THE DIFFUSIVE MONITOR Current news in the field of Diffusive Sampling in the Workplace and in the Environment issued by HSE/CAR Working Group 5 Issue 8 Sept 1996BY WAY OF INTRODUCTION Welcome to the eighth edition of The Diffusive Monitor. As indicated on the title Page, The Diffusive Monitor is a publication of the Health and Safety Executive CAR Committee (Committee on Analytical Requirements), Working. Group §. This working group is concerned with workplace and environmental applications of diffusive sampling for assessing air quality. Contributions to the newsletter are not intended to be exclusively from HSE/CAR/WGS5, and any reader is welcome to submit a contribution for consideration. The only limitations are that contributions should concentrate on diffusive sampling applications and not be too obviously commercial. The newsletter has a world circulation of some 400 People, all of whom have specifically requested the publication, so you can be assured of a wide and receptive audience. IMPORTANT NOTICE: WITH THIS EDITION, THE CIRCULATION LIST IS BEING REVIEWED. PLEASE RETURN THE ENCLOSED FORM IF YOU WISH TO CONTINUE TO RECEIVE COPIES. FUTURE EDITIONS MAY BE DISTRIBUTED VIA INTERNET. PLEASE INDICATE IF YOU CAN ACCESS INTERNET. CURRENT NEWS CEN/TC137 CARIWGS continues to press for progress in the development of CEN (Comité Européen de Normalisation) Standards for workplace air monitoring through TC137 (Hazardous Substances in the Workplace). Significant progress has been made since the last newsletter; a number of drafts having reached EN status. Readers may wish to have a check list of current documents; see Table below. ENs, prENs and some other drafts which are available for public comment may be ordered from your national Standards Organisation. CEN/TC 264 CARIWGS has also become involved, since the last newsletter, in the development Of CEN Standards for ambient air monitoring through TC 264 (Air Quality). As with C137, not all of the Working Groups are directly concerned with diffusive sampling, but readers may wish to know of their existence. WG11, however is concerned Specifically with diffusive sampling and WG12 and 13 are developing reference methods for monitoring ambient air inorganic gas pollutants and benzene respectively.‘Working Grou 19 Emission of specie olamants (stack gases) Woding Geoun 11 ‘Ditusive samplers (ambient ar montoring) “Ambient air quay - Diffusive samplers forthe determination Of gases and vapours - Part 1: Genel requirements; latest ‘raf CEWTCIS7IWG!1IN17 (duly 1996) “Ambient ar qualty - Ditusive samplers for the determination of gases and vapours - Part 2: Specie requirements and test methods; latest draft CEN/TCIS7WWGI1/N18 (July 1986) ‘Ambient air quay - Diffusive samplers forthe determination of gases and vapours - Part 3: Gude for selection, instalation, Use and maintenance; latest drat CEN/TCIS7WVGIH/NIS (uty 1996) ‘Working Group 12 Reference method for eterminaton of SO/NO/O/CO in ‘ambient ar ‘The task of this working group will be to prepare four drat Standards for use as reference methods forthe measurement Of these gases in ambient air in ine with the Ambient Air Quaity Framework Directive Working Group 13 Reference mathod tor determination of benzene in emibent ‘The task of this working group wil be to prepare a drat standards for use as a reference method for he measurement ‘of benzene in ambient air in ine with the Ambient A Qually | Framework Directive Wotking Group 14 Reference method for determination of Pa/Ca/As Nin ‘ambient air. THE EFFECTS OF MEASURES TO ALLEVIATE THE SYMPTOMS OF ASTHMA ON CONCENTRATIONS OF VOCs AND FORMALDEHYDE IN UK HOMES \V.M Brown, D.R. Crump and H.S, Mann Bung Research Establishment, Garston, Watford, WO2 TR The homes of 30 asthmatic patients in the South of England have been subjected to interventions involving the installation of a ‘mechanical ventilation system and/or the supply of a high efficiency vacuum cleaner. A further ten homes of asthmatic patients were fecruited to the study as a control group. The interventions were aimed primarily at reducing the number of house dust mites in the home. Concentrations of volatile organic compounds (VOCs) and