Planar monolithic porous polymer layers functionalized with gold nanoparticles as large-area substrates for sensitive surface-enhanced Raman scattering sensing of bacteria

For the first time, large-area surface-enhanced Raman scattering sensing active substrates using porous polymer monolithic layers have been successfully prepared. Our approach includes a simple photoinitiated polymerization process using glycidyl methacrylate and ethylene dimethacrylate in a glass mold, followed by a chemical reaction of the epoxy functionalities leading to thiols, and the attachment of preformed gold nanoparticles. We demonstrated that this very simple process produced uniform and reproducible large area surfaces that significantly enhance sensitivity of Raman spectroscopy. Experiments were also carried out that confirmed preferential adsorption of living bacteria Escherichia coli from a very dilute solution on the surface of the monolithic layer, and immediate detection of the captured microorganisms using the SERS spectrum.     

A device for fully automated on-site process monitoring and control of trihalomethane concentrations in drinking water

An instrument designed for fully automated on-line monitoring of trihalomethane concentrations in chlorinated drinking water is presented. The patented capillary membrane sampling device automatically samples directly from a water tap followed by injection of the sample into a gas chromatograph equipped with a nickel-63 electron capture detector. Detailed studies using individual trihalomethane species exhibited method detection limits ranging from 0.01–0.04 μg L⁻¹. Mean percent recoveries ranged from 77.1 to 86.5% with percent relative standard deviation values ranging from 1.2 to 4.6%. Out of more than 5200 samples analyzed, 95% of the concentration ranges were detectable, 86.5% were quantifiable. The failure rate was less than 2%. Using the data from the instrument, two different treatment processes were optimized so that total trihalomethane concentrations were maintained at acceptable levels while reducing treatment costs significantly. This ongoing trihalomethane monitoring program has been operating for more than ten months and has produced the longest continuous and most finely time-resolved data on trihalomethane concentrations reported in the literature.     

Flow injection method for the determination of silver concentration in drinking water for spacecrafts

A flow injection method has been developed for determination of silver. The method is based on a reduction reaction with sodium borohydride which leads to the formation of a colloidal species which is monitored at a wavelength of 390 nm.The reaction variables flow rate, sodium borohydride concentration and pH, which affect sensitivity, were investigated and their effects were established using a two-levels, three-factor experimental design. Further optimization of manifold variables (reaction coil and injection volume) allowed us to determine silver in the range 0.050-5.0 mg L⁻¹ with a minimum detectable concentration of 0.050 mg L⁻¹. Silver is added, as biocide, to drinking water for spacecrafts. The chemical species of silver, present in this kind of sample, were characterized by a procedure based on the selective retention of Ag⁺ onto a 2.2.2. cryptand based substrate followed by determination of the non-bound and bound (after elution) Ag⁺ by the FIA method. The method optimized was applied to a drinking water sample provided for the launch with the Automated Transfer Vehicle (ATV) module Jule Verne to the International Space Station (March 9, 2008).     

微通道SERS器件的制备及对有害化学品的检测

在微通道内表面通过化学吸附组装上银纳米粒子制成了微通道表面增强拉曼散射(SERS)器件,其对常见探针分子罗丹明6G(R6G)和4-巯基吡啶(4-MPY)的最低检测浓度分别达到10-11和10-8mol/L,说明其具有很好的增强效果.用该器件对2种有害化学药品进行了检测,三聚氰胺的最低检测浓度可到10-6mol/L,而福美双的最低检测浓度可达到10-7mol/L,说明所制备的微通道器件可用于对有害化学品的检测.微通道SERS器件具有体积小、取样少、制备简单、能够进行现场实时动态检测等特点,具有广阔的应用前景.     

