A qualitative and quantitative method for formaldehyde in alcohol was established based on ultra-performance liquid chromatography mass spectrometry (UPLC-MS/MS). Formaldehyde in the sample reacts with 2,4-dinitrophenylhydrazine under acidic conditions to form a stable derivative formaldehyde-2,4-dinitrophenylhydrazone. The product was analyzed by UPLC-MS/MS and external standard method was used for quantification. The results showed that formaldehyde had a good linear relationship in 0.01-0.2 mg/L, the correlation coefficient was more than 0.999, the detection limit was 0.002 mg/L, and the recovery rate of standard addition in beer, liquor, wine and rice wine could reach 93.7%-97.5%, the relative standard deviation (RSD) of the precision test results was 2.71% to 4.98%. The presented method is easy to operate with high sensitivity, and can accurately and rapid quantitative analysis of formaldehyde in different wine samples, which provides a reference for the detection of formaldehyde content in wine.
[1] PENG W X, YUE X C, CHEN H L, et al.A review of plants formaldehyde metabolism:Implications for hazardous emissions and phytoremediation[J].Journal of Hazardous Materials, 2022, 436:129304.
[2] LIU Y, YUAN Y, LEI X Y, et al.Purification and characterisation of two enzymes related to endogenous formaldehyde in Lentinula edodes[J].Food Chemistry, 2013, 138(4):2 174-2 179.
[3] REINGRUBER H, PONTEL L B.Formaldehyde metabolism and its impact on human health[J].Current Opinion in Toxicology, 2018, 9:28-34.
[4] 汪咏曾, 祝胡仙, 朱教胜.酒类产品中甲醛检测方法(紫外分光法)研究与改进[J].农产品加工, 2022(10):79-81.
WANG Y Z, ZHU H X, ZHU J S.Research and improvement of detection method of formaldehyde in alcohol products(UV spectrophotometry)[J].Farm Products Processing, 2022(10):79-81.
[5] NOWSHAD F, ISLAM M N, KHAN M S.Concentration and formation behavior of naturally occurring formaldehyde in foods[J].Agriculture & Food Security, 2018, 7(1):17.
[6] 崔娜, 张曼玲, 田艳玲.乙酰丙酮法测定啤酒中甲醛含量的研究[J].食品安全质量检测学报, 2016, 7(3):906-910.
CUI N, ZHANG M L, TIAN Y L.Determination of the formaldehyde content in beer by acetyl acetone method[J].Journal of Food Safety & Quality, 2016, 7(3):906-910.
[7] 丁怀宇, 张静文.分光光度计法测定啤酒中甲醛含量[J].长春工业大学学报(自然科学版), 2008, 29(6):657-660.
DING H Y, ZHANG J W.Test of formaldehyde content in beer with spectrophotometer[J].Journal of Changchun University of Technology (Natural Science Edition), 2008, 29(6):657-660.
[8] DENG Z F, HU K, ZHANG Y M, et al.On-cartridge derivatisation using a calixarene solid-phase extraction sorbent for facile, sensitive and fast determination of formaldehyde in beer[J].Food Chemistry, 2016, 211(15):314-319.
[9] 袁彩霞, 钱滢文, 柴宗龙, 等.气相色谱法同时测定啤酒中的甲醛和乙醇[J].酿酒科技, 2018(5):117-121.
YUAN C X, QIAN Y W, CHAI Z L, et al.Simultaneous determination of formaldehyde and ethanol in beer by gas chromatography[J].Liquor-Making Science & Technology, 2018(5):117-121.
[10] 曾文祥, 李珍妮, 曾川, 等.高效液相色谱柱后衍生法测定啤酒中甲醛含量[J].食品安全导刊, 2021(34):75-78.
ZENG W X, LI Z N, ZENG C, et al.Determination of formaldehyde in beer by HPLC with post-column derivatization[J].China Food Safety Magazine, 2021(34):75-78.
[11] PENG Z F, LUO Y K, SONG C C, et al.A novel methodology and strategy to detect low molecular aldehydes in beer based on charged microdroplet driving online derivatization and high resolution mass spectrometry[J].Food Chemistry, 2022, 383:132380.
[12] KISHIKAWA N, EL-MAGHRABEY M H, KURODA N.Chromatographic methods and sample pretreatment techniques for aldehydes determination in biological, food, and environmental samples[J].Journal of Pharmaceutical and Biomedical Analysis, 2019, 175:112782.
[13] 赵云鹏, 徐晓飞, 刘星汶, 等.食品中甲醛含量的检测方法研究进展[J].中国食品添加剂, 2020, 31(12):112-116.
ZHAO Y P, XU X F, LIU X W, et al.Research progress in detection methods for formaldehyde[J].China Food Additives, 2020, 31(12):112-116.
[14] LIPSKEROV F A, SHESHUKOVA E V, KOMAROVA T V.Approaches to formaldehyde measurement:From liquid biological samples to cells and organisms[J].International Journal of Molecular Sciences, 2022, 23(12):6642.
[15] 刘建强. LC-MS/MS法测定啤酒中的微量甲醛和乙醛[J].中国酿造, 2008, 27(11):87-90.
LIU J Q.Determination of trace formaldehyde and acetaldehyde in beer by LC-MS/MS[J].China Brewing, 2008, 27(11):87-90.
[16] 顾亚萍, 乔方, 方长发, 等.液相色谱串联质谱法测定白菜中的甲醛含量[J].食品与发酵工业, 2017, 43(12):214-217.
GU Y P, QIAO F, FANG C F, et al.Determination of formaldehyde in Chinese cabbage by high performance liquid chromatography tandem mass spectrometry[J].Food and Fermentation Industries, 2017, 43(12):214-217.
[17] 李俊, 刘永翔, 王辉, 等.高效液相色谱法定量测定果蔬中甲醛含量[J].食品科学, 2016, 37(22):198-204.
LI J, LIU Y X, WANG H, et al.Determination of formaldehyde in fruits and vegetables by HPLC[J].Food Science, 2016, 37(22):198-204.
[18] 朱梦旭, 范文来, 徐岩.我国白酒蒸馏过程以及不同年份产原酒和成品酒中甲醛的研究[J].食品与发酵工业, 2015, 41(9):153-158.
ZHU M X, FAN W L, XU Y.Characterization of formaldehyde from distillation cut, raw liquor of different vintage, and finished Chinese liquor[J].Food and Fermentation Industries, 2015, 41(9):153-158.
[19] 于欣禾, 李明慧, 孙珍.LC-MS/MS分析结合优化提取工艺探究啤酒中麸质蛋白[J].质谱学报, 2022, 43(2):242-251.
YU X H, LI M H, SUN Z.Analysis of the gluten map in beers by LC-MS/MS combined with optimized extraction protocol[J].Journal of Chinese Mass Spectrometry Society, 2022, 43(2):242-251.
[20] VARTIAINEN E, BLOMBERG P, ILMÉN M, et al.Evaluation of synthetic formaldehyde and methanol assimilation pathways in Yarrowia lipolytica[J].Fungal Biology and Biotechnology, 2019, 6:27.