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The presence of trace contaminants in ultra-pure water (UPW) used in fabrication process can greatly affect the yield and quality of industrial products. In the present study, the electrodialytic enrichment of metal cations as a means of continuously monitoring the UPW quality was studied. A newly designed electrodialytic enrichment device (EED) was used to quantitatively transfer metal ions from samples to dilute nitric acid, which was then directly introduced into an inductively coupled plasma-mass spectrometry (ICP-MS) instrument. This process could be performed without contamination of the sample, and the enrichment factor was solely dependent on the flow rate ratio of the sample and acceptor solutions. The transference of analytes into the acidic solution improved the responsivity of the ICP-MS analysis, especially at low concentrations of less than 1 μg/L. Blank solutions to support the analysis of UPW could be produced using the EED effluent, from which metal ions were quantitatively removed. In addition, calibration curves with concentration ranges of several nanograms per liter were obtained by preparing standards using a dynamic gravimetric method while employing a single bottle and continuous mass monitoring to avoid any contamination from the volumetric flasks. The sensitivities associated with the ICP-MS analysis of a number of trace metal ions were improved by one or two orders of magnitude. The data show that the present EED is able to continuously produce enriched analyte solutions to allow the ongoing monitoring of UPW quality.

Gas- and particle-phase nitrophenols are collected separately and preconcentrated for HPLC analysis. Time variations in concentrations and partitioning into particles of nitrophenols are obtained with a resolution of 2 h.

Phytoplankton dinoflagellate forms colonies between vertical ice crystals during the ice-melting season in Lake Baikal: how the plankton survive the freezing conditions was previously not known. Here we show that the phytoplankton produces large amounts of dimethylsulfoniopropionate (DMSP) known as a marine compound. Lake-water DMSP concentrations in the spring season are comparable with those in the oceans, and colony water in ice exhibits extremely high concentrations. DMSP concentration correlates with plankton density and reaches maximum in mid-April with exhibiting temperature-dependent fluctuations. DMSP is released from plankton cells into water in warm days. DMSP is a characteristic osmolyte of marine algae; our results demonstrate that the freshwater plankton has the DMSP-producing ability, and efficiently uses the limited sulfur resource (only 1/500 of sea sulfate) to survive in freshwater ice. Plankton in Lake Baikal do not need an osmolyte, and our results indicate that DMSP plays a purely cryoprotective role.

The standard addition method is a powerful tool to eliminate matrix interferences and enables accurate determinations, but it is time-consuming and labor-intensive. This paper proposes a feedback standard addition method coupled flow injection analysis, FB-SAM/FIA, for the rapid and accurate determination of trace interest in seawater samples. This approach automatically prepares spiked samples by feeding back the peak height in the fiagram, thus significantly improving the sample throughput compared to the manual standard addition method. Spectrophotometric determination of NO2- with the Griess assay was used as an evaluation model. The proposed technique demonstrated a sample throughput of 3 samples/h, ranging from 0.0050 mg L-1 (LOD) to 0.125 mg L-1 NO2-. The accuracies of NO2- determination with FB-SAM/FIA and an absolute calibration method were tested using natural seawater and pseudo-seawater samples containing 0.040 mg L-1 NO2- in 0, 1, 2, 3, and 4% sodium chloride media. With the absolute calibration method, the calculated concentration increased with an increase in salinity, reaching an overestimation of about 40%. On the other hand, FB-SAM/FIA suppressed the errors in the range of -7.8% to 1.3% and applied successfully to the determination of NO2- in the natural seawater samples.

A portable chemical analysis system for monitoring ambient carbonyl sulfide (COS) was investigated for the first time. COS is paid attention to from the perspectives of photosynthesis tracer, breath diagnosis marker, and new process-use in the manufacture of semiconductors. Recently, the threshold level value of COS was settled at 5 ppm in volume ratio (ppmv) for workplace safety management. In this work, COS was converted to H2S by a small column packed with alumina catalyzer at 65 °C. Then, the H2S produced was collected in a small channel scrubber to react with fluorescein mercuric acetate (FMA), and the resulting fluorescence quenching was monitored using an LED/photodiode-based miniature detector. The miniature channel scrubber was re-examined to determine its robustness and easy fabrication, and conditions of the catalyzer were optimized. When the FMA concentration used was 1 μM, the limit of detection and dynamic range, which were both proportional to the FMA concentration, were 0.07 and 25 ppbv, respectively. Ambient COS in the background level and even contaminated COS in the nitrogen gas cylinder could be detected. If necessary, H2S was removed selectively by reproducible adsorbent columns. COS concentrations of engine exhaust were measured by the proposed method and by cryo-trap-gas chromatography-flame photometric detection, and the results obtained (0.5–5.9 ppbv) by the two methods agreed well (R2 = 0.945, n = 19). COS in ambient air and exhaust gases was successfully measured without any batchwise pretreatment.