formaldehyde were recorded in the homes on three occasions prior to and on five ‘occasions following the interventions. Diffusive ‘sampling was used involving the GMD 570 series dosimeters for 3-day mean formaldehyde measurements; Perkin-Eimer tubes packed with Tenax TA were used for measuring VOCs, No significant differences in the concentrations of total VOCs was found in any group of homes before and after intervention. Homes in which @ mechanical ventilation system had been installed showed significantly lower. formaldehyde concentrations in the bedroom after the installation than before this time; no significant difference was found in the groups that were controls or received a vacuum Cleaner without mechanical ventilation. © Crown Copyright 1996 - Building Research Establishment Presented at the Indoor Air '96 Conference, Japan, July 21-26. $$, DIFFUSIVE SAMPLING OF AROMATIC VOCS IN AMBIENT AIR IN SWITZERLAND Christian Monn and Markus Hangartner Federal instiute of Technology, ETH-Z, Clausiusstr. 21, 092 Zurich, Switzerland Concentrations of aromatic VOCs, such as benzene, toluene and xylene, (BTX) were measured at urban, suburban, rural and alpine sites in Switzerland. Concentrations of benzene were between 0.8 and 3.9 g/m. The ratios between benzene, toluene and xylene Concentrations were on average 1:3:1.1. Air samples were taken diffusively with a sampler consisting of @ 6 cm diameter aluminium Container filled with 1.0 9 of activated carbon held between two stainless steel gauzes. Samplers were calibrated by exposure to standard vapour atmospheres. They were also compared with pumped charcoal tubes in field exposures, where the two methods agreed within 15%. Duplicate diffusive samplers exposed in the field agreed within 5% in 95% of the comparisons.EVALUATION OF DIFFUSIVE SAMPLER METHODS FOR MEASURING OZONE IN THE EUROPEAN ALPS Markus Hangartner’, Manfred Kirchner? and Herbert Wemer? “institute of Applied Ergonomics and Hyplene, EHT Ztxich, ‘Switzerland; *GSF Research Centre for Envionmental and Human Heath, Neunerberg. Germany, Insite for Bleclmatology and Envconmental Research, University of ‘Munich, Germany, Eleven research groups undertook an intercomparison of diffusive sampling methods for monitoring ozone at environmental monitoring stations in the Alps. Six different monitoring methods were used, with sampling Periods of one or two weeks, and results were compared with measurements. from conventional fixed monitoring station instruments integrated over the same sampling periods. The diffusive methods were as follows: presented as correlations of each individual diffusive method against the ‘reference’ fixed monitoring station instrument at each location. Table 1 Description of methods used ‘Method sampling description ceference peciod A 1 week diffusion tube, using 1,2-di(4-pyridyl)ethylene(DPE) 4 in acetic acid and glycol 8 1 week Permeation sampler, using DPE in acetic acid 4,2 c 1 week indigo papers without diffusion gradients; 3 extraction of isatin by ethanol and spectrophotometric determination at 403nm D1 1 to 2 weeks indigo papers with diffusion gradients, 4 exposed in protective tubes D2 tweek ‘as D1 but buffered to pH 2.2 4 E 1t0 2 weeks Potassium iodide on fiter papers with polyethylene 4 frit as diffusion barrier; determination of iodide by ion chromatography F 1 week surface active monitoring using potassium iodide 5 starch solution; spectrophotometric determination of iodine at 575m The results of the intercomparison are Values in Table 2 are linear correlation coefficients, and in the case of the last column, the 68% confidence interval (one standard deviation) of the ‘true’ value predicted from the diffusive sampler results. significant at 53 level refers to ciferet instutes using this method Table 2 Correlation between integrated methods and continuous ozone monitors ‘method exposure Gammisch Wank Bozen Ritten Milan Isora overall 68% irchen iaterval ‘om 730m 1780 m 260 m 100 m 100 m 240 m A 7 0.85* 0.88" 0.84" 0.89" 0.89" 0.82" 0.91" 12.4" B 7 0.27 0.69" 0.72" 0.52* 0.78" 0.57" 0.62" Ola" 7 075° 0.21 . 