The HEMICPD project comparing emission test protocols

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The HEMICPD project comparing emission test protocols E Goelen 1, F Maes 1, M Lor 2, K Vause 2, K Dinne 2, A-C Romain 3, C Degrave 3, J Nicolas 3 VITO 1 Unit Environmental Risk and Health Boeretang 200, 2400 Mol, Belgium BBRI 2 ULg 3 1

Overview Hemicpd introduction Results monitoring IAQ Results Hemicpd (ongoing) Future work Conclusions 2

HEMICPD programme Horizontal evaluation method for the implementation of the construction products directive evaluation method implementation cpd - - - standardisation (CEN TC 351 WG 2) - - - building materials Programme (2007-2010) Inventory of relevant information : standards, test methods, labels,substances, emission data Selection building materials ; development of test methods Comparison of different complementary test methods Validation & possible modification of test methods Outcome : proposal for an evaluation model/method for implementation in Belgium BBRI Belgian Science Policy Solving the tvoc challenge! --- IAQ monitoring 3

FLIES Flanders Indoor Exposure Survey 2005-2007 Study : http://wwwb.vito.be/flies all data and reports Micro environments (appr 90) : dwellings ; transport ; leisure-sport; schools-day care (selection of indoor environments) VOC s+tvoc/aldehydes/no 2 /PM time activity patterns exposure risk evaluation (selection of pollutants) to determine for children the indoor environment exposure as a result of contaminants that occur in outdoor and indoor air (through measurements indoor-outdoor : status pollution) 4

Onderzoeksproject FLIES Flanders Indoor Exposure Survey 2005-2007 Urban background locations Stedelijke Achtergrond (n=25) Stedelijke Achtergrond (n=25) 14 12 10 8 6 4 2 0 Achterdeur Voordeur Woonkamer Slaapkamer 5 Benzeen Trichloroetheen Tolueen Tetrachloroetheen Ethylbenzeen m- + p-xyleen Styreen o-xyleen Gemiddelde Concentratie (µg/m³) +/- Standaard Afwijking) 1,2,4-Trimethylbenzeen p-dichloorbenzeen Vluchtige Organische Stof 50 45 40 35 30 25 20 15 10 5 Gemiddelde Concentratie (µg/m³) +/- Standaard Afwijking) 0 Achterdeur Voordeur Woonkamer Slaapkamer NO2 Formaldehyde Acetaldehyde

FLIES: results Comparison with IE decree Compound TVOC Benzene Formaldehyde PM2.5 PM10 Time basis 0,5h Year 24h Guideline value (µg/m³) 200 2 10 15 40 Number of exceedences 51 30 48 Living room (n=52) Maximum (µg/m³) Second highest res (µg/m³) 2793 1298 23,7 15,1 91 91 Minimum (µg/m³) 229 0,77 3,0 Number of exceedences 49 24 43 8 2 Bedroom (n=50) Maximum (µg/m³) Second highest (µg/m³) 1195 1003 14,5 7,1 124 84 43 32 58 46 Minimum (µg/m³) 222 0,69 2,01 16,5 19,8 There must be something else 6

Long term health survey of dwellings&dealing with complaints Investigation of health complaints in relation to the IAQ Training of regional teams for field work and feedback ; web based registration ; routine hand held instrumentation in combination with sampling/lab analysis ; back up from scientists through call center function. Initiation through medicins or public health workers Normal values : see routine programme below Surveillance of IAQ in dwellings/public buildings (5 y programme) : needs Fysical parameters : noise and thermal comfort (T, %RH, air velocity), ventilation Chemical parameters : aldehydes (form, acet, TCarbonyl), individual VOC s, TVOC, CO2, NO2, asbestos maybe, PM2.5, PM10, POP s (PAH) ; individual VOC s : BTEX, styrene, 1,2,4TMB, p-dichlorobenzene, tri and tetrachloroethylene, MTBE (traces) Biological (moulds and spores) Ambitious : 90 buildings/year ; location, type of building, socio econ factors Current programme : parameters underlined, 1 year running Regional Ministry of Public Health VITO : intention is untill 2012 7