Radioactive metals are applied in biochemistry, medical diagnosis such as positron emission tomography (PET), and cancer therapy. However, the activity of radioisotopes exponentially decreases with time; therefore, rapid and reliable probe preparation methods are strongly recommended. In the present study, electrodialytic radioactive metal ion handling is studied for counter ion conversion and in-line probe synthesis. Presently, counter ion conversion and probe synthesis are achieved by evaporative dryness and solution mixing, respectively. Evaporative dryness is time-consuming and is a possible process that can lead to loss of radioactive metal ions. Mixing of solutions for synthesis makes dilution and undesirable effects of counter ion on the synthesis. An optimized electrodialytic flow device can transfer a radioisotope

Heavy metals in particulate matter (PM) are of great concern, and their effects on the environment and human health depend on their solubilities and species present. In this study, the solubility of As, Se, Sb, V and Cr and their species eluted in water was investigated. As, Se, Sb, and V were present mostly in fine particles, and they were predominantly water-soluble in fine particles ( 2.5 μm). Solubility of Cr was poor even in fine particles. It was found that for fine particles, solubilities of the heavy metals were related to the nitrate and sulfate contents. This suggests that the higher the acidity of the particles, the higher the solubility of the heavy metals. Oxoanions of the five kinds of heavy metals in water extracts of fine particles were determined by inductively coupled plasma mass spectrometry preceded by ion chromatography. The results suggested the presence of atmospheric oxidation during the aerosol transportation. Also, the As(iii)/As(v) (arsenite/arsenate) ratios for the fine particle extracts were related to the transition metal concentrations, which indicated that Fe, Cu, etc. in fine particles affected the As redox equilibrium. It was suggested that the heavy metals exist as complexes with iron hydroxide and dissolved organic matter in addition to the free oxoanions. These investigations were performed for PM samples collected in winter and summer in Kumamoto, west Japan, where the site is strongly exposed to westerly winds from continental East Asia. The obtained results improve our understanding of the behavior of the heavy metals in airborne PM after depositing on a wet environment and biota.

Preparing compounds containing the radioisotope

Short-lived radioactive metals are important tracers in clinical diagnosis. Radioactive metals for clinical use are produced from suitable target metals in cyclotrons. The trace amount of radioactive metal produced is contained in a relatively large amount of target metal. A rapid and effective method is required to isolate the radioactive metal. In the present study, selective complex formation followed by cation-exchange adsorption was performed in a continuous flow-based system. Ethylenediamine

A fast response potentiometric flow-through pH sensor was applied for organic acid determination. The analyte response with the pH sensor was obtained by eluent pH modification following ion exclusion chromatography with HClO4 as an eluent. The response characteristics depend on the adjusted baseline pH. The baseline pH adjustment was successfully done with an ammonia permeation device without solution mixing, which may cause analyte dilution, dispersion, and mixing noise. After pH adjustment, the pH response was universal to the equivalent of introduced analyte acids because the pH response was obtained by the titration of the permeant ammonia by the analytes. The average of limit of detections (S/N = 3) was 0.06 mM for seven target organic acids. Furthermore, the pH response follows the theoretical pH calculation with the concentrations of the eluent, pH modifier, and analyte. Thus, the analyte concentration in the sample can be theoretically calculated from the pH response without calibration by the analyte standard. Predicted concentrations of injected standards were within 5% of the actual standard concentration. Additionally, analysis of real samples was performed and compared with the conventional post-column reaction with a bromothymol blue (BTB) method. The results obtained with the present system (absolute quantification with theoretical calculation) and conventional BTB method agreed within 10% of errors.

