Indirect Potentiometric pH Detection of Weak Acids with Absolute Quantitation by a Theoretical Approach.

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.

Rapid Flow-Based System for Separation of Radioactive Metals by Selective Complex Formation.

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-N,N,N',N'-tetraacetic acid (EDTA) was selected as the ligand after simulation of the separation of radioactive Ga from the target (Zn). Selectively, the Ga-EDTA complex passed through the cation trap, while Zn2+ was trapped. This separation principle is opposite to that of typical solid-phase extraction, which captures the target ion. The proposed separation was performed in a flow-based system with a parallel, open-channel ion trap. The performance was optimized by altering the channel dimensions, channel-filling mesh, and flow rate. Finally, the target radioactive metal, Ga, was selectively and effectively (>99%) separated from a mixture of 50 fg Ga/L and 100 mg Zn/L. The concentration of Zn remaining in the Ga solution was 2.3 µg/L. The complexed Ga was converted to free Ga3+ by a simple UV irradiation method. The proposed method effectively and rapidly separates trace amounts of radioactive metals contained in larger amounts of target metals using a simple flow system that can be operated on site.

Electrodialytic Handling of Radioactive Metal Ions for Preparation of Tracer Reagents.

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, 64Cu2+, with high recovery from HCl matrices to HNO3 (∼100%). Matrices can also be transferred into acetic acid and citric acid, even though the concentration of the metal ion is at the picomolar level. The ion transfer can also be achieved with simultaneous counter ion conversion, complex synthesis, and enrichment. When the ligand was dissolved in an acceptor solution, the transferred metal ions from the donor were well mixed and formed a complex with the ligand in-line. The efficiency of the synthesis was ∼100% for 1.0 pM 64Cu. A relatively larger donor-to-acceptor flow rate can enrich the metal ion in the acceptor solution continuously. The flow rate ratio of 10 (donor/acceptor) can achieve 10 times enrichment. The present electrodialytic ion handling method can treat ultra-trace radioisotopes in a closed system. With this method, rapid, effective, and safe radioisotope treatments were achieved.

High Sensitivity Monitoring Device for Onboard Measurement of Dimethyl Sulfide and Dimethylsulfoniopropionate in Seawater and an Oceanic Atmosphere.

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.

Universal HPLC Detector for Hydrophilic Organic Compounds by Means of Total Organic Carbon Detection.

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 compounds. The universality and quantification were evaluated with organic compounds, including organic acids, sugars, and amino acids. Furthermore, the system was successfully applied to evaluation of the purity of formaldehyde in formalin solution, and determination of sugars in juices. The results show the universal carbon detector has good universality and can quantify many kinds of organic compounds with a single standard such as sodium bicarbonate.

Simultaneous Electrodialytic Preconcentration and Speciation of Chromium(III) and Chromium(VI).

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.

Micro Ion Extractor for Single Drop Whole Blood Analysis.

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.

Formaldehyde content of atmospheric aerosol.

Formaldehyde (HCHO) is a highly soluble polar molecule with a large sticking coefficient and thus likely exists in both gaseous and particulate forms. Few studies, however, address particulate HCHO (HCHO(p)). Some report that HCHO(p) concentrations (obtained only with long duration sampling) are very low. The lack of data partly reflects the difficulty of specifically measuring HCHO(p). Long duration filter sampling may not produce meaningful results for a variety of reasons. In this work, gaseous HCHO (HCHO(g)) and (HCHO(p)) were, respectively, collected with a parallel plate wet denuder (PPWD) followed by a mist chamber/hydrophilic filter particle collector (PC). The PPWD quantitatively removed HCHO(g) and the PC then collected the transmitted aerosol. The collected HCHO from either device was alternately analyzed by Hantzsch reaction-based continuous flow fluorometry. Each gas and particle phase measurement took 5 min each, with a 10 min cycle. The limits of detection were 0.048 and 0.0033 µg m(-3), respectively, for HCHO(g) and HCHO(p). The instrument was deployed in three separate campaigns in a forest station in western Japan in March, May, and July of 2013. Based on 1296 data pairs, HCHO(p), was on the average, 5% of the total HCHO. Strong diurnal patterns were observed, with the HCHO(p) fraction peaking in the morning. The relative humidity dependence of the partition strongly suggests that it is driven by the liquid water content of the aerosol phase. However, HCHO(p) was 100× greater than that expected from Henry's law. We propose that the low water activity in the highly saline droplets lead to HCHO oligomerization.

Measurement of atmospheric amines and aminoamides by column adsorption/extraction and hydrophilic liquid chromatography-electrospray-tandem mass spectrometry.