Measurement methods VOC Aldehydes NO 2 CO 2 Air velocitu T en RH 8

Indoor Measurement Set Up 9

concentratie in µg/m 3 9,0 8,0 7,0 6,0 5,0 4,0 3,0 2,0 1,0 0,0 gans Vlaanderen Results VOC-TVOC Mediane concentraties van alle woningen voor gans Vlaanderen en per provincie met inbegrip van TVOC (85 woningen, stand 6/10/08) West-Vlaanderen Oost-Vlaanderen Antwerpen Limburg Vlaams-Brabant 450 400 350 300 250 200 150 100 50 0 µg/m 3 TVOC MTBE Benzene Trichloroethene Toluene Tetrachloroethene Ethylbenzene m- + p-xylene Styrene o-xylene 1,2,4- Trimethylbenzene 1,3- Dichlorobenzene 1,2- Dichlorobenzene tvoc 10

Results CO 2 700 Mediane concentraties van alle woningen voor gans Vlaanderen, opgesplitst per woningtype 600 500 ppm 400 300 200 (half)open bebouwing gesloten bebouwing appartementen 100 0 CO2 11

25 Results aldehydes Mediane concentraties van alle woningen voor gans Vlaanderen, opgesplitst per type omgeving (omgevingsdruk) 20 µg/m 3 15 10 stedelijk centrum stedelijke achtergrond 5 landelijke achtergrond 0 Formaldehyde Acetaldehyde Andere aldehyden (totaal) 12

Conclusion Results VS guideline values (Indoor Air Decree BS 19/10/04) exceedence % of guideline value CO 2 (83% exceedences) ----- guideline 900 mg/m³ formaldehyde (90%) ----- 10 µg/m³ other aldehydes (48%) ------- 20 µg/m³ TVOC (73%) --------- 200 µg/m³ benzene (14 %) ---------- 2 µg/m³ RH (17%) no exceedences for NO 2 (135 µg/m³), acet (4600 µg/m³), T3CE (200 µg/m³), Tol (260 µg/m³), T4CE (100 µg/m³) 13

BiBa : IAQ schools Influence of ventilation, outdoor(location), materials, building parameters 2008-2009 Strategy and programme : Each school : FD, BD, min. 3 class rooms ; 30 schools(6000), 90, class rooms Calculate from meas results exposure (time-activity patterns) and benchmarking Infiltration from outdoor to indoor (calculate) Distribute questionnaires : building, overall perception of the Ind Env, ventilation, time patterns Winter : november - february What to measure(public available end 2009) : PM2.5 ; distribution continuous PM10/PM2.5/PM1 Aldeh (2) ; VOC s (7) ; TVOC as VOC and SVOC CO2 (ventilation) Mould(visual), T, %RH Effect of sensibilisation (ventilation) Effect of air purifier 14

Database http://www.ktl.fi/expoplatform/co ncdb_ui Measured exposure conc in diff micro environments ; mainly VOC s, metals http://wwwb.vito.be/flies Indoor air quality in Flanders 15

Database http://www.ktl.fi/expoplatform/co ncdb_ui http://wwwb.vito.be/flies 16

Conclusie 17

HEMICPD programme Horizontal evaluation method for the implementation of the construction products directive evaluation method implementation cpd - - - standardisation (CEN TC 351 WG 2) - - - building materials Programme (2007-2010) Inventory of relevant information : standards, test methods, labels,substances, emission data Selection building materials ; development of test methods Comparison of different complementary test methods Validation & possible modification of test methods Outcome : proposal for an evaluation model/method for implementation in Belgium 18

Methodology : chambers, standards, instrumentation C 19

Selection of test methods - overview Procedure Sampling time What FLEC ISO 16000-10 3, 7 and 28 days 10 highest VOCs TVOC (+indiv) µcte - literature - manual - (ISO 16000-25) 0 and 3 days: after 5, 20 and 40 min precond. TSVOC Analysis: ISO 16000-6 Test chamber ISO 16000-9 3, 7 and 28 days 1 m³ Odour Test chamber 50.5 m³ (ISO 16000-9) 3, 7 and 28 days Aldehydes ISO 16000-3 Sampling, storage of samples and preparation of test specimens: ISO 16000-11 20

