Final Report

AIR QUALITY IMPACTS OF LOW VAPOR PRESSURE-

VOLATILE ORGANIC COMPOUNDS

(Contract Number: 13-302)

Principal Investigator:

David R. Cocker III

951 231 0729

Prepared for:

State of California Air Resources Board

Research Division

PO Box 2815

Sacramento, CA 95812

Prepared by:

David Cocker, Weihua Li, Lijie Li, Mary Kacarab, Weihan Peng

University of California, Riverside

College of Engineering Center for Environmental Research and Technology (CE-CERT)

1084 Columbia Ave

Riverside, CA 92507

Phone: (951) 781 5791

Fax: (951) 781-5790

December 13, 2016

2

ACKNOWLEDGEMENTS AND DISCLAIMER

This work was funded by the California Air Resources Board (ARB) through contract number 13-302.

The UCR EPA chamber experiments were carried out at the College of Engineering, Center for

Environmental Research and Technology (CE-CERT) primarily by Weihua Li, Lijie Li, and Mary

Kacarab with assistance from Weihan Peng, Dana Maxie, Robert Espinoza, and Kurt Bumiller.

Helpful discussions with Jin Xu and Eileen McCauley of the ARB staff, Doug Fratz of the Consumer

Specialty Products Association, and Naveen Berry of the SCAQMD staff concerning research directions

for the project are acknowledged. We also acknowledge input from other members of the LVP-VOC

advisory group concerning selection of compounds for this project and other input. Helpful discussions

with Dr. William P.L. Carter concerning the experimental protocols and chemical reactivity modeling are

also gratefully acknowledged.

Although this work was funded primarily by the ARB, it reflects only the opinions and conclusions of

the author. Mention of trade names and commercial products does not constitute endorsement or

recommendation for use.

3

Table of Contents

List of Tables ............................................................................................................................................... 5

List of Figures .............................................................................................................................................. 6

EXECUTIVE SUMMARY ...................................................................................................................... 11

I. INTRODUCTION ............................................................................................................................. 15

II. EXPERIMENTAL SET-UP ......................................................................................................... 19

1. Investigation of LVP-VOC volatilization rates using an evaporation chamber .............................. 19

2. Selection of LVP-VOCs and mixtures: ........................................................................................... 20

3. Laboratory chamber experiments on LVP-VOCs ........................................................................... 22

a. Environmental chamber facility .................................................................................................. 22

b. Analytical methods ..................................................................................................................... 24

c. Gas-phase analysis ...................................................................................................................... 24

d. Particle-phase analysis ................................................................................................................ 24

e. LVP-VOC injection .................................................................................................................... 26

III. RESULTS AND DISCUSSION ................................................................................................... 28

1. Atmospheric availability ................................................................................................................. 28

a. Individual LVP-VOCs ................................................................................................................ 28

b. LVP-VOC in consumer product surrogate mixtures ................................................................... 31

c. Wall effects ................................................................................................................................. 42

d. Chamber background .................................................................................................................. 42

e. LVP-VOC stability within the UCR environmental chamber .................................................... 42

f. Particle wall loss correction ........................................................................................................ 44

g. Chamber characterization run ..................................................................................................... 44

h. Experimental types ...................................................................................................................... 45

2. Individual LVP-VOC experiments ................................................................................................. 52

a. Ozone experimental results ......................................................................................................... 52

b. Ozone modeling results ............................................................................................................... 55

c. SOA results ................................................................................................................................. 62

d. Seeded experiment-vapor wall loss effects ................................................................................. 69

e. In depth glycol ether study .......................................................................................................... 71

4

f. Individual LVP-VOC with NO and UV only ............................................................................. 73

g. Individual LVP-VOC with H2O2 only ........................................................................................ 74

3. Consumer products ......................................................................................................................... 76

a. Ozone results ............................................................................................................................... 76

b. SOA results ................................................................................................................................. 78

c. Comparison with single compounds ........................................................................................... 80

4. Hydrocarbon solvent mixtures ........................................................................................................ 81

a. Ozone formation ......................................................................................................................... 81

b. SOA formation ............................................................................................................................ 83

c. Hydrocarbon solvent mixture experimental repeatability ........................................................... 85

5. Overall ozone and SOA formation comparison .............................................................................. 87

6. Chemical composition characteristics of SOA formation ............................................................... 90

a. Volume fraction remaining (VFR) .............................................................................................. 90

b. Average oxidation state of carbon (OSc) .................................................................................... 90

c. SOA density ................................................................................................................................ 91

IV. SUMMARY ................................................................................................................................... 95

V. REFERENCES ..................................................................................................................................... 98

5

List of Tables

Table 1: Individual LVP-VOCs tested ........................................................................................................ 20 Table 2: Surrogate consumer products studied ........................................................................................... 20 Table 3: The recipes of selected consumer products .................................................................................. 21 Table 4: The recipe and manufacturing process of hand lotion .................................................................. 21 Table 5: List of analytical and characterization instrumentation used in this project ................................. 24 Table 6: Individual LVP-VOCs tested ........................................................................................................ 29 Table 7 : Viscosity and diffusivity of water, honey and propylene glycol at room condition .................... 40 Table 8: Stability run .................................................................................................................................. 43 Table 9 : Tested LVP-VOCs ..............................................................................................