Indian River Power Plant Impact Study

Fall 2011 Summary Report

June 28, 2012

Prepared for State of Delaware Department of Natural Resources and Environmental Control and Delaware Health and Social Services Dover, DE

Prepared by RTI International 3040 Cornwallis Road Research Triangle Park, NC 27709-2194

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IRPPS Fall 2011 Summary Report June 28, 2012

Table of Contents
List of Tables ................................................................................................................................................. ii List of Figures ................................................................................................................................................ ii Forward ........................................................................................................................................................ iii Executive Summary...................................................................................................................................... iv 1. 2. Introduction .......................................................................................................................................... 1 Data Quality Indicators ......................................................................................................................... 3 Precision ................................................................................................................................................ 3 Accuracy and Bias ................................................................................................................................. 3 Completeness........................................................................................................................................ 4 Other Quality Criteria............................................................................................................................ 4 3. 4. 5. 6. 7. 8. 9. Data Validation and Results .................................................................................................................. 7 Outdoor PM2.5 Residential Samplers .................................................................................................... 8 Indoor PM2.5 Residential Samplers ....................................................................................................... 9 MicroPEM Personal Samplers ............................................................................................................. 11 Fixed Site Samplers ............................................................................................................................. 12 Seaford Sampling Site ......................................................................................................................... 14 Residential Temperature and Humidity Data ..................................................................................... 16

10. Questionnaire Data ............................................................................................................................. 16 11. Biological Specimen Data.................................................................................................................... 16 12. Interim Summary ................................................................................................................................ 17 13. Corrective Action Steps for Fall 2012 sampling phase ....................................................................... 18 14. APPENDIX A: Participant and Residential Survey Summary Statistics ................................................ 20 15. APPENDIX B: Reference Values for Metals (Blood and Urine)............................................................ 22 16. APPENDIX C: Reference Values for Volatile Organic Compounds (VOCs) (Blood).............................. 23 17. APPENDIX D: Metal Levels (μg /L) in Urine and Blood of the 32 Participants. ................................... 24 18. APPENDIX E: Volatile Organic Componds (VOCs) Levels (parts per billion) in Blood of the 32 Participants ................................................................................................................................................. 26 19. References .......................................................................................................................................... 28

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IRPPS Fall 2011 Summary Report June 28, 2012

LIST OF TABLES
Table 1-1 Sampling schedule of participants and fixed sites during the October 2011 phase..................... 2 Table 2-1 Target DQI's for each metric and analyte ..................................................................................... 5 Table 2-2 Target quantitative DQI's for XRF analysis .................................................................................... 6 Table 3-1 Data validity distributions for PM2.5 samples by sampling location.............................................. 7 Table 4-1 Outdoor residential mass concentrations (µg/m3) and DQI values .............................................. 8 Table 4-2 Results from outdoor residential XRF analysis ............................................................................. 9 Table 5-1 Indoor residential mass concentrations (µg/m3) and DQI values ............................................... 10 Table 5-2 Results from indoor residential XRF analysis .............................................................................. 10 Table 6-1 MicroPEM sampler mass concentrations (µg/m3) and DQI values............................................. 11 Table 6-2 Results from MicroPEM filter XRF analysis ................................................................................. 11 Table 7-1 Fixed site sampler mass concentrations (µg/m3) and DQI values .............................................. 12 Table 7-2 Results from fixed sites filter XRF analysis .................................................................................. 13 Table 8-1 Seaford site sampler mass concentrations (µg/m3) and DQI values .......................................... 14 Table 8-2 Results from Seaford site filter XRF analysis ............................................................................... 15 Table 11-1 Urine specimen data during first sampling phase .................................................................... 17

LIST OF FIGURES
Figure 1-1 Map of sampling area including participant (red) and background (green) sampling sites along with IRPP location (yellow). .......................................................................................................................... 1 Figure 7-1 Elemental composition by fixed site .......................................................................................... 14 Figure 8-1 Comparsion between Seaford FRM and PEM samplers ............................................................ 16

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IRPPS Fall 2011 Summary Report June 28, 2012

FORWARD
This interim report of the Indian River Power Plant Impact Study (IRPPS) covers the first sampling period from late October of 2011 through late November of 2011. The report gives a broad overview of the results from the first phase only. The report does not attempt to answer any study hypotheses. Additional personal, residential and regional sampling is required to strengthen any statistical findings and reduce the impact of variability in the data. This sampling is scheduled to occur in OctoberNovember 2012. Furthermore, back-trajectory modeling is needed to fully understand the contribution of out-of-state, local, and personal sources to the Sussex County population’s exposure to PM2.5. As such, it should be stressed that linkages between particulate matter sources and environmental or biological concentrations presented in this interim report cannot be determined at this point. The final report to be prepared after the Fall 2012 phase will use all data to answer the research questions raised in the study design. This study is a partnership between the Delaware Department of Natural Resources and Environmental Control and Delaware Health and Social Services. RTI International is contracted to perform the environmental sampling and analysis.

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IRPPS Fall 2011 Summary Report June 28, 2012

EXECUTIVE SUMMARY
The Indian River Power Plant Impact Study (IRPPS) was initiated to improve our understanding of the exposures of residents of Sussex County, Delaware to fine particulate matter (PM2.5) and associated inorganic species. The study is focused on out-of-state, local regional and local point sources, in particular, the Indian River Power Plant (IRPP), that contribute to the overall exposures of the residents. The study is designed to estimate the relative contributions of these sources by sampling indoor, outdoor, and personal air for PM2.5 in locations both upwind and downwind of the power plant. Samples are assessed for PM mass, environmental tobacco smoke (ETS) in personal samples, and a suite of inorganic elements with selenium, arsenic, mercury, nickel, and chromium of special interest. The environmental samples are supplemented with blood, urine, and hair samples for analysis of volatile organic compounds (VOCs) and metals in blood and metals in urine and, in the future, hair. The sampling plan is designed to capture exposures during the Fall season in 2011 and 2012. During the Fall 2011 season, the IRPP was not operating while engineering upgrades were made that are designed to reduce pollutant emissions. When sample collection is repeated in Fall 2012, the power plant is anticipated to be operational and sampling during that period will permit an indication of the IRPP contribution to local PM exposures. The Fall 2011 sample collection period included 32 participants recruited from the vicinity of the IRPP in Sussex County, Delaware. The participants allowed personal, indoor residential and outdoor residential particulate matter samples to be collected over three consecutive days. Surveys characterized participant demographics and residence characteristics. Metrological records will permit assessment of upwind or downwind location relative to the power plant when both phases of sampling are completed and data are analyzed. Participants also provided blood, urine, and hair samples. Regional background particulate matter samplers were deployed to obtain a broader picture of the regional air quality. Average outdoor residential PM2.5 mass loadings were 17.8 µg/m3, which were higher than the Federal standard of 15 µg/m3, while indoor residential samples indicated PM2.5 levels of 43.3 µg/m3. This increase in PM2.5 mass concentrations between outdoor and indoor is expected and follows similar patterns observed throughout the country 1. A Federal standard for indoor air quality currently does not exist. Personal concentrations however were bounded by outdoor and indoor concentrations. One possible reason for this is that personal samples are influenced by the mixture of indoor and outdoor activities which is supported by time activity diary information provided by the participants 2. Ambient average particulate concentrations were the lowest of all four measurement locations which, given their location relative to urban sources, is expected1. The intercomparison between ambient monitors located around IRPP and the Seaford FRM monitor requires further study with possible back-trajectory modeling to elucidate causes. Elemental analysis of filters collected during the Fall 2011 sampling period displayed similar elements and concentrations as has been found elsewhere 3. There were two exceptions to this during the sampling phase. Personal samples were, on average, enriched with bromine, copper, and iv

