Investigation of filter temperatures and desorption of volatiles from carbon filters under different smoking regimes. B. Teillet, X. Cahours and S. Purkis 1 Science & Stewardship 1 Background z Previous work carried out by C. Mueller Poster SSPT21 z Loss of efficiency of carbon filter for the retention of volatiles in the last puffs during Canadian Intense (CI) smoking regime z Higher filter temperature in the last puffs Î Hypothesis : thermal desorption from the carbon filter might occur during CI and may not in ISO 2 Science & Stewardship 2 From ISO to CI Smoking regimes z Smoking parameters CI versus ISO ISO CI Puff volume 35 ml 55 ml Puff duration 2 sec 2 sec Higher filter load Puff flow rate 1,05 L/min 1,65 L/min Higher flow rate Higher filter temperature Puff frequency 60 sec 30 sec Vent blocking No Yes 100% Î Experimental design focussed on temperature effects but additional phenomena to be taken into 3 consideration Science & Stewardship 3 ISO and CI Experimental set-up 1. Evaluation of filter temperature 2. Volatiles distribution between filter and vapour phase with the filter temperature effect 3. Volatiles distribution between filter and vapour phase without the filter temperature effect 4. Impact of filter temperature effect on the filter/vapour phase distribution 4 Science & Stewardship 4 Evaluation of filter temperature: experimental A 7 mg ISO tar commercial cigarette (filter vent 38%) modified by addition of 50 mg of carbon after the filter ventilation holes Temperature measurement Experimental conditions Probe in the middle of carbon section (axial and longitudinal) Linear smoking machine equipped with a digital recorder (Sodim) acquisition period 50 msec 3 replicates 5 Science & Stewardship 5 Evaluation of filter temperature: ISO smoking 70 ISO Smoking regime 60 Slight increase during each puff 50 ure in °C Maximum temperature 27°C in the last puff 40 mperat e t 30 20 time 6 Science & Stewardship 6 Evaluation of filter temperature: Canadian Intense smoking 70 60 50 erature in °C p 40 tem 30 CI Smoking regime High increase during 20 whole smoking period time Maximum temperature: 70°C in the last puffs 7 Science & Stewardship 7 Evaluation of filter temperature: Summary Differences in filter temperature according to the smoking regimes z ISO z Constant z Slight increase only in the last puff z Maximum temperature Î 27°C z Canadian Intense z High increase during the whole smoking period z Maximum temperature Î 70°C 8 Science & Stewardship 8 Filter/vapour phase volatiles distribution with the filter temperature effect Experimental Filter pad Vapour phase trap 7 mg ISO tar commercial cigarette placed behind the filter pad modified by addition of carbon Analysis focus on 13 volatiles compounds VOC : 1,3-butadiene; Isoprene; Acrylonitrile; Benzene. Carbonyls : Acetaldehyde, Propionaldehyde, Acetone, Isobutyraldehyde, Butyraldehyde, Methyl Ethy Ketone (MEK), Crotonaldehyde. Semi-volatiles : Toluene, Styrene. Method limitation : Acrolein excluded (lack of specificity), Formaldehyde excluded (highly reactive compound), Lower molecular weight compounds excluded (not detectable) 9 Science & Stewardship 9 Filter/vapour phase volatiles distribution with the filter temperature effect Volatiles analysis Thermal desorption Gas Chromatography Analysis (TDS-GC/MS) Experimental conditions : TDS-GC/MS Gerstel/Agilent system, RTX VMS column - multi ion monitoring acquisition - Total desorption : 350°C for 5 min - 3 replicates Acetaldehyde Isoprene Acetone Propionaldehyde 1,3-butadiene 10 Science & Stewardship 10 Filter/vapour phase volatiles distribution with the filter temperature effect Results expression Thermal desorption Gas Chromatography Analysis (TDS-GC/MS) filter vapour phase Results : Area response for each compound 100% 90% from the total desorption of the filter or the vapour phase trap % 80% e 70% nc Expression : for each compound and each 60% replicate, the relative distribution filter/vapour unda b 50% phase was calculated a e 40% v i t 100% corresponding to the sum of filter + a 30% l e r 20% vapour phase allowing comparison of different 10% smoking regimes. 