HP 10 ‘Toxic for reproduction’ and the fourth most frequent hazard is HP 4 “Irritant – skin irritation and eye damage”. In a stepwise approach, it seems relevant to assess HP 14 first, then, if the waste is not classified as hazardous, to assess subsequently HP 7, HP 10 and HP 4, and then if still not classified as hazardous, to assess the remaining properties.The elements triggering the HP 14 classification in order of importance are Zn, Cu, Pb, Cr, Cd and Hg. Progress in the speciation of Zn and Cu is essential for HP 14. Organics were quantified by the proposed method (AFNOR XP X30-489) and need no speciation. Organics can contribute significantly to intrinsic toxicity in many waste materials, but they are only of minor importance for the assessment of HP 14 as the metal concentrations are the main HP 14 classifiers. Organic compounds are however responsible for other toxicological characteristics (hormone disturbance, genotoxicity, reprotoxicity…) and shall be taken into account when the waste is not HP 14 classified.     

Metal distribution characteristic of MSWI bottom ash in view of metal recovery

Bottom ash is the major by-product of municipal solid waste incineration(MSWI), and is often reused as an engineering material, such as road-base aggregate. However, some metals(especially aluminum) in bottom ash can react with water and generate gas that could cause expansion and failure of products containing the ash; these metals must be removed before the ash is utilized. The size distribution and the chemical speciation of metals in the bottom ash from two Chinese MSWI plants were examined in this study, and the recovery potential of metals from the ash was evaluated. The metal concentrations in these bottom ashes were lower than that generated in other developed countries. Specifically, the contents of Al,Fe, Cu and Zn were 18.9–29.2, 25.5–32.3, 0.7–1.0 and 1.6–2.5 g/kg, respectively. Moreover,44.9–57.0 wt.% of Al and 55.6–75.4 wt.% of Fe were distributed in bottom ash particles smaller than 5 mm. Similarly, 46.6–79.7 wt.% of Cu and 42.9–74.2 wt.% of Zn were concentrated in particles smaller than 3 mm. The Fe in the bottom ash mainly existed as hematite, and its chemical speciation was considered to limit the recovery efficiency of magnetic separation.     

Nano-sized Fe2O3/Fe3O4 facilitate anaerobic transformation of hexavalent chromium in soil–water systems

The purpose of this study is to investigate the effects of nano-sized or submicro Fe_2O_3/Fe_3O_4 on the bioreduction of hexavalent chromium(Cr(VI)) and to evaluate the effects of nano-sized Fe_2O_3/Fe_3O_4 on the microbial communities from the anaerobic flooding soil.The results indicated that the net decreases upon Cr(VI) concentration from biotic soil samples amended with nano-sized Fe_2O_3(317.1 ± 2.1 mg/L) and Fe_3O_4(324.0 ± 22.2 mg/L) within21 days,which were approximately 2-fold of Cr(VI) concentration released from blank control assays(117.1 ± 5.6 mg/L).Furthermore,the results of denaturing gradient gel electrophoresis(DGGE) and high-throughput sequencing indicated a greater variety of microbes within the microbial community in amendments with nano-sized Fe_2O_3/Fe_3O_4 than the control assays.Especially,Proteobacteria occupied a predominant status on the phylum level within the indigenous microbial communities from chromium-contaminated soils.Besides,some partial decrease of soluble Cr(VI) in abiotic nano-sized Fe_2O_3/Fe_3O_4 amendments was responsible for the adsorption of nano-sized Fe_2O_3/Fe_3O_4 to soluble Cr(VI).Hence,the presence of nano-sized Fe_2O_3/Fe_3O_4 could largely facilitate the mobilization and biotransformation of Cr(VI) from flooding soils by adsorption and bio-mediated processes.     

原子吸收法测定海水中铁含量的不确定度评定

为了保证海水中铁元素含量的检测质量,更好地深入了解铁在整个海水体系的生物地球化学中扮演的角色,需科学地评定检测结果的分散性。文章依据《测量不确定度的评定与表示》(JJF1059-1999)的理论,以浙江近海海水为例,评定原子吸收法测定海水中铁含量的不确定度。测得浙江近海样品中铁的浓度为5.2μg/L,扩展不确定度U=0.8μg/L(k=2)。通过对各不确定度分量进行评定发现,利用该方法测定海水中铁含量时,对其合成标准不确定度的主要贡献来自于样品制备过程,尤其是萃取过程。     

某钢铁企业颗粒物无组织排放核算与监测对比分析

以济南东部老工业区一家大型钢铁企业为例,通过前期调研和排放系数核算出颗粒物(TSP)排放总量,再运用公式计算出厂区周边不同距离颗粒物(TSP)的落地浓度。将该落地浓度与厂区周边颗粒物(TSP)的监测值进行对比分析,充分印证了连续点源扩散的高斯模式的准确性和可行性。随着气流经过该厂区,对比上下风向监测点位颗粒物(TSP)浓度迅速升高(增大1.04倍),下风向颗粒物(TSP)浓度超出二级标准1.32倍;颗粒物(TSP)的落地浓度在厂区不同距离上的浓度变化明显,从0.1到10 km其落地浓度稀释了约3 500倍,距离>4 km时,无组织排放的颗粒物(TSP)对周围空气质量直接影响有限。     

一种简便高效的土壤石油烃提取方法的建立

通过开展单因子实验与正交实验,考察不同参数下超声萃取法对土壤中总石油烃(TPH)的提取效率,并对比了超声萃取法、超声-索氏萃取法及传统索氏萃取法对不同原油污染土壤的提取效果。结果表明:超声萃取法的最优工作参数为20 m L二氯甲烷,超声10 min,4000 r/min离心10 min,萃取4次。3种提取方法中,超声萃取法对石油烃平均回收率最高,为100.95%,而传统的索氏萃取法最低,仅为94.54%。可见,超声萃取法操作简单,效率高,可广泛用于土壤中总石油烃含量的提取测定。     

烟草废弃物快速堆肥过程中重金属Cd形态变化特征

以烟草废弃物为原料,活性土壤为载体建立堆体,研究重金属镉的形态变化,及堆肥过程中的动态变化规律。结果表明,烟草废弃物与活性土壤混合能快速腐熟。堆肥总质量下降,重金属镉含量相对增加。重金属镉的铁锰氧化态比例增加19%,有机结合态比例在堆肥升温阶段增加,腐熟后有所下降。残渣态比例大幅度上升,增加达到5倍,且在腐熟阶段增幅最大。说明堆肥处理有利于降低重金属镉的活性。     

电晕放电辐射信号的特征提取和模式识别方法研究

目的研究电晕放电辐射信号的特征提取和模式识别方法。方法在分析信号特征提取方法的基础上,对实测的电晕放电辐射信号特征提取,利用概率神经网络开展电晕放电辐射信号目标识别,检验特征提取的有效性。结果以奇异值作为输入特征量的PNN在整体上效果更优,稳定性好,对两类不同放电辐射信号的正确识别率均可达到80%以上,并且当输入特征量个数达到10个时,对实测样本的正确识别率均达到了最高值。电晕放电的正确识别率为96.7%,火花放电的正确识别率为93.3%。结论该方法能基本满足实际放电信号的识别应用。