Environmental exposures in early childhood education environments

Environmental Exposures in Early Childhood Education Environments Agreement Number 08-305 Principal Investigator: Asa Bradman, PhD, MS Center for Environmental Research and Children’s Health University of California - Berkeley April 5, 2012 Prepared for the California Air Resources Board California Environmental Protection Agency Report Authors Asa Bradman, PhD Fraser Gaspar, MPH Rosemary Castorina, PhD Elodie Tong-Lin, BSc Thomas McKone, PhD Center for Environmental Research and Children’s Health University of California - Berkeley 1995 University Avenue, Suite 265 Berkeley, CA 94704 Randy Maddalena, PhD Indoor Environment Department Lawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley, CA 94720

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Disclaimer The statements and conclusions in this Report are those of the contractor and not necessarily those of the California Air Resources Board. The mention of commercial products, their source, or their use in connection with material reported herein is not to be construed as actual or implied endorsement of such products.

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Acknowledgements The authors wish to thank the California Air Resources Board (CARB) for sponsoring this study and especially CARB staff members Jeff Williams and Peggy Jenkins for ongoing technical and administrative support. We thank Drs. Walter Weathers, Mark Strynar, and Peter Egeghy of the U.S. Environmental Protection Agency National Exposure Research Laboratory for measurements of PFCs and flame retardants in dust and review of the final report. We also thank Marcia Nishioka of Battelle Memorial for measurements of pesticides and phthalates in dust and these compounds as well as flame retardants in air. Dr. Vickie Leonard assisted with participant recruitment, helped review the questionnaires and protocols, and advised us on returning results to participants. We also thank Dr. Rachel Morello-Frosch for assistance with returning results to participants. We thank Drs. Kazukiyo Kumagai, Jed Waldman, and Zhong Min-Wang from the California Department of Public Health Environmental Health Laboratory Branch for advice on the research, loaning us a DustTrak and reviewing the final report. We thank Dr. Martha Sandy of the Office of Environmental Health Hazard Assessment (OEHHA) for reviewing risk evaluation methods and approaches to incorporate age-specific sensitivity factors when evaluating OEHHA No Significant Risk Levels (NSRLs). We also thank Dr. William Nazaroff for advice on strategies to measure air exchange rates. We thank individuals at the Community Child Care Council of Alameda County and Monterey County Child Care Resource and Referral for help with participant recruitment. Finally, we thank the child care programs that participated in this study. This Report was submitted in fulfillment of ARB Contract No. 08-305, “Environmental Exposures in Early Childhood Education Environments”, by the Center for Environmental Research and Children’s Health, School of Public Health, UC Berkeley, under the [partial] sponsorship of the California Air Resources Board. Work was completed as of April 5, 2012.

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Table of Contents Abstract.................................................................................................................................... xiv Executive Summary .................................................................................................................. xv Background ........................................................................................................................... xv Methods ................................................................................................................................. xv Results .................................................................................................................................xvii Conclusions ........................................................................................................................... xx Body of Report ............................................................................................................................1 1

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3

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Introduction .......................................................................................................................1 1.1

Relevant Research ....................................................................................................2

1.2

Health Effects from Environmental Contaminants......................................................3

1.3

Importance of Air and Dust in Children’s Exposures ..................................................5

1.4

Research Objectives .................................................................................................5

Materials and Methods ......................................................................................................6 2.1

Research Approach Summary...................................................................................6

2.2

Phases of Study ........................................................................................................6

2.3

Child Care Recruitment .............................................................................................7

2.4

Site Visits ..................................................................................................................9

2.5

Environmental Sampling and Laboratory Analysis Summary ................................... 11

2.6

Quality Assurance and Quality Control Procedures ................................................. 24

2.7

Data Management and Analysis ..............................................................................25

Results ............................................................................................................................26 3.1

ECE Facility Characteristics ....................................................................................26

3.2

Volatile Organic Compound Results and Discussion ............................................... 32

3.3

Phthalate Results and Discussion ...........................................................................52

3.4

Flame Retardant Results and Discussion ................................................................58

3.5

Perfluorinated Compounds Results and Discussion ................................................ 69

3.6

Pesticide Results and Discussion ............................................................................72

3.7

Particle Measurement Results and Discussion ........................................................89

3.8

Metals Results and Discussion .............................................................................. 103

Health Risk Characterization .........................................................................................106 4.1

Reference Air Concentration Levels ...................................................................... 107

4.2

Inhalation and Oral Exposure Dose Calculations ................................................... 107

4.3

Oral Reference Dose .............................................................................................109