0% compound 11 Science & Stewardship 11 Filter/vapour phase volatiles distribution with filter temperature effect ISO smoking regime 100% 90% e % c n 80% a d n 70% u 60% 50% 40% relative ab 30% 20% 10% FILT 0% ER Hig Volatility h est 1,3 Butadiene the Acetaldehyde VAPO Isoprene U R PHASE Propionaldehyde Acetone Isobutyraldehyde Butyraldehyde c Acrylonitrile o m p ounds MEK Benzene Crotonaldehyde Science & Stewardship Toluene Styrene L o 12 Volatilitywest 12 Filter/vapour phase volatiles distribution with filter temperature effect CI smoking regime 100% 90% e % 80% 70% undanc b 60% a 50% tive la 40% re 30% 20% 10% 0% FIL T ER Hig Volatility h est 1,3 Butadiene the Acetaldehyde VAPOUR PHASE Isoprene Propionaldehyde Acetone Isobutyraldehyde Butyraldehyde c Acrylonitrile o m p ounds MEK Benzene Crotonaldehyde Science & Stewardship Toluene Styrene L o Volatilitywest13 13 Filter/vapour phase volatiles distribution without the filter temperature effect Experimental An 50 mg external carbon Same 7 mg ISO tar commercial filter placed between the cigarette modified by addition of filter pad assembly and the 50 mg of inert semolina in order entrance of the smoking to maintain the pressure drop machine syringe during the smoking (temperature checked : room temperature) vapour phase trap behind the external filter Filter pad Analysis of volatiles 14 Science & Stewardship 14 Filter/vapour phase volatiles distribution with filter temperature effect ISO smoking regime 100% 90% 80% 70% undance % b 60% a 50% 40% relative 30% 20% 10% 0% FILT ER 1,3 Butadiene the Acetaldehyde VAPOUR PHASE Isoprene Propionaldehyde Acetone Isobutyraldehyde Butyraldehyde c Acrylonitrile o m p ounds MEK Benzene Crotonaldehyde Science & Stewardship Toluene Styrene 15 15 Filter/vapour phase volatiles distribution without the filter temperature effect CI smoking regime 100% 90% % e c 80% n 70% 60% 50% lative abunda40% re 30% 20% 10% 0% FIL T E R 1,3 Butadiene Acetaldehyde VAPOUR PHASE Isoprene Propionaldehyde Acetone Isobutyraldehyde Butyraldehyde compoundsAcrylonitrile MEK Benzene Crotonaldehyde Science & Stewardship Toluene Styrene 16 16 ISO smoking with/without filter temperature effect: summary 100 % % 90 % nce 80 % 70 % 60 abunda % 50 % 40 relative % 30 % 20 % 10 % 0% FILTER 10 0% % 90 1,3 B%utadiene nce 80 % 70 Acetaldehyde VAPO % bunda 60 a % Isoprene e 50 UR PHASE lativ % e 40 Propionaldehyde r % 30 % 20 Acetone % 10 Isobutyraldehyde % 0% Butyraldehyde FIL T ER c Acrylonitrile 1,3 Butadiene o mpo MEK Acetaldehyde unds BenzeneVAPOUR PHASE Isoprene No major difference Crotonaldehyde Propionaldehyde volatiles distribution between Toluene Acetone filter and vapour phase whit or Styrene Isobutyraldehyde without temperature effect in Butyraldehyde ISO. co Acrylonitrile mpou Temperature profile showed low MEK nds temperature during the whole Benzene smoking period. Crotonaldehyde among Toluene Styrene Î carbonNo filter temperature efficiency effect in ISO. on Science & Stewardship 17 17 CI smoking with/without filter temperature effect: summary te mperatWith e ffe ct ure 10 0% % 90 % 80 ance % 70 % bund 60 % ve a 50 lati % e 40 r % 30 % 20 Without te % mperat 10 % e 0% FI ffe LT ure ER ct 10 0% 1,903 Butadiene % % 80 % Acetaldehyde VAPOUR PHASE 70 % 60 Isoprene % ive abundance50 t % Propionaldehyde ela 40 r % 30 Acetone % 20 % Isobutyraldehyde 10 % Butyraldehyde 0% F ILT co AcrylonitrERile Slight differences mpoun 1,3 Butadiene MEK maximum filter relative abundance ds Acetaldehyde BenzenVAe (Cambridge filter pad in front of the PO Isoprene CrotonaldehyURde PH external filter : filter load difference) Propionaldehyde TolueneASE Huge differences Acetone Styrene relative abundance for the Isobutyraldehyde volatility compounds. between the Butyraldehyde Temperature profile showed high compo Acrylonitrile MEK temperature during the whole un d smoking period. s Benzene Crotonaldehyde Î between the filter Toluene filter efficiencyTemperature suspected effect on in carbon CI. Styrene Further investigations : Desorption estimation by TDS-GC/MS highest Science & Stewardship 18 18 Filter temperature effect on volatiles distribution: CI experimental 7 mg ISO tar commercial cigarette modified by addition external carbon filter of semolina Vapour phase trap 1 TDS-GC/MS Analysis Analysis in 2 steps thermal desorption until maximum occurring temperature 60°C/min up to 70°C during 6 sec 2 full desorption 19 350°C 5 min Science & Stewardship 19 Impact of filter temperature effect on the filter/vapour phase distribution CI desorption desorption 100% 90% 80% simulation loss 70% ndance % 60% ve abu 50% ti FIL a 40% T rel ER 30% 20% 10% DESORPT 0% 45% 15% ION 1,3 Butadiene <10% Acetaldehyde 25% VAPOUR Isoprene Propionaldehyde PH ASE Acetone <10% 25% Isobutyraldehyde Negligible Butyraldehyde compoundsAcrylonitrile MEK Benzene ScienceCrotonal &d Stewardshipehyde Toluene Styrene 20 20 CI smoking with filter temperature effect /TDS simulation : summary te mperatWith e ffe ct ure 10 0% % 90 % 80 ance % 70 % bund 60 % ve a 50 lati % e 40 r % 30 % 20 % 10 % 0% FI LT ER 10 1,3 B0%utadiene 90 % e % 80 Acetaldehyde VAPOUR PHASE nc % da 70 % Isoprene bun 60 a e % iv 50 PropionaldehyFIde t % L la 40 T e ER r % Acetone 30 % 20 Isobutyraldehyde % 10 DESORPT % Butyraldehyde 0% co Acrylonitrile I mpoun ON 1,3 Butadiene MEK Relative abundance of volatiles in ds Benzene Acetaldehyde VAP the filter after desorption Isoprene CrotonaldehOURyde