An Improved Reflection Colorimeter Integrated with a Coaxial Optical-fiber Cable for Highly Sensitive Solid-phase Colorimetry Using a Membrane Filter.

Highly sensitive solid-phase colorimetry for nickel ion was demonstrated using an improved reflection colorimeter equipped with a coaxial optical-fiber cable. The nickel complex with α-furil dioxime was collected on a small-size membrane filter embedded in a disposable syringe filter unit. The leading edge of the optical-fiber cable was connected to the syringe filter unit via a Luer-lock fitting, and the color intensity of the sample on the filter was evaluated accurately. The detection limit was 0.8 ng in 2.5 mL of the complex solution (0.3 µg L-1). This improved configuration is applicable to highly sensitive on-site analysis without expensive instruments nor high laboratory skills.

Droplet-counting Microtitration System for Precise On-site Analysis.

A new microtitration system based on the counting of titrant droplets has been developed for precise on-site analysis. The dropping rate was controlled by inserting a capillary tube as a flow resistance in a laboratory-made micropipette. The error of titration was 3% in a simulated titration with 20 droplets. The pre-addition of a titrant was proposed for precise titration within an error of 0.5%. The analytical performances were evaluated for chelate titration, redox titration and acid-base titration.

On-site Determination of Trace Arsenic by Reflection-Absorption Colorimetry of Molybdenum Blue Collected on a Membrane Filter.

An on-site determination method for trace arsenic has been developed by collecting it as molybdenum blue (MB) in the presence of tetradecyldimethylbenzylammonium chloride on a mixed cellulose ester membrane filter and by measuring reflection absorbance (RA) of MB on the filter using a laboratory-made palm-top size reflection-absorbance colorimeter with a red light-emitting diode. The value of RA was proportional to the amount of arsenic up to 0.5 µg with a detection limit of 0.01 µg. The proposed method was successfully applied to soil extract and hot-spring water samples.

Ion-responsive Intramolecular Charge-transfer Absorption Using a Pyridinium Benzocrown Ether Conjugate.

A pyridinium benzocrown ether conjugated compound, 1, and its analogue with a non-crown ether unit, 2, have been prepared. Both compounds showed similar absorption spectra with two absorption bands at around 260 and 330 nm in acetonitrile. The bands at the longer wavelength side are associated with intramolecular charge transfer (ICT) absorption, in which the dialkoxyphenyl unit in benzocrown ether and the pyridinium unit act as the donor and acceptor, respectively. The addition of a guest, such as Li(+) or Mg(2+), caused a blue shift in the ICT absorption band for 1, but not for 2. This is explained by the formation of a 1:1 host-guest inclusion complex of 1 with the guest. The guest-induced absorption variation of 1 can be used for alkali and alkaline metal ion sensing. Compound 1 could detect divalent cations, especially for Mg(2+), rather than univalent ones (Li(+), Na(+), K(+), Rb(+), and Cs(+)), although Li(+) was detected with high sensitivity among the alkali metal ions. Compound 3, which has a pyridyl unit at the para position on the pyridinium of 1, showed a similar trend to that of 1 with lower sensitivity than that of 1. The fact that the Mg(2+)/Li(+) sensitivity ratio of 1 and 3 was estimated to be 8.63 and 5.08, respectively, suggests a higher Mg(2+)-preference of 1 rather than 3, while the Ca(2+)/Na(+) ones were 4.98 and 4.85, respectively, when compared ions with similar ionic radii. The sensitivity values of 1 were roughly proportional to their binding constants, as shown by the binding constants with Li(+), Na(+), Mg(2+), and Ca(2+) with values of 2100, 910, 11500, and 2000 M(-1) for 1, respectively. The binding constants of 3 were estimated to be 1710, 650, 3000, and 1400 M(-1) for Li(+), Na(+), Mg(2+), and Ca(2+), respectively, but could not be obtained for alkaline metal ions. The limit concentration for the detection of 1 for Mg(2+) was estimated to be 0.0156 mM, which was the smallest value in this system.