IRPPS Fall 2011 Summary Report June 28, 2012

magnesium when compared to other filters. These elements have several potential sources which require further sampling and data analysis to identify 4,5. Additionally, the Northeast background site particulate matter contained elevated levels of silicon when compared to the four other background sites. Identifying the reason for this will require regional air quality modeling coupled with additional sampling. Results for the biospecimens showed that none of the analytes were above the reference values in the blood samples for the 32 participants. Urinary arsenic (As) and/or selenium (Se) were above the reference ranges in 12 of the participants and might represent dietary additions such as multi-vitamins (Se) or consumption of seafood (As). The first sampling phase of the IRPPS resulted in high quality data that will act as a baseline for the additional sampling to be started during October of 2012. Data revealed expected spatial and elemental distributions with concentration differences being observed between indoor, personal, outdoor, and background sampling locations. It is anticipated that the second phase of sampling will provide additional quality data which allow for the hypotheses in the study design to be properly evaluated.

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IRPPS Fall 2011 Summary Report June 28, 2012

1.

INTRODUCTION

This report describes the outcome of the Fall 2011 sample collection for the Indian River Power Plant Impact Study (IRPPS). This study was designed to address four objectives over the course of an 18month period. • • • • Evaluate the impacts of the NRG Energy Indian River Power Plant (IRPP) operating capacity on PM2.5 exposure levels of the Sussex County population. Ascertain the relative contributions of upwind sources in Maryland, Pennsylvania, and Virginia on the PM2.5 exposure of the Sussex County population. Establish the contribution of point, local, and personal sources to the Sussex County population’s exposure to PM2.5. Collect biological samples for dose measurements of the Sussex County population.

Samples were collected during October and November of 2011 from 32 participants (Figure 1-1). Five fixed sites operated continuously with filters being replaced every 24 hours, except at the Seaford site, which operated on a 1-in-3 day schedule corresponding to the DNREC PM2.5 FRM monitor. Data acquired during the first phase captured PM concentrations while the IRPP was shut down for the installation of pollution control technologies. The second phase, scheduled to begin in October of 2012, will take place after the power plant has resumed operation.

Figure 1-1 Map of sampling area including participant (red) and background (green) sampling sites along with IRPP location (yellow).
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IRPPS Fall 2011 Summary Report June 28, 2012

This report describes data quality objectives and measures obtained by RTI International during the first phase of the IRPPS. Fixed sites along with indoor and outdoor platforms were outfitted with Personal Exposure Monitors (PEMS, MSP Corporation Minneapolis MN) while person-level data were acquired using RTI’s MicroPEM. A PEM unit was comprised of single channel PM2.5 inlet operating at 2 liters per minute (LPM) with a 37 mm Teflo filter (Gelman Sciences, Ann Arbor, Michigan); a MicroPEM unit operated at 0.5 LPM and collected PM2.5 on a 25 mm Teflo filter. Data quality indicators for all metrics, defined in Section 2, are compiled in this Quality Assurance (QA) summary report. Section 3 describes the number of valid samples for each metric along with reasons identified by RTI for invalid samples. Gravimetric data from Teflo filters collected during outdoor residential sampling are presented in Section 4; those collected during indoor residential sampling, along with corresponding environmental tobacco smoke (ETS) and black carbon (BC) measurements, are presented in Section 5. Summary statistics of MicroPEM personal monitors, along with particulate metals analysis performed by X-ray fluorescence (XRF) is presented in Section 6. Sections 7 and 8 summarize the results obtained at the fixed site samplers and the Seaford sampling site, respectively. Sections 9 through 11 provide data, respectively, on residential temperature and humidity, questionnaire responses, and biological specimens. Following the data presentation, Section 12 provides an interim summary and Section 13 describes the corrective actions that will be undertaken by RTI during the second phase scheduled for October 2012. Table 1-1 provides a detailed overview of the sampling schedule and frequency of visits during the first phase. Eight participants per week were scheduled to complete the phase within the 4-week window available. Residential sampling occurred over two weekdays plus one weekend day for each participant, totaling three complete and consecutive days of sampling. There was one exception to this

Table 1-1 Sampling schedule of participants and fixed sites during the October 2011 phase
Participant Sampling Schedule Cohort 1 Oct 27-29 Cohort 5 Nov 10-12 Cohort 2 Oct 30-Nov 1 Cohort 6 Nov 13-15 Cohort 3 Nov 3 -5 Cohort 7 Nov 17-19 Cohort 4 Nov 6-8 Cohort 8 Nov 19-21

Fixed Site Sampling Schedule Northwest Oct 27-Nov 21 Southeast Oct 27-Nov 21 Northeast Oct 27-Nov 21 West-SW Oct 27-Nov 21

Seaford Site Sampling Schedule Oct 27, Oct 30, Nov 2, Nov 5, Nov 8, Nov 11, Nov 14, Nov 17, Nov 20

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sampling schedule: The last cohort ( 4 participants) was sampled for two weekend days and one weekday. This schedule minimized time burdens on the participants and avoided conflict with the Thanksgiving holiday. Personal, indoor, and outdoor sampling occurred daily for each participant. After each 24-hour period, technicians arrived at a prearranged time to retrieve the used samplers and replace them with fresh samplers. Also during this time, technicians administered a short questionnaire (time-activity diary or TAD) about the participant’s activities the previous day. At the beginning of each participant three-day sampling period, technicians also conducted a residential survey to gather information about each residence. Lastly, a temperature and humidity sensor (HOBO) was placed within each participant’s household during the three-day sampling period.

2.