0.48" 0.18 0.32 0.33° Dia 14 0.88" 0.86" 0.77" 0.85" 0.96" 0.75" 0.84" D2a 14 0.78" 0.49 0.72" 0.89" 0.91* 0.81" 0.84* /D2b 14 0.81" 0.62 0.89" 0.91" 0.97* 0.81" 0.62*cause of accurate prediction of U,,, but the ‘method still requires Freundlich isotherms to be determined for the sorbent-sorbate combi concemed. The determination of Freundlich isotherms requires the generation of standard atmospheres at a range of concentrations. These atmospheres “are then sampled to determine the breakthrough volume at each Concentration, This relatively complex Procedure limits the usefulness of the approach, Recent work" sponsored by the European Commission Measurements and Testing Programme (formerly known as BCR), has shown that, under certain conditions, Uy for the Perkin-Elmer tube can be predicted to 10% from V, (the dynamic specific retention volume) alone. ‘Broadly, these conditions are: Total atmospheric concentration _< 10 ppm Exposure time 2-8 hours vy 100L.g" 106, Carbopack 8, Carbotrap, Tenax GC and a graphitised form of Tenax, Tenax GR. in the main phase tests, Chromosorb 108 was the ‘front runner, Performing satisfactorily against pre-set criteria for 16 out of the 19 VOCs, against 8 for Tenax cc, As a result, HSL can recommend Chromosorb 108 as a suitable sorbent for the 16 test ‘compounds and by implication for all VOCs in a similar volatility range. Only for the most volatile and polar compounds, i.e. for propane, methanol and ethylene oxide, was Chromosorb unsatisfactory and here an alternative sorbent, Carboxen §69 is recommended, For all practical purposes, therefore, HSL can Fecommend a single universal sorbent for nearly all VOCs. In contrast, NIOSH's Manual of Analytical Methods, the 4th edition of which has just been published, recommends for the 16 available methods (there are none for Propane, a-pinene or decane) no less than six different sample tubes and seven different desorption solvents; a headache if you want to monitor more than one component at a time! The new data on Chromosorb 106 will be incorporated into a revision of MOHS 72 (the Pumped tube method) and the corresponding ISO method is also in course of revision. Overall, the research will enable HSE's enforcement arm to be more cost-effective in undertaking assessments where monitoring of VOCs is required. ‘Summary A recent study, funded by the Measurements and Testing Programme of the European Commission, has recommended a single collection medium which is suitable for the sampling of nearly all volatile organic. compounds of interest to the occupational hygienist. This medium; a chromatographic sorbent known as Chromosorb 106, is used in Conjunction with thermal desorption and gas chromatography to give a fast and efficient Measurement of these compounds in workplace air. The results will be used in revisions of MDHS 72 and MDHS 80. Overall, 13 the research will enable HSE's enforcement arm to be more cost-effective in undertaking assessments where monitoring of VOCs is required. © Crown Copyright 1996 - Health and Satety Executive — MATHEMATICAL MODEL FOR PREDICTING SAMPLING CAPACITY OF CHROMOSORB 106 J.L. Sanz and M.J. Quintana INSHT, La Dinamita &.n, Mente Basab - Cruces, €-48603, Barakaido, Spain Data from the ~— above _—study (EC-MAT-CT92-0038) has been evaluated together with information on polarity (dielectric constant) and boiling point. This indicates that @ good correlation can be obtained between predicted and actual values of dynamic sp fetention volume, V, (L.g"), if the following empirical equation is used: 0.562706 - 0.06141 x, + 0.023803 x, X,-ilectric constant (NBS circular 514) X= boing point (°C) F 209706 Some examples are given in the following table; Table 1 predicted and measured retention volumes on Chromosorb 106 compound tea Vatobs) [09 Va (calc) ug Lg? Propane 0.54 0.34 methanol ot 0.106 ethylene oxide 0.14 0.03 ethanol 0.73 0.94 ichloromethane 1.06 0.96 methyl acetate 1.37 1.51 methyl! ethy! ketone 1.45 1.31 pentane 1.63 1.31 hexane 1.94 2.09 benzene 1.97 231 butanol 2.35 2.26 ‘a-pinene 3.78 an decane 5.03 4.59 Presented at XIVth World Congress on Occupational Safety and Health, Madrid, 1996‘Compound Seent Level Uptake Source Compound Serbert Level Uptake Source Ree partoromatyeyiopentane (ot) 4-rathycateranone Certcrap 8 1SmLnour 7 