4.4

No Significant Risk Levels (NSRL) for Cancer ....................................................... 110

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4.5

Definition of Hazard Quotient.................................................................................111

4.6

Maximum Allowable Dose Levels (MADL) for Reproductive Effects ...................... 112

4.7

Health Risk Characterization Results .................................................................... 112

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Summary and Conclusions ............................................................................................127

6

Strengths and Limitations ..............................................................................................131

7

Recommendations ........................................................................................................132

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References ....................................................................................................................134

Glossary of Terms, Abbreviations, and Symbols .................................................................. 144 APPENDIX A- Supplemental Tables and Figures ................................................................ 148 Sampling Information Supplemental .................................................................................149 VOC Supplemental ...........................................................................................................151 Flame Retardant Supplemental ........................................................................................152 Pesticide Supplemental ....................................................................................................154 Health Risk Characterization Supplementary Tables ........................................................ 156 APPENDIX B- Group Maps..................................................................................................157 APPENDIX C- Additional QA/QC Information ...................................................................... 162 VOC QA/QC .....................................................................................................................163 Carbonyl QA/QC...............................................................................................................175 Phthalate QA/QC ..............................................................................................................178 Flame Retardant QA/QC ..................................................................................................180 Perfluorinated Compound QA/QC ....................................................................................183 Pesticide QA/QC ..............................................................................................................187 Ultrafine Particle QA/QC ...................................................................................................190 RealTime PM2.5 QA/QC ....................................................................................................191 Gravimetric PM QA/QC ....................................................................................................193 Metals QA/QC ..................................................................................................................196 QTrak QA/QC ...................................................................................................................197 List of Real-Time Malfunctions..........................................................................................198 APPENDIX D- Analysis of VOC Unknowns .......................................................................... 199 APPENDIX E- Chemical Inventory .......................................................................................208 APPENDIX F- Questionnaire, Inspection, and Visit Material Packet .................................... 213 Questionnaire Form for Early Childcare Facilities ............................................................. 214 Inspection Form for Early Childcare Facilities ................................................................... 252 Visit Materials Packet .......................................................................................................277 Sample Code Naming Convention .......................................................................................320 APPENDIX G- Sample Collection and Laboratory Analysis Standard Operating Procedures ..........................................................................................................................323 v

Dust Collection Protocol ...................................................................................................324 HVS3 Cleaning Protocol ...................................................................................................327 DustTrak Protocol .............................................................................................................328 Q-Trak Protocol ................................................................................................................330 CPC Protocol....................................................................................................................332 PUF Collection Protocol....................................................................................................334 VOC Collection Protocol ...................................................................................................336 Gravimetric PM2.5/ PM10 Collection Protocol .................................................................. 340 Standard Operating Procedure for Sieving Vacuum Cleaner Dust Prior to Analysis ......... 342 Standard Operating Procedure For Extracting and Preparing Air Samples for Analysis of Pesticides .....................................................................................................................345 Standard Operating Procedure for Extracting and Preparing Dust Samples for Analysis of Pesticides .....................................................................................................................348 Standard Operating Procedure for Determination of Pesticides in Sample Extracts by Gas Chromatography/ Mass Spectrometry ....................................................................... 351 Standard Operating Procedure for Extracting and Preparing Air Samples for Analysis of Phthalates ........................................................................................................................357 Standard Operating Procedure for Determination of Phthalates in Sample Extracts by Gas Chromatography/ Mass Spectrometry ....................................................................... 360 Standard Operating Procedure for Extracting and Preparing Air Samples for Analysis of BDEs ................................................................................................................................366 Standard Operating Procedure for Determination of Brominated Diphenyl Ethers in Sample Extracts by Negative Chemical Ionization (NCI) Gas Chromatography/ Mass Spectrometry ....................................................................................................................370 Extraction, Cleaning, and Method Performance Procedures for PBDEs in Dust ............... 376 Standard Operating Procedure for Analysis of Polybrominated Diphenyl Ethers by GC/MS/NCI ......................................................................................................................391 Standard Operating Procedure for Extracting and Preparing Air Samples for Analysis of Perfluorinated Acids .........................................................................................................398 Standard Operating Procedure for Determination of Perfluorinated Acids in Sample Extracts by Ion Chromatography Tandem Mass Spectrometry ......................................... 401 Standard Operating Procedure for Extraction and High Performance Liquid Chromatography/ Mass Spectrometry Analysis of Perfluorinated Acids and Sulfonates from House Dust...............................................................................................................407 Standard Operating Procedure for Analysis of VOC ......................................................... 411 Standard Operating Procedure for the Quantification of Particle Mass Collected on Teflon Filters.....................................................................................................................412

