Formaldehyde in Alcoholic Beverages: Large Chemical Survey Using Purpald Screening Followed by Chromotropic Acid Spectrophotometry with Multivariate Curve Resolution
A strategy for analyzing formaldehyde in beer, wine, spirits, and unrecorded alcohol was developed, and 508 samples from worldwide origin were analyzed. In the first step, samples are qualitatively screened using a simple colorimetric test with the purpald reagent, which is extremely sensitive for formaldehyde (detection limit 0.1？mg/L). 210 samples (41%) gave a positive purpald reaction. In the second step, formaldehyde in positive samples is confirmed by quantitative spectrophotometry of the chromotropic acid-formaldehyde derivative combined with Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS). Calculation of UV-VIS and 13C NMR spectra confirmed the monocationic dibenzoxanthylium structure as the product of the reaction and disproved the widely cited para,para-quinoidal structure. Method validation for the spectrophotometric procedure showed a detection limit of 0.09 mg/L and a precision of 4.2–8.2% CV. In total, 132 samples (26%) contained formaldehyde with an average of 0.27？mg/L (range 0–14.4？mg/L). The highest incidence occurred in tequila (83%), Asian spirits (59%), grape marc (54%), and brandy (50%). Our survey showed that only 9 samples (1.8%) had formaldehyde levels above the WHO IPCS tolerable concentration of 2.6？mg/L. 1. Introduction The International Agency for Research on Cancer (IARC) has upgraded the cancer classification of formaldehyde in 2006 to now being clearly “carcinogenic to humans” (group 1) [1]. More recently, formaldehyde has been implicated by the IARC as a causative agent of leukemia as well as nasopharyngeal cancer in humans [2]. The US EPA provides a reference dose for chronic oral exposure (RfD) of 0.2？mg/kg bodyweight/day [3]. The WHO IPCS [4] has established a tolerable concentration (TC) of 2.6？mg/L in ingested products based on animal experiments [5]. Systematic data are currently lacking regarding the formaldehyde content of alcoholic beverages or indeed of most food in general. Feron et al. [6] estimated that the formaldehyde intake by food may range between 1.5 and 14？mg/person/day, which could, therefore, exceed the RfD in a worst case scenario. As we had previously conducted in-depth research into acetaldehyde content of alcoholic beverages [9, 10], we were recently asked if we had similar data on formaldehyde and if this compound may pose a risk to consumers in addition to the risk of ethanol [11]. We had no such data, because formaldehyde cannot be analyzed along with the other volatiles (e.g., acetaldehyde and methanol) during a typical gas chromatographic reference method [12]. For this
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