An automated device has been developed to measure aqueous dimethyl sulfide (DMSaq), its precursor dimethylsulfoniopropionate (DMSP), and atmospheric gaseous dimethyl sulfide (DMSg). In addition to having a role in the oceanic atmosphere, DMS and DMSP have recently gained substantial interest within the biosciences and are suspected as chemoattractants for predators searching for prey. To provide the spatial resolution relevant for biogeochemical functions, fast and on-site analysis of these compounds is an important technique. The system described measures the dimethyl sulfur compounds by sequential vaporization of DMSaq and DMSP to their gas phase, which is then analyzed by chemiluminescence detection (SVG-CL). The device has five analysis modes (full, DMS, water, gas, and DMSP mode) that can be selected by the user depending on the required analyte or desired sampling rate. Seawater analyses were performed by the developed SVG-CL system and, simultaneously, by an ion molecule reaction-mass spectrometer and a gas chromatograph-flame photometric detector to verify quantitative analysis results. Results obtained by the new method/device agreed well with those by the other methods. Detection limits of the SVG-CL system are 0.02 ppbv and 0.04 nM for DMSg and DMSaq/DMSP, respectively, which are much better than those of the mass spectrometer. The SVG-CL system can be easily installed and operated on a boat. Spatial variability in DMS and DMSP off the coast of Japan were obtained, showing significant changes in the concentrations of the components at the brackish/saline water interface and at the channel between the closed and open seas.

Electrodialytic separation of Cr(VI) and Cr(III) followed by graphite furnace atomic absorption spectrometry for monitoring of soil extraction was studied. The sensitivity was improved by in-line purification of the solutions and bi-polar pulse cleaning. The detection limit for both Cr(VI) and Cr(III) was 0.01 μg L-1. The system was successfully used to monitor the concentration change during soil extraction with dual solution line filtration. The results demonstrate the difference in concentration changes with the different sources of Cr(VI).

This work presents diurnal variations of gas- and particle-phase dicarbonyls (glyoxal (Gly) and methylglyoxal (Mgly)) in the atmosphere, which are important compounds that contribute to the formation and growth of atmospheric particulate matter. To obtain variations in partitioning, continuous collection of gaseous dicarbonyls was performed using a parallel plate wet denuder, and at the same time, the dicarbonyls in particle were collected using a spray-type particle collector downstream. Hourly samples were analyzed by high performance liquid chromatography–electrospray ionization–tandem mass spectrometry. This method is advantageous to monitor the gaseous and particulate carbonyls separately without loss during sampling. Sampling was performed in summer and winter in a midsize city (Kumamoto, Japan). The concentrations of the dicarbonyls increased in the summer daytime, which suggests that they are mostly formed by secondary production in the local atmosphere. The dicarbonyls and formaldehyde (HCHO) wer...

Monitoring of trace water in industrial gases is strongly recommended because contaminants cause serious problems during use, especially in the semiconductor industry. An ultra-sensitive trace-water sensor was developed with an in situ-synthesized metal-organic framework as the sensing material. The sample gas is passed through the sensing membrane and efficiently and rapidly collected by the sensing material in the newly designed gas collection/detection cell. The sensing membrane, glass paper impregnated with copper 1,3,5-benzenetricarboxylate (Cu-BTC), is also newly developed. The amount and density of the sensing material in the sensing membrane must be well balanced to achieve rapid and sensitive responses. In the present study, Cu-BTC was synthesized in situ in glass paper. The developed system gave high sensing performances with a limit of detection (signal/noise ratio = 3) of 9 parts per billion by volume (ppbv) H2O and a 90% response time of 86 s for 200 ppbv H2O. The reproducibility of the responses within and between lots had relative standard deviations for 500 ppbv H2O of 0.8% (n = 10) and 1.5% (n = 3), respectively. The long-term (2 weeks) stability was 7.3% for 400 ppbv H2O and one-year continuous monitoring test showed the sensitivity change of

A gas sensor was developed for arsine (AsH 3 ) which is the most toxic inorganic gas. The sensor was prepared from reduced graphene oxide (rGO), modified with a thin gold film, on an interdigitated array electrode. The conductance of the Au/rGO sensor was monitored in the presence of flowing AsH 3 that was prepared by reduction of aqueous arsenite with borohydride and vaporization of the hydride. Gas sensors fabricated with only rGO or Au did not exhibit AsH 3 sensitivity. However, rGO sensors combined with Au exhibited reversible conductivity enhancement with AsH 3 . The increase in conductivity probably occurred because the AsH 3 depleted adsorbed oxygen on the Au islands, resulting in the enhancement of hole conduction in the rGO film. Responses were observed for sub-ppmv levels of AsH 3 . The amounts of gold and rGO, the GO reduction, and the operating temperature were optimized to obtain a detection limit of 0.01 ppmv (determined from a signal level three times the baseline noise). Interference from other gases and vapors was examined. The sensor responded to NO 2 , but this is not expected to be present in air-quality-controlled clean rooms. AsH 3 is one of the most toxic chemicals used in the semiconductor industry, and the Au/rGO-based AsH 3 sensor is expected to have widespread applications.