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Figures Figure 1. Typical products recorded in the inspection chemical inventory form, including pesticides, cleaners, metal polishers, paints, and other items that could affect indoor air quality. ...................................................................................................................................10 Figure 2. Indoor equipment set-up at an ECE facility. Left image includes the flowmeters and integrated samplers. Right image shows real-time devices. ..................................................10 Figure 3. PUF cartridge used to sample SVOCs with corresponding sample label affixed to cartridge. ................................................................................................................................16 Figure 4. Figure showing measured and predicted CO2 concentrations at ECE 29. By fitting the predicted CO2 model with the measured CO2 levels, air exchange rates were calculated for the different time periods when a field technician noted a change in the ECE environment (i.e., open window or door). ............................................................................................................31 Figure 5. Relationship between VOC analyte concentrations measured with standard calibration curves versus estimated concentrations from semi-quantitative method. Lines in graph are the linear regression and one to one slope...................................................................................47 Figure 6. Box plots of indoor (n=40) vs. outdoor (n=19) formaldehyde, acetaldehyde, and acetone concentrations. Acetone box plot does not include ECE 17 as it was an extreme outlier. ....................................................................................................................................50 Figure 7a. PBDE congener proportion of total PBDE concentration sorted on BDE-209. Each “stacked” bar is a PBDE congener measurement from one ECE facility (n=39)......................64 Figure 7b. Color version of PBDE congener proportion of total PBDE concentration sorted on BDE-209. Each “stacked” bar is a PBDE congener measurement from one ECE facility (n=39). ...................................................................................................................................65 Figure 8. Cumulative probability of child care day average indoor and outdoor ultrafine particle concentrations........................................................................................................................91 Figure 9. Comparison of full day ultrafine particle concentrations at two separate ECE facilities (ECE 18 and 19). In ECE 18, combustion sources were not present and ultrafine concentrations were low. In ECE 19, ultrafine concentrations rose twice due to use of a gas stove. .....................................................................................................................................93 Figure 10. Cumulative distribution plots of minute-by-minute (left) and child care day averages of PM2.5 (right) concentrations indoors and outdoors ..............................................................95 Figure 11. Scatter plot of paired indoor and outdoor PM2.5 and PM10 measurements at 12 ECE facilities. A one-to-one linear line was fit to each graph ..........................................................98 Figure 12. Indoor integrated PM2.5 and PM10 concentrations by county (left figure) and by child care type (right figure) ............................................................................................................99 Figure 13. Scatterplot of paired DustTrak and PEM PM2.5 indoor concentrations (n=35). DustTrak concentrations are averages over the entire child care day. Line represents linear regression between paired results. .......................................................................................102 Figure 14. Lead concentrations and their association with building age. Note lead concentrations are in the log scale. ......................................................................................105 Figures in Appendices Figure 15. Comparison of the three sorbent materials. Graph shows that the original method of sampling onto Tenax-TA backed by Carbosieve is adversely affected by the presence of volatile alcohols while the Tenax-TA in series with the CarboTrap 300 effectively separates the alcohol from the other VOCs. .........................................................................................165

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Figure 16. Inverted overlay of chromatograms from VOC sample collected in office room using Tenax-TA only (top chromatogram) and Tenax-TA/Carbosieve (inverted chromatogram) in the presence of hand sanitizers. ................................................................................................166 Figure 17. First round of washed silica gel run through HVS3- labeled silica 01 ......................184 Figure 18. Second round of washed silica gel run through HVS3- labeled silica 02 .................184 Figure 19. Washed silica deposited directly into sample container and not run through HVS3labeled silica 03. ..................................................................................................................185 Figure 20. Lab prepared dust blank- labeled DB .....................................................................185 Figure 21. Lab prepared methanol blank- labeled MeOH blank ...............................................186 Figure 22. Side-by-side CPC measurements taken at ECE 12 on 7/8/2010 and taken in UCB office building at the conclusion of air sampling campaign on 5/19/2011 ..............................190 Figure 23. Graphs showing hourly trend between MLD and DustTrak 1 PM2.5 measurements (left) and MLD and DustTrak 1 measurements plotted against each other with a linear fit line. .............................................................................................................................................191 Figure 24. Side-by-Side DustTrak Measurements Taken in UC Office Building on 1/24/2011 and After Sampling (5/19/2011). .................................................................................................192 Figure 25. Scatter Plots of Pre- and Post-Sampling Side-by-Side DustTrak PM2.5 ..................193 Figure 26. Side-by-side QTrak measurements at ECE 11, 12, and 13. ...................................197