DATA QUALITY INDICATORS

Quantitative data quality indicators (DQIs) targeted for each metric collected are presented in Tables 2-1 and 2-2. These DQIs include lower detection level (LDL), precision, accuracy, and completeness. Qualitative DQIs include representativeness and comparability. Quality control sample results from the outdoor, indoor, and fixed sites were combined to increase the statistical strength of the DQIs. Collocated duplicate samples from all locations were combined to calculate the precision of the PEMs. Field blanks and standard weight analyses were combined when calculating the method detection limit (MDL) and method quantitation limit (MQL) values for the PEMs. This approach is reasonable given the same sampler (PEMs) was deployed at each location and the filter underwent identical analysis (gravimetric, ETS, and BC). Precision Precision is the agreement between the measurements collected by two identical devices or measures under similar conditions. Collection of co-located duplicate samples provides information on the variability in the sample collection, handling, storage, and analysis. Precision is reported as percent relative standard deviation (% RSD) between replicate samples or sample analyses and is defined as

where SD is the standard deviation and Mean is the mean value of the measurements from each replicate set. Accuracy and Bias Accuracy is the measure of the closeness of a measured value to a known or true value and includes both random error (precision) and systematic error (bias). Precision was discussed previously. Bias is the distortion of the data in a consistent direction due to measurement or analytical error. Measurement and analytical bias should be estimated using materials as independent as possible from the measurement system.

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Measurement accuracy is used to assess sample collection with the integrated and continuous instrumentation. Measurement accuracy will be reported as a comparison between the measured value and the known value of a standard. Accuracy is defined as

where Cstd and Csample are the values for the standard and the sample, respectively. Measurement accuracy for instrumentation typically is determined by the validation of the instrument performance during instrument development. For continuous monitors, accuracy also is determined during instrument calibration certification. Analytical accuracy will be reported as recovery from spiked control samples during sample analysis. The composition and concentration of the spiked sample will come from a standard reference material (e.g., National Institute of Standards and Technology [NIST]). Recovery is defined as

where Cm, Cu, and Cs are the concentration of each target analyte measured in the spiked sample, in the unspiked sample, and the spiking solution, respectively. This definition of analytical accuracy incorporates matrix recovery into the assessment. A documented, consistent spiking protocol is essential to obtain useful accuracy estimates. Completeness Completeness is a measure of valid data obtained from each metric. Completeness consists of sample collection and analysis components. Completeness requirements for sample collection and analysis aspects are presented because their relative importance varies between metrics. Completeness is typically defined by RTI as follows for all chemical and physical measurements:

where V is the number of measurements judged valid, and N is the number of measurements planned. The anticipated influence of completeness for each metric on the ability to answer the study hypotheses should be considered when the statistical design for the study is being developed. Other Quality Criteria Instrument Detection Limit (IDL) The quantity of the target analyte that can be measured and distinguished from zero on a continuous monitor provides direct output of the metric of interest. It is the lowest level readable on a display or recorded that can be distinguished from background.

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Method Detection Limit (MDL), Corrected for Optimal Sample Volume The method detection limit (MDL) is defined as the minimum concentration of substance that can be measured and reported with a known confidence that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte. For all applicable metrics, the equation to determine the MDL for a given analyte is: MDL = t(n-1, a=0.68)S where, t(n-1, a = 0.68) represents the Students’ t-test t value appropriate for a 68% confidence level (84% one-tailed) and a standard deviation estimate with n-1 degrees of freedom. S is equal to the standard deviation of the replicate (usually seven samples) analyses. This value is obtained from analyzing standard samples containing the target mass between the IDL and the lowest target analyte mass expected to be observed (or blank filters for filter media). This value is then divided by the theoretical sample volume. For example, the theoretical volume for a 24 h PM sample collected on a PEM sampler operating at 4 L per minute is 5,760 L or 5.76 cubic meters. Method Quantitation Limit (MQL) For other analyses, such as gravimetric, the MQL is three times the MDL [MQL = 3 x MDL] and within the specified limits of precision and accuracy during routine analytical operating conditions. Tables 2-1 and 2-2 contain the current values of MQL.

Table 2-1 Target DQI's for each metric and analyte
% Complete Metric RTI MicroPEM Analysis Gravimetric ETS BC XRF 2 Lpm PEM Gravimetric ETS BC XRF Questionnaires HOBO NA NA NA NA NA NA 0.2/0.6 µg/m3 0.3/0.9 µg/m3 0.1/0.3 µg/m
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MDL/MQL 1.4/4.2 µg/m3 2.4/7.2 µg/m3 0.4/1.2 µg/m3

Precision ±10% ±10% ±10%

Accuracy ±15% ±15% ±15% See Table 2-2

Collection 95% 95% 95%

Analysis 99% 99% 99%

±10% ±10% ±10%

±10% ±10% ±10% See Table 2-2 NA NA

95% 95% 95%

99% 99% 99%

99% 99%

NA NA

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IRPPS Fall 2011 Summary Report June 28, 2012

Table 2-2 Target quantitative DQI's for XRF analysis*
% Completeness Element Sodium Magnesium Aluminum Silicon Phosphorous Sulfur Chlorine Potassium Calcium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Arsenic Selenium Bromine Rubidium Strontium Zirconium Silver Cadmium Tin Antimony Cesium Barium MDL/MQL ng/filter 70/210 70/210 500/1,500 170/510 120/360 70/210 50/150 30/90 40/120 70/210 25/75 10/30 10/30 30/90 20/60 15/45 15/45 10/30 15/45 8/24 10/30 10/30 10/30 80/240 50/150 60/180 80/240 90/270 133/400 170/510 6 Precision 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Accuracy 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Collection 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% 95% Analysis 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99% 99%

IRPPS Fall 2011 Summary Report June 28, 2012

% Completeness Element Mercury Lead Cerium MDL/MQL ng/filter 23/70 24/72 467/1,400 Precision 20 20 20 Accuracy 10 10 10 Collection 95% 95% 95% Analysis 99% 99% 99%

*Elements appear in the order they occur on the periodic table.

3.

DATA VALIDATION AND RESULTS

Data validity was determined on three levels: 1) review of data collection sheets recorded by field technicians during sampling, 2) physical inspection of filters, and 3) comparison of analysis results against other filters collected. During each of these steps filters were given one of three levels of validity: • • Invalid (code = 0; noted handling issue or obvious filter damage which precludes analysis) Suspect (code = 1; no noted issues, but reported value is more or less than twice the standard deviation of the mean) Valid (code = 2; no noted issues and data value is within two standard deviations of the mean)

During the first level of data validation, any filters that were noted as incorrectly handled were marked as invalid due to possible contamination. The second level of data review involved visual inspection of filters for any holes which might induce errors in analytical analysis. The final level of data validation resulted from comparison of analytical data amongst all filters of similar sample collection parameters. All data was entered into a comprehensive file in order to provide a unified space for data to be housed. Results from the validation procedures are displayed in Table 3-1.