离子色谱-质谱联用技术测定饮用水及环境水样中的痕量高氯酸盐

建立了一种测定痕量高氯酸盐的离子色谱-质谱联用方法.选用高容量、强亲水性的阴离子交换柱IonPac AS20(2 mm)进行分离,以淋洗液自动发生器在线产生的KOH为淋洗液,采用等浓度淋洗.在不添加有机溶剂的情况下,淋洗液经过抑制器抑制后直接进入电喷雾-串联质谱(ESI-MS-MS),以负离子模式进行检测.同时采用多元反应监测(MRM)模式对高氯酸盐进行监控,以100.8/84.9、 98.8/66.9和100.8/68.9为监控离子对,以98.8/82.9离子对的峰面积进行定量.高氯酸盐质量浓度在0.05～50 μg/L范围内具有良好的线性(r＝0.9985),检出限(S/N=3)为0.01 μg/L.将该方法用于饮用水以及地下水、雪水等环境水样中高氯酸盐的分析,并进行了加标回收实验,回收率在86%～110%之间,将实际自来水样品连续11次进样,所得高氯酸盐的峰面积的相对标准偏差(RSD)为1.6%.     

ICP-OES法与石墨炉原子吸收法测定饮用水中重金属元素比较

通过对比电感耦合等离子体发射光谱法(ICP-OES)与石墨炉原子吸收法(AAS)测定水中重金属的检出限、重复性、加标回收率等实验,验证两种方法的准确性,从而为饮用水中重金属的测定提供可靠的方法。结果表明,石墨炉原子吸收法测定饮用水中砷、镉、铬、铅、汞、硒检出限均低于ICP-OES法,但ICP-OES法测定线性范围宽,重复性和加标回收率均优于石墨炉原子吸收法,分析速度快,操作便捷,结果满意,是目前饮用水中重金属的测定非常可靠的方法。     

Liquid‐phase microextraction by solidification of floating organic microdrop and GC‐MS detection of trihalomethanes in drinking water

A simple and sensitive methodology based on liquid‐phase microextraction (LPME) followed by GC‐MS, was developed for the determination of trihalomethanes (THMs) in drinking water. A microdrop of organic solvent was floated on the surface of the aqueous sample and it was agitated for a desired time. Then, the sample vial was cooled by inserting it into an ice bath for 4 min. The solidified solvent was transferred into a suitable vial and immediately melted. The extract was directly injected into the GC. Microextraction efficiency factors were investigated and optimized: 7 μL 1‐undecanol microdrop exposed for 15 min floated on the surface of a 10.0 mL aqueous sample with the temperature of 60°C containing 3 M of NaCl and stirred at 750 rpm. Under the selected conditions, enrichment factors (EFs) up to 482‐fold, LOD of 0.03–0.08 μg/L (S/N = 3) and dynamic linear ranges of 0.10–100 μg/L were obtained. A reasonable repeatability (RSD < 8.6%, n = 8) with satisfactory linearity (r² ? 0.9947) of results illustrated a good performance of the present method. The protocol proved to be rapid, cost‐effective, and is a green procedure for the screening purposes.     

Development of a drinking water regulation for perchlorate in California

Perchlorate is an environmental contaminant often associated with military installations and rocket propellant manufacture and testing facilities across the U.S. Highly water soluble, perchlorate has been found by federal and state agencies at almost 400 sites within the U.S. in groundwater, surface water, soil or public drinking water. There is no federal drinking water standard for perchlorate, but it is on the drinking water Contaminant Candidate List, and falls under the Unregulated Contaminant Monitoring Rule (UCMR) for which monitoring is required. The recent National Academy of Science (NAS) report on the potential health effects of perchlorate recommended a perchlorate reference dose of 0.0007 mg/kg of body weight which would be equivalent to a drinking water concentration of 24.5 μg/L.In California, approximately 395 wells in 96 water systems have been shown to contain perchlorate, and about 90% of these are located in Southern California. Water taken from the Colorado River, a major surface water supply to Southern California, has had reported detections of perchlorate ranging from non-detect to 9 μg/L. California has established a Public Health Goal (PHG) of 6 μg/L for perchlorate, and a proposed drinking water regulation is imminent. This review details the regulatory process involved with particular attention given to the occurrence of perchlorate in California drinking water sources and analytical methodology utilized.     

