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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.

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.

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

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).

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

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.

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.

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.

A simple, sensitive optical analyzer for the rapid determination of cyanide in blood in point of care applications is described. HCN is liberated by the addition of 20% H3PO4and is absorbed by a paper filter impregnated with borate-buffered (pH 9.0) hydroxoaquocobinamide (hereinafter called cobinamide). Cobinamide on the filter changes color from orange (λmax= 510 nm) to violet (λmax= 583 nm) upon reaction with cyanide. This color change is monitored in the transmission mode by a light emitting diode (LED) with a 583 nm emission maximum and a photodiode detector. The observed rate of color change increases 10 times when the cobinamide solution for filter impregnation is prepared in borate-buffer rather than in water. The use of a second LED emitting at 653 nm and alternate pulsing of the LEDs improves the limit of detection by 4 times to ∼0.5 μM for a 1 mL blood sample. Blood cyanide levels of imminent concern (≥10 μM) can be accurately measured in ∼2 min. The response is proportional to the mass of cyanide in the sample: smaller sample volumes can be successfully used with proportionate change in the concentration LODs. Bubbling air through the blood-acid mixture was found effective for mixing of the acid with the sample and the liberation of HCN. A small amount of ethanol added to the top of the blood was found to be the most effective means to prevent frothing during aeration. The relative standard deviation (RSD) for repetitive determination of blood samples containing 9 μM CN was 1.09% (n = 5). The technique was compared blind with a standard microdiffusion-spectrophotometric method used for the determination of cyanide in rabbit blood. The results showed good correlation (slope 1.05, r20.9257); independent calibration standards were used. © 2011 American Chemical Society.

本研究では，簡易でかつ時間分解能の比較的高いイソプレンの分析装置を開発し，森林大気のオンサイト分析に応用した．測定では4分間の大気サンプリングに続いて，加熱脱着によって化学発光セルに導入した．本装置によりppbvレベルのイソプレンを10分ごとに測定することが可能になり，検出限界は0.15 ppbvであった．植物をチャンバー内に設置したラボ実験では，チャンバー内イソプレン濃度は光照射とともに増大し消灯とともに減少した．この結果は加熱脱着－ガスクロマトグラフ－質量分析による結果とよい一致を示した．森林内測定においては有意な日内変化がみられ，日中イソプレン濃度が増大し夜間はほとんど見られなかった．これに対し同じ植物起源のα-ピネンは夜間濃度のほうが高く，α-ピネン放出の常時性と日中の高い分解速度に起因していると考えられる．このほかホルムアルデヒド，オゾン，窒素酸化物，有機・無機酸についても測定を行い，日内変化の追跡や季節変動の考察を行った．また，発生・消失のモデル構築を行い，日内変動よりイソプレンやα-ピネンの森林内発生のシミュレーションを行った．さらに実大気におけるイソプレンの発生とオゾン増幅の関係について考察を行った．

An open channel scrubber is proposed as a miniature fieldable gas collector. The device is 100mm in length, 26 mm in width and 22 mm in thickness. The channel bottom is rendered hydrophilic and liquid flows as a thin layer on the bottom. Air sample flows atop the appropriately chosen flowing liquid film and analyte molecules are absorbed into the liquid. There is no membrane at the air-liquid interface: they contact directly each other. Analyte species collected over a 10 min interval are determined by fluorometric flow analysis or ion chromatography. A calculation algorithm was developed to estimate the collection efficiency a priori; experimental and simulated results agreed well. The characteristics of the open channel scrubber are discussed in this paper from both theoretical and experimental points of view. In addition to superior collection efficiencies at relatively high sample air flow rates, this geometry is particularly attractive that there is no change in collection performance due to membrane fouling. We demonstrate field use for analysis of ambient SO(2) near an active volcano. This is basic investigation of membraneless miniature scrubber and is expected to lead development of an excellent micro-gas analysis system integrated with a detector for continuous measurements.

