Search

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.

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.

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.

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%).

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.

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.

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 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 NO(2) after removal of pre-existing NO(2) and conversion of NO to NO(2). 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 NO(2) 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.

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.

We show a practical sequential injection/zone fluidics-based analyzer that measures waterborne arsenic. The approach is capable of differentiating between inorganic As(III) and As(V). The principle is based on generating AsH3 from the sample in a confined chamber by borohydride reduction at controlled pH, sparging the chamber to drive the AsH3 to a small reflective cell located atop a photomultiplier tube, allowing it to react with ozone generated from ambient air, and measuring the intense chemiluminescence that results. Arsine generation and removal from solution results in isolation from the sample matrix, avoiding the pitfalls encountered in some solution-based analysis techniques. The differential determination of As(III) and As(V) is based on the different pH dependence of the reducibility of these species to AsH3. At pHor =1, both As(III) and As(V) are quantitatively converted to arsine in the presence of NaBH4. At a pH of 4-5, only As(III) is converted to arsine. In the present form, the limit of detection (S/N = 3) is 0.05 microg/L As at pHor =1 and 0.09 microg/L As(III) at pH approximately 4-5 for a 3-mL sample. The analyzer is intrinsically automated and requires 4 min per determination. It is also possible to determine As(III) first at pH 4.5 and then determine the remaining As in a sequential manner; this requires 6 min. There are no significant practical interferences. A new borohydride solution formulation permits month-long reagent stability.

A light emitting diode (LED)-based photometric method for the measurement of gaseous acetone in human breath is presented. The detection chemistry is based on the reaction of acetone with alkaline salicylaldehyde to form a colored product, which absorbs in the blue and can be monitored with GaN-based LEDs with emission centered at 465 nm. Gaseous acetone in breath is sampled with a porous membrane based diffusion scrubber (DS). The collected sample in the continuously flowing water carrier reacts with the reagent solution. We have used two approaches to collect breath acetone: the use of a face mask and a Mylar balloon as a collection bag. With the face mask approach, the expired air can be measured over long periods without major subject discomfort, balloon collection (5 l) permits four measurements from a single fill. The LED-based liquid core waveguide (LCW) absorbance detector utilized sapphire ball lenses to prevent exposure of other optical components to a hot alkaline reagent solution. The high refractive index of the final mixture permitted the use of an inexpensive fluorinated ethylene copolymer (FEP Teflon®) tube as a 10 cm long LCW. The limit of detection (S/N = 3) is 14 ppbv gaseous acetone, and the linear range extends to 1.21 ppmv. The concentration range in 11 volunteer subjects ranged from 176 to 518 ppbv.

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.

A robust and fully automated indoor ammonia gas monitoring system with an open channel scrubber (OCS) was developed. The sample gas channel dimensions, hydrophilic surface treatment to produce a thin absorbing solution layer, and solution flow rate of the OCS were optimized to connect the OCS as in-line gas collector and avoid sample humidity effects. The OCS effluent containing absorbed ammonia in sample gas was injected into a derivatization solution flow. Derivatization was achieved with o-phthalaldehyde and sulfite in pH 11 buffer solution. The product, 1-sulfonateisoindole, is detected with a home-made fluorescence detector. The limit of detection of the analyzer based on three times the standard deviation of baseline noise was 0.9 ppbv. Sample gas could be analyzed 40 times per hour. Furthermore, relative humidity of up to 90% did not interfere considerably with the analyzer. Interference from amines was not observed. The developed gas analysis system was calibrated using a solution-based method. The system was used to analyze ammonia in an indoor environment along with an off-site method, traditional impinger gas collection followed by ion chromatographic analysis, for comparison. The results obtained using both methods agreed well. Therefore, the developed system can perform on-site monitoring of ammonia in indoor environments with improved time resolution compared with that of other methods.

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.

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.

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.

In this work, a portable and reliable instrument based on manual hydride generation and subsequent ozone induced chemiluminescence analysis was developed and optimized for measurement of aqueous arsenic in drinking water. The aim was to develop a system for use in the field in villages in developing countries where water treatment systems have been installed. Consequently, it is beneficial that the system could be operated without reagent solutions or purified water. Arsenic trihydride (arsine) was generated by reaction with solid acid and solid borohydride, and then introduced to a chemiluminescence cell where the arsine was mixed with ozone to generate chemiluminescence. The measurement could be repeated with the throughput of 60 times h(-1), and the limit of detection was 0.4 µg L(-1). The measurable arsenic concentration was up to 1 mg L(-1) for 2 mL samples. The system was evaluated for analysis of natural water samples, and the obtained data agreed well with those from ICP-MS and sequential hydride generation flow analysis. We expect this small and inexpensive instrument will be used in developing countries.

A needle-shaped sampler/reactor was developed for an electrochemical enzyme immunoassay with the direct sampling of living sample blood. This device was evaluated using IgG determination chemistry. Antibodies were immobilized on an inner wall of the sampler/reactor. Incubation for the enzyme reaction was not needed because this reactor was very small (250 microm in diameter). The analysis was conducted within 15 min in the simplest protocol including the reactor refreshment. The limit of detection was 3 pg, and 20 attomol in the most sensitive protocol. Furthermore, the sampling of a solution contained in an agar block and a whole-blood analysis were demonstrated.

A sensitive (limit of detection approximately100 pptv at S/N = 3), fully automated, portable (32 x 25 x 38 cm, 4.5 kg) instrument has been designed for continuous field measurement of atmospheric hydrogen sulfide. Air is sampled by a PTFE membrane-based diffusion scrubber and collected into an aLkaline fluorescein mercuric acetate (FMA) solution flowing under a controlled and constant pneumatic pressure. The collected sulfide quenches the fluorescence that is measured with a miniature blue LED photodiode-based fluorescence detector. Acquisition and interpretation of signal and all flow control are carried out via a mininotebook personal computer (PC) using custom software written in HP-VEE. The instrument provides for self-calibration and zero functions using an on-board permeation tube enclosed in a thermostated block, at any preprogrammed desired interval. During sampling, the computed H2S concentration is stored every 2 min. The complete system, including the PC, is operated in the field by a 12-V marine battery. The system was field tested near oil field operations in West Texas and showed good correlations with a concurrently operated lead acetate tape-based commercial sampler, with a response speed and time resolution much better than that of the latter instrument.