### APPENDIX IV

MATES III

FINAL REPORT

Measurements of Ambient Naphthalene and Other Polyc yclic Aromatic Hydrocarbons

Author
Jason LowMATES III Final Report

Appendix IV-1 

### Appendix IV Measurements of Ambient Naphthalene and Other Polyc yclic Aromatic Hydrocarbons
IV-1 Background Naphthalene is the most abundant PAH present in the atmosphere and exists primarily in the gas phase under ambient conditions. Major sources of n aphthalene are shown in Figure IV-1. The total estimated inventory of naphthalene in the Sou th Coast Air Basin (Basin) is 1,535 lbs./day for 2005 (see Chapter 3 of this report). Naphthalene was identified in 1990 as a Hazardous A ir Pollutant (HAP) and classified by ARB in 1993 as a toxic air contaminant (TAC). The Nati onal Toxicology Program has recently listed naphthalene as a human carcinogen. Additionally, t he California EPA Office of Environmental Health Hazard Assessment (OEHHA) has determined amb ient naphthalene as a health risk and as a toxic air contaminant under California’s Air T oxics Program with a unit risk value of 3.4 x 10-5 (μg/m 3 ) -1

.

Figure IV-1: Naphthalene Emission Inventory in the South Coast Basin

Particle-bound PAHs are an important class in the c omplex mixture of chemical compounds observed in ultrafine particles. PAHs and the orga nic carbon component of ultrafine particles have been shown to be directly correlated to marker s for oxidative stress (Li, et al. 2000; Li, et al. 2003; Cho, et al. 2003). Past monitoring in th e Basin has shown that individual particle37%

25% 25% 13%



### On Road Motor Vehicles
Off Road Mobile Sources
Consumer Products Stationary and Other Area SourcesMATES III Final Report

Appendix IV-2 bound PAHs are minor contributors to risk (SCAQMD, 2000), despite their high carcinogenicity, because of their low ambient air concentrations whi ch have been decreasing over time (Figure IV-2). Also, some PAHs, such as benzo[g,h,i]pyrele ne, have been suggested to be a tracer for light-duty vehicle exhaust (Miguel, et al. 2005).



### 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40

1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 200 2 2003ng/m3

BaP BGP IDP
Figure IV-2: CARB Trend Data from 1990 through 2003 for Benzo[a]Pyrene (BaP),

Benzo[g,h,i]perylene (BGP), and Indeno[1,2,3-cd]pyr ene (IDP)

The MATES II cancer risk assessment showed that the particle-bound PAH contribution-tocancer risk was insignificant compared to other sou rces. However, the assessment did not include the semi-volatile or the volatile PAHs such as naphthalene (SCAQMD, 2000). Before 1994, measurements (Table IV-1) showed ambient naph thalene ranging from 750 to 1,300 ng/m 3 in the spring with concentrations reaching more tha n 4,000 ng/m 3 during high NOx or ozone events. In 1996 California Phase II reformulated g asoline (RFG) was introduced which decreased the amounts of alkenes, aromatics, sulfur compounds, and total volatility. Kirchshstetter, et al. (1999) showed that the conce ntrations of naphthalene and benzene in RFG sampled in Berkeley, California were reduced signif icantly. After implementation of RFG, significantly lower concentrations ranging from 200 to 575 ng/m 3 were observed in the Los Angeles Basin as shown in the Southern California C hildren’s Health Study (CHS) from 2001 to 2002 and subsequent studies by Reisen and Arey (200 5). Recent measurements have shown that annual averages of naphthalene are at levels about 1,000 times higher than those of other PAHs (Eiguren-Fernandez, 2004).MATES III Final Report

Appendix IV-3 Table IV-1 Previous measurements of ambient naphth alene in the South Coast Air Basin

Period of
Measurement Location [Naphthalene] ng/m 3 (day) [Naphthalene]

ng/m 3 (night) 1986 (late winter, high NOx episode) 1 Torrance 3,315 2,875
1986 (summer, smog episode) 2 Glendale 3,100 4,300
1987 (spring) 3 Reseda 750 1,300 1993 (fall, smog episode) 4 Los Angeles 6,000