An automated atmospheric elemental mercury analyzer based on the dielectric barrier discharge (DBD) atomic emission technique was developed. The instrument is based on a gold-on tungsten coiled filament preconcentrator fashioned from commercial quartz-halogen lamps, a DBD excitation source and a radiation detector. An in-house program provided system control and data collection. Several types of radiation detectors, e.g., charge coupled device (CCD) array spectrometers, photomultiplier tubes (PMTs) and phototube (PT) are investigated. An argon plasma provided better performance than a nitrogen plasma. With ∼0.88 standard liters per min sampling rate and preconcentration for 2 min, the estimated (S/N = 3) detection limit was 0.12 ng/L (Hg0), the linear range extended at least to 6.6 ng Hg/L. Typical RSD values for determination at the single digit ng/L level ranged from 2.8 to 4.9%. In 19 separate calibrations conducted over 7 days, the calibration slope had a standard error of 1%. The system was applied to the determination of atmospheric mercury in two different locations.

We describe matrix-isolated, reaction chemistry based measurement of arsenic in water down to submicrograms per liter levels in a system that requires only air, water, electricity, and dilute sulfuric acid, the bulk of the latter being recycled. Gas phase chemiluminescence (GPCL) measurement of arsenic is made in an automated batch system with arsenic in situ electroreduced to arsine that is reacted with ozone to emit light. The ozone is generated from oxygen that is simultaneously anodically produced. Of 22 different electrode materials studied, graphite was chosen as the cathode. As(V) is reduced much less efficiently to AsH(3) than As(III). Prereducing all As to As(III) is difficult in the field and tedious. Oxidizing all As to As(V) is simple (e.g., with NaOCl) but greatly reduces subsequent conversion to AsH(3) and hence sensitivity. The rate of the AsH(3)-O(3) GPCL reaction and hence signal intensity increases with [O(3)]. Using oxygen to feed the ozonizer produces higher [O(3)] and substantial signal enhancement. This makes it practical to measure all arsenic as As(V). The system exhibits an LOD (S/N = 3) for total arsenic as As(V) of 0.36 microg/L (5 mL sample). Comparison of total As results in native and spiked water samples with those from inductively coupled plasma mass spectrometry (ICPMS) and other techniques show high correlation (r(2) = 0.9999) and near unity slopes.

An inexpensive sensitive gas-phase chemiluminescence (GPCL) based analyzer for arsenic is described; this device utilizes manual fluid dispensing operations to reduce size, weight and cost. The analyzer in its present form has a limit of detection (LOD, S/N = 3) of 1.0 microg/L total inorganic As (peak heightbased, 3 mL sample). The system was used to measure low level arsenic in tap water samples from Texas and New Mexico and compared with results obtained by inductively coupled plasma-mass spectrometry (ICP-MS) as well as those from an automated GPCL analyzer. Good correlations were observed. Higher levels of As (50-500 microg/L, As(III), As(V) and mixtures thereof) were spiked into local tap water; the recoveries ranged from 95 +/- 2% to 101 +/- 1%. A single instrument weighs less than 3 kg, consumes25 W in power, can be incorporated in a briefcase and constructed for$US $1000. It is easily usable in the field.

We describe a novel optical sensor for the simultaneous measurement of atmospheric nitrogen dioxide (NO(2)), ozone (O(3)), and relative humidity (RH). A transparent backing thin layer silica gel chromatographic plate impregnated with 8-amino-1-naphthol-5-sulfonic acid (ANS) is used as the collection/sensor element. The plate transmittance is probed by three discrete light emitting diodes (LEDs) centered, respectively, at 442, 525, and 850 nm. The transmission of the plate changes reversibly across visible to NIR wavelengths as the RH around the plate changes; this is the basis for a limited-resolution RH sensor. The ANS on the plate reacts to form brown and pink colored products, respectively, when it reacts with NO(2) and O(3). The sample air impinges on the plate via an entrance nozzle. The LEDs are alternately turned on in a preprogrammed manner and the light is brought to the impregnated face of the plate by a three-legged fiber optic. The transmitted light is detected on the obverse side of the plate. The 850 nm signal provides the RH value and optionally serves as the reference measurement for the other two wavelengths; the NO(2) and O(3) reaction products do not absorb at this wavelength. The absorbance at 442 and 525 nm, thus referenced against 850 nm, are used to obtain NO(2) and O(3) concentrations from a pair of simultaneous equations. For a sampling period of 5 min, the limits of detection (LOD) based on 3 times the standard deviation of blank responses were 0.64 and 0.42 ppbv for NO(2) and O(3), respectively. Data obtained with collocated commercial instruments (O(3) induced chemiluminescence analyzer for NO(2) and UV-absorption for O(3)) show good agreement. Overall, this provides a viable affordable approach for inexpensive measurement of atmospheric NO(2) and O(3).