Kinetic Spectrophotometric Determination of Trace Cadmium in Environmental Fresh Water with 5,10,15,20-Tetraphenyl-21H,23H-porphinetetrasulfonic Acid.

Cadmium-catalyzed complexation of zinc with 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (TPPS) was monitored spectrophotometrically. A kinetic parameter for the determination was obtained under kinetic consideration. Absorbance of zinc-TPPS at a fixed reaction time was proportional to the concentration of cadmium at pH 8 and 25°C. Tolerable concentration of interfering ions were 200, 200, 2000, 50, 500 and 1 µg L(-1) for Mg(II), Al(III), Ca(II), Fe(III), Zn(II) and Hg(II), respectively, in the determination of 20 µg L(-1) of cadmium, indicating Ca(II) and Mg(II) interferes with the analysis of natural fresh water. Such interference became tolerable at 5 mg L(-1) by the addition of an excess Ca(II) (50 mg L(-1)) in the reacting solution of sample and cadmium standards. A calibration curve of Cd(II) was linear up to 100 µg L(-1) with a detection limit of 2 µg L(-1). The reliability of the proposed method was confirmed by the recovery test of cadmium spiked into tap, river and reservoir water samples.

Determination of very volatile organic compounds in water samples by purge and trap analysis with a needle-type extraction device.

Very volatile organic compounds (VVOCs), such as methanol, acetaldehyde, ethanol, acetone, acetonitrile, and dichloromethane, were extracted from water samples using a needle-type extraction device based on purge and trap analysis. The extracted analytes could then be determined by gas chromatography-mass spectrometry. By introducing carbon molecular sieves as the extraction medium, aqueous VVOCs could be successfully extracted using the extraction needle. The limit of quantification for methanol, acetaldehyde, ethanol, acetone, acetonitrile, and dichloromethane were 75, 75, 7.5, 0.5, 10 and 0.5 µg/L, respectively. This newly developed method was also successfully applied to the determination of VVOCs in commercial samples, such as fruit juice.

On-site catalytic determination of trace manganese in fresh water using oxidation of malachite green with periodate.

An on-site determination method for trace manganese has been developed using the manganese-catalyzed oxidation of Malachite Green (MG) with potassium periodate. Absorbance measurement of MG was carried out using a laboratory-made palm-top size colorimeter with a red-green-blue light-emitting diode. The reciprocal value (1/τ) of the reaction time at a fixed absorbance value for red light was chosen as a kinetic parameter for simple on-site analyses. The value of 1/τ was proportional to the concentration of manganese in the range of 2 - 20 µg L(-1). At a reaction temperature (T) of 20°C or more, manganese was determined within a reaction time of 25 min. The calibration equation was approximated by 1/τ = (aT + b)[Mn] + (cT + d), where a to d were constants in a range of 10 - 40°C. The two equations for 30°C (for the laboratory-preparation of the calibration equation) and T give the value of 1/τ at 30°C as 1/τ(f) = (30a + b)(1/τ - cT - d)/(aT + b) + 30c + d. Without any temperature control, 1/τ(f) can be calculated by this equation and measurements of 1/τ and T. The calculation introduced analytical errors of within 1 µg L(-1). The proposed method was successfully applied to tap-, river- and lake-water samples.

An on-site colorimetric technique for routine determination of chromium, iron and copper in bath solutions for chromium(III) conversion coating.

An on-site colorimetric technique was developed for the routine determination of chromium, iron and copper in bath solutions for the chromium(III) conversion coating. A portable colorimeter with a red-green-blue light emitting diode was used for the absorbance measurements. Iron and copper were determined as Fe(III)-thiocyanate and Cu(I)-bathocuproindisulfonate, respectively. Chromium(III) was determined simultaneously with iron or copper using green and blue light. A correction method of the matrix effect was proposed and its applicability was demonstrated. Analytical errors were within 500, 5 and 0.3 mg L(-1) for chromium(III), iron and copper, respectively.