1995 5 Redlands 348 to 715
2001 to 2002 6 Southern California 200 to 575 2002 (summer) 7 Los Angeles ~ 350 ~ 140 2002 (summer) 7 Riverside ~ 225 ~ 40 2003 (winter) 7 Los Angeles ~ 1,400 ~ 1,000 2003 (winter) 7 Riverside ~ 500 ~ 150

1 Arey, et al. 1987; 2 Arey, et al. 1989; 3 Atkinson, et al. 1994; 4 Fraser, 1998; 5 Gupta, 1995; 6 Calvert, et al. 2002; Eiguren-Fernandez, et al. 200 4; 7 Reisen, 2003

PAHs were measured at three of the MATES III monito ring stations using EPA method TO-13A as a guideline. The West Long Beach and Central Los Angeles sites were selected because of their proximity to mobile emissions sources. Also, Lu, et al. (2005) incorporated ambient data from the Southern California CHS and showed the hig hest naphthalene emissions rate in those regions. The Rubidoux site was selected as a recep tor site and also for its particle-bound PAH measurement history as part of the ARB toxics netwo rk. Also, collocated samples were done once a month at the Rubidoux site. Table IV-2 prov ides a list of the 16 PAHs analyzed as part of MATES III.

Table IV-2: List of PAHs Measured in the MATES III Study

Acenaphthene Chrysene Acenaphthylene Dibenzo[a,h]anthracene
Anthracene Fluoranthene Benzo[a]anthracene Fluorene Benzo[a]pyrene Indeno[1,2,3-cd]pyrene Benzo[b]fluoranthene Napthalene Benzo[g,h,i]perylene Phenanthrene Benzo[k]fluoranthene PyreneMATES III Final Report

Appendix IV-4 IV-2 Methodology
IV-2-1 Sampling The sampling protocol was based on EPA TO-13A in wh ich 24-hour integrated air samples were collected at eight cubic feet per minute (cfm) in a Tisch TE-1000 PUF (polyurethane foam) monitor. The particle phase sample was collected o n a quartz fiber filter (102 mm) located upstream from a glass cartridge holding 20 grams of XAD-4 which collected the semi-volatile and vapor phase PAHs. XAD-4 was selected as the sa mpling media because it has more surface area than XAD-2, allowing for higher collection eff iciency of the PAHs. A comparison was done with the PUF/XAD-4/PUF sandwich to ensure that results would not differ significantly from other sampling methodologies, and a breakthrou gh study was done to ensure that PAHs were not escaping through the XAD-4 cartridge.
Since ambient PAH concentrations in the South Coast Basin have shown seasonal variation (Eiguren-Fernandez, 2004) with higher and more vari able concentrations in the winter and lower concentrations in the spring and summer, the sample s were collected every third day in the winter of 2004 and 2005 and every sixth day in the spring and summer of 2005. After collection, the samples were chilled and transported to Southwe st Research Institute for extraction and analysis.
IV-2-2 Sample Extraction As with sample collection, the extraction protocol was based on EPA TO-13A. The method was enhanced by using higher internal standard (IS) con centrations of the more volatile PAHs and lower concentrations of the particle-bound PAHs whi ch are reflective of the ratios found in ambient air. This differs from TO-13A which just u ses the same concentration for each compound in the IS. Prior to extraction, 25 μ l of deuterated PAH IS mixture was added into each sample. The deuterated PAH IS mixture containe d the following compounds: Naphthalened8 (1000 ng/ μ l), Acenaphthylene-d8 (300 ng/ μ l), 100 ng/ μ l each of Phenanthrene-d10 and Fluoranthene-d10, and 5.0 ng/ μ l each of Benzo[a]anthracene-d12, Chrysene-d12, Benzo[b]fluoranthene-d12, Benzo[a]pyrene-d12, Inden o[1,2,3-cd]pyrene-d12, Dibenz[a,h]anthracene-d14, and Benzo[g,h,i]perylene -d12. The XAD-4 glass cartridge and the matching filter w ere extracted together using 1-Liter Soxhlet extractor with dichloromethane (DCM) as the extract ing solvent. The extraction lasted for eight hours with a siphoning rate of 3-4 siphons per hour . At the end of the extraction, the sample extracts were concentrated to about 20 ml by using a rotary evaporator under a gentle vacuum. With each batch of field samples, four lab QC sampl es were created and extracted alongside the field samples as follows: solvent blank, XAD-4 blan k, lab control spike (LCS), and lab control spike duplicate (LCSD). The solvent blank had 350 ml of DCM only. The XAD-4 blank consisted of 20 grams of clean XAD-4. The LCS and L CSD each had 20 grams of clean XAD-4 and one clean filter and each was spiked with 25 μ l of target PAH mix with the concentration similar to that of the PAH IS. Prior to the extrac tion, each of the QC samples was spiked with the same amount of PAH IS mixture as described abov e.MATES III Final Report