Calixarenes are interesting building blocks in supramolecular receptor design. They can be easily functionalized to give the desired guest binding and sequestration properties. We demonstrate here the use of simple alkylated calixarenes as novel NO(2) sensors. Upon reacting with gaseous NO(2), alkylated calixarenes form stable calixarene-NO(+) (nitrosonium) complexes that have a deep purple color. This specific and selective formation of the colored complex was used to develop a fiber optic based colorimetric NO(2) sensor. Several alkylated calixarenes are used and tested as sensing materials. The calixarene compound was immobilized on a fine mesh silica-gel coated thin layer chromatography plate. The sensing plate was coupled with a fiber optic based photodetector. Gas samples were sampled in a manner where they impinged on the surface of sensing plate. The light transmission through the plate was continuously monitored. For a 5 min sample, the limit of detection was 0.54 ppmv with 1,3-alternate O-hexyl calix[4]arene (1a). There were no significant response differences between different conformations of calixarenes such as 1,3-alternate or cone. This chemistry can form the basis of a colorimetric sensor that relies on extant filter tape technology. With calixarenes however, such a reaction is potentially reversible - color formed upon reaction with NO(2) can be reversed by flushing the sensing plate by purified air. While we found that the removal of the developed color can be accelerated by simultaneous heating and suction, permitting the reuse of the same sensing area multiple times, we also observed that the sensitivity gradually decreased. The nitrosonium calixarene derivative tends to transform to the nitrated form; this process is catalyzed by light. Several methylated calixarenes were synthesized and tested but a fully satisfactory solution has proven elusive.

A versatile, simple, liquid core waveguide (LCW)-based fluorescence detector design is described for capillary systems. A Teflon AF coated fused silica capillary serves as the LCW. The LCW is transversely excited. The light source can be a conventional or high power (HP) light emitting diode (LED) or a laser diode (LD). The source can be coupled to the LCW directly or via an optical fiber. Fiber coupling is convenient if a high power (necessarily heat sink mounted) emitter is used. The LCW is concentrically placed within a slightly larger opaque jacket tube and the LCW terminates just short of the jacket terminus, which is sealed with an optical window. The influent liquid thus exits the LCW tip, flows back around the LCW through the jacket annulus to exit via an aperture on the jacket tube. The problem of coupling the emitted light efficiently to the photodetector is thus solved by placing the tip of the annular tubular assembly directly on the detector. For excitation wavelengths of 365 nm (LED/HPLED) and 405 nm (LD), the tris(8-hydroxyquinoline-5-sulfonic acid (sulfoxine)) chelate of aluminum (λem,max ∼ 500 nm) and Coumarin 30 were respectively used as the model analyte. For source–detector combinations comprising (a) a UV LED (∼1.5 mW @ 15 mA) and a photodiode, (b) a LD (∼5 mW, abstracted from a “Blu-Ray” recorder) and a miniature photomultiplier tube (mPMT), and (c) a high power (210 mW @ 500 mA) surface-mount HPLED–mPMT, the S/N = 3 LODs were, respectively, 1.7 pmol Al, 3–100 fmol Coumarin 30 (depending on laser intensity and integration time), and 4 fmol Al. In the last case, the relative standard derivation (R.S.D.) at the 20 fmol level was 1.5% (n = 10).