After the Fukushima disaster, power generation from nuclear power plants in Japan was completely stopped and old coal-based power plants were re-commissioned to compensate for the decrease in power generation capacity. Although coal is a relatively inexpensive fuel for power generation, it contains high levels (mgkg(-1)) of selenium, which could contaminate the wastewater from thermal power plants. In this work, an automated selenium monitoring system was developed based on sequential hydride generation and chemiluminescence detection. This method could be applied to control of wastewater contamination. In this method, selenium is vaporized as H2Se, which reacts with ozone to produce chemiluminescence. However, interference from arsenic is of concern because the ozone-induced chemiluminescence intensity of H2Se is much lower than that of AsH3. This problem was successfully addressed by vaporizing arsenic and selenium individually in a sequential procedure using a syringe pump equipped with an eight-port selection valve and hot and cold reactors. Oxidative decomposition of organoselenium compounds and pre-reduction of the selenium were performed in the hot reactor, and vapor generation of arsenic and selenium were performed separately in the cold reactor. Sample transfers between the reactors were carried out by a pneumatic air operation by switching with three-way solenoid valves. The detection limit for selenium was 0.008 mg L(-1) and calibration curve was linear up to 1.0 mg L(-1), which provided suitable performance for controlling selenium in wastewater to around the allowable limit (0.1 mg L(-1)). This system consumes few chemicals and is stable for more than a month without any maintenance. Wastewater samples from thermal power plants were collected, and data obtained by the proposed method were compared with those from batchwise water treatment followed by hydride generation-atomic fluorescence spectrometry.

To monitor the fluctuations of dimethyl sulfur compounds at the seawater/atmosphere interface, an automated system was developed based on sequential injection analysis coupled with vapor generation-ion molecule reaction mass spectrometry (SIA-VG-IMRMS). Using this analytical system, dissolved dimethyl sulfide (DMS(aq)) and dimethylsulfoniopropionate (DMSP), a precursor to DMS in seawater, were monitored together sequentially with atmospheric dimethyl sulfide (DMS(g)). A shift from the equilibrium point between DMS(aq) and DMS(g) results in the emission of DMS to the atmosphere. Atmospheric DMS emitted from seawater plays an important role as a source of cloud condensation nuclei, which influences the oceanic climate. Water samples were taken periodically and dissolved DMS(aq) was vaporized for analysis by IMRMS. After that, DMSP was hydrolyzed to DMS and acrylic acid, and analyzed in the same manner as DMS(aq). The vaporization behavior and hydrolysis of DMSP to DMS were investigated to optimize these conditions. Frequent (every 30 min) determination of the three components, DMS(aq)/DMSP (nanomolar) and DMS(g) (ppbv), was carried out by SIA-VG-IMRMS. Field analysis of the dimethyl sulfur compounds was undertaken at a coastal station, which succeeded in showing detailed variations of the compounds in a natural setting. Observed concentrations of the dimethyl sulfur compounds both in the atmosphere and seawater largely changed with time and similar variations were repeatedly observed over several days, suggesting diurnal variations in the DMS flux at the seawater/atmosphere interface.

The sensitivity of an ion chromatography system was improved using electrodialytic post-column enrichment. Even though post-column reactions, such as suppression, have been used to enhance the sensitivity, there are only a few methods available to increase the concentration and improve the sensitivity. Post-column in-line enrichment was achieved with a miniaturized crossflow ion transfer device (ITD) prepared in our laboratory. In the crossflow ITD, separated ionic solutes in the suppressed eluent were transferred into the acceptor solution (in-line purified ultrapure water), which had a flow rate less than that of the eluent. Because of highly efficient ion transfer, the analytes were enriched in the acceptor solution and the enrichment factor was depending on flow rate ratio of acceptor to eluent. Furthermore, the crossflow ITD minimized peak dispersion in the channel. The limit of detection improved by 5.0 ± 0.3 times when the flow rate ratio was 10.

Most quantifications are achieved by comparison of the signals obtained with the sample to those from a standard. Thus, the purity and stability of the standard are key in chemical analysis. Furthermore, if an analyte standard cannot be obtained, quantification cannot be achieved, even if the chemical structures are identified by a qualification method (e.g., high-resolution mass spectrometry). Herein, we describe a universal and analyte standard-free detector for aqueous-eluent-based high-performance liquid chromatography. This universal carbon detector (UCD) was developed based on total organic carbon detection. Separated analytes were oxidized in-line and converted to carbon dioxide (CO2). Generated CO2 was transferred into the gas phase and collected into ultrapure water, which was followed by conductivity detection. The system can be applied as a HPLC detector that does not use an organic solvent as an eluent. The system can be calibrated with a primary standard of sodium bicarbonate for organic comp...