Appendix IV-5 IV-2-3 Sample Extract Cleanup for PAH Analysis One quarter of each sample extract was archived as reserve. The remaining extract was solvent exchanged into 0.5 ml of hexane. Six ml of hexane was then added to the extract. The extract was then vigorously partitioned with 2.0 ml of 25% sulfuric acid in water for 20 seconds. A disposable pipette (8 mm i.d. x 30 cm long) packe d with 5” of activated silica gel was used for sample extract cleanup. The column was pre-cleaned first with 20 ml of distilled DCM and then with 5 ml of hexane. The hexane layer of the acid- washed sample extract was quantitatively transferred onto the silica gel column using hexane as a rinsing solvent. Ten ml of hexane (~3 ml at a time) was used to elute the column and the collected eluent discarded. The PAH fraction was then eluted with 23 ml of DCM/pentane (60/40, ~ 3 ml at a time).
The collected PAH fraction was mixed well and divid ed into two parts. The first portion of the cleaned-up extract was carefully blown down to a fi nal volume of 1.0 ml in DCM using a gentle stream of charcoal-filtered nitrogen. This final e xtract was used for naphthalene through pyrene analysis plus two PAH surrogates. The second portion of the cleaned-up extract was ca refully blown down to 100 μ l in two stages. This final extract was used for benzo[a]anthracene through benzo[g,h,i]perylene analysis.
IV-2-4 Sample PAH Analysis by GC/MS The GC/MS (gas chromatograph/mass spectrometer) use d was an Agilent 6890N GC interfaced with an Agilent 5973N MSD (mass spectrometer detect or). The column used was a DB-5ms 30 m x 0.25 mm i.d. with 25 μ m film thickness. The GC injector and GC/MS interf ace temperature were held at 290 o C. The GC oven temperature program was as follows: 40 o C held for 1.5 minutes, 15 o C/min to 220 o C, then 8 o C/min to 310 o C and held for 3.5 minutes. The carrier gas was helium at a constant flow rate of 1.5 ml/min. The GC/MS was operated under EI/PI/SIM mode (electr on impact/positive ion/selective ion monitoring). Only the characteristic ions such as molecular ions of PAH ISs, and molecular and major fragment ions of PAH targets were monitored. Acenaphthene-d10, pyrene-d10, and benzo[e]pyrene-d12 were used as recovery standards (RSs). These RSs were spiked into the final sample extracts just prior to GC/MS analysis and were used to quantify the recoveries of the 11 PAH ISs. The GC/MS analysis was carried out in two stages: t he first GC/MS analysis quantified for naphthalene through pyrene on diluted sample extrac t (1.0 ml); the second GC/MS analysis quantified for benzo[a]anthracene through benzo[g,h ,i]perylene on a concentrated sample extract (0.1 ml). Also the lowest calibration point was 10 pg/ μ l instead of 100 pg/ μ l as listed in Table 4 of TO-13A. A five-point initial calibration (ICAL) curve was e stablished using five PAH standard mixtures containing all PAH targets, PAH ISs, surrogates, an d RSs. The PAH targets in the five-point curve were at five different levels namely 10, 30, 100, 300, and 1000 pg/ μ l. The relative response factors (RRFs) of the PAH targets were est ablished using the five-point curve. The relative standard deviation (RSD) of the RRF of eac h PAH target had to be equal to or less than 25% in order for the ICAL to be considered valid. The RRFs for the ISs relative to the RSs were also established for the five calibration standards in the same way. The ISs and RSs were at 750 pg/ μ l for all calibration standards.MATES III Final Report