Paper test strip for silver ions detection in drinking water samples based on combined fluorometric and colorimetric methods

In this study, a portable silver ion (Ag⁺) sensor was fabricated based on a dual signal output system using black phosphorus quantum dots (BPQDs) as probes. It is the first work for Ag⁺ detection using paper test strip based on BPQDs. The color change of BPQDs paper sensor for the determination of Ag⁺ was easily identified by naked eye. BPQDs were synthesized from bulk black phosphorus (BP) by mechanical exfoliation combined with a solvothermal method. BPQDs exhibited blue fluorescence with a quantum yield of 8.82 %. The fluorescence of BPQDs can be quenched by Ag⁺, and the absorbance of BPQDs is increased with increasing Ag⁺ concentration. The mechanism of the interaction between BPQDs and Ag⁺ involving fluorescence quenching and bonding was investigated by experimental and computational methods. The detection limit of Ag⁺ was 1.56 μg/mL and 0.19 μg/mL using fluorometry and colorimetry methods, respectively. A portable visual sensor based on paper test strip was constructed for Ag⁺ detection using the colorimetric approach. The strategy was employed to determine Ag⁺ successfully in drinking water samples. Therefore, the proposed portable Ag⁺ sensor can be potentially utilized for the lab-free analysis of drinking water and even dietary samples.     

Rapid and sensitive determination of acrylamide in drinking water by planar chromatography and fluorescence detection after derivatization with dansulfinic acid

On the basis of a novel derivatization, a new planar chromatographic method has been developed for the determination of acrylamide (AA) in drinking water at the ultra-trace level. After SPE, the water extracts were oversprayed on a high-performance thin-layer chromatography (HPTLC) silica gel plate with the derivatization agent dansulfinic acid and derivatized in situ. Chromatography was performed with ethyl acetate and the fluorescent product was quantified at 366/>400 nm. Verification was based on HPTLC-ESI/MS, HPTLC-direct analysis in real-time (DART)-TOF/MS and NMR. The routine HPTLC-fluorescence detection (FLD) method was validated for spiked drinking water. The regression analysis was linear (r >0.9918) in the range of 0.1-0.4 microg/L. LOD was calculated to be 0.025 microg/L and experimentally proved for spiked samples at levels down to 0.05 microg/L (S/N = 6) which was suited for monitoring the EU limit value of 0.1 microg/L in drinking water (0.5 microg/L demanded by World Health Organization (WHO)/US Environmental Protection Agency (EPA)). Within-run precision and the mean between-run precision (RSD, n = 3, three concentration levels each) were evaluated to be 4.8 and 11.0%, respectively. The mean recovery (0.1, 0.2, and 0.3 microg/L) was 96% corrected by the internal standard. The method, in comparison with HPLC-MS/MS showed comparable results and demonstrated the accuracy of the method.     

Analysis of volatiles and semivolatiles in drinking water by microextraction and thermal desorption

A new technique to analyze aqueous samples for nanograms per liter levels of volatile and semivolatile compounds using microextraction and thermal desorption into a gas chromatograph/ion trap mass spectrometer (GC/MS) is described. This method is inherently sensitive (50 mL of aqueous sample is extracted prior to each desorption), uses no solvents, and detects volatiles and semivolatiles in the same analysis. Aqueous standards and environmental samples are pumped through a length of porous-layer open-tubular capillary column, which is then thermally desorbed onto a 30 m × 0.25 mm i.d. analytical column interfaced to an ion trap mass spectrometer for subsequent separation and detection. Sharp chromatographic peaks and reproducible retention times (RT) were observed. Replicate injections of surrogates (n = 6) averaged 32.6% R.S.D. Analysis of domestic tap water detected 55 analytes, some at the low-nanograms per liter level, and detected 3 halogenated ethenes, not previously reported in drinking water. Analysis of an aqueous sample from a municipal ground water source detected the presence of numerous semivolatile compounds at trace-levels.     