Large amounts of chromium (Cr) compounds are used for manufacturing of various products and various chemical processes. Some inevitably find their way into the environment. Environmental Cr is dominantly inorganic and is either in the cationic +3 oxidation state or in the anionic oxochromium +6 oxidation state. The two differ dramatically in their implications; Cr(III) is essential to human nutrition and even sold as a supplement, while Cr(VI) is a potent carcinogen. Drinking water standards for chromium may be based on total Cr or Cr(VI) only. Thus, Cr speciation analysis is very important. Despite their high sensitivity, atomic spectrometric techniques or induction coupled plasma-mass spectrometry (ICP-MS) cannot directly differentiate the oxidation states. We present here a new electrodialytic separation concept. Sample analyte ions are quantitatively transferred via appropriately ionically functionalized dialysis membranes into individual receptors that are introduced into the ICP-MS. There was no significant conversion of Cr(VI) to Cr(III) or vice versa during the very short (6 s) separation process. Effects of salinity (up to ∼20 mM NaCl) can be eliminated with proper membrane functionalization and receptor optimization. With the ICP-MS detector we used, the limits of detection for either form of Cr was 0.1 μg/L without preconcentration. Up to 10-fold preconcentration was readily possible by increasing the donor solution flow rate relative to the acceptor solution flow rates. The proposed approach permits simultaneous matrix isolation, preconcentration, and chromium speciation.

This article presents the effect of phosphate ion on the potential leaching of arsenic from the contaminated sediment under anaerobic conditions near neutral pH for 120 h. Arsenic content in the selected sediments was 450 mg/kg. In the leaching experiment, 50 g of sediment sample was added into 400 mL of five different concentrated 0 (no phosphate), 3, 10, 15, and 20 mg/L phosphate solutions, and leachates were analyzed by distinguishing As(III) and As(V) with the sequential hydride generation flow injection analyzer (SHGFIA). The results indicate that arsenic concentration in the leachates was increased for As(V) up to 72 h, and subsequently As(V) concentration was decreased in the suspension. The leached amount of As(V) concentration in the aqueous phase was increased with increasing the phosphate concentration in the suspensions, and statistically significant correlation (R 2 = 0.9959) was found. Conversely, As(III) concentration in the leachates was almost constant up to 24 h then As(III) concentration was decreased in the suspension. The phosphate ion was potentially leached arsenic, especially As(V) as phosphate (PO4 3−) ion has more charge density than arsenate (AsO4 3−) resulting more As(V) was leached from the contaminated sediment with increasing the phosphate concentration in the suspensions.

PM_中の多環芳香族炭化水素 (polycyclic aromatic hydrocarbons:PAHs) を簡便かつ高感度に分析を行うため，従来の溶媒抽出 (solvent extraction:SE) に代わり，加熱脱着法によるガスクロマトグラフィー質量分析 (thermal desorption–gas chromatography/mass spectrometry:TD-GC/MS) について検討した．本研究では，フィルター捕集したPM_中のPAHsについてTDの条件検討を行うとともに，TD法とSE法の比較検討を行った．その結果，煩雑で時間のかかるSE法に比べTD法では溶媒を用いる前処理が不要なばかりか，同じフィルターを処理した場合桁違いに高感度なことが示された．簡便かつ高感度なため，比較的短いサンプリング (1～3日) を長期間続けることができ，PM_中PAHsの詳細な季節変動の追跡が達成された．PM_濃度は四季を通じて大きな推移を示さない一方，PM_中のPAHsは冬から春に高く，逆に夏にはほとんど観測されなかった．これは冬場の中国大陸におけるPAHsの放出とその移流が主な原因と考えられる．さらに，本法の高感度な特性を生かし，短時間のサンプリングによるPAHsの変動をみることができた．例えば4時間ごとにサンプリングを行い，日内でPAHs濃度が推移する様子を捉えることができた．また，阿蘇山の草原を20 km程度自家用車で走行し，野焼きで発生したPAHsの組成を調べることができた．野焼きの際に得られたPAHsは，季節変動の調査で得られたPAHsに比べて3～4環の低分子量のPAHsが多く，市内で1～3日採取したPM_中のPAHsと組成が異なった．以上のようにTD-GC/MSによるフィルターに捕集したPM中PAHsの分析条件を確立し，特徴ある分析結果を示して本法の有用性を示した．

Electrodialytic ion transfer was studied as a matrix isolation tool for heavy metal determinations. An ion transfer device (ITD) was used for the transfer of heavy metal cations. Under optimized flow rates applied voltage and receptor composition, heavy metal ions were quantitatively transferred at concentrations spanning µg L−1 to mg L−1. As long as the sample pH was acidic, there was no significant sample pH effect on the transfer efficiencies. Significant salt concentrations (>1 mM NaCl), however, decreased the transfer efficiency. This could be ameliorated (up to 5 mM NaCl) by transient instead of continuous sample introduction. The device was applied to the determination of Fe, Cu and Zn in equine and bovine serum; the reproducibility was better than conventional digestion method.

