Surface-enhanced Raman spectroscopy for emerging contaminant analysis in drinking water

● Definition of emerging contaminants in drinking water is introduced. ● SERS and standard methods for emerging contaminant analysis are compared. ● Enhancement factor and accessibility of SERS hot spots are equally important. ● SERS sensors should be tailored according to emerging contaminant properties. ● Challenges to meet drinking water regulatory guidelines are discussed. Emerging contaminants (ECs) in drinking water pose threats to public health due to their environmental prevalence and potential toxicity. The occurrence of ECs in our drinking water supplies depends on their physicochemical properties, discharging rate, and susceptibility to removal by water treatment processes. Uncertain health effects of long-term exposure to ECs justify their regular monitoring in drinking water supplies. In this review article, we will summarize the current status and future opportunities of surface-enhanced Raman spectroscopy (SERS) for EC analysis in drinking water. Working principles of SERS are first introduced and a comparison of SERS and liquid chromatography-tandem mass spectrometry in terms of cost, time, sensitivity, and availability is made. Subsequently, we discuss the strategies for designing effective SERS sensors for EC analysis based on five categories—per- and polyfluoroalkyl substances, novel pesticides, pharmaceuticals, endocrine-disrupting chemicals, and microplastics. In addition to maximizing the intrinsic enhancement factors of SERS substrates, strategies to improve hot spot accessibilities to the targeting ECs are equally important. This is a review article focusing on SERS analysis of ECs in drinking water. The discussions are not only guided by numerous endeavors to advance SERS technology but also by the drinking water regulatory policy.     

Application of an inclusion complex for determination of dithianon residues in water and fruits

A 3,3′-benzidine/β-cyclodextrin fluorescence derivative (BCDFD) was prepared and characterized by means of elemental analysis and ¹H NMR. An inclusion complex was formed between BCDFD and the pesticide dithianon based on the internal cavity of β-cyclodextrin (β-CD), and the binding constant (K_S ) of the inclusion complex was investigated. The inclusion complex could be applied for the determination of dithianon residues. Based on this, a sensitive method for the determination of dithianon was established. The linear dynamic range was from 0.63 to 12.5?mg?L^?1 with a correlation coefficient of 0.9927. The limit of detection for an aqueous solution of standard and the relative standard deviation (RSD) were 10.6?µg?L^?1 and 0.76%, respectively. The proposed method has been successfully applied for the determination of dithianon residues in water and fruit samples with satisfactory results, and recoveries in the range of 96.0–108% were obtained. The method is rapid, direct, economical, and sensitive for dithianon analysis.     

Examination of the influence of phenyltrimethylammonium chloride (PTMA) concentration on acetochlor adsorption by modified montmorillonite

The results presented in this paper show an impact of the concentration of the aromatic organic cation on the adsorption of acetochlor on the surface of the organic-modified montmorillonite. Natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification in this experiment. Cation exchange capacity of this montmorillonite (86 mmol 100 g^?1 of clay) was determined using the methylene blue method. In pretreatment, montmorillonite was modified with NaCl. For the purpose of organic modification, three different concentrations of phenyltrimethylammonium chloride (PTMA) have been selected, based on calculated CEC value: 43 mmol 100 g^?1 of clay (0.5 CEC), 86 mmol 100 g^?1 of clay (1 CEC) and 129 mmol 100 g^?1 of clay (1.5 CEC). The changes in the properties of the inorganic and organic modified montmorillonite were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and batch equilibrium method. Freundlich coefficients show higher uptake of the herbicide by montmorillonite modified with PTMA, compared to inorganic-modified montmorillonite. The results also indicate the influence of the organic cation concentration on the adsorption of the selected herbicide.     

CeO2-CuO/粉煤灰吸附SO2/NO性能分析

利用室温液相浸渍法将粉煤灰制备成CeO2-CuO/粉煤灰,提高了粉煤灰对SO2/NO的吸附效率。采用XRF、XRD、SEM等手段对其进行表征测试,结果表明,粉煤灰的晶相结构主要为石英和莫来石,且改性后表面变得更为粗糙,孔隙增多。利用吸附反应装置优化SO2/NO的反应条件,结果表明：在样品量为0.3 g、温度为50 ℃、SO2流速为8 mL·min-1、O2流速为4?mL·min-1时,CeO2-CuO/粉煤灰对SO2吸附效果最佳;在样品量为0.4?g、温度为70?℃、NO流速为6?mL·min-1、O2流速为4?mL·min-1时,对NO吸附效果最佳。共吸附会降低各自的吸附效率。利用原位FTIR分析表明：SO2在CeO2-CuO/粉煤灰表面主要生成硫酸盐和亚硫酸盐物种;NO则主要生成硝酸盐和亚硝酸盐物种。     