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Tables Table 1. Sample Collection and Analytical Methods Summary. ................................................ xvi Table 2. Child Care Facilities by County and License Type ........................................................ 8 Table 3. Subject Areas for Study Instruments ............................................................................ 9 Table 4. Sample Collection and Analytical Methods Summary ..................................................12 Table 5. Integrated Air Sample Counts .....................................................................................13 Table 6. Indoor and Outdoor Average Integrated Air Sample Flow Rates and Sample Volumes .............................................................................................................................................13 Table 7. Real-time Sample Count Breakdown ...........................................................................14 Table 8. VOC Analytes Measured in Air ....................................................................................15 Table 9. SVOC Air Analytes Measured with PUF Cartridges .....................................................16 Table 10. Sample and Analysis Counts for Dust .......................................................................20 Table 11. BDE, Other Flame Retardants, and Phthalate Esters Dust Sample Target Analytes .20 Table 12. Pesticide, Metals, and PFCs Dust Sample Target Analytes .......................................20 Table 13. ECE Facility Characteristics ......................................................................................26 Table 14. Average Time Children Spent Outdoors ....................................................................27 Table 15. Average Education of Child Care Staff ......................................................................27 Table 16. Child Care Building Descriptive Statistics ..................................................................28 Table 17. Child Care Building Type ...........................................................................................28 Table 18. Unwanted Pests Observed Inside Facility .................................................................28 Table 19. Summary of Average Indoor Environmental Parameters (n=40) ................................29 Table 20. Summary of Average Outdoor Environmental Parameters (n=30) .............................29 Table 21. Summary of Average Air Exchange Rates during Air Sampling .................................30 Table 22. Calculated AER for Four Time Periods at ECE 29 .....................................................31 Table 23. VOC Analytes and Sources .......................................................................................33 Table 24. Summary of Indoor VOC Analyte Concentrations (μg/m³) .........................................36 Table 25. Summary of Outdoor VOC Analyte Concentrations (μg/m³) (n=20) ...........................38 Table 26. VOC Indoor to Outdoor (I/O) Concentration Ratios (n=20 ECE facilities)...................41 Table 27. Summary Traffic Metric Statistics (n=40) ...................................................................42 Table 28. Summary of Traffic Metric Statistics by County .........................................................42 Table 29. Association between Indoor and Outdoor VOC Concentrations and Nearby Traffic Intensity Tested with Spearman Correlations (rho) ...............................................................43 Table 30. Difference in VOC Concentrations between Facilities Reporting No Air Freshener Use and Air Freshener Use..........................................................................................................44 Table 31. Summary of Indoor Carbonyl Concentrations (µg/m³) (n=40) ...................................49 Table 32. Summary of Outdoor Carbonyl Concentrations (µg/m³) (n=19)..................................49 Table 33. Summary of Carbonyl Concentrations (µg/m³) by ECE Type .....................................50 Table 34. Summary of Indoor Air Phthalate Detection Frequencies and Concentrations (µg/m³) (n=40 ECE Facilities) ............................................................................................................54 Table 35. Summary of Outdoor Air Phthalate Detection Frequencies and Concentrations (µg/m³) (n=14 ECE Facilities) ............................................................................................................54 Table 36. Summary of Indoor/Outdoor Air Concentrations Ratios for Phthalates (n=14 ECE Facilities) ..............................................................................................................................54 Table 37. Summary of Phthalate Dust Concentrations (µg/g) (n=39) ........................................56 Table 38. Summary of Phthalate Dust Loading (µg/m²) (n=39) .................................................56 Table 39. Spearman Correlation of Phthalate Concentrations in Air and Dust Concentrations and Loading (n=39). .............................................................................................................57 Table 40. Summary of Flame Retardant Indoor Air Concentrations (ng/m³) ..............................59 Table 41. Summary of Flame Retardant Outdoor Air Concentrations (ng/m³) ...........................59

