A gas sensor was developed for arsine (AsH3) 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 AsH3 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 AsH3 sensitivity. However, rGO sensors combined with Au exhibited reversible conductivity enhancement with AsH3. The increase in conductivity probably occurred because the AsH3 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 AsH3. 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 NO2, but this is not expected to be present in air-quality-controlled clean rooms. AsH3 is one of the most toxic chemicals used in the semiconductor industry, and the Au/rGO-based AsH3 sensor is expected to have widespread applications.Download high-res image (118KB)Download full-size image

We developed a novel flow system for monitoring selenium in power plant wastewater.Sub-ppm selenium is detected by hydride generation and chemiluminescence detection.Arsenic is removed by selective vaporization before selenium hydride generation.Organic decomposition and reduction of selenate were performed in a hot reactor.Selenium can be determined automatically for a month without maintenance.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 (mg kg−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.

•Flow system for simultaneous analysis of formaldehyde and ozone was developed.•The two gases are both collected together in a single absorbing solution.•The system consumes small sample air and is advantageous for chamber experiment.•Gaseous formaldehyde is produced from hexamethylenetetramine.•Pesticide, Jimandisen, emits formaldehyde largely in the presence of ozone.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.

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 (DMSaq) and dimethylsulfoniopropionate (DMSP), a precursor to DMS in seawater, were monitored together sequentially with atmospheric dimethyl sulfide (DMSg). A shift from the equilibrium point between DMSaq and DMSg 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 DMSaq was vaporized for analysis by IMRMS. After that, DMSP was hydrolyzed to DMS and acrylic acid, and analyzed in the same manner as DMSaq. The vaporization behavior and hydrolysis of DMSP to DMS were investigated to optimize these conditions. Frequent (every 30 min) determination of the three components, DMSaq/DMSP (nanomolar) and DMSg (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.

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.

•An inexpensive and small system is developed for analysis of CH3SH in ambient air.•CH3SH is collected by a microchannel scrubber and reacted with DBD-F.•DBD-F reacts with CH3SH to produce fluorescence for fluorometric analysis.•With this method, CH3SH can be detected at the odor threshold.•CH3SH emitted from pulping and a piggery could be monitored continuously.The highly odorous compound methanethiol, CH3SH, is commonly produced in biodegradation of biomass and industrial processes, and is classed as 2000 times more odorous than NH3. However, there is no simple analytical method for detecting low parts-per-billion in volume ratio (ppbv) levels of CH3SH. In this study, a micro gas analysis system (μGAS) was developed for continuous or near real time measurement of CH3SH 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. CH3SH 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 CH3SH 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. CH3SH 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 CH3SH levels in near-real time in a stockyard and it was shown that the major odor component, CH3SH, presented and its concentration varied dynamically with time.

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.

The weak affinity of bare carbon based electrodes for biological molecules or charged species is a major drawback for their direct application in analytical electrochemistry. We observed that the surfaces of graphite rods and glassy carbon (GC) ring electrodes can be modified by oxygenated functional groups through controlled electrochemical oxidation in aqueous media. Study of their cyclic voltammetry, surface conductivity, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, infrared spectroscopy (IR) and powder X-ray diffraction (PXRD) spectroscopy confirmed the chemical change. In the electrodynamics study, the modified GC ring in a rotating ring-disk electrode (RRDE) assembly showed better electron transfer efficiency than the virgin electrode when evaluated using a Ru(bpy)32+/3+ couple. In comparison to the virgin electrode, the modified graphite rod exhibited better affinity toward polyvinylpyrrolidone protected reduced graphene oxide (PVP-rGO) attached to glucose oxidase enzymes (GOx), and showed the direct attachment of mediators to the oxygenated electrode surface. These observations imply that a small oxygenated layer on the carbon electrode surface can significantly increase its activity. The present evidence indicates the possibility for the oxygenous functionalization of carbon based electrodes for applications in areas like electrokinetics studies and biosensing, where strong analyte–electrode interactions are useful.

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 Cd2+ 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 (R2 = 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.

Underground fluids are important natural sources of drinking water, geothermal energy, and oil-based fuels. To facilitate the surveying of such underground fluids, a novel microchannel extraction device was investigated for in-line continuous analysis and flow injection analysis of sulfide levels in water and in oil. Of the four designs investigated, the honeycomb-patterned microchannel extraction (HMCE) device was found to offer the most effective liquid–liquid extraction. In the HMCE device, a thin silicone membrane was sandwiched between two polydimethylsiloxane plates in which honeycomb-patterned microchannels had been fabricated. The identical patterns on the two plates were accurately aligned. The extracted sulfide was detected by quenching monitoring of fluorescein mercuric acetate (FMA). The sulfide extraction efficiencies from water and oil samples of the HMCE device and of three other designs (two annular and one rectangular channel) were examined theoretically and experimentally. The best performance was obtained with the HMCE device because of its thin sample layer (small diffusion distance) and large interface area. Quantitative extraction from both water and oil could be obtained using the HMCE device. The estimated limit of detection for continuous monitoring was 0.05 μM, and sulfide concentrations in the range of 0.15–10 μM could be determined when the acceptor was 5 μM FMA alkaline solution. The method was applied to natural water analysis using flow injection mode, and the data agreed with those obtained using headspace gas chromatography-flame photometric detection. The analysis of hydrogen sulfide levels in prepared oil samples was also performed. The proposed device is expected to be used for real time survey of oil wells and groundwater wells.Graphical abstractHighlights► We have developed a membrane-based microchannel extraction (HMCE) device. ► Extraction efficiency was examined theoretically and experimentally for this device. ► Quantitative extraction can be performed with the HMCE device while partial extraction with other conventional membrane-based devices. ► The HMCE device was applied for the measurement of free sulfide or hydrogen sulfide contained in water and oil samples. ► The presented device is expected to be used for survey of underground fluid such as groundwater and oil in future.