1H-NMR-based metabolomic study on toxicity of methomyl and methidathion in fish

A ¹H-nuclear magnetic resonance (NMR) spectroscopy with multivariate analysis was applied to detect the toxicity of antiacetylcholinesterase insecticides, methomyl (methyl (1E)-N-(methylcarbamoyloxy)ethanimidothioate) and methidathion (3-(dimethoxyphosphinothioyl sulfanylmethyl)-5-methoxy-1,3,4-thiadiazol-2-one), using zebrafish (Danio rerio) and Chinese bleak (Aphyocypris chinensis). Generally, methomyl and methidathion have been believed not to highly accumulate in fish tissues. However, these pesticides showed their toxicity by altering patterns of whole-body metabolites in neurotransmitter balance, energy metabolism, oxidative stress, and muscle maintenance in low concentrations. We used Pearson correlation analysis to contextualize the metabolic markers in pesticide treated groups. We observed that the positive correlations of choline with acetate and betaine in untreated control were shifted to null correlations showing acetylcholinesterase specific toxicity. This research demonstrated the applicability and potential of NMR metabolomics in detecting toxic effects of insecticide with a modicum of concentrations in aquatic environment.     

水稻秸秆生物炭对罗丹明B的吸附与降解

生物炭对污染物的吸附是生物炭环境效应研究的重要环节,而生物炭中的自由基对有机污染物降解行为的影响还没有得到应有的关注。以水稻秸秆为原材料,研究不同热解温度下制备的生物炭对罗丹明B的吸附和降解,通过荧光光谱法分析生物炭-罗丹明B体系反应前后上清液荧光光谱特性的变化来表征其中的降解现象。结果表明,在350℃和500℃生物炭-罗丹明B反应体系中,其上清液荧光光谱明显发生蓝移现象,表明该体系中存在着明显的降解现象。通过对这2个体系反应后生物炭固体颗粒的萃取来对降解作用进行定量分析,降解作用在这2个体系中所占的比例分别为28%和30%。水稻秸秆生物质炭对罗丹明B具有较好的吸附效果,Freundlich方程可以较好地描述水稻秸秆生物质炭对水中罗丹明B的吸附行为,固液比在3：1 000时生物炭最大吸附量为3.33 mg·g-1。这表明在水稻秸秆生物炭-罗丹明B反应体系中,不仅存在吸附作用,还伴随降解作用。     

绿色屋顶蒸散发及其降温效果

植被的蒸散发潜热使得绿色屋顶具有明显的降温效果。但是,如何准确地观测绿色屋顶蒸散发量一直是蒸散发研究中的难点问题,这影响了绿色屋顶的降温机理研究和推广应用。为此,尝试利用热红外遥感+三温模型的方法,探讨亚热带城市深圳的绿色屋顶蒸散发量的定量观测及其降温效果。结果表明：在日变化方面,雨后4 d的日蒸腾量逐渐下降,分别为1.95、1.91、1.66、1.55 mm·d-1;相应的绿色屋顶表面温度逐渐上升,日平均温度分别为21.62、22.50、23.67、24.74℃,与参考叶片（无蒸腾叶片）表面温度的差值也逐渐缩小,分别为9.08、8.66、7.97、7.38℃;对屋顶气温（1 000 m3空气柱）的降温效果也逐渐降低,分别为1.82、1.79、1.17、1.10℃。在夏季和冬季的晴天条件下,绿色屋顶的白天蒸腾速率的变化范围分别可达0.04~0.54 mm·h-1和0.03~0.09 mm·h-1;在夏季和冬季,绿色屋顶与大理石屋顶的表面温度差分别可达到4.54和4.35℃,与水泥屋顶的表面温度差可达到9.94、9.35℃。在夏季晴天条件下,绿色屋顶、大理石屋顶和水泥屋顶表面温度的日较差分别是10.30、14.80、20.70℃。这些结果表明,绿色屋顶不仅可以显著地降低屋顶的表面温度和周围气温,而且可以有效地减弱屋顶表面温度的变化幅度,对城市人居环境的调节具有积极意义。     

导数恒能量同步荧光法同时分析咔唑、苯并(a)芘、苝和2,3-苯并蒽

建立了咔唑、苯并(a)芘、苝和2,3-苯并蒽四组分同时测定的导数恒能量同步荧光分析法,该法简便快速,无需对混合物进行分离,只需一次扫描,就可实现四组分的同时鉴别和定量测定．该方法用于海水、自来水和大气飘尘的分析,取得了良好的效果,回收率分别为94％-104％,91．7％-104％和82．3％-112．5％．     

能量色散X射线荧光法快速测定生物质燃料中的磷含量

应用能量色散X射线荧光光谱法建立了生物质燃料中磷含量的快速测定方法。对比分析压片压力条件、基体效应和干扰元素,明确了能量色散X射线荧光光谱法的测试条件,通过加标回收率实验、标准样品测试、ICP-OES方法对比等获得实验结果。实验结果表明:能量色散X射线荧光光谱法用于生物质燃料样品的分析,标准工作曲线线性相关系数为0.998 3,方法检出限为0.4 mg/kg,平均加标回收率为98.1%,测定值的相对标准偏差为1.36%~4.92%,标准样品磷含量在标准值不确定度内,能量色散X射线荧光光谱法与行业标准ICP-OES方法的准确度和精密度不存在显著性差异,可应用于生物质中磷含量的环境监测。