Table 3-1 Data validity distributions for PM2.5 samples by sampling location
validity code 0 1 2 % valid Outdoor 4 1 101 95.28 Indoor 6 0 104 94.55 Personal (MicroPEM) 21 11 64 66.67 Fixed Sites 1 4 110 95.65 Seaford 0 0 11 100.00

Reasons for invalid samples can be divided into three categories: • • Hardware issues (e.g. pump failure; 20 samples) Sample issues (e.g. filters physically damaged; 7 samples) 7

IRPPS Fall 2011 Summary Report June 28, 2012

Participant coordination issues (e.g. participant not home at time of visit; 5 samples)

MicroPEM instrument issues led to the majority of invalid samples. However, these were mostly limited to the first 10 days of the sampling period; this is discussed further in Section 6. Subsequent to this point, the number of invalid samples was limited. Reported RSD values were obtained from 13 duplicate measurements done at indoor and outdoor residential sampling locations throughout the course of the first sampling phase.

4.

OUTDOOR PM2.5 RESIDENTIAL SAMPLERS

Including duplicate (8 samples) and filter blanks (2 samples), 106 filters were planned for outdoor residential sampling. The actual number of filters deployed and retrieved was 102, resulting in a capture rate of 96.23%. Capture rate along with blank corrected average mass concentrations and actual DQI are presented in Table 4-1. MDL/MQL targets listed in Table 2-1 were met during outdoor residential sampling. However, ETS precision values exceeded those of the target DQI’s. This was primarily due to two very low ETS concentrations which caused minor variations in measured ETS to result in large % differences between duplicate samples.

Table 4-1 Outdoor residential mass concentrations (µg/m3) and DQI values
PM2.5 Capture rate 96% % RSD 10.1 % RSD 17.6 % RSD 2.6 MDL 0.3 ETS MDL 0.3 BC MDL 0.1 MQL 0.9 MQL 1.0 MQL 0.2 Avg. 16.4 Avg. 3.5 Avg. 1.1

Metals analysis of the PM2.5 filter samples was conducted by X-Ray Fluorescence, with values below detection limit recorded as

The XRF data from outdoor residential samplers is listed in Table 4-2. The major elemental species identified were iron, potassium, silicon, and sulfur. Elemental species of interest for this study (selenium, arsenic, mercury, nickel, and chromium) were all below detection limit, with the exception of mercury which was not tested.

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Table 4-2 Results from outdoor residential XRF analysis
Outdoor Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter)
Silver Aluminum Arsenic Barium Bromine Calcium

< 636 212 636
Cadmium

< 357 119 357
Cerium

< 36 12 36
Chlorine

0 59 178
Cobalt

< 37 12 37
Chromium

< 68 23 68
Cesium

< 849 283 849
Copper

0 30 91
Iron

68 23 68
Indium

< 19 6 19
Potassium

< 33 11 33
Magnesium

< 182 61 182
Manganese

< 30 10 30
Sodium

73 11 32
Nickel

< 1102 367 1102
Phosphorus

170 19 57
Lead

< 170 57 170
Rubidium

< 26 9 26
Sulfur

< 394 131 394
Antimony

< 18 6 18
Selenium

0 46 137
Silicon

< 75 25 75
Tin

< 41 14 41
Strontium

1539 30 89
Titanium

< 2138 713 2138
Vanadium

< 40 13 40
Zinc

286 57 172
Zirconium

< 1492 497 1492

< 55 18 55

< 68 23 68

< 46 15 46

< 30 10 30

< 418 139 418

5.

INDOOR PM2.5 RESIDENTIAL SAMPLERS

Resident households were also outfitted with indoor sampling platforms which contained PEM samplers operating at 2 liters per minute. Total samples taken include 110 filters, with 6 filter blanks and 6 duplicates. Table 5-1 details the indoor residential capture rate, actual DQIs, and blank corrected average indoor PM2.5 mass concentrations of particulate matter, ETS, and BC. Table 5-2 details the XRF elemental analysis of indoor residential filters. XRF data indicated the presence of several elements not above the MQL for the outdoor samples. Notable is the increased abundance of calcium, chlorine, and zinc. The increase in PM2.5 concentration and associated elements is consistent with what we would expect given the lower ventilation rates indoors and multiple indoor sources.

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IRPPS Fall 2011 Summary Report June 28, 2012

Table 5-1 Indoor residential mass concentrations (µg/m3) and DQI values
PM2.5 Capture rate 95% % RSD 10.1 % RSD 17.6 % RSD 2.6 MDL 0.3 MQL 0.9 Avg. 43.3 Avg. 22.7 Avg. 3.2

ETS MDL MQL 0.3 BC MDL 0.1 MQL 0.2 1.0

Table 5-2 Results from indoor residential XRF analysis
Indoor Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter)
Silver Aluminum Arsenic Barium Bromine Calcium

< 636 212 636
Cadmium

< 357 119 357
Cerium

< 36 12 36
Chlorine

0 59 178
Cobalt

< 37 12 37
Chromium

76 23 68
Cesium

< 849 283 849
Copper

< 91 30 91
Iron

577 23 68
Indium

< 19 6 19
Potassium

< 33 11 33
Magnesium

< 182 61 182
Manganese

< 30 10 30
Sodium

78 11 32
Nickel

< 1102 367 1102
Phosphorus

978 19 57
Lead

< 170 57 170
Rubidium

< 26 9 26
Sulfur

< 394 131 394
Antimony

< 18 6 18
Selenium

< 137 46 137
Silicon

< 75 25 75
Tin

< 41 14 41
Strontium

1011 30 89
Titanium

< 2138 713 2138
Vanadium

< 40 13 40
Zinc

498 57 172
Zirconium

< 1492 497 1492

< 55 18 55

< 68 23 68

< 46 15 46

38 10 30

< 418 139 418

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IRPPS Fall 2011 Summary Report June 28, 2012

6.

MICROPEM PERSONAL SAMPLERS

Summary statistics of MicroPEM personal monitors are presented in Table 6-1. The reported average PM2.5 mass is blank corrected. The low capture rate for these samplers was due to a loose electrical connection within the first batch of MicroPEM monitors used during the first 10 days of the sampling phase. MDL and MQL DQI indicators for ETS and BC are not included because these data are being re-evaluated due to optical analysis difficulties encountered with the 25mm filters. % RSD values are not presented due to IRB concerns with the additional participant burden associated with obtaining duplicate samples.

Table 6-1 MicroPEM sampler mass concentrations (µg/m3) and DQI values
PM2.5 Capture rate, % 73.96 % RSD % RSD % RSD MDL MQL Avg. 24.3 Avg. Avg. -

< 0.1 0.1 ETS MDL MQL BC MDL MQL -

XRF analysis of the MicroPEM filters (Table 6-2) revealed markedly different elemental composition from both indoor and outdoor PEM filters. Elements of particular interest which displayed increases between indoor and MicroPEM filters were bromine, copper, and magnesium.