Development of a simple and low-cost device for fluorometric determination of selenium in water samples.

A portable spectrofluorometer device comprising an ultraviolet LED (380 nm) as a light source, an LED driver, a microsyringe as a cell, an optical fiber cable, a CCD spectrometer and a personal computer was used on-site. The device works on a battery for 3 h without the need to re-charge. The consumptions of reagents and sample solution can be reduced by using the device. Using fluorescein solution as a standard, the performance of this device was compared with that of a bench-top spectrofluorometer. The device applicability was demonstrated by the determination of selenium content in river water as a model of hazardous elements in the environment. Selenium reacted with 2,3-diaminonaphthalene to form piazselenol, which was then extracted with cyclohexane. The determination was carried out with both the portable device and the spectrofluorometer. The entire process was completed in approximately 15 min. The recovery of selenium in a river-water sample ranged from 104-112% and the detection limit was 0.5 microg L(-1).

Development of a discrete flow system using a microsyringe as a cell for the photometric determination of iron.

A simple discrete flow system for the photometric determination of iron using a glass syringe as a mixer of a solution and as a sample cell has been developed. The system was assembled from a coupler combining a light source (a light-emitting diode, LED), a glass syringe, a photodiode detector (PD) and two plastic core fiber optics. The reagent and sample solutions were sucked into a syringe, and were then mixed by a reciprocating motion of a plunger, or simply turning the syringe upside down several times, manually. After mixing, the absorbance of the solution was measured in situ. The analytical figures of this system and the mixing method were tested with a methyl orange solution and evaluated through iron(III) determination by a 1,10-phenanthroline method. The proposed system was applied to the determination of iron(III) using 1,10-phenanthroline and thiocyanate as chelating reagents and an off-line concentration method using an activated-carbon column. By this simple system, iron(III) in a river-water certified reference material (CRM), JSAC 0302-3, and river-water samples were successfully determined with a detection limit (3sigma) of 20 microg L(-1).

Host-guest complexation affected by pH and length of spacer for hydroxyazobenzene-modified cyclodextrins.

Three modified beta-cyclodextrins appended with a hydroxyazobenzene as a dye unit, 1, 2, and 3, each incorporating a different length spacer between the beta-CD and the dye unit with a bis(propyl(oxyethylene)), butylene, and amide bond spacer, respectively, were synthesized in order to investigate their spectroscopic changes induced by pH and host-guest complexation as well as to investigate their conformations and guest-binding properties by means of absorption and induced circular dichroism spectroscopies in aqueous solutions. All hosts accommodated the dye unit in their own CD cavities with an orientation parallel to the CD axis, forming intramolecular complexes. When the pH of the solution changed, the structure changed in response to pH without conformational changes. Existing as the phenol form under acidic condition, they were converted to the yellow phenolate form by dissociation of a proton of the hydroxyl group in the dye unit with increasing pH (pK(a1); 7.62 for 1, 7.44 for 2, 8.00 for 3). Further increase in pH led to the dissociation of the ammonium proton in the secondary amine group in the spacer of 1 and 2 (pK(a2); 8.76 for 1, 8.67 for 2). Upon addition of 1-adamantanol (AN) as a guest, all hosts accommodated AN in their CD cavities, forming 1:1 host-guest inclusion complexes. The complexation phenomena were accompanied with changes in the conformation of the hosts, in which the dye units of 1 and 2 are excluded to outside of the cavity, but not for 3. The dye unit of 3 remained in the cavity, where the guest was also included partly. Therefore, the guest-binding abilities of 1 and 2 were larger than that of 3, which has poor binding ability. The binding constants of 1, 2, and 3 for AN are estimated to be 7400, 1940, and 140 M(-1) at pH 3.2, respectively. However, the guest-binding abilities of 1 and 2 were dependent on the pH of the solution. The ability of 1 under weak alkaline condition was stronger than under acidic or alkaline conditions, while that of 2 increased with increasing pH. Under the condition from neutral to weak alkaline media, 1 and 2 demonstrated color changes from colorless to yellow upon formation of inclusion complexes. When 1-adamantanecarboxylic acid (AC) was used as the charged guest, 1 and 2 bound to AC with a larger binding constant than AN. On the other hand, 1 and 2 bound to 1-adamantineamine (AA) with a smaller binding constant than AN. All these results demonstrate that the complexation phenomena depend on the pH of the solution as well as the length of the spacer of the hosts and that the electrostatic interaction between the host and the guest is also important for forming a stable complex.