Methodology : chambers, standards, instrumentation, materials Resilient flooring materials : correlation between chambers, influence climatic conditions Vinyl (pvc) floor covering (3 types) Linoleum Vinyl (pvc) floor covering Full wooden parquet : time profile (Flec, µchamber) Wood based panels : effects ozone/pm measurements Liquid products : sealant, paints (single and on surface) : substrate effect Parameters Values µ-cte FLEC 1m 3 50m 3 Chamber volume (m 3 ) 0.0000032 0.000035 1 50.53 Exchange rate (h -1 ) 1875 514 0.5 0.5 Load factor (m 2 /m 3 ) 400.6 507 0.4 0.42 Area specific air flow rate (m 3 /m 2 h) 4.68 1.01 1.25 1.19 21

Overview of SERa (µg/m²h) and TVOC/TSVOC of different test chambers for sample 1 (floor covering) Compound FLEC FLEC FLEC µcte µcte µcte µcte µcte µcte 3 days 7 days 31 days 0 days 5 min 0 days 20 min 0 days 40 min 3 days 5 min 3 days 20 min Phenol 27 19 7 249 210 83 169 120 85 Heptane, 2,2,4,6,6-pentamethyl- 13 8 5 239 163 178 317 211 54 Decane 18 11 5 194 173 125 259 184 45 1-Hexanol, 2-ethyl- + butylcyclohexane 36 15 11 527 525 397 500 430 287 Ethanol, 2-(2-butoxyethoxy)- 54 32 19 486 212 402 517 374 Pentanoic acid,2,2,4-trimethyl-3- carboxyisopropyl, isobutyl ester 118 89 81 948 884 930 946 1591 386 TVOC / TSVOC 1104/181 639/77 348/52 10222 /1254 8041/ 847 6960/ 683 Compound 1 m³ 1 m³ 50,5m³ 50,5m³ 50,5m³ 3 days 28 days 3 days 7 days 28days Phenol 22 10 16 Heptane, 2,2,4,6,6-pentamethyl- 14 7 6 7 Decane 15 8 11 6 1-Hexanol, 2-ethyl- + butylcyclohexane 26 17 8 10 14 Ethanol, 2-(2-butoxyethoxy)- 40 14 Pentanoic acid, 2,2,4-trimethyl-3- carboxyisopropyl, isobutyl ester 116 152 5 1 14 TVOC / TSVOC 1024/206 348/ 483/70 646/74 640/52 11275/ 754 11594/ 2162 3 days 40 min 4900/ 1002 22

SER of the most abundant components in the different emission experiments 1800 1600 1400 phenol 1200 Heptane, 2,2,4,6,6-pentamethyl- SER m³/m²h 1000 800 600 400 Decane 1-Hexanol, 2-ethyl- + butylcyclohexane Ethanol, 2-(2-butoxyethoxy)- Pentanoic acid, 2,2,4-trimethyl-3- carboxyisopropyl, isobutyl ester 200 0 flec 3 days flec 7 days flec 31 days 0 days 5 min 0 days 20 min 0 days 40 min 3 days 5 min 3 days 20 min 3 days 40 min 1m³ 3 days 1 m³ 28 days 50,5m³ 3 days 50,5 m³ 7 days 50,5 m³ 28 days experiments 23

Overview of SERa (µg/m²h) and TVOC/TSVOC of different test chambers for sample 1 (floor covering) 7000 SERa (µg/m²h) TVOC+TSVOC 6000 5000 4000 3000 2000 1000 flec 1 m³ 50 m³ µchamber 0 3 days 7 days 28 days 24

Overview of SERa (µg/m²h) and TVOC/TSVOC of different test chambers for sample 2 (floor covering) 35000 SERa(µg/m²h) TVOC+TSVOC 30000 25000 20000 15000 10000 5000 flec 1 m³ 50 m³ µchamber 0 3 days 7 days 28 days 25

Overview of SERa (µg/m²h) and TVOC/TSVOC of the different test methods of sample 2 Compound FLEC FLEC FLEC µcte µcte µcte 1 m³ 1 m³ 1 m³ 50 m³ 50 m³ 50 m³ 3 days 7 days 28 days 3 days 40 min 7 days 40 min 28 days 3 days 7 days 28 days 3 days 7 days 28 days Tridecane 1673 1531 501 4939 2793-2119 1811 503 1061 860 208 Dodecane, 2,6,10- trimethyl 490 640 263 2208 1044-786 618 344 398 371 145 Tetradecane 1823 2100 830 5321 3813-2382 2069 907 1110 1064 404 Dodecane, 2,6,11- trimethy m 388 448 216 1183 775-453 403 277 212 211 118 Pentadecane 565 667 361 1062 1087-591 629 367 223 221 149 TVOC / TSVOC 7726/19 74 1054/249 2 3376/122 8 27940/128 40 12840/30 70-9550/17 35 6994/153 2 5272/11 6 3 4888/46 4 4845/65 1 1460/57 5 26