Chromatographic determination of organic acids is widely performed, but the matrix often calls for lengthy and elaborate sample preparation prior to actual analysis. Matrix components, e.g., proteins, non-ionics, lipids etc. are typically removed by a combination of centrifugation/filtration and solid phase extraction (SPE) that may include the use of ion-exchange media. Here we report the quantitative electrodialytic transfer of organic acids from complex samples to ultrapure water in seconds using cellulose membranes modified with N,N-dimethylaminoethyl methacrylate, which essentially eliminates the negative ζ-potential of a regenerated cellulose membrane surface. The transfer characteristics of the ion transfer device (ITD) were evaluated with linear carboxylic acids. While the ion transfer efficiencies may be affected by the acid dissociation constants, in most cases it is possible to achieve quantitative transfer under optimized device residence time (solution flow rate) and the applied voltage. In addition, the transfer efficiency was unaffected by the wide natural variation of pH represented in real samples. The approach was applied to organic acids in various samples, including red wine, considered to represent an especially difficult matrix. While quantitative transfer of the organic acids (as judged by agreement with standard pretreatment procedures involving SPE) was achieved, transfer of other matrix components was5%. The processed samples could then be chromatographically analyzed in a straightforward manner. We used ion exclusion chromatography with direct UV detection; in treated samples; there was a dramatic reduction of the large early peaks observed compared to only 0.45μm membrane filtered samples.

A method to introduce target analytes to a chromatograph from a single drop of whole blood was investigated for minimally invasive monitoring of anionic pharmaceuticals. In this work, salicylate and loxoprofen were examined as organic anions. A micro ion extractor (MIE) has been developed for extraction of inorganic trace anions from whole blood, but this device is not suitable for extraction of pharmaceuticals. In the present study, we improved and optimized the MIE device for organic anion extraction. Various supported liquid membranes were evaluated for use as the ion transfer membrane, with each membrane placed between a droplet sample (donor) and an acceptor solution. A supported liquid membrane of porous polypropylene impregnated with 1-butanol was selected. In addition, the methods for electric field creation and electrode contact were examined to improve the characteristics of the MIE device. The current and extraction time were also optimized. With the optimized method, salicylate and loxoprofen were successfully extracted from a single drop of whole blood. Changes in the concentrations of these pharmaceuticals in blood over time were monitored after administration. As only 25μL of whole blood was required for analysis, repeat measurements could be conducted to monitor changes in the concentrations. This MIE will be useful for monitoring pharmaceutical concentrations in blood.

Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%).

Whole column detection (WCD) is as old as chromatography itself. WCD requires an ability to interrogate column contents from the outside. Other than the obvious case of optical detection through a transparent column, admittance (often termed contactless conductance) measurements can also sense changes in the column contents (especially ionic content) from the outside without galvanic contact with the solution. We propose here electromechanically scanned admittance imaging and apply this to open tubular (OT) chromatography. The detector scans across the column; the length resolution depends on the scanning velocity and the data acquisition frequency, ultimately limited by the physical step resolution (40 μm in the present setup). Precision equal to this step resolution was observed for locating an interface between two immiscible liquids inside a 21 μm capillary. Mechanically, the maximum scanning speed was 100 mm/s, but at 1 kHz sampling rate and a time constant of 25 ms, the highest practical scan speed (no peak distortion) was 28 mm/s. At scanning speeds of 0, 4, and 28 mm/s, the S/N for 180 pL (zone length of 1.9 mm in a 11 μm i.d. column) of 500 μM KCl injected into water was 6450, 3850, and 1500, respectively. To facilitate constant and reproducible contact with the column regardless of minor variations in outer diameter, a double quadrupole electrode system was developed. Columns of significant length (1 m) can be readily scanned. We demonstrate its applicability with both OT and commercial packed columns and explore uniformity of retention along a column, increasing S/N by stopped-flow repeat scans, etc. as unique applications.