Sampling and chromatography-mass spectrometry methods were investigated to measure atmospheric amines and aminoamides. Amines and their amide derivatives play significant roles in new particle formation (NPF) in the atmosphere, especially diamines and aminoamides have higher NPF potentials compared to monoamines. For amine sampling, silica gel tube collection and formic acid extraction gave good overall recoveries (>93 ± 8%) for mono-, di-, tri-, tetramines, and aminoamides. Two chromatography methods were subjected to analyze the extracted amines. One involved direct analysis using hydrophilic interaction liquid chromatography with carboxyl or diol group functioned separation column (carboxyl-HILIC or diol-HILIC), and the other utilized derivatization with 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (DBD-F) and subsequent reversed-phase chromatography (HPLC). Separated amines were detected by electrospray ionization and tandem mass spectrometry in both cases. DBD-F-HPLC method provided good sensitivity for mono- and all polyamines (limit of detection (LOD) < 4.6 nM, relative standard deviation (RSD) for 100 nM < 9.2%). However, aminoamides could not be detected by DBD-F-HPLC. Carboxyl-HILIC provided good sensitivities for mono- and diamines and aminoamides (LOD < 1.6 nM, RSD < 4.8%). Forest air measurement was performed and data obtained by carboxyl-HILIC and DBD-F-HPLC showed good agreement for 1,3-diaminopropane, 1,4-diaminobutane (putrescine) and 1,5-diaminopentane (cadaverine) (R2 = 0.9215-0.9739, n = 7-14). Carboxyl-HILIC method was the best for the amine analysis, and combination with silica gel tube sampling provides atmospheric monitoring available. The developed method can be used not only to study atmospheric chemistry of diamines and aminoamides but also to analyze flavor/odor of foods, flowers and wastes.

Two-step extraction for the evaluation of metal-organic framework impregnated materials.

Metal-organic frameworks (MOFs) are widely used for gas adsorption, separation, and sensing materials. In most cases, MOFs are not used in their crystal form but as impregnated materials because the fine crystals result in high-pressure drops. One key characteristic of MOF-impregnated materials is the amount of MOF in the material. This is evaluated using the wet digestion method; however, it is limited to determining only the metal content. Moreover, some metal, denoted as free metal, will not react with ligands to form MOFs. Additionally, it is crucial to determine the ligand amount, which cannot be determined using wet digestion. In the present study, a two-step extraction method for copper (II) benzene-1,3,5-tricarboxylate (Cu-BTC MOF) impregnated materials was developed to determine the MOF formed and free metals and ligands. Various solvents were applied to evaluate the extraction efficiencies. The results led to the selection of ethanol (EtOH) for extracting free Cu2+ and BTC, while 0.3 M HNO3 was chosen to extract MOF-formed Cu2+ and BTC. The MOF-impregnated sample material was first extracted using EtOH and then 0.3 M HNO3. The Cu2+ and BTC in the obtained extract solutions, as well as EtOH and HNO3, were analyzed using flame atomic absorption spectroscopy and high-performance liquid chromatography, respectively. In standard addition tests, free and MOF-formed Cu2+ and BTC were quantitatively extracted from MOF-impregnated materials. The developed two-step analysis method was successfully applied to Cu-BTC-impregnated materials used in gas sensing.

Simple field device for measurement of dimethyl sulfide and dimethylsulfoniopropionate in natural waters, based on vapor generation and chemiluminescence detection.

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.

Abundant production of dimethylsulfoniopropionate as a cryoprotectant by freshwater phytoplanktonic dinoflagellates in ice-covered Lake Baikal.

Phytoplanktonic dinoflagellates form colonies between vertical ice crystals during the ice-melting season in Lake Baikal, but how the plankton survive the freezing conditions is not known. Here we show that the phytoplankton produces large amounts of dimethylsulfoniopropionate (DMSP), which is best-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 of surface water correlates with plankton density and reaches a maximum in mid-April, with 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 freshwater plankton, Gymnodinium baicalense, has 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 clearly indicate that DMSP plays a cryoprotective role. DMSP, although a characteristic marine compound, could also be an important zwitterion for algae of other boreal lakes, alpine snow, and glaciers.

Radioactive isotope separation with 3D-printed flow-based device.

Radioactive isotope (RI) metals are a new type of tracer for positron emission tomography generated from the target metal by proton irradiation using a cyclotron. The generated metal RIs need to be separated from the target metal rapidly and effectively. In the present study, we developed a 3D-printed flow device to separate metal RIs from target metals. The separation was performed with selective formation of ethylenediaminetetraacetic acid (EDTA) complex based on the difference in formation constants. The RI metal selectively formed a EDTA complex, thus changing its ionic charge in solution. The solution was then introduced into a cation exchange column for selective adsorption of the target metal. The solution with added chelator and controlled pH was introduced into the developed system and automatically separated metal RI from target metals within 14 min. The separation method was applied to separate RI 67Ga from target metal Zn using a mixture of 107 pg L-1 67Ga in 250 mg L-1 Zn2+. The recoveries of 67Ga and Zn were 97% and 100%, respectively. Furthermore, an ultraviolet (UV) radiation reactor was integrated into the system to decompose the EDTA complex and recover the Ga3+ ion. Ga3+ recovery by UV radiation was effective, 87%. The developed system was also successfully applied to the separation of Zr and Y. Therefore, the method and system can be applied to separate other metal RIs from target metals.