Tristimulus colorimetry using a digital still camera and its application to determination of iron and residual chlorine in water samples.

Tristimulus colorimetry using a digital still camera (DSC) as a colorimeter has been developed. A photograph of a sample and standard solutions was taken simultaneously with the DSC, and it was transferred to a PC. On the PC, the colors of the sample and of the standard solutions were analyzed and L* (brightness), a* (red-green component), and b* (yellow-blue component) values were determined with laboratory-made software. A dedicated light-box containing white-color LEDs as light source was made of white acrylic to make constant exposure at each photograph. Various settings of the DSC, such as exposure mode, white balance, and so on, that affect analytical figures, were studied with determination of iron with 1,10-phenanthroline. This method was successfully applied to the determinations of iron in a river water sample and of residual chlorine in tap water samples with N,N-diethylphenylenediamine (DPD).

A simple and portable colorimeter using a red-green-blue light-emitting diode and its application to the on-site determination of nitrite and iron in river-water.

A portable colorimeter using a red-green-blue light-emitting diode as a light source has been developed. An embedded controller sequentially turns emitters on and off, and acquires the signals detected by two photo diodes synchronized with their blinking. The controller calculates the absorbance and displays it on a liquid-crystal display. The whole system, including a 006P dry cell, is contained in a 100 x 70 x 50 mm aluminum case and its mass is 280 g. This colorimeter was successfully applied to the on-site determination of nitrite and iron in river-water.

A miniaturized FIA system for the determination of residual chlorine in environmental water samples.

The present study was aimed at developing a portable miniaturized FIA system with a two-electrode based amperometric detector for on-site monitoring of residual chlorine in environmental samples. The electrode potential control and current data collection were conducted with a home-designed potentiostat with a size of 150 x 100 x 40 mm and the weight of 350 g. It was confirmed that the amperometric response increased in proportion to the chlorine concentration up to 5 microg/ml, and the detection limit for chlorine was 0.05 microg/ml. Besides a drastic reduction in the size of the analytical system, such miniaturization achieved the advantages of increased speed, minimal mobile-phase consumption, and high sensitivity. The proposed method was successfully applied to the determination of residual chlorine in samples of pool water and tap water. The results were well agreed with those obtained by the N,N-diethyl-p-phenylenediamine (DPD) photometric method.

A four-wavelength channel absorbance detector with a light emitting diode-fiber optics assembly for simplifying the flow-injection analysis system.

A four-channel absorbance detector was developed for simplifying the flow-injection analysis (FIA). This detector used four light-emitting-diodes (LEDs) as light sources; their wavelengths were 470, 495, 590 and 635 nm, respectively. Their amplitudes were modulated electronically with different frequencies. The light emissions from them were merged by plastic-core fiber optics, and were detected by a photo-diode (PD). The mixed signal was then sent to and discriminated by a four-channel lock-in amplifier corresponding to each modulation frequency. Neither a monochromator nor an optical filter was used. This detector was conveniently applied to the determination of iron in river water by FIA using 1,10-phenanthroline. Though a noisy peristaltic pump was used to propel the solutions, practical precision and accuracy were obtained by means of on-line dual-wavelength measurements and off-line moving average calculations.