A gas phase chemiluminescence (GPCL)-based method for trace measurement of arsenic has been recently described for the measurement of arsenic in water. The principle is based on the reduction of inorganic As to AsH(3) at a controlled pH (the choice of pH governs whether only As(III) or all inorganic As is converted) and the reaction of AsH(3) with O(3) to produce chemiluminescence (Idowu et al., Anal. Chem. 78 (2006) 7088-7097). The same general principle has also been used in postcolumn reaction detection of As, where As species are separated chromatographically, then converted into inorganic As by passing through a UV photochemical reactor followed by AsH(3) generation and CL reaction with ozone (Idowu and Dasgupta, Anal. Chem. 79 (2007) 9197-9204). In the present paper we describe the measurement of As in different soil and dust samples by serial extraction with water, citric acid, sulfuric acid and nitric acid. We also compare parallel measurements for total As by induction coupled plasma mass spectrometry (ICP-MS). As(V) was the only species found in our samples. Because of chloride interference of isobaric ArCl(+) ICP-MS analyses could only be carried out by standard addition; these results were highly correlated with direct GPCL and LC-GPCL results (r(2)=0.9935 and 1.0000, respectively). The limit of detection (LOD) in the extracts was 0.36 microg/L by direct GPCL compared to 0.1 microg/L by ICP-MS. In sulfuric acid-based extracts, the LC-GPCL method provided LODs inferior to those previously observed for water-based standards and were 2.6, 1.3, 6.7, and 6.4 microg/L for As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA), respectively.

In this review, novel microsystems and microdevices to measure gaseous species for environmental analysis and medical diagnostics are described. Miniaturization of analyzers makes field measurements affordable. As well, high sensitivity and good time resolution can be achieved by miniaturization. Some such devices have already been successfully applied to real environmental analyses. Mobile monitoring is available with the use of micro gas analyzers to investigate the natural environment, air pollution and to detect nerve or explosive gases released accidentally or through terrorist activities. Miniature devices are also attractive for medical analyses. Gases produced from the human body reflect gases contained in the blood and certain metabolic conditions. Noninvasive monitoring using miniature devices is available in hospitals and in a patient's home. Many investigations have been conducted using wet and dry chemistry methods for both applications. Instruments employing wet chemistries, which comprise liquid droplets, liquid film, miniature diffusion scrubbers, and microfluidic devices have been studied. Among the instruments using dry methods, miniature samplers, portable gas chromatographs, and microfabricated gas chromatographs have all been investigated. These instruments are expected to usher in a new era of environmental monitoring and will find uses in many medical applications.

This manuscript describes an easy, simple and small system for gas generation. The aim of this work was to establish gas generation for on-site checking or on-site calibration of a micro gas analysis system, microGAS. The new technology, microGAS, achieves real-time measurement of trace level gases in the field. To make the measurement more reliable and convenient, a small gas generation system has been developed. Source reagent solution and generator solution are made to flow by micropumps, mixed in a miniature coil, and then introduced into a microchannel gas desorber. The gas desorber is comprised of a honeycomb-shaped microchannel covered with a thin porous polytetrafluoroethylene membrane. A good generation factor is obtained due to the wide vaporization area and thin solution layer of the microchannel desorber. Generation of H(2)S, SO(2), CH(3)SH and NH(3) gases were examined. Concentrations of the gases are easily controlled by the source reagent concentration and the solution flow rates. At 100 microL min(-1) flow rates for both the source and generator solutions, 30 ppbv to 2 ppmv concentrations are formed with a gas flow rate of 200 mL min(-1). The gas concentration is proportional to the source concentration. The gas generation can be performed only when needed. The gas generation system is combined with microGAS for on-site calibration.

Sequential injection analysis (SIA) was applied to multi-gas monitoring for atmospheric analysis. HONO, NO(2) or NO was collected in an individual diffusion scrubber in which the channel array was filled with either HCl or triethanolamine solution. All analytes were collected in the form of nitrite ions in the scrubber, and were transferred via a 12-port selection valve into a 2.5-ml syringe. The reagent, 3-amino-1,5-naphthalenedisulfonic acid (C-acid) solution was subsequently introduced into the syringe, and inter-mixed with the nitrite sample, whereafter the mixed solution was transferred to a heated reactor and held for 3min at 100 degrees C. After that, the sample/reagent solution was returned to the syringe and alkalinized. Then, the final solution was analyzed using a homemade fluorescence detector. Atmospheric HONO, NO(2) and NO were successfully monitored 3 or 4times/h. The limits of detection were 0.22, 0.28 and 0.35ppbv for HONO, NO(2) and NO, respectively. It was demonstrated for the first time that SIA is a good tool for multi-gas atmospheric analysis. These nitrogen-oxygen compounds are interconvertible, and the simultaneous measurement of these gases is important. Especially, HONO is a source of OH radicals which contribute greatly to atmospheric pollution, and indeed atmospheric chemistry. This method allows the three gases to be measured using one system. The NO(2) and NO data obtained by SIA was compared with those obtained using chemiluminescence instrument. SIA has been successfully applied to atmospheric measurements. Interestingly, it was observed that HONO levels rose toward the end of periods of rain.

