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We have previously developed a new method using trans-1,2-bis-(4-pyridyl)ethylene (4-BPE) and 2,4-dinitrophenythydrazine (DNPH) for the simultaneous determination of ozone and carbonyls in air using a two-bed cartridge system. In this method, 4-BPE was used to capture ozone. However, the method suffered from long reaction times in the eluate, low solubility of the DNPH derivative, and a strong dependence on atmospheric moisture. These problems could be overcome by using Wans-1,2-bis-(2-pyridyl)ethylene (2-BPE) in place of 4-BPE. The efficiency of the reaction of ozone with 2-BPE to form pyridine-2-aldehyde (2PA) is higher than the corresponding reaction with 4-BPE. Under the optimized elution conditions, the reaction times of 2PA and 4PA with DNPH are within 15 and 120 min, respectively. In the elution from the sampling cartridge, 2PA formed from 2-BPE and ozone is easier to dissolve in the elution solvent. A stronger influence of humidity was observed in ozone recovery by the 4-BPE/DNPH method. 2-BPE exhibits a maximum reaction efficiency of 84% at 32% relative humidity (RH), while 4-BPE attains a maximum reaction efficiency of 82% at 49% RH. Humidity has much less influence on the reaction of 2-BPE with ozone. Above 18% RH, the reaction efficiency of 2-BPE with ozone is In the range 80-84%. Thus, 2-BPE is the more useful reagent for ozone analysis. The concentrations of ozone and carbonyls by the improved 2-BPE/DNPH method corresponded with the mean value by an ozone auto analyzer in an air monitoring station and a DNPH cartridge coupled with a KI-ozone scrubbing cartridge.

A new method for the determination of carbonyls in air using 2,4-dinitrophenylhydrazine (DNPH) has been developed. The traditional method for the measurement of carbonyl compounds, using DNPH to form the corresponding 2,4-dinitrophenylhydrazone (DNPhydrazone) derivatives, is subject to analytical errors because DN-Phydrazones form both E- and Z-geometrical isomers as a result of the C=N double bond. To overcome this issue, a method for transforming the C=N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been developed. Reductive amination of aldehyde DNPhydrazones was carded out by adding 2-picoline borane acetonitrile solution in eluate through the DNPH-cartridge. The amination reactions of [C.sub.1]-[C.sub.10] aldehyde DNPhydrazones were completely converted into the reduced forms within 40 min in the presence of 1 mmol/L 2-picoline borane and 20 mmol/L of phosphoric acid. These reduced forms were very stable and did not change when stored for 2 weeks at room temperature. The absorption maximum wavelengths of the reduced forms from [C.sub.1]-[C.sub.10] aldehyde DNPhydrazones were 351-352 nm and shifted 6-7 nm toward shorter wavelengths when compared to the corresponding DNPhydrazones, and the molar absorption coefficients were 1.5 x [10.sup.4] ([C.sub.1]) to 2.2 x [10.sup.4] L/mol/cm ([C.sub.10]). Complete separation between [C.sub.1]-[C.sub.10] aldehyde DNPhydrazones and the corresponding reduced forms can be achieved by operating the HPLC in gradient mode using an Ascentis RP-Amide column (150 mm x 4.6 mm i.d.). The RSDs of DNPhydrazone (Z + E) peak areas ranged from 0.40-0.66 and those of the corresponding reduced forms ranged from 0.26-0.41. It was shown that the reductive amination method gave improved HPLC analytical precision because of the absence of isomers.

A new method for the determination of carbonyls in air using 2,4-dinitrophenylhydrazine (DNPH) has been developed. The traditional method for the measurement of carbonyl compounds, using DNPH to form the corresponding 2,4-dinitrophenylhydrazone (DNPhydrazone) derivatives, is subject to analytical errors because DN-Phydrazones form both E- and Zgeometrical isomers as a result of the C=N double bond. To overcome this issue, a method for transforming the C=N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been developed. Reductive amination of aldehyde DNPhydrazones was carried out by adding 2-picoilne borane acetonitrile solution in eluate through the DNPH-cartridge. The amination reactions of C1-C10 aldehyde DNPhydrazones were completely converted into the reduced forms within 40 min in the presence of 1 mmol/L 2-picoline borane and 20 mmol/L of phosphoric acid. These reduced forms were very stable and did not change when stored for 2 weeks at room temperature. The absorption maximum wavelengths of the reduced forms from C1-C10 aldehyde DNPhydrazones were 351-352 nm and shifted 6-7 nm toward shorter wavelengths when compared to the corresponding DNPhydrazones, and the molar absorption coefficients were 1.5 × 104 (C1) to 2.2 × 104 L/mol/cm (C10). Complete separation between C1-C10 aldehyde DNPhydrazones and the corresponding reduced forms can be achieved by operating the HPLC in gradient mode using an Ascenlis RP-Amide column (150 mm × 4.6 mm i.d.). The RSDs of DNPhydrazone (Z + E) peak areas ranged from 0.40-0.66 and those of the corresponding reduced forms ranged from 0.26-0.41. It was shown that the reductive amination method gave improved HPLC analytical precision because of the absence of isomers. [ABSTRACT FROM AUTHOR]