Table 6-2 Results from MicroPEM filter XRF analysis
MicroPEM Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter)
Silver Aluminum Arsenic Barium Bromine Calcium

< 253 84 253
Cadmium

< 175 58 175
Cerium

< 21 7 21
Chlorine

< 112 37 112
Cobalt

70 8 25
Chromium

189 5 16
Cesium

< 304 101 304
Copper

< 82 27 82
Iron

482 11 32
Indium

< 14 5 14
Potassium

< 25 8 25
Magnesium

< 104 35 104
Manganese

18 6 18

119 8 23 11

< 252 84 252

661 7 22

53 16 48

< 20 7 20

IRPPS Fall 2011 Summary Report June 28, 2012

MicroPEM Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter)

Sodium

Nickel

Phosphorus

Lead

Rubidium

Sulfur

252 54 161
Antimony

< 12 4 12
Selenium

< 48 16 48
Silicon

< 55 18 55
Tin

< 20 7 20
Strontium

704 15 44
Titanium

< 644 215 644
Vanadium

< 27 9 27
Zinc

230 32 97
Zirconium

< 326 109 326

< 19 6 19

< 45 15 45

< 34 11 34

33 5 15

< 213 71 213

7.

FIXED SITES SAMPLERS

PEM samplers were attached to permanent structures at four locations (west-southwest, northwest, northeast, and southeast) within approximately 2.5 miles of the IRPP. Fixed site samplers operated continuously for 24 hours, with filters from these samplers being collected each day throughout the sampling phase. Data quality indicators from these samplers along with blank corrected average PM2.5 mass concentrations are presented in table 7-1. As stated previously, quality control sample results from the outdoor, indoor, and fixed sites were combined to increase the statistical strength of the DQIs. This approach is reasonable given the same sampler (PEMs) was deployed at each location and the filter underwent identical analysis (gravimetric, ETS, and BC).

Table 7-1 Fixed site sampler mass concentrations (µg/m3) and DQI values
PM2.5 Capture rate 100% % RSD 10.1 % RSD 17.6 % RSD 2.6 MDL 0.3 MQL 0.9 Avg. 17.8 Avg. 1.0 Avg. 0.5

ETS MDL MQL 0.3 BC MDL 0.1 MQL 0.2 1.0

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IRPPS Fall 2011 Summary Report June 28, 2012

XRF data from all four fixed sites is presented in Table 7-2. This data matched well with the XRF data obtained from residential outdoor samplers, with the exception of elevated silicon levels. A more detailed analysis of fixed site XRF data to understand the cause for elevated silicon levels in fixed site data demonstrated that the majority of the silicon was present in samples from the northeast fixed site (Figure 7-1). This indicates that a local source might be the cause, however further study to identify this potential source would necessitate use of meteorological data collected at the Seaford site.

Table 7-2 Results from fixed sites filter XRF analysis
Fixed Sites Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter)
Silver Aluminum Arsenic Barium Bromine Calcium

0 212 636
Cadmium

< 357 119 357
Cerium

< 36 12 36
Chlorine

0 59 178
Cobalt

< 37 12 37
Chromium

< 68 23 68
Cesium

< 849 283 849
Copper

< 91 30 91
Iron

77 23 68
Indium

< 19 6 19
Potassium

< 33 11 33
Magnesium

< 182 61 182
Manganese

< 30 10 30
Sodium

74 11 32
Nickel

< 1102 367 1102
Phosphorus

114 19 57
Lead

< 170 57 170
Rubidium

< 26 9 26
Sulfur

< 394 131 394
Antimony

< 18 6 18
Selenium

0 46 137
Silicon

< 75 25 75
Tin

< 41 14 41
Strontium

1578 30 89
Titanium

< 2138 713 2138
Vanadium

< 40 13 40
Zinc

604 57 172
Zirconium

< 1492 497 1492

< 55 18 55

< 68 23 68

< 46 15 46

< 30 10 30

< 418 139 418

13

IRPPS Fall 2011 Summary Report June 28, 2012

1800 1600 Elemental composition (ng/filter) 1400 1200 1000 800 600 400 200 0 Chlorine Iron Potassium Sulfur Silicon Northwest Southeast Northeast West-Southwest

Figure 7-1 Elemental composition by fixed site

8.

SEAFORD SAMPLING SITE

RTI operated a PEM sampler at the Department of Natural Resources and Environmental Control (DNREC) Seaford site. This PEM was collocated with a FRM sampler operated by DNREC. Filter sampling for this location followed the 1-in-3 day cycle of the DNREC FRM sampler. Average mass concentrations of PM2.5 (blank corrected), ETS, and BC along with DQI’s are listed in Table 8-1.

Table 8-1 Seaford site sampler mass concentrations (µg/m3) and DQI values
Capture rate 100 PM2.5 % RSD 10.1 % RSD 17.6 % RSD 2.6 MDL 0.3 MQL 0.9 Avg. 11.9 Avg. 0.2 Avg. 0.5

ETS MDL MQL 0.3 BC MDL 0.1 MQL 0.2 1.0

Elemental analysis of the filters collected from the Seaford site (Table 8-2) is quite consistent with outdoor residential and fixed site data, with a slight enrichment of iron observed in Seaford site 14

IRPPS Fall 2011 Summary Report June 28, 2012

samples. The similarity between fixed site data, outdoor residential data, and Seaford data indicates that the air mass over southern Delaware was well mixed and that any source contributions were not localized to the immediate study area.

Table 8-2 Results from Seaford site filter XRF analysis
Seaford Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter) Avg (ng/filter) MDL (ng/filter) MQL (ng/filter)
Silver Aluminum Arsenic Barium Bromine Calcium

< 636 212 636
Cadmium

< 357 119 357
Cerium

< 36 12 36
Chlorine

0 59 178
Cobalt

< 37 12 37
Chromium

169 23 68
Cesium

< 849 283 849
Copper

0 30 91
Iron

< 68 23 68
Indium

< 19 6 19
Potassium

< 33 11 33
Magnesium

0 61 182
Manganese

< 30 10 30
Sodium

111 11 32
Nickel

< 1102 367 1102
Phosphorus

134 19 57
Lead

< 170 57 170
Rubidium

< 26 9 26
Sulfur

< 394 131 394
Antimony

< 18 6 18
Selenium

0 46 137
Silicon

< 75 25 75
Tin

0 14 41
Strontium

1691 30 89
Titanium

< 2138 713 2138
Vanadium

< 40 13 40
Zinc

326 57 172
Zirconium

0 497 1492

< 55 18 55

< 68 23 68

< 46 15 46

< 30 10 30

< 418 139 418

As a further quality check, Seaford PM2.5 concentrations (not blank corrected) measured by the PEM were compared to those obtained from the collocated FRM. Figure 8-1 presents the comparison between these two samplers. The resulting comparison indicates reasonably good agreement between the two samplers with the PEM samplers showing a slight high bias. One potential reason for this is that the PEM operates at 2 liters per minute, resulting in a much lower face velocity than the FRM which operates at 16.7 liters per minute. This increased face velocity compared to the PEM could lead to the possible volatilization of ammonium nitrate from the filter.