Microfluidic device embedding electrodes for dielectrophoretic manipulation of cells‐A review

Microfluidic device embedding electrodes realizes cell manipulation with the help of dielectrophoresis. Cell manipulation is an important technology for cell sorting and cell population purification. Till now, the theory of dielectrophoresis has been greatly developed. Microfluidic devices with various arrangements of electrodes have been reported from the beginning of the single non‐uniform electric field to the later multiple physical fields. This paper reviews the research status of microfluidic device embedding electrodes for cell manipulation based on dielectrophoresis. Firstly, the working principle of dielectrophoresis is explained. Next, cell manipulation approaches based on dielectrophoresis are introduced. Then, different types of electrode arrangements in the microfluidic device for cell manipulation are discussed, including planar, multilayered and microarray dot electrodes. Finally, the future development trend of the dielectrophoresis with the help of microfluidic devices is prospected. With the rapid development of microfluidic technology, in the near future, high precision, high throughput, high efficiency, multifunctional, portable, economical and practical microfluidic dielectrophoresis will be widely used in the fields of biology, medicine, agriculture and so on.     

Chloride interference in the determination of bromate in drinking water by reagent free ion chromatography with mass spectrometry detection

Bromate, a well known by-product of the ozonation of drinking water, has been included among the substances which have to be monitored in the drinking water according to the last EC Directive 251/98 on potable water with a regulated limit of 10 microg l(-1). The need of performing routine analysis at this limit is a driving force for the developing of new simple and sensitive methods of detection, which should be also able to overcome the effect of matrix composition. This work explored the use of mass spectrometry detection with electrospray ionisation hyphenated to a reagent free ion chromatograph with hydroxide gradient elution for the determination of bromate in drinking water. The use of a high capacity hydroxide selective column operated in gradient mode allowed to avoid the interference by carbonate peak, which moved to longer retention times. The effect of increasing chloride concentrations from 0 to 250 mg l(-1), which is the guideline limit for drinking water in Directive 251/98/EC, was to decrease absolute mass spectrometric response and chromatographic efficiency and, on the consequence, to increase the effective detection limits. The effect of the chloride concentration on the detection of bromate is discussed.     

A novel polymeric membrane electrode for the potentiometric analysis of Cu in drinking water

Based on a novel ionophore, an ion-selective electrode has been developed for the determination of Cu²⁺ in drinking water. Its selectivity behavior is characterized and its lower detection limit optimized for measurements with different electrolyte backgrounds. The lower detection limit was 2 × 10⁻⁹ M Cu²⁺ for samples with low ionic background and 1 × 10⁻⁷ M Cu²⁺ with ionic background typically found in drinking water.     

The defluoridation of drinking water using multi-walled carbon nanotubes

In this study, the potential sorption capacity of multi-walled carbon nanotubes (MWCNTs) was investigated as a means of removing fluoride from the drinking water of a number of regions in Iran and from experimental solutions. The test was conducted in both batch and continuous operation modes. Batch mode experiments were used to study the effect of parameters such as pH, contact time, ionic strength, adsorbent dose, adsorbent capacity, and the presence of foreign anions on the efficiency of fluoride removal. The results showed that the highest level of sorption occurs at pH 5 (about 94% at 18 min). The ionic strength of the solutions and the presence of co-anions such as chloride, nitrate, sulfate, hydrogen carbonate, perchlorate had a negligible effect on the sorption of F⁻ onto MWCNTs. Sorption capacity measurements revealed that MWCNTs have a saturation capacity of 3.5 mg of F⁻ per gram. Sorption data were best fitted with the Fruendlich sorption isotherm equation, which indicates that F⁻ tends to be adsorbed on MWCNTs in a multilayered manner. Experiments using Kohbanan city drinking water, which contains the highest level of F⁻ among the drinking water samples studied, showed that MWCNTs can remove over 85% of fluoride content.     