A capacitance sensor for water: trace moisture measurement in gases and organic solvents.

The determination of water in various matrices is one of the most important analytical measurements. We report on a high-resolution capacitance-based moisture sensor utilizing a thin film of a perfluorosulfonate ionomer (PFSI)-H(3)PO(4) composite in a flow-through configuration, for both gas and liquid samples. Incorporation of H(3)PO(4) into a PFSI sensing film improved the limit of detection (LOD) (signal-to-noise ratio, S/N = 3) by a factor of 16 in the gas phase to 0.075% relative humidity (RH) (dew point = -56 °C). The response time was dependent on the sensing film thickness and composition and was as low as ∼60 ms. The temperature dependence of the sensor response, and its relative selectivity over alcohol and various other solvents, are reported. Measurement of water in organic solvents was carried out in two different ways. In one procedure, the sample was vaporized and swept into the detector (e.g., in a gas chromatograph (GC) without a column); it permitted a throughput of 80 samples/h. This is well-suited for higher (%) levels of water. In the other method, a flow injection analysis system integrated to a tubular dialysis membrane pervaporizer (PV-FIA) was used; the LOD for water in ethanol was 0.019% (w/w). We demonstrated the temporal course of drying of ethanol by Drierite; the PV-FIA results showed excellent correspondence (r(2) > 0.99) with results from GC-thermal conductivity detection. The system can measure trace water in many types of organic solvents; no reagent consumption is involved.

Electrodialytic ion isolation for matrix removal.

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.

Mobile monitoring along a street canyon and stationary forest air monitoring of formaldehyde by means of a micro-gas analysis system.

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.

Electrodialytic Universal Synthesis of Highly Pure and Mixed Ionic Liquids.

Ionic liquids (ILs) have attracted significant attention from researchers in various fields as a result of their unique properties. As new and important applications are identified for these materials, there is also a drive to develop methods for accessing a wider range of ILs. However, despite this demand, only a few techniques have so far been reported and, more importantly, general but efficient processes for IL synthesis have been lacking. Thus, it would be beneficial to devise a cost-effective, environmentally friendly means of producing a wide variety of pure ILs. The present work demonstrates a general purpose electrodialysis approach to the formation of highly pure ILs, based on the formation of nine different ILs from various combinations of cations and anions. In each case, the IL is obtained with a purity of greater than 99%. This method offers the advantages of avoiding the use of hazardous organic solvents and eliminating tedious and costly purification processes. Unlike conventional methods, this membrane-based technology also prevents the generation of side products. Mixed ILs have many potential applications, and the present technique readily generates various mixed ILs based on a simple adjustment of the applied current.

Electrodialytic Enrichment and Matrix Conversion for the Determination of Trace Metals in Ultra-Pure Water.

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.

Highly Efficient Separation of Ultratrace Radioactive Copper Using a Flow Electrolysis Cell.

Preparing compounds containing the radioisotope 64Cu for use in positron emission tomography cancer diagnostics is an ongoing area of research. In this study, a highly efficient separation method to recover 64Cu generated by irradiating the target 64Ni with a proton beam was developed by employing a flow electrolysis cell (FE). This system consists of (1) applying a reduction potential for the selective adsorption of 64Cu from the target solution when dissolved in HCl and (2) recovering the 64Cu deposited onto the carbon working electrode by desorbing it from the FE during elution with 10 mmol/L HNO3, which applies an oxidation potential. The 64Cu was selectively eluted at approximately 30 min under a flow rate of 0.5 mL/min from the injection to recovery. The newly developed flow electrolysis system can separate the femtomolar level of ultratrace radioisotopes from the larger amount of target metals as an alternative to conventional column chromatography.

On-site measurement of trace-level sulfide in natural waters by vapor generation and microchannel collection.

Aqueous sulfide plays an important role in the environment even at low concentrations. However, it is unstable, which means field samples cannot be transported to the laboratory for analysis without fixation. In this work, a novel method was developed to determine trace levels of sulfide on site. This method is based on vapor generation and collection in a special microchannel device followed by fluorescence measurement (VG-µGAS). The microchannel scrubber gave a high enrichment factor, and a high sensitivity was achieved, which allowed measurement of nanomolar (nM) levels of sulfide. The theoretical approach to vapor generation for several compounds is discussed to evaluate the applicability of the method to these analytes, and compounds having a low Henry's law constant (<1 M atm(-1)) are suitable to measure by VG-µGAS. Under optimized conditions, concentrations of 1.0-100 nM of sulfide could be measured. The sulfide contents of hot spring, aquarium, pond, and seawater were successfully measured by this method. Nanomolar levels of sulfide could be measured on site without loss of analyte, and results were obtained instantly in the field, both of which are advantageous for effective field surveys. The method was also applied to field measurements of aqueous sulfide in the Ariake Sea and Lake Baikal.