15

IRPPS Fall 2011 Summary Report June 28, 2012

30 Seaford FRM mass loading (µg/m3) 25 20 15 10 5 0 0 5 10 15 20 (µg/m3) 25 30 Seaford PEM mass loading y = 1.0615x - 5.2906 R² = 0.8463

Figure 8-1 Comparsion between Seaford FRM and PEM samplers

9.

RESIDENTIAL TEMPERATURE AND HUMIDITY DATA

Technicians placed temperature and humidity sensors inside each participant’s household at the beginning of the three-day sampling period. The data capture rate was 100%. Average temperatures and humidity for all 32 households was 69.8 degrees Fahrenheit and 51.1 percent relative humidity.

10.

QUESTIONNAIRE DATA

Residents were given two questionnaires during the three-day sampling period. The first questionnaire (Residential Survey) covered details about the physical residence participants were living in including age of dwelling, types of heating, number of persons living there, etc. The second questionnaire was a time activity diary. Participants were asked to keep track of their movements and actions during the course of the three sampling days. Data from both questionnaires is included in Appendix A. The capture rate for these questionnaires was 91%. Some participants who were not wearing a MicroPEM monitor did not keep a complete TAD due to a miscommunication between technicians and participants.

11.

BIOLOGICAL SPECIMEN DATA

Hair, blood, and urine samples were collected from all participants by a registered Delaware Health and Social Services (DHSS) nurse. Urine samples were tested by Delaware Public Health Laboratory (DPHL) for metals and Volatile Organic Compounds (VOCs) (1,2-Dichloroethane, Benzene, Carbon tetrachloride, Chloroform, Ethyl benzene, m & p-xylene, o-xylene, Styrene, Tetrachloroethylene, and Toulene). VOCs were analyzed by Solid Phase MicroExtraction-Gas Chromatography (SPME-GC). Metals 16

IRPPS Fall 2011 Summary Report June 28, 2012

in both blood and urine samples were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICPMS). No metals were speciated or creatinine adjusted. Efforts are currently underway at DPHL to provide creatinine adjusted levels for the second sampling phase of this study. Reference values for metals and VOCs in blood and urine are presented in Appendices B and C. Appendices D and E contain metals and VOC concentrations in blood and urine for all participants during the first sampling phase. No analytes were above these concentrations in the blood samples for the 32 participants. Urine samples were elevated for arsenic and selenium in 12 of the participants (Table 111). Arsenic was elevated in four of the participants while nine participants had elevated levels of selenium. One participant had both arsenic and selenium levels elevated. These elevated levels may represent dietary additions such as multi-vitamins (selenium)or consumption of seafood (arsenic). Hair samples were not tested but were archived for later testing along with remaining blood and urine samples.

Table 11-1 Urine specimen data during first sampling phase
Participant ID
DE190 DE238 DE566 DE553 DE554 DE564 DE346 DE560 DE290 DE211 DE563 DE558

Arsenic (ppb) 234.52 >650 88.20 86.36 -

Selenium (ppb) 251.13 98.55 92.91 123.63 72.16 74.84 210.97 96.18 105.83

12.

INTERIM SUMMARY

Average outdoor residential PM2.5 mass loadings were 17.8 µg/m3, which were higher than the Federal standard of 15 µg/m3, while indoor residential samples indicated PM2.5 levels of 43.3 µg/m3. This increase in PM2.5 mass concentrations between outdoor and indoor is expected and follows similar patterns observed throughout the country1. Personal concentrations however were bounded by outdoor and indoor concentrations. One possible reason for this is that personal samples are thought to be influenced by the mixture of indoor and outdoor activities which is supported by TAD information provided by the participants2. Ambient average particulate concentrations were the lowest of all four measurement locations which, given their location relative to urban sources, is expected1. The

17

IRPPS Fall 2011 Summary Report June 28, 2012

intercomparison between ambient monitors located around IRPP and the Seaford FRM monitor requires further study with possible back-trajectory modeling to elucidate causes. Elemental analysis of filters collected during the Fall 2011 sampling period displayed similar elements and concentrations as have been found elsewhere3. There were two exceptions to this during the sampling phase. Personal samples were, on average, enriched with bromine, copper, and magnesium when compared to other filters. These elements have several potential sources which require further sampling and data analysis to identify4,5. Additionally, the Northeast background site particulate matter contained elevated levels of silicon when compared to the four other background sites. Identification of the reason for this would require regional air quality modeling coupled with additional sampling. The first sampling phase of the IRPPS resulted in high quality data that will act as a baseline for the additional sampling to be started during October of 2012. Data revealed expected spatial and elemental distributions with concentrations differences being observed between indoor, personal, outdoor, and background sampling locations. It is anticipated that the second phase of sampling will provide additional quality data which allow for the hypotheses in the study design to be properly evaluated.

13.

CORRECTIVE ACTION STEPS FOR FALL 2012 SAMPLING PHASE

Results from the first sampling phase indicated several areas where improvements could be made for the second sampling phase. These improvements include: • • • • • Improved data capture by MicroPEM units; Better ETS and BC quantification procedure for MicroPEM filters; Increased agreement of Seaford PEM and FRM samplers; Increased number of quantifiable XRF elements; Increased communication with participants.

To achieve these improvements, RTI will institute the following corrective actions. • Improved MicroPEM data capture: RTI will undertake more intensive pre-deployment instrument check-out of devices, including pre-deployment operational tests of all units. Increase ETS and BC quantification: RTI will refine the ETS and BC measurement standard operating procedures for MicroPEM filters to ensure high quality data capture and construct a filter mask for optical measurements of 25 mm filters. Filters from Fall 2011 will be re-analyzed once these procedures are implemented. Increase Seaford FRM/Seaford PEM precision: RTI will investigate the potential for quantification of ammonium nitrate on Seaford PEM filters. Alternatively, placement of a second FRM operated by RTI would allow for intra-lab comparison of PEM and FRM filters. 18

IRPPS Fall 2011 Summary Report June 28, 2012

Increased number of quantifiable XRF elements: RTI will replace 2 Lpm PEMS with 4 Lpm PEM units in order to the increase signal-to-noise ratio during XRF analysis. The improved signal-tonoise ratio will decrease the MDL/MQL for each element. Increase communication with participants: RTI will confirm at the end of each appointment the time for the next appointment, minimizing time burdens on the participants. RTI also will ensure that participants fully understand the requirements of the study.

19

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix A

14.