Microfluidic device integrating single-cell extraction and electrical lysis for mass spectrometry detection of intracellular compounds

Analysis of cellular composition and metabolism at a single-cell resolution allows gaining more information about complex relationships of cells within tissues or whole living organisms by resolving the variance stemming from the cellular heterogeneity. Mass spectrometry (MS) is a perfect analytical tool satisfying the demanding requirements of detecting and identifying compounds present in such ultralow-volume samples of high chemical complexity. However, the method of sampling and sample ionization is crucial in obtaining relevant information. In this work, we present a microfluidic sampling platform that integrates single-cell extraction from MS-incompatible media with electrical cell lysis and nanoESI-MS analysis of human erythrocytes. Hemoglobin alpha and beta chains (300 amol/cell) were successfully identified in mass spectra of single-erythrocyte lysates.     

Cross-flow microfiltration system for rapid enrichment of bacteria in water

Permanent monitoring of waterborne pathogens is important for securing the hygiene of water. Enumerating bacteria in water at low concentrations and minute quantities demands rapid and efficient enrichment methods in order to improve the signal-to-noise ratio of subsequent determination methods. In this work an automated cross-flow microfiltration (CFM) system is presented which is usable in the field to concentrate large volumes of environmental water for analytical purposes. It was designed as a rapid enrichment apparatus achieving high recovery and high concentration factors. The efficiency of the CFM system was studied for E. coli spiked in a 10-L tap water sample. By this technique, a 10-L water sample was concentrated by a factor of 200 in 15 min. The high and consistent recovery of 91.3 ± 5.4% living cells in the concentration range 0.01 and 100 cfu mL⁻¹ is suitable for rapid enumeration of bacteria in water.     

固相萃取-液质联用法同时测定饮用水中双酚A和邻苯二甲酸二丁酯

建立了饮用水中痕量双酚A和邻苯二甲酸二丁酯同时测定的LC/MS-MS快速分析方法.水样中双酚A和邻苯二甲酸二丁酯经HLB固相萃取小柱富集,以V(乙腈)∶V(水)＝90∶10为流动相,选择双酚A m/z 227/212、邻苯二甲酸二丁酯m/z 301/228为检测离子对,利用多反应监测(MRM)和扫描时间分段检测技术实现正、负离子不同扫描模式一次完成.该方法对水样体积为250 mL时双酚A和邻苯二甲酸二丁酯的线性范围为0.4～40 ng/L,检出限分别为0.16和0.10 ng/L,低中高3个不同水平的加标平均回收率均在90%以上.应用于5种不同来源的饮用水及原水中双酚A和邻苯二甲酸二丁酯的测定.     

Development of a solid surface fluorescence-based sensing system for aluminium monitoring in drinking water

A novel, single and robust solid surface fluorescence-based sensing device assembled in a continuous flow system has been developed for the determination of trace amounts of aluminium in water samples. The proposed method is based on the transient immobilization of the target species on an appropriate active solid sensing zone (C₁₈ silica gel). The target species was the fluorogenic chelate, formed as a result of the on-line complexation of Al(III) with chromotropic acid (CA) at pH 4.1. The fluorescence of the complex is continuously monitored at an emission wavelength of 390 nm upon excitation at 361 nm. The instrumental, chemical and flow-injection variables affecting the fluorescence signal were carefully investigated and optimized. After selecting the most suitable conditions, the sensing system was calibrated in the range 10–500 μg l⁻¹, obtaining a detection limit of 2.6 μg l⁻¹, and a R.S.D. of 2.2%, with a sampling frequency of 24 h⁻¹. In addition, the selectivity of the proposed methodology was evaluated by performing interference studies with different cations and anions which could affect the analytical response. Finally, the proposed method, which meets the EU regulations regarding the aluminium content in drinking waters, was satisfactorily applied to different water samples, with recoveries between 97 and 105%. The simplicity, low cost and easy operation are the main advantages of the present procedure.