Selective separation and sensitive detection of dissolved silicon and boron (DSi and DB) in aqueous solution was achieved by combining an electrodialytic ion isolation device (EID) as a salt remover, an ion-exclusion chromatography (IEC) column, and a corona charged aerosol detector (CCAD) in sequence. DSi and DB were separated by IEC on the H(+)-form of a cation exchange resin column using pure water eluent. DSi and DB were detected after IEC separation by the CCAD with much greater sensitivity than by conductimetric detection. The five-channel EID, which consisted of anion and cation acceptors, cathode and anode isolators, and a sample channel, removed salt from the sample prior to the IEC-CCAD. DSi and DB were scarcely attracted to the anion accepter in the EID and passed almost quantitatively through the sample channel. Thus, the coupled EID-IEC-CCAD device can isolate DSi and DB from artificial seawater and hot spring water by efficiently removing high concentrations of Cl(-) and SO4(2-) (e.g., 98% and 80% at 0.10molL(-1) each, respectively). The detection limits at a signal-to-noise ratio of 3 were 0.52μmolL(-1) for DSi and 7.1μmolL(-1) for DB. The relative standard deviations (RSD, n=5) of peak areas were 0.12% for DSi and 4.3% for DB.

A micro ion extractor (MIE) was developed for trace anion determination by ion chromatography-mass spectrometry from a single drop (25 μL) of whole blood without pretreatment. Target analytes were iodide and thiocyanate, which play key roles in thyroid hormone production. Whole blood (25 μL) was pipetted from an earlobe or finger prick and placed in the 16 μL cavity of the device. A reproducible fraction of iodide and thiocyanate was transferred through a membrane to an acceptor solution layer by electromigration for 60 s. An isolator solution layer and a cation exchange membrane is provided between the acceptor and the anode to prevent gas formation or redox processes in the acceptor. The acceptor contents are transferred online to the ion chromatograph. Isolator solution composition and applied voltage were optimized. Recoveries from samples from 16 different volunteers of both sexes and differing ages were the same within ±10% relative standard deviation. Dietary effects on blood iodide and thiocyanate levels are reported. The very low sample requirement permitted multiple sample collections per day. The MIE device is expected to be useful for clinical studies that require several/many temporally spaced blood samples by keeping the invasive nature of blood collection as minimal as possible.

Industrial gases such as nitrogen, oxygen, argon, and helium are easily contaminated with water during production, transfer and use, because there is a high volume fraction of water in the atmosphere (approximately 1.2% estimated with the average annual atmospheric temperature and relative humidity). Even trace water (

Simultaneous analysis of HCHO and O3 was performed by the developed flow analysis system to prove that HCHO vapor is produced from solid pesticide in the presence of O3. HCHO is produced in many ways, including as primary emissions from fuel combustion and in secondary production from anthropogenic and biogenic volatile organic compounds by photochemical reactions. In this work, HCHO production from pesticides was investigated for the first time. Commonly pesticide contains surfactant such as hexamethylenetetramine (HMT), which is a heterocyclic compound formed from six molecules of HCHO and four molecules of NH3. HMT can react with gaseous oxidants such as ozone (O3) to produce HCHO. In the present study, a flow analysis system was developed for simultaneous analysis of HCHO and O3, and this system was used to determine if solid pesticides produced HCHO vapor in the presence of O3. HMT or the pesticide jimandaisen, which contains mancozeb as the active ingradient and HMT as a stabilizer was placed at the bottom of a 20-L stainless steel chamber. Air in the chamber was monitored using the developed flow system. Analyte gases were collected into an absorbing solution by a honeycomb-patterned microchannel scrubber that was previously developed for a micro gas analysis system (μGAS). Subsequently, indigotrisulfonate, a blue dye, was added to the absorbing solution to detect O3, which discolored the solution. HCHO was detected after mixing with the Hantzsch reaction reagent. Both gases could be detected at concentrations ranging from parts per billion by volume (ppbv) to 1000 ppbv with good linearity. Both HMT and jimandaisen emitted large amount of HCHO in the presence of O3.