APPENDIX A: PARTICIPANT AND RESIDENTIAL SURVEY SUMMARY STATISTICS

race average age 63.2 average weight (lbs.) 173.2 average height (inches) 64.6

transportation to work car, truck, or van 8 bus or trolley 1 average transit time (minutes) 26 average number of years lived in Sussex County 18.7

males 11

females 21

white 32

numbers reporting knowingly been exposed to any of the following average hours away from home 4.2 average hours outside 2.3 asbestos 4 chemicals 6 coal/dust 2 coal tar/asphalt 0 diesel engine exhaust 1 dyes 9 formaldehyde 4 gasoline exhaust 0

numbers reporting knowingly been exposed to any of the following, continued pesticides 6 textile fibers 1 wood dust 3 x-rays / radioactive material 17

20

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix A type of home mobile home 9 one-family detached one family attached 19 1 building with 2 or more apartments 0 boat, RV, van, etc 0 other 2

location and use of garage none, detached, or separate carport 19 parking more than storage only 2 cars 0 4

attached

underneath

parking one car

parking two cars

N/A

12

0

12

3

10

Type of heating forced air gas 12 forced air oil 2 forced air electric 6 forced water, radiator 0 heat pump 5 wood burning stove fireplace, gas fireplace, wood 3 1 1

Type of heating, continued gas space heater kerosene space heater electric space heater 1 0 4 open stove/oven 0 other 5

average number of years resident of this building 12.9

average age of building (years)

average # of people in house 2

average # of children in house 0

how many how many window central AC units AC units (per residence) (per residence) 1 1

storm windows present (yes) 20

kitchen exhaust fan (yes) 27

23.1

21

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix B

15.

APPENDIX B: REFERENCE VALUES FOR METALS (BLOOD AND URINE)
Fluid Urine Urine Urine Urine Urine Urine Urine Urine Urine Urine Urine Urine Urine Urine Reference Ranges [1] < 0.13 1.32 178 1.36 0.42 11.4 6.8 0.5 < 0.04 0.45 2.9 0.046 31.1 30.9 High Value (μg/L, PPB*) 0.2 2.83 293.5 2.54 0.8 16.5 17.1 1.38 0.1 0.62 7.8 0.277 64.5 68 Fluid Reference Ranges [2] High Value (μg/L, PPB*)
[3]

Element/ Isotope Monitored Beryllium Cobalt Molybdenum Cadmium Antimony Cesium Barium Tungsten Platinum Thallium Lead Mercury Uranium Arsenic, total Selenium, total
*Parts per billion 1.

Blood

<5 μg/L

> 5 μg/L

Blood Blood

<30 μg/dL <10 μg/L

> 40 μg/dL >200 μg/L

(95th Percentile, μg/L) weighted, non-creatinine corrected NHANES 1999 & 2000 results); Second National Report on Human Exposure to Environmental Chemicals, http://www.cdc.gov/exposurereport/2nd/metals.htm Centers for Disease Control and Prevention, 2003. Tietz Textbook of Clinical Chemistry, edited by C.A. Burtis and E.R. Ashwood, 1999. Carson B.L., Ellis III H.V., McCann J.L., Toxicology and Biological Monitoring of Metals in Humans, Lewis Publishers, 1986.

2. 3.

22

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix C

16.

APPENDIX C: REFERENCE VALUES FOR VOLATILE ORGANIC COMPOUNDS (BLOOD)
Fluid Blood Blood Blood Blood Blood Blood Blood Blood Blood Blood Minimum Risk Level(MRL) (PPM*)[2] 0.6 0.0009 0.03 0.1 5.0 2.0 2.0 5.0 0.2 1.0

Volatile Organic Compounds [1] 1,2-dichloroethane Benzene Carbon Tetrachloride Chloroform Ethyl benzene m,p-xylene o-xylene Styrene Tetrachloroethylene Touline
*Parts per million.

1.

The health effects resulting from exposure to low levels of volatile organic compounds are not well defined. Therefore, no critical call (high) values are available (Blount, Benjamin. Volatile Organic Compounds in Whole Blood, Solid Phase Microextraction Benchtop GCMS. CDC January, 2005). MRL (Minimal Risk Level) estimate of daily human exposure to a substance that is likely to be without an appreciable risk of adverse effects (non-carcinogenic) over a specified duration of exposure http://www.atsdr.cdc.gov/toxprofiles/index.asp.

2.

23

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix E

17.

APPENDIX D: CONCENTRATIONS OF INORGANIC ELEMENTS (µG /L) IN URINE AND BLOOD FOR THE 32 PARTICIPANTS.

PARTICIPANT ID
Element/ Isotope Monitored Beryllium Cobalt Molybdenum Cadmium Antimony Cesium Barium Tungsten Platinum Thallium Lead Mercury Uranium Arsenic Selenium
• • • DE136 DE169 DE551 DE156 DE177 DE139 DE168 DE211 DE552 DE190 DE553 DE556 DE325 DE249 DE298 DE290
<0.2500 0.609 59.696 1.048 1.147 <0.100 5.095 2.252 <0.100 <0.125 0.216 1.013 <10 1.685 <0.0125 24.004

<0.2500 0.1250 17.3470 <0.125 <0.5 <0.100 <0.5 <0.5000 <0.1 0.133 0.0720 <0.3750 19.016 1.212 <0.0125 <8.125

<0.2500 0.6440 8.7750 0.7620 0.788 <0.100 4.153 0.6680 <0.1 <0.125 0.0500 <0.3750 <10 <1 <0.0125 <8.125

<0.2500 1.2080 16.5380 <0.125 1.316 <0.100 3.152 <0.5000 <0.1 <0.125 <0.0500 <0.3750 <10 <1 <0.0125 12.37

<0.2500 0.2490 41.1080 0.1320 <0.5 <0.100 4.307 1.1720 <0.1 <0.125 0.1340 1.0100 16.699 2.886 <0.0125 9.53

<0.2500 0.1810 <7.5000 <0.125 <0.5 <0.100 1.071 0.2200 <0.1 <0.125 <0.0500 <0.3750 12.723 <1 <0.0125 <8.125

<0.2500 0.3620 <7.5000 0.1280 1.329 0.1340 1.245 1.2090 <0.1 <0.125 0.0590 <0.3750 10.931 <1 <0.0125 <8.125

<0.2500 0.2360 38.0660 0.2760 <0.5 <0.100 4.714 1.7960 <0.1 <0.125 0.1160 <0.3750 <10 <1 <0.0125 <8.125

<0.2500 0.539 180.421 0.794 <0.5 <0.100 7.248 2.562 <0.1 <0.125 0.102 1.4270 10.89 3.048 <0.0125 86.361

<0.2500 0.1250 12.3800 <0.125 <0.5 <0.100 <0.5 1.4500 <0.1 <0.125 <0.0500 <0.3750 <10 <1 <0.0125 <8.125

<0.2500 0.2640 32.7820 0.7420 0.698 <0.100 6.656 <0.5000 <0.1 <0.125 0.3040 0.6640 26.652 <1 <0.0125 234.524

<0.2500 0.4720 61.7050 <0.125 0.681 0.1150 13.378 4.8600 0.213 <0.125 0.3390 1.8950 23.818 2.088 0.0340 88.202