Overview of SERa (µg/m²h) and TVOC/TSVOC of different test chambers for sample 3 (floor covering) 700 SERa(TVOC+TSVOC) µg/m²h 600 500 400 300 200 100 flec 1 m³ µchamber 0 3 days 7 days 28 days 27

Overview of SERa (µg/m²h) and TVOC/TSVOC of different test chambers for sample 4 (floor covering) 180 SERa (TVOC+TSVOC) µg/m²h 160 140 120 100 80 60 40 20 flec 1 m³ 50 m³ 0 3 days 7 days 28 days 28

Overview of SERa (µg/m²h) and TVOC/TSVOC of the different test methods of sample 4 (linoleum) Compound 1m³ 1m³ 1m³ Flec Flec Flec 3 days 7 days 28 days 3 days 7 days 28 days Hexanal 12 11 11 4 3 3 Hexanoic acid 28 26 18 18 15 11 Nonanal 5 6 6 5 5 1 Heptanoic acid 6 5 4 6 4 4 Octanoic acid 5 6 4 7 5 4 TVOC / TSVOC 143/20 131/25 99/17 118/39 92/35 67/29 Compound 50m³ 50m³ 50m³ 3 days 7 days 28 days Hexanal 9 7 4 Octanal 1 1 0 Nonanal 4 3 3 Decanal 3 2 3 TVOC / TSVOC 98/12 112/12 94/18 29

Comparison based on identified chemical groups 30

Cétone, 2% Aromatique, 9% Comparison based on identified chemical groups Sample 2, Flec, day 3 Ether, 1% CycloAlcane, 6% HAP, 3% Alcool, 1% Sample 2, 1 m³, day 3 Alcane, 78% CycloAlcane, 6% HAP, 3% Ether, 1% Aromatique, 8% Alcool, 1% Alcane, 81% Sample 2, 50 m³, day 3 CycloAlcane, 7% HAP, 3% Ether, 1% Aromatique, 6% Alcool, 1% Alcène, 1% Alcane, 81% 31

3,0 2,5 2,0 1,5 sample 2 sample 4 chemical families PCA analysis 50 m³ Factor 2 (28%) Factor 2 (28%) 1,0 0,5 0,0-0,5-1,0 Cyclo 3 chambers HAP Ether Alkane Alcohol Aromatic FLEC Ketone Alkene Fatty acid Aldehyde 1 m³ -1,5-2,0-1,5-1,0-0,5 0,0 0,5 1,0 1,5 2,0 Factor 1 (58%) HEMICPD 32

Comparison of test protocols (ongoing) Application of 3 evaluation protocols on 7 building materials (all in 1 m³ test chambers) AgBB (2008); AFFSETT (2006), ECA report nr 18(1997) Loading factors AgBB : quantitative 177 LCI compounds AFSETT : quantitative 214 LCI compounds Check results VS quantification based on 1 comp/chem class (ANSI-BIFMA M7.1-2007 procedure) Materials : wooden panel(osb), acryl paint, wall plaster (knauf), glue, glue with floor covering, rockwool insulation, wooden panel (MDF) 33

Acknowledgement Co-workers BBRI : M Lor, K Vause, K Dinne VITO : F Maes, E Goelen ULg : C Degrave, A-C Romain, J Nicolas Co-funding Belgian Science Policy, Belgian Fed Min Economy, Belgian Flanders Reg Min of Environment, Flanders Reg Min of Health 34

IAQ instrumentation and methods FLIES and other studies T en %RV Air velocity CO2 PM 10 / PM 2.5 /PM 1 Lab analyses Aldehydes / VOS / TVOS / SVOS CO2 35

Specific studies : PAH as a start to go for POP Indoor exposure to PAH 25 dwellings : winter and summer (twice each dwelling) New method : 16 EPA PAH PE : PDMS/tenax includes. ; analyses GC-MS (J of Chrom 1190(2008), 286-293) Indoor and outdoor simultaneously Scheduled to run in 2009 36