The highly odorous compound methanethiol, CH 3 SH, is commonly produced in biodegradation of biomass and industrial processes, and is classed as 2000 times more odorous than NH 3 . However, there is no simple analytical method for detecting low parts-per-billion in volume ratio (ppbv) levels of CH 3 SH. In this study, a micro gas analysis system (μGAS) was developed for continuous or near real time measurement of CH 3 SH at ppbv levels. In addition to a commercial fluorescence detector, a miniature high sensitivity fluorescence detector was developed using a novel micro-photomultiplier tube device. CH 3 SH was collected by absorption into an alkaline solution in a honeycomb-patterned microchannel scrubber and then mixed with the fluorescent reagent, 4-( N , N -dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (DBD-F). Gaseous CH 3 SH was measured without serious interference from other sulfur compounds or amines. The limits of detection were 0.2 ppbv with the commercial detector and 0.3 ppbv with the miniature detector. CH 3 SH produced from a pulping process was monitored with the μGAS system and the data agreed well with those obtained by collection with a silica gel tube followed by thermal desorption–gas chromatography–mass spectrometry. The portable system with the miniature fluorescence detector was used to monitor CH 3 SH levels in near-real time in a stockyard and it was shown that the major odor component, CH 3 SH, presented and its concentration varied dynamically with time.

A small, simple device was developed for trace analysis of dimethyl sulfide (DMS) and dimethylsulfoniopropionate (DMSP) in natural waters. These compounds are known to be the major sources of cloud condensation nuclei in the oceanic atmosphere and ideally should be measured onsite because of their volatility and instability. First, chemical and physical vapor generations were examined, and simple pressurizing by injection of 30 mL of air using a syringe was adopted. Pressurized headspace air above a 10 mL water sample was introduced to a detection cell as a result of the pressure differential and mixed with ozone to induce chemiluminescence. Although the measurement procedure was simple, the method was very sensitive: sharp peaks appeared within seconds for nanomolar levels of DMS, and the limit of detection was 0.02 nmol L(-1) (1 ng L(-1)). Although interference from methanethiol was significant, this was successfully addressed by adding a small amount of Cd(2+) before DMS vapor generation. DMSP was also measured after hydrolysis to DMS, as previously reported. Pond water and seawater samples were analyzed, and DMS was found in both types of sample, whereas DMSP was observed only in seawater. The DMS/DMSP data obtained using the developed method were compared with data obtained by purge/trap and gas chromatography-mass spectrometry, and the data from the two methods agreed, with good correlation (R(2) = 0.9956). The developed device is inexpensive, light (5 kg), simple to use, can be applied in the field, and is sensitive enough for fresh- and seawater analysis.

Perchlorate is an iodine-uptake inhibitor and common contaminant of food and drinking water. Understanding the amount of perchlorate exposure occurring through non-water sources is essential for accurate estimates of human exposure levels, and establishment of drinking water limits for this pervasive contaminant. The study objective was to determine the amount of perchlorate intake derived from diet rather than water. Subjects provided drinking water samples, detailed fluid-intake records, 24 h urine collections and four milk samples for nine days. Samples were analyzed for perchlorate by isotope dilution ion chromatography–tandem mass spectrometry. Amounts of perchlorate derived from drinking water and dietary sources were calculated for each individual. Water of local origin was found to contribute a minor fraction of perchlorate intake. Estimated fraction intake from drinking water ranged from 0 to 36%. The mean and median dose of perchlorate derived from non-water sources by lactating women was 0.18 μg/kg/day (range: 0.06 to 0.36 μg/kg/day.) Lactating women consumed more fluid (mean 2.424 L/day) than has been assumed in recent risk assessments for perchlorate. The data reported here indicate that lactating women may be exposed to perchlorate through dietary sources at markedly higher levels than estimated previously. Exposures to perchlorate from non-water sources may be higher than recent estimates, including those used to develop drinking water standards.