Appendix IV-6 At the beginning of each sample analysis sequence, a continuing calibration (CC) PAH standard mixture at 300 pg/ μ l was analyzed. The RRF of each PAH target was est ablished using this CC standard. The percent difference of the RRF of eac h PAH target in the CC compared with the mean RRF of the ICAL had to be equal to or less tha n 25%. This CC criterion had to be met before the sample analysis could proceed. The same calibration criterion applied to the ISs as well.
IV-2-5 Analysis of Standard Reference Material (SRM ) from the National Institute of Standards and Technology (NIST)
The PAH SRM 1597 was diluted 160 folds and 320 fold s in DCM. An aliquot of each of the diluted SRM was then spiked with the same PAH IS mi x which had been spiked into the field and lab QC samples prior to their extraction. The two NIST PAH SRM solutions were then analyzed alongside the field and lab QC samples. The analytical concentrations of various PAHs in th e diluted SRM solutions were then compared with that of the expected PAH concentrations based on the NIST certified values. A list of PAH concentration ratios, expected/found, was establish ed for those PAHs which had a value in the SRM certificate of analysis. These ratios were use d as correction factors to adjust the found PAH concentrations of the field ambient air samples . This is an improvement from TO-13A which just calls for stating the percent recovery o f the particular component.

IV-3 Results The monthly averages for naphthalene over the monit oring period for PAHs are shown in Figure IV-3.
Table IV-3 summarizes the results of the PAH ambien t monitoring for MATES III year 2. Consistent with other studies, the highest levels o f naphthalene were measured during the fall and winter season. This is also consistent with me asurements of other volatile organic compounds, such as benzene, that are higher during this time period. This is likely due to cooler temperatures and lower mixing height.
The levels of the other PAHs measured were substant ially lower than naphthalene. This is also consistent with previous measurements in the Basin.MATES III Final Report

Appendix IV-7 Naphthalene

0 50 100 150 200 250 300 350 400 450 500DecJanFebMarAprMaJunJulAuSepOctNoDecJanFebMar

2004 2005 2006ng/m3 Central LA Rubidoux W. Long Beach

Figure IV-3 Monthly Average Levels of NaphthaleneMATES III Final Report

Appendix IV-8 Table IV-3 MATES III Year 2 Monitored PAH Levels ( ng/m 3 )

Site

Central L.A. Rubidoux N. Long Beach Acenaphthene Avg 7.61 4.65 8.49 SD 4.76 2.92 6.70 N 91 91 91 95% CI 0.98 0.60 1.38 Max 21.39 13.42 34.78 Min 0.85 0.80 1.46

Acenaphthylene Avg 5.08 4.40 5.23 SD 4.05 4.50 5.38 N 91 91 91 95% CI 0.83 0.92 1.10 Max 16.02 20.92 24.68 Min 0.51 0.29 0.56

Anthracene Avg 1.19 0.72 1.07 SD 3.07 1.62 2.53 N 91 91 91 95% CI 0.63 0.33 0.52 Max 21.64 10.67 22.34 Min 0.09 0.06 0.12

Benz(a)Anthracene Avg 0.10 0.12 0.14 SD 0.08 0.12 0.13 N 91 91 91 95% CI 0.02 0.03 0.03 Max 0.34 0.46 0.65 Min 0.01 0.01 0.01

Benzo(a)pyrene Avg 0.12 0.14 0.18 SD 0.10 0.15 0.17 N 91 91 91 95% CI 0.02 0.03 0.04 Max 0.51 0.62 0.82 Min 0.01 0.02 0.02

Benzo(b+j+k)Fluoranthene Avg 0.34 0.40 0.39 SD 0.26 0.37 0.37 N 91 91 91 95% CI 0.05 0.08 0.08 Max 1.03 1.38 1.59 Min 0.04 0.03 0.03MATES III Final Report

Appendix IV-9 Table IV-3 MATES III Year 2 Monitored PAH Levels ( ng/m 3 )

Site

Substance Central L.A. Rubidoux N. Long Beach Benzo(ghi)perylene Avg 0.35 0.33 0.40 SD 0.24 0.31 0.36 N 91 91 91 95% CI 0.05 0.06 0.07 Max 1.04 1.33 1.85 Min 0.04 0.04 0.04

Chrysene Avg 0.32 0.35 0.43 SD 0.19 0.29 0.31 N 91 91 91 95% CI 0.04 0.06 0.06 Max 0.89 1.15 1.51 Min 0.08 0.03 0.05