<0.2500 0.1250 <7.5000 <0.125 <0.5 <0.100 <0.5 0.5030 <0.1 <0.125 <0.0500 <0.3750 <10 1.854 <0.0125 <8.125

<0.2500 0.1250 9.1170 0.1490 <0.5 <0.100 <0.5 <0.5000 <0.1 <0.125 <0.0500 0.3750 <10 <1 <0.0125 <8.125

<0.2500 0.1250 <7.5000 <0.125 <0.5 <0.100 1.141 <0.5000 <0.1 <0.125 <0.0500 <0.3750 <10 <1 <0.0125 <8.125

<0.2500 0.3070 <7.5000 0.2020 0.812 <0.100 1.201 3.9390 <0.1 <0.125 0.3000 <0.3750 11.306 1.144 <0.0125 <8.125

33.252

24.955

29.917

59.135

21.302

44.465

40.224

210.974

31.305

52.994

36.07

19.948

23.054

12.192

27.154

74.835

Values for urine and blood metal levels shown in this table are in microgram per liter (μg /liter) or parts per billion (ppb). Three metals were measured in blood (cadmium, mercury, and lead). For these metals, the values in bold (second row for these analytes) indicate the concentrations of the three metals in blood specimens. Values highlighted in grey indicate high levels.

24

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix E

Appendix D (continued). CONCENTRATIONS OF INORGANIC ELEMENTS (μg/L) IN URINE AND BLOOD FOR THE 32 PARTICIPANTS.

PARTICIPANT ID
Element/ Isotope Monitored Beryllium Cobalt Molybdenum Cadmium Antimony Cesium Barium Tungsten Platinum Thallium Lead Mercury Uranium Arsenic Selenium
• • • DE346 DE559 DE561 DE557 DE342 DE238 DE564 DE554 DE562 DE563 DE565 DE560 DE566 DE558 DE352 DE567
<0.2500 0.1250 <7.5000 <0.1250 0.644 <0.100 3.030 <0.5000 <0.1 <0.125 <0.050 <0.3750 <10 <1 <0.0125 <8.125 20.866

<0.2500 0.1670 17.617 0.2380 <0.5 <0.100 2.639 <0.5000 <0.1 <0.125 0.0900 <0.3750 <10 1.429 <0.0125 <8.125 123.634

<0.2500 0.1510 25.2050 0.1250 <0.5 <0.100 3.601 <0.5000 <0.1 <0.125 0.1480 <0.3750 <10 <1 <0.0125 26.692 31.569

<0.2500 0.5410 29.8620 0.2770 <0.5 <0.100 3.421 2.6850 0.100 <0.125 0.1630 1.1600 <10 <1 <0.0125 <8.125 52.915

<0.2500 0.125 14.525 <0.125 <0.5 <0.100 1.506 0.638 <0.125 <0.500 <0.050 <0.375 <10 <1 <0.0125 9.118 28.766

<0.2500 0.2670 55.0100 0.7460 <0.5 <0.100 6.917 7.7570 <0.1 <0.125 0.2660 0.5000 <10 <1 <0.0125 <8.125 57.772

<0.2500 1.1320 337.4490 2.0950 <0.5 <0.100 20.661 2.4230 0.379 <0.125 0.3920 1.2860 <10 <1 <0.0125 14.048 251.126

<0.2500 0.310 69.406 0.500 <0.5 0.150 5.771 3.034 <0.1 <0.125 0.104 0.878 17.537 <1 <0.0125 <8.125 92.909

<0.2500 0.5110 73.7110 0.1670 <0.5 <0.100 4.957 3.5810 0.278 <0.125 0.3490 0.9880 <10 2.324 <0.0125 <8.125 98.551

<0.2500 0.1250 <7.5000 <0.125 <0.5 <0.100 <0.5 <0.5000 <0.1 <0.125 <0.050 0.3750 11.63 <1 <0.0125 <8.125 19.596

<0.2500 0.4830 97.0920 1.0800 0.681 <0.100 6.147 1.2940 <0.1 <0.125 0.1630 <0.3750 <10 <1 <0.0125 11.005 96.178

<0.2500 0.4560 13.6130 <0.125 <0.5 <0.100 1.533 1.0010 <0.1 <0.125 <0.050 <0.3750 <10 1.302 <0.0125 8.204 27.648

<0.2500 0.4130 80.512 1.817 <0.5 <0.100 8.839 2.243 0.158 <0.125 0.1290 1.2600 <10 <1 <0.0125 62.788 72.161

<0.2500 0.7190 51.2010 0.1910 <0.5 0.1670 5.852 3.0650 0.171 <0.125 0.4730 2.6010 14.736 1.474 0.0160 >650 56.821

<0.2500 0.2420 41.0820 0.2260 <0.5 <0.100 12.306 1.1430 <0.1 <0.125 0.4410 0.4800 <10 <1 <0.0125 15.458 105.83

<0.2500 0.2030 56.1520 0.1720 <0.5 <0.100 3.706 1.4580 0.127 <0.125 0.1140 0.7730 21.599 2.043 0.0020 11.678 44.381

Values for urine and blood metal levels shown in this table are in microgram per liter (μg /liter) or parts per billion (ppb). Three metals were measured in blood (cadmium, mercury, and lead). For these metals, the values in bold (second row for these analytes) indicate the concentrations of the three metals in blood specimens. Values highlighted in grey indicate high levels.

25

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix E

18.

APPENDIX E: VOLATILE ORGANIC COMPOUNDS (VOCS) LEVELS (PARTS PER BILLION) IN BLOOD SAMPLES OF THE 32 PARTICIPANTS

PARTICIPANT ID
DE136 DE169 DE551 DE156 DE177 DE139 DE168 DE211 DE552 DE190 DE553 DE556 DE325 DE249 DE298
<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

1,2-dichloroethane Benzene Carbon Tetrachloride Chloroform Ethyl benzene m,p-xylene o-xylene Styrene Tetrachloroethylene Touline

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

26

DE290

Volatile Organic Compound

IRPPS Fall 2011 Summary Report 6/28/2012 Appendix E

Appendix E (continued): VOLATILE ORGANIC COMPOUNDS (VOCS) LEVELS (parts per billion) IN THE BLOOD SAMPLES OF THE 32 PARTICIPANTS

PARTICIPANT ID
DE346 DE559 DE561 DE557 DE342 DE238 DE564 DE554 DE562 DE563 DE565 DE560 DE566 DE558 DE352
<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

1,2-dichloroethane Benzene Carbon Tetrachloride Chloroform Ethyl benzene m,p-xylene o-xylene Styrene Tetrachloroethylene Touline

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<50 <50 <50 <50 <50 <50 <50 <50 <50 <50

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

<100 <100 <100 <100 <100 <100 <100 <100 <100 <100

27

DE567

Volatile Organic Compound

IRPPS Fall 2011 Summary Report 6/28/2012

19.
1

REFERENCES

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