PCB: Detoxification of building materials in DK Presentation for EURITS d. 14 May 2012 Lars Gunnarsen Danish Building Research Institute, Aalborg University Polychlorinated biphenyl PCB fundamentals Sum 7 congeners: 28, 52, 101, 118, 138, 153 og 180 2 dioxin-like congeners: 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, og 189 All PCB congeners akkumulate in human bodies 105 og 118 has WHO TEF på 0,0001 and for 156 it is 5 times bigger Highest TEF has nr. 126 with TEF equal 0,1 Vapor pressure of PCB 118 at 25 C is 8.974 × 10–6 mmHg = 0.001196 Pa = 1.18 × 10-8 atm. In air at 1,013 × 105 Pa (1 atm) this is equal to 12 ppb or 160 µg/m3 Occupational TLV is 0 µg/m3 The national Board of Health reccomends action limits set at 3 and 0,3 µg/m3 for indoor air Construction products Indoor air Surface Dust Soil Fø r 19 190 0 00 -19 19 05 04 19 190 9 10 -19 19 15 14 19 191 9 20 -19 19 25 24 19 192 9 30 -19 19 35 34 19 193 9 40 -19 19 45 44 19 194 9 50 -19 19 55 54 19 195 9 60 -19 19 65 64 19 196 9 70 -19 19 75 74 19 197 9 80 -19 19 85 84 19 198 9 90 -19 19 95 94 -19 99 20 00 - Building area (mio m 2 ) Bygningsbestand 50 45 40 35 30 25 20 15 10 5 0 Opførelsesår Erection Year 1950 to 1976 where PCB containing sealant were on the marked 143 mill. m2 new buildings have been erected which is 37 % of the total building stock of 389 mill. m2. Have not got new windows since 1976 61 % Have rubber-like inner sealants 59 % Have rubber-like outer sealants 22 % Length inner sealants per area 0,47 m/m2 Length inner sealants per area 0,47 m/m2 Some inofficial guestimates Total remaining PCB in construction products Mass primary PCB sources 20 x103 kg 6.6x106 kg Mass secondary sources 3.4x109 kg Temperature dependency of vapor pressure PCB 28 0.7 EKSP(34,92 - 11,624*1000/(t + 273)) Vapor pressure (Pa) 0.6 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40 50 Temperature (oC) Equation valid 40-55 oC 60 > 50 mg PCB/kg Dangerous waste To be destructed at approved inceneration plant or deposited underground (not possible in Denmark) 0,1 – 50 mg PCB/kg Not dangerous waste •Waste with PCB content of less than 1 mg/kg may be deposited at depot for inert waste •Waste with PCB content between 1 and 50 mg/kg, may be deposited at depot for for mineral waste or mixed waste < 0,1 mg PCB/kg Products for reuse May be reused according to other specific rules after notification of municipal authorities PCB exposure from indoor air and health risks in relation to recommendations from National Board of Health Recommendations are based on occupancy of buildings 24-7 for several years. Action values for building occupancy. > 3.000 ng PCB/m3 air Highest level. Immediate action required. Durable sollutions - could be evacuation of building - should take place before 6 months. 300 – 3.000 ng PCB/m3 air Intermediate level. An action plan required to after some time assure indoor air concentrations below 300 ng PCB/m3 luft. At 2.000 – 3.000 ng PCB/m3 it is recommended that a maximum of one year may pas before a durable solution is commenced. At 300 – 2.000 ng PCB/m3 it is recommended that a maximum of two years may pas before a durable solution is commenced. Temporary alleviation measures should be considered. < 300 ng PCB/m3 air Lowest level that does not increase the health risks. Homepage of the project SBi.dk/pcb (in Danish) Projekt planning 1. år F1. Planning Litterature survey F2. Laboratory tests Field tests Data analysis F3. PCB instruction guide Field tests Data analysis F5. Improved guide 2. år 3. år 4. år Recent measurements 24 congeners included in the analysis: PCB-28, 52, 66, 74, 77, 81, 99, 101, 105, 114, 118, 123, 126, 138, 153, 156, 157, 167, 169, 170, 180, 183, 187 og 189. (Dioxin-like in red) Blood samples furthermore included congener number 69, 178, 182 og 190. Sample summary • Results from: – 83 air samples (Birkhøj) – 20 sealant samples (Birkhøj) – 21 air samples (uncontaminated parts of Farum Midtpunkt) – Approx. 