“Smoke pH”: A Review

The analytical methods developed since the 1950s to determine the “smoke pH” of cigarette mainstream smoke (MSS) are reviewed. Most of the methods involve averaging the values obtained with all the puffs from a cigarette or averaging values from the total number of puffs from several cigarettes plus solution of the MSS in various quantities of water prior to pH determination. “Smoke pH” values thus obtained have little relevance to the situation involving a smoker who smokes a cigarette one puff at a time. In the human biological situation, the smoke components must traverse a layer of buffered fluid separating the smoke-filled respiratory tract cavity and the underlying tissue. Seldom is the effect of either the volume or the pH of the buffered fluid taken into account in determining the “smoke pH” of cigarette MSS taken one puff at a time. While numerous recent discussions have dealt with the effect of pH on the nature (degree of protonation) of nicotine in cigarette MSS and its rate of absorption by the smoker, seldom is the volume and/or pH of oral cavity saliva or of the fluid coating the lung surface considered in the assessment of either the nature or absorption of nicotine by the smoker. If the degree of protonation of nicotine be pH dependent, then the degree of protonation of nicotine as it traverses the film of fluid separating the respiratory tract cavity and the underlying tissue must be dependent on the pH of the buffered fluid and not on the “smoke pH” per se. Statements that adjustment of the “smoke pH” by ammoniation of one or more tobacco blend components increases both the level of MSS nicotine and its rate of absorption, thus resulting in greater consumer acceptance and continuation of smoking, fail to take into account the other changes that occur in the MSS composition to enhance its consumer acceptability. Inclusion of modest percentages of ammoniated tobacco in the blend increases the “smoke pH” of the MSS but does not necessarily increase MSS nicotine level. Not only are the MSS levels of several low molecular acids, aldehydes, and ketones known to be respiratory tract irritants substantially reduced but also the MSS levels of several highly flavorful pyrazines are substantially increased. These MSS composition changes yield an MSS classified as milder and more flavorful and whose consumer acceptability is considerably enhanced. Until the pH of MSS is determined on a per puff basis in a system simulating that in the oral cavity or the lung of the smoker, the nature of specific smoke components at the time of contact and their reactivity with respiratory tract tissue remain highly speculative. “Smoke pH” value for MSS, like the “tar” value for MSS, provides little, if any, useful information about the chemical composition of the source of the MSS or about its chemical and biological properties.