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

Granica izlaganja formaldehidu u alkoholnim pićima

Formaldehyde has been classified as carcinogenic to humans (WHO IARC group 1). It causes leukaemia and nasopharyngeal cancer, and was described to regularly occur in alcoholic beverages. However, its risk associated with consumption of alcohol has not been systematically studied, so this study will provide the first risk assessment of formaldehyde for consumers of alcoholic beverages. Human dietary intake of formaldehyde via alcoholic beverages in the European Union was estimated based on WHO alcohol consumption data and literature on formaldehyde contents of different beverage groups (beer, wine, spirits, and unrecorded alcohol). The risk assessment was conducted using the margin of exposure (MOE) approach with benchmark doses (BMD) for 10 % effect obtained from dose-response modelling of animal experiments. For tumours in male rats, a BMD of 30 mg kg-1 body weight per day and a “BMD lower confi dence limit” (BMDL) of 23 mg kg-1 d-1 were calculated from available long-term animal experiments. The average human exposure to formaldehyde from alcoholic beverages was estimated at 8·10-5 mg kg-1 d-1. Comparing the human exposure with BMDL, the resulting MOE was above 200,000 for average scenarios. Even in the worst-case scenarios, the MOE was never below 10,000, which is considered to be the threshold for public health concerns. The risk assessment shows that the cancer risk from formaldehyde to the alcohol-consuming population is negligible and the priority for risk management (e.g. to reduce the contamination) is very low. The major risk in alcoholic beverages derives from ethanol and acetaldehyde.Formaldehid je kancerogen za ljude te je klasificiran u skupinu 1 prema WHO IARC-u. Uzrokuje leukemiju i nazofaringealni karcinom, a navodi se i kao redoviti sastojak alkoholnih pića. Međutim, rizik od izlaganja formaldehidu konzumacijom alkoholnih pića nije sustavno istražen pa će ovo istraživanje pružiti prvu takvu procjenu rizika. Količina formaldehida koju ljudi unose alkoholnim pićima u Europskoj je uniji procijenjena temeljem podataka Svjetske zdravstvene organizacije o konzumaciji alkohola i literature o sadržaju formaldehida u različitim skupinama alkoholnih pića (pivo, vino, jaka alkoholna pića i neregistrirani alkohol). Procjena rizika obavljena je korištenjem pristupa granice izlaganja (eng. margin of exposure, MOE) i graničnih doza (eng. benchmark doses, BMD) za 10 %-tni učinak koji se postiže modeliranjem odnosa doza-odgovor u ispitivanjima provedenima na životinjama. BMD od 30 mg kg-1 tjelesne težine na dan i BMD s nižom granicom pouzdanosti (BMDL) od 23 mg kg-1 d-1 izračunati su za tumore kod mužjaka štakora temeljem raspoloživih dugotrajnih ispitivanja provedenih na životinjama. Prosječno izlaganje ljudi formaldehidu u alkoholnim pićima procijenjeno je na 8·10-5 mg kg-1 d-1. U usporedbi s BMDL vrijednošću krajnji MOE je iznosio više od 200.000 u prosječnim situacijama. Čak i u najlošijim situacijama MOE nije nikada bio niži od 10.000, što se smatra graničnom vrijednošću za zdravlje ljudi. Procjena rizika pokazuje da je rizik od nastanka karcinoma uslijed izlaganja formaldehidu iz alkoholnih pića zanemariv te da je prioritet upravljanja rizikom u takvim slučajevima (npr. kako bi se smanjila kontaminacija) vrlo nizak. Najveći rizik proizlazi iz etanola i acetaldehida koji se također nalaze u alkoholnim pićima

Research Article Formaldehyde in Alcoholic Beverages: Large Chemical Survey Using Purpald Screening Followed by Chromotropic Acid Spectrophotometry with Multivariate Curve Resolution

Copyright © 2011 Julien A. Jendral et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 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 13 C 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 tolerabl