Ion exchangers are ionic equivalents of doped semiconductors, where cations and anions are equivalents of holes and electrons as charge carriers in solid state semiconductors. We have previously demonstrated an ion exchange membrane (IEM) based electrolyte generator which behaves similar to a light-emitting diode and a charge detector (ChD) which behaves analogous to a p–i–n photodiode. The previous work on the charge detector, operated at a constant voltage, established its unique ability to respond to the charge represented by the analyte ions regardless of their redox properties, rather than to their conductivities. It also suggested that electric field induced dissociation (EFID) of water occurs at one or both ion exchange membranes. A logical extension is to study the behavior of the same device, operated in a constant current mode (ChD i ). The evidence indicates that in the present operational mode the device also responds to the charge represented by the analytes and not their conductivity. Injection of a base into a charge detector operated in the constant voltage mode was not previously examined; in the constant current mode, base injection appears to inhibit EFID. The effects of applied current, analyte residence time and outer channel fluid composition were individually examined; analyte ions of different mobilities as well as affinities for the respective IEMs were used. While the exact behavior is somewhat dependent on the applied current, strong electrolytes, both acids and salts, respond the highest and in a near-uniform fashion, weak acids and their salts respond in an intermediate fashion and bases produce the lowest responses. A fundamentally asymmetric behavior is observed. Injected bases but not injected acids produce a poor response; the effects of incorporating a strong base as the electrolyte in the anion exchange membrane (AEM) compartment is far greater than incorporating an acid in the cation exchange membrane (CEM) compartment. These observations suggest that EFID occurs primarily at the anion exchange membrane and is inhibited by the presence of OH − . Analyte peak widths and peak asymmetries were found to be governed by the mobility of the analyte ions and their affinities for the IEMs, respectively.

Chromium speciation by spectrophotometric determination of hexavalent chromium (Cr(VI)) with diphenylcarbazide (DPC) has several problems. These include: (1) the inability to directly detect trivalent chromium (Cr(III)) with DPC, (2) positive interference in Cr(VI) determination by other metal cations and (3) negative interference by any reducing agent present in the sample. These are addressed with an ion transfer device (ITD) in a flow injection analysis system. We previously developed the ITD for electrodialytic separations. Here we separate oppositely charged Cr(III) and Cr(VI) species by the ITD into two different acceptor solutions within ~5 s. The acceptor solutions consist of buffered H2O2 to oxidize the Cr(III) to Cr(VI). Then DPC is added to either acceptor to measure Cr(III) and Cr(VI) spectrophotometrically. The system was optimized to provide the same response for Cr(VI) and Cr(III) with limits of detection (LODs, S/N=3) of 0.5 μg L-1 for each and a throughput rate of 30 samples h-1. The ITD separation was also effective for matrix isolation and reduction of interferences. Potential cationic interferences were not transferred into the anionic Cr(VI) acceptor stream. Much of the organic compounds in soil extracts were also eliminated as evidenced from standard addition and recovery studies.

We report a fully automated online sample pretreatment system for ionic analytes that extracts the ionic analytes from the sample and largely removes the nonionic sample matrix and can preconcentrate the analyte. Sample pretreatment is a key analytical process; conventional pretreatment is conducted in a difficult to automate batchwise manner. The present system relies on the transport of ions induced by an electric field to a water acceptor. Cations and anions are simultaneously and separately collected into individual acceptor streams which can be directly introduced to a chemical analyzer. Common inorganic ions (≤10 meq/L) are quantitatively transferred from samples within a few seconds. Small nonionic molecules are transferred by 0.5-10%, and proteins are not transferred at all. The method has been successfully applied to drinking water, urine, and cow's milk with 3.7 ± 2.5, 3.8 ± 2.6, and 4.6 ± 2.6%, respectively, in variance (n = 10). Present results agreed well with those from conventional pretreatment methods. Interestingly, when calcium in milk is measured by the present method, the results correspond to the total calcium by conventional methods; i.e., it can extract calcium from its protein-bound form in milk.

A micro-gas analysis system (μGAS) was developed for mobile monitoring and continuous measurements of atmospheric HCHO. HCHO gas was trapped into an absorbing/reaction solution continuously using a microchannel scrubber in which the microchannels were patterned in a honeycomb structure to form a wide absorbing area with a thin absorbing solution layer. Fluorescence was monitored after reaction of the collected HCHO with 2,4-pentanedione (PD) in the presence of acetic acid/ammonium acetate. The system was portable, battery-driven, highly sensitive (limit of detection = 0.01 ppbv) and had good time resolution (response time 50 s). The results revealed that the PD chemistry was subject to interference from O(3). The mechanism of this interference was investigated and the problem was addressed by incorporating a wet denuder. Mobile monitoring was performed along traffic roads, and elevated HCHO levels in a street canyon were evident upon mapping of the obtained data. The system was also applied to stationary monitoring in a forest in which HCHO formed naturally via reaction of biogenic compounds with oxidants. Concentrations of a few ppbv-HCHO and several-tens of ppbv of O(3) were then simultaneously monitored with the μGAS in forest air monitoring campaigns. The obtained 1 h average data were compared with those obtained by 1 h impinger collection and offsite GC-MS analysis after derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA). From the obtained data in the forest, daily variations of chemical HCHO production and loss are discussed.