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Table 42. Summary of Indoor to Outdoor (I/O ratio) Flame Retardant Air Concentrations ........60 Table 43. Summary of Flame Retardant Concentrations (ng/g) in Dust (n=39) .........................62 Table 44. Summary of Flame Retardant Loading (ng/m²) in Dust (n=39) ..................................63 Table 45. Spearman Rank Correlation Coefficients Testing the Relationship between Flame Retardant Air and Dust Concentrations and Loading in Dust ................................................66 Table 46. Comparison of Flame Retardant Dust Concentrations between Facilities with and without Upholstered Furniture Present in Child Care Room ..................................................67 Table 47. Comparison of Flame Retardant Dust Concentrations between Facilities with and without Foam Napping Equipment Present in Child Care Room ...........................................68 Table 48. Summary of PFC Concentrations (ng/g) in Dust (n=39).............................................71 Table 49. Summary of PFC Loading (ng/m²) in Dust (n=39) ......................................................71 Table 50. Summary of Indoor Air Pesticide Concentrations (ng/m3) (n=40) ...............................74 Table 51. Summary of Outdoor Air Pesticide Concentrations (ng/m3) (n=14) ............................74 Table 52. Summary of Indoor to Outdoor Ratios for Air Pesticide Concentrations (n=14)..........75 Table 53. Indoor Air Pesticide Concentrations by County ..........................................................75 Table 54. Indoor Air Pesticide Concentrations by Agricultural versus Non-agricultural Area......76 Table 55. Summary of Pesticide Concentrations (ng/g) in Dust (n=39) .....................................78 Table 56. Summary of Pesticide Loading (ng/m²) in Dust from ECE Facilities (n=39) ...............78 Table 57. Summary of Pesticide Dust Concentrations by County ..............................................79 Table 58. Pesticide Dust Concentrations by Agricultural Location .............................................80 Table 59. Spearman Rank Correlation Coefficients Testing the Relationship Between Pesticide Air Concentrations and Pesticide Concentrations and Loading in Dust .................................81 Table 60. Summary of Reported Pesticide/Insecticide Use within the Past Year .......................82 Table 61. Active Ingredients in Pesticides Stored Inside Child Care Facilities ...........................83 Table 62. Pesticide Usage Inside or Outside within the Last Year and Indoor Air Concentrations .............................................................................................................................................84 Table 63. Indoor Air Pesticide Concentrations by Reported Pesticide Use (yes/no) ..................85 Table 64. Pesticide Usage Inside or Outside within the Last Year and Dust Concentrations .....86 Table 65. Pesticide Usage Inside within the Last Year and Dust Concentrations ......................87 Table 66. Summary of One-Minute and Child Care Day Averages for Indoor and Outdoor Ultrafine Concentrations (#/ccm)...........................................................................................90 Table 67. Distribution of Child Care Full Day Average Indoor and Outdoor Ultrafine Concentrations (#/ccm) by County ........................................................................................92 Table 68. Distribution of Child Care Full Day Average Indoor and Outdoor Ultrafine Concentrations (#/ccm) by ECE Type ...................................................................................92 Table 69. Summary of Ultrafine Particle Concentration Means (#/ccm) in Child Care Facilities with and without a Combustion Source Present ....................................................................92 Table 70. Summary of One-Minute and Child Care Day Averages of DustTrak PM2.5 Concentrations (μg/m³) .........................................................................................................94 Table 71. Comparison of Child Care Day Average DustTrak PM2.5 Concentrations (μg/m³) by County ..................................................................................................................................95 Table 72. Comparison of Child Care Day Average DustTrak PM2.5 Concentrations (μg/m³) by ECE Type .............................................................................................................................96 Table 73. Summary of Indoor and Outdoor PM2.5 and PM10 Concentrations (µg/m³) .................97 Table 74. Distribution of Indoor to Outdoor Gravimetric PM2.5 and PM10 Concentration Ratios (n=12) ...................................................................................................................................97 Table 75. Summary Statistics for Indoor Gravimetric PM2.5 and PM10 Concentrations (µg/m³) by County ..................................................................................................................................98 Table 76. Summary Statistics for Indoor Gravimetric PM2.5 (µg/m³) by ECE Type .....................99 Table 77. Pairwise Spearman Rank Correlation (rho) between Particulate Measurements .....100 Table 78. Spearman Correlation Rho Between Traffic Metrics and Particle Concentrations ....101 x

Table 79. Summary Comparison of Mean DustTrak PM2.5 and PEM PM2.5 Concentrations (μg/m³) ................................................................................................................................102 Table 80. Distribution of Metals in Dust (μg/g) (n=38) .............................................................104 Table 81. Distribution of Metal Loading (μg/m²) (n=38) ...........................................................104 Table 82. Summary of Health-Based Benchmarks Used for Risk Evaluation ..........................106 Table 83. Inhalation Rates Based on U.S. EPA’s Child-Specific Exposure Factors Handbook 108 Table 84. Mean Body Weights and Inhalation Rates Used ......................................................111 Table 85. Ratios of VOC Air Concentrations to the Acute Reference Exposure Level (aREL), the 8-hour REL, the Chronic REL (cREL) and the Reference Concentration (RfC) ...................113 Table 86. Inhalation VOC Exposure Estimates Compared to NSRLchild (0 to