200 blood samples 100 from contaminated and 100 from PCB free appartments Sealant samples were taken by knife for single use after removal of temporary sealing with aluminum tape and wodden panels. Air samples were taken by adsorption on XAD-2 and a total sampling volume during approx. 24 hours of approx. 2.7 m3. Results, air Birkhøj (n=83), PCBtot • Average: 1030 ng/m3 • Interval: 168-3843 ng/m3 • 80 appa. > 300 ng/m3 ; 8 appa. > 2000 ng/m3 ; 1 appa. >3000 ng/m3 Øvrige (n=21), • PCB > LOQ in 52% • Average = 6.0 ng/m3 ; interval <LOQ – 254 ng/m3 • OBS! one appartment with high PCB-level. The occupant had lived 31 years in contaminated part and indoor air contamination from household contents suspoected. Resultats, sealants • Average ∑24PCB: 100 817 mg/kg (187 – 221 667 mg/kg) • Average PCBtot: 252 150 mg/kg (436 – 718 430 mg/kg) 6 Group C Ar-1254 414E 414F 439E 410F 422E PC 2 (23%) 4 2 Group A 0 Group B 406C Group D Ar-1232 410D 410E 413D 427A 401A 446D 444F 456F 448A 456A 435D 434D 435A 433C -2 Ar-1242 -4 -10 -5 0 PC 1 (76%) 5 Air vs. selants PCB-28 in air and sealant PCB-52 in air and sealant 100000 PCB-52 in sealant (mg/kg) PCB-28 in sealant (mg/kg) 10000 1000 100 10 10 100 1000 3 PCB-28 in air (ng/m ) 10000 1000 100 10 10 100 1000 3 PCB-52 in air (ng/m ) • Good correlation for low-chlorinated (even intercorrelation) • No correlation between air and sealants for highly-chlorinated Sum of 24 measured congeners in indoor air (ng/m3) Sum of 12 non-dioxinlike congeners in indoor air (ng/m3) Sum of 12 dioxinlike congeners in indoor air (ng/m3) ,7 PCB 118 in plasma, ug/l 241 ,6 240 ,5 201 ,4 219 103 165 127 ,3 35 ,2 94 79 3 273 41 250 75 ,1 0,0 -,1 N= 134 Non-exposed PCB exposure in apartment 139 Expose 20 15 10 5 PCB exposure 0 Exposed -5 Non-exposed -5 0 5 10 15 20 25 30 35 40 Number of years living in Farum Midtpunkt dwelling Correlation coefficient 0.69 ; p<0.001 (Spearman); n = 154 12 10 8 6 PCB 28 in plasma, ug/l Sum of 3 - 4 chlorine PCB in plasma, ug/l 25 4 2 0 0 PCB 28 in air of dwelling, ng/m3 100 200 300 PCB content in selants in contaminated part PCB congener Number Concentration, mg/kg Average Min 25 percentile Median 75 percentile Max Sum 24 20 100817,4 187,0 4556,5 101040,0 168584,8 221677,0 Sum_DL 19 13472,3 29,4 1071,7 15836,8 22370,7 26382,3 Sum_NDL 20 87274,4 157,5 3465,9 80113,3 152273,9 206043,0 Total PCB (6) 20 252149,7 436,0 7005,2 165207,5 500091,3 718430,0 Total PCB (6+1) 20 283017,0 511,6 9678,8 210992,5 538203,8 749330,0 PCB in indoor air in contaminated part PCB congener Sum 24 Concentration, ng/m3 Average Min 25 percentile Median 75 percentile Max 284,90 43,31 150,13 235,77 350,57 1060,02 3,21 0,18 1,20 2,19 3,53 16,53 281,68 43,10 146,96 233,73 349,21 1043,48 Total PCB (6) 1030,15 167,97 531,21 858,75 1333,83 3842,88 Total PCB (6+1) 1038,90 167,95 534,55 861,95 1343,75 3888,30 Sum_DL1 Sum_NDL2 Questionnaire results b) Dusting a) Vacuuming 2000 2000 PCBtot, air (ng/m 3 ) PCBtot, air (ng/m 3 ) * 1500 1000 500 0 1500 1000 500 0 Daily Weekly Monthly Less Daily Weekly Monthly Less (n=9) (n=61) (n=10) (n=1) (n=3) (n=57) (n=19) (n=2) d) Airing 2000 1500 1500 PCBtot, air (ng/m 3 ) PCBtot, air (ng/m 3 ) c) Floor washing 2000 1000 500 0 1000 500 0 Daily Weekly Monthly Less Daily Weekly Monthly Less (n=2) (n=41) (n=29) (n=8) (n=54) (n=21) (n=5) (n=3) Cleaning does help Conclusions There still is PCB in some buildings – maybe in approximately 10% of the buildings from the relevant period Old sealants with PCB, will still be a significant source of PCB in indoor air, surface dust and the soil around the buildings. In rare cases this may lead to health risks for the building occupants PCB in dwellings leads to a significantly increased PCB contamination of building occupants. For these people the dwelling causes by far the most PCB intake Better ability to identify buildings with PCB is recommended More efficient means of renovation of PCB contaminated buildings are recommended More rigorous waste hanling recommended More reseach, innovation and consistency recommended