Teta 0 214 27 perfooromethytcjccherae (not) furturat Toma A 28) 10 Carbone B 1SmLnour 7 evar Tata 0 fea a7 ecana TowTA 0 2% stem and Stal Ethers ‘Alcohols sirytacette —crvom 108. B 98 ToatA 8 $65 propant-ot—Chrom105 «447 nivifacdate TemacTA 8B 18325 Propan-2-opropane) Chom 08 8 218 Spheccrd C20 TomcR 8 19 Chemi0s « ts2 ar Woo neetate Chom 106. «D217? butanol Gwem108. «174 ar a Oe Tour D189 FF sectueceite Chrom i060 229 Zr ‘aebutael Chom.106 8 181 TomTA 0 190 ar TemGR 8 1 tatbuty ecetate Chrom108 0 238 2 Tomita 8 138 Trata 0 170 futur skohot_ Tena TA «D280 vin acetate Chom 108 «D183 2 teahjeroturtun acto! mati methecryate Pork 8 20,18 Chom ios D239 ar Chom 05 0 314 27 Tea TA D190 TemxTa, tT? oF rath acrfate —Chrom106 DB teo Zr Mascelaneaus TeataA D180. 2 butiecryate — TeraxTA B28 scrfoniile ——PorspakN A138 23 tryhenf acryfate TenaxTA D299 27 Chom 106 Das 27 2methonyatanel Porpaka ok 1s 21 estontne Porapak NR 4.002) i Chomios 8 218 PorapakN A O8(6ms) 11 Zatnonetnanct Tene ke 21 Chrem 108 0 Sas ar 2methonyety acetate Propontrie Porapak” A 1.4(3hre) if Porpako A 28 at PoapakN A 13(6hs) 11 Chom 10s @ 308 2 catbondisuphie Sprercars A | ae TeaecR 8 th hiro ode rte2) Mol Seve SAB 1352 Toate 8 teh stiyere onde” Spheeeno B18 13 2ehowytyacatateCrvom 108 B23 ‘dorane Spheres «C30 Teta 8 2054 sv oveieyetner chrom. 108 240 Tenm GR 20 TeaTA 0 8 2 butowetnanel — Cham0s. «Bo 208 but yeyletner Chrom.108 D261 a7 Teta Bia? Teta 0 23827 1 metho propanol tetranyctotran Chom 108 tee Chom ios 8 tes 4 rvmethypyreidone TenaxTA S183. 37 Toate 8 158 4 Teak 8 188 2 Ne onie 8 250 ENVIRONMENTAL APPLICATIONS Teta Bast Temon 8 a OB Compound Sorbent Level Uptake Source t-athon-2-popanal Chrom 106 Bot 3s Rate Teck 8 fe Hudeocartons Teta 8 te os Dbutowyey acetateChrom. 108 8279S benzene Tenax TA os 24 Tense 8 bie Teck 8 08 TewTA 8 22 Chom ios 8 4 Propocytnanst — Chrom108 Digs a Sarbogapnt 8 2005-08 38 Tata 0 tes totvene Toate B12 3 Chram 105 B24 ‘Aldehwies and Ketones Covogapns 8-228 68H — sfene TemrTe B48! 8 2bdanone Chom. 108 «BTS monfene Chrem 0s B 2088.09 28 Tock 8 ia Carbograph 8 2198.03 28 TrmTA 8 14 2B ttimetyberzene Tenuta B 265 3 ‘math isobuy ketene (meth f-+pertanone) ecane TomTa 8 298 3 Teta B74 Undecane Toma 8338 3 ToaeGR B69 25 Chromo 8 201 4 opeorecarene —TerasTA D178 os Nate: Chom 106 8 196 Bs ois sc2 og. ppm'smin'; most values sre for 8 ts; TraGR 8 1 trvronmerial values ae for 4 weeks 2 methyecoheranane bold rmeans peered sorter Teta 0 231 2 fe not ocormened because of varying uptake ate ‘Smetryeyceneanone “sampler wih memtrane TemTA 0 2m 15CONFERENCE NEWS. ‘THERMAL DESORPTION - 15 YEARS ON A joint meeting of the Automatic Methods Group and South East Region of the Royal Society of Chemistry is to be held on 17 December 1996 at the Scientific Societies’ Lecture Theatre, London The meeting will combine an examination of the theoretical basis for thermal desorption with @ number of brief application papers covering workplace, indoor and ambient air monitoring, Purge and trap, residual solvents, volatiles from plants and building materials and finally, Biological monitoring, Further information on the meeting may be obtained by photocopying and sending. the reply slip below to Dr Alan Braithwaite, address below. Response form RSC meeting Please send further details about the RSC meeting THERMAL DESORPTION - 15 YEARS ON Name and Titl.... Position, Organisation... Address. Post code.. Country. Telephone... FAX... email. SIGNED. Data Protection Act: The above details wil be colated on a Computer database for the purpose of maling RSC Conference information only Relum to: Dr A Brathwaite, Nottingham Trent University, Dept of Chemistry, Cliton Main Site, Notingham NOt! NS. tel, #44-115-9411-8418 x 3345 lat. ema x* 7 THE DIFFUSIVE MONITOR Response form .- Please retain my name on the mailing list + Please delete my name from the mailing list NB. Nil replies will be deleted!!! .. lean access intemevwww .. lean access e:mail only ~» | eannot access internet’ e:mail Other comments.. Correct address as follows: Name and Title. Position... Organisation... Address... Post code Country.. Telephone. FAX. email... SIGNED. 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