In this work, a method for measuring polychlorinated biphenyls (PCBs) in contaminated solid waste was investigated. This waste includes paper that is used in electric transformers to insulate electric components. The PCBs in paper sample were extracted by supercritical fluid extraction and analyzed by gas chromatography-electron capture detection. The recoveries with this method (84–101%) were much higher than those with conventional water extraction (0.08–14%), and were comparable to those with conventional organic solvent extraction. Limit of detection was 0.0074 mg kg−1 and measurable up to 2.5 mg kg−1 for 0.5 g of paper sample. Data for real insulation paper by the proposed method agreed well with those by the conventional organic solvent extraction. Extraction from wood and concrete was also investigated and good performance was obtained as well as for paper samples. The supercritical fluid extraction is simpler, faster, and greener than conventional organic solvent extraction.Highlights► Insulation paper in transformers could be contaminated with PCBs. ► PCBs are extracted from solid waste by supercritical fluid extraction (SFE). ► PCB recovery with conventional water extraction is much lower than that with SFE. ► The results obtained with SFE and conventional solvent extraction are similar. ► SFE is simpler, faster, and uses less solvent than conventional solvent extraction.

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 O3. 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 O3 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.

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.

In this work, a new analytical method for gasifiable compounds based on sequential hydride generation flow injection analysis (SHGFIA) was applied to water analysis and leaching investigation. For water analysis, it was confirmed that 1 μg L−1 As(III) and As(V) were stable for a few days when EDTA was added in the sample waters. Dissolved As(III) and total arsenic (As(III) + As(V)) were converted to AsH3 in neutral and acidic medium, respectively, to transfer to a miniature gas scrubber (100 μL in absorber volume). The collected arsenic was successively measured by flow analysis based on molybdenum blue chemistry. With this system, changes in As(III) and As(V) concentrations of water placed with arsenic-contaminated-sediment was monitored in near real time. From these data, kinetic analyses were carried out and kinetic constant was obtained from plot of ln{(C∞ − C)/C∞} where C and C∞ were leached arsenic concentration and its final concentration, respectively. It was found that rate of As(III) leaching was much faster than that of As(V) while As(V) leached more in amount compared to As(III). In this work, it was demonstrated that kinetic investigation is also one of the important application of flow analysis. The SHGFIA system showed excellent performance for leaching analysis of arsenic with discrimination of As(III) and As(V).

An open channel scrubber is proposed as a miniature fieldable gas collector. The device is 100 mm 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 SO2 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.

A novel method is proposed to measure NO in breath. Breath NO is a useful diagnostic measure for asthma patients. Due to the low water solubility of NO, existing wet chemical NO measurements are conducted on NO2 after removal of pre-existing NO2 and conversion of NO to NO2. In contrast, this study utilizes direct measurement of NO by wet chemistry. Gaseous NO was collected into an aqueous phase by a honeycomb-patterned microchannel scrubber and reacted with diaminofluorescein-2 (DAF-2). Fluorescence of the product was measured using a miniature detector, comprising a blue light-emitting diode (LED) and a photodiode. The response intensity was found to dramatically increase following addition of NO2 into the absorbing solution or air sample. By optimizing the conditions, the sensitivity obtained was sufficient to measure parts per billion by volume levels of NO continuously. The system was applied to real analysis of NO in breath, and the effect of coexisting compounds was investigated. The proposed system could successfully measure breath NO.

Here, a simple new method is proposed to evaluate water for the presence of pesticides. Specifically, pesticides for golf link maintenance were used as the targets for this investigation. Water samples containing the pesticides were mixed with particulate adsorbent, after which the pesticides were extracted from the adsorbents using supercritical fluid carbon dioxide and then analyzed by gas chromatography–mass spectrometry. The recoveries of pesticides were examined with several types of adsorbents and found to be related to their octanol/water partition coefficients (Kow) for most of the adsorbents. Good recoveries were obtained when the water samples were mixed with octadecylsilane (ODS) and stylene-divinylbenzene copolymer (XAD) resins for 15 and 30 min, respectively. In the supercritical fluid extraction, extraction pressure affected the efficiency of extraction from XAD while a little effect on extraction from ODS, probably due to the internal structure of the adsorbents. The limit of detection ranged from 0.002 to 2.3 μg L−1 and the method is suitable for the measurement of golf link pesticides in μg L−1 order to 100 μg L−1. The procedure of the proposed method was simpler than the conventional solid-phase extraction method. Finally, the method presented here was used to identify pesticides present in actual wastewater from golf links.