Dibenz(a,h)anthracene Avg 0.03 0.04 0.06 SD 0.02 0.05 0.06 N 91 91 91 95% CI 0.01 0.01 0.01 Max 0.13 0.44 0.53 Min 0.00 0.00 0.00

Fluoranthene Avg 2.12 1.37 1.90 SD 0.86 0.64 1.07 N 91 91 91 95% CI 0.18 0.13 0.22 Max 4.37 3.09 4.84 Min 0.48 0.33 0.54

Indeno(1,2,3-cd)pyrene Avg 0.17 0.18 0.18 SD 0.12 0.16 0.17 N 91 91 91 95% CI 0.02 0.03 0.03 Max 0.53 0.60 0.70 Min 0.02 0.02 0.01

Naphthalene Avg 201.29 154.91 183.78 SD 110.52 110.68 150.79 N 91 91 91 95% CI 22.71 22.74 30.98 Max 447.60 533.56 726.14 Min 35.29 24.30 29.95MATES III Final Report

Appendix IV-10 Table IV-3 MATES III Year 2 Monitored PAH Levels ( ng/m 3 )

Site

Substance Central L.A. Rubidoux N. Long Beach Phenanthrene Avg 14.35 8.96 13.65 SD 6.52 4.39 8.40 N 91 91 91 95% CI 1.34 0.90 1.73 Max 34.54 20.99 37.59 Min 2.62 2.24 3.47

Pyrene Avg 1.67 1.19 1.68 SD 0.73 0.70 1.01 N 91 91 91 95% CI 0.15 0.14 0.21 Max 3.41 3.56 5.09 Min 0.42 0.25 0.39MATES III Final Report

Appendix IV-11 References

Arey, J., Zielinska, B., Atkinson, R., Winer, A.M., Atmos. Environ ., 21, 6, 1437-1444, 1987.
Arey, J., Atkinson, R., Zielinska, B., McElroy, P.A
., Environ. Sci. Tech ., 23, 3, 321-327, 1989.
Atksinson, R., Arey, J., Environ. Health Perspectives , 102 (Suppl. 4), 117-126, 1994.
CARB, California Air Resources Board, 1994.
Calvert, J. G., Atkinson, R., Becker, K.H., Kamens, R.M., Seinfeld, J.H., The Mechanisms of Atmospheric Oxidation of Aromatic Hydrocarbons , Oxford University Press, New York, p. 348, 2002. Eiguren-Fernandez, A. Miguel, A.H., Froines, J.R., Thurairatnam, S., Avol, E., Aerosol Science & Technology, 38, 447-445, 2004.
Cho, A.K., DiStefano, E., You, Y., Rodriquez, C.E., Schmitz, D.A., Kumagai, Y., Miguel, A.H., Eiguren-Fernandez, A., Kobayashi, T., Avol, E ., Froines, J.R., Aerosol Science and Technology, 38 (Suppl. 1), 68-81, 2004.
Fraser, M.P., Cass, G.R., Simoneit, B., Rasmussen, R.A., Environ. Sci. Tech., 32, 12, 1760- 1770, 1998.
Gupta, P., Master’s Thesis, University of Californi a, Riverside, 1995.
Kircshtetter, T.W., Singer, B.C., Harley, R.A., Ken dall, G.R., Hesson, J.M., Environ. Sci. Tech., 33, 329-336, 1999.
Li, N. Venkatesan M.I., Miguel, A., Kaplan, R., Guj uluva, C., Alam, J., Nel, A. The Journal of Immunology , 165, 3393-3401, 2000.
Li, N., Sioutas C., Cho A., Schmitz, D., Misra, C., Sempf, J., Wang, M.Y., Oberley, T., Froines, J., Nel, A., Environonmental Health Perspectives , 111, 455-460, 2003.
Lu, R., J. Wu, R.P. Turco, A.M. Winer, R. Atkinson, J. Arey, S.E. Paulson, F.W. Lurmann, A.H. Miguel and A.E. Fernandez. "Naphthalene distr ibutions and human exposure in southern California." Atmospheric Environment, 39: 489-507, 2005.
Reisen, F., Ph. D. Thesis, University of California , Riverside, 2003.
SCAQMD, Multiple Air Toxics Exposure Study (MATES I I) Final Report, March 2000.