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.

In this paper, novel microsystems for gas analysis and gas generation are described. The same microchannel devices covered with a gas permeable membrane were used for both the gas collection and the gas generation. For the first time, a dual liquid flow system was utilized in a micro-gas analysis system. Even though micropumps are utilized in the dual line microsystem, a good baseline was obtained in the NO2 measurement with Griess–Saltzman chemistry. The system was developed for on-site measurements in medical treatment; the treatment is of respiratory disease syndrome by NO inhalation and the monitoring is of the product NO and the harmful byproduct NO2. The system was also applied to mobile atmospheric monitoring. Chemical NO generation using the microchannel device was investigated for safe NO inhalation as an alternative to a NO generator based on pulsed arc discharge.

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, μGAS. The new technology, μGAS, 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 H2S, SO2, CH3SH and NH3 gases were examined. Concentrations of the gases are easily controlled by the source reagent concentration and the solution flow rates. At 100 μL 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 μGAS for on-site calibration.

Sequential injection analysis (SIA) was applied to multi-gas monitoring for atmospheric analysis. HONO, NO2 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 3 min at 100 °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, NO2 and NO were successfully monitored 3 or 4 times/h. The limits of detection were 0.22, 0.28 and 0.35 ppbv for HONO, NO2 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 NO2 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.

A honeycomb structure microchannel scrubber was developed to achieve efficient and stable gas collection. A thin porous membrane was pasted on a microchannel by the adhesive force of a fresh polydimethylsiloxane surface. The microchannel scrubber achieved much more efficient gas collection than conventional impingers and diffusion scrubbers. Two sets of the microchannel scrubbers and detectors were integrated in a 10 cm × 9 cm plastic board to create a micro gas analysis system (μGAS) for simultaneous measurements of H2S and SO2. The whole system including a battery was incorporated in a carrying case 34 cm W × 16 cm D × 17 cm H for use in the field. Liquid flows at 30 µl min−1 were obtained by bimetal micropumps. The estimated detection limits were 0.1 ppbv for H2S and 1 ppbv for SO2. The system was demonstrated for real atmospheric gas analysis, and the results agreed well with data concurrently obtained by ion chromatography coupled with a cylindrical diffusion scrubber. The system we developed allowed automated continuous analyses in the field and achieved a much higher time resolution compared to those by ion chromatographic analysis.

Formaldehyde, HCHO, is one of the important causal agents of sick-building syndrome. It is also an important product of ambient air photochemistry. We report here a portable instrument capable of a 0.08 ppbv limit of detection (LOD) and a time resolution of 5 min that is useful for both indoor and ambient air applications. The detection is based on efficient gas collection and chromogenic reaction with 3-methyl-2-benzothiazolone hydrazone (MBTH) through a pair of alternately sampling small-bore porous-membrane tube diffusion scrubbers (DS). The chemistry is well established, requires no special reagent preparation or elevated reaction temperatures and permits the use of inexpensive light emitting diode (LED)-based detectors without need for long path cells. Stopped flow alternate sampling allows an HCHO collection performance, an order of magnitude better than any previous system with high throughput and high sensitivity. Results for indoor and ambient air analyses are presented.

Arsenic water pollution is a big issue worldwide. Determination of inorganic arsenic in each oxidation state is important because As(III) is much more toxic than As(V). An automated arsenic measurement system was developed based on complete vaporization of As by a sequential procedure and collection/preconcentration of the vaporized AsH3, which was subsequently measured by a flow analysis. The automated sensitive method was applied to monitoring As(III) and As(V) concentrations in contaminated water standing overnight. Behaviors of arsenics were investigated in different conditions, and unique time dependence profiles were obtained. For example, in the standing of anaerobic water samples, the As(III) concentration immediately began decreasing whereas dead time was observed in the removal of As(V). In normal groundwater conditions, most arsenic was removed from the water simply by standing overnight. To obtain more effective removal, the addition of oxidants and use of steel wools were investigated. Simple batch wise treatments of arsenic contaminated water were demonstrated, and detail of the transitional changes in As(III) and As(V) were investigated.

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 (DMSaq) and dimethylsulfoniopropionate (DMSP), a precursor to DMS in seawater, were monitored together sequentially with atmospheric dimethyl sulfide (DMSg). A shift from the equilibrium point between DMSaq and DMSg 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 DMSaq was vaporized for analysis by IMRMS. After that, DMSP was hydrolyzed to DMS and acrylic acid, and analyzed in the same manner as DMSaq. The vaporization behavior and hydrolysis of DMSP to DMS were investigated to optimize these conditions. Frequent (every 30 min) determination of the three components, DMSaq/DMSP (nanomolar) and DMSg (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.

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 O3. 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 O3 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.