1 

### ANNUAL REPORT ON

VOLATILE ORGANIC COMPOUND EMISSIONS

FROM PESTICIDES: EMISSIONS FOR 1990

– 20 10

Rosemary Neal, Ph.D.

Staff Environmental Scientist

Frank Spurlock, Ph. D

Research Scientist III

and

Randy Segawa Environmental Program Manager I

March 2012

California Environmental Protection Agency Department of Pesticide Regulation Environmental Monitoring Branch

P.O. Box 4015
Sacramento, California 95812-4015
(916) 324-4039

AIR2012-12 EXECUTIVE SUMMARY

Preface

This report fulfills the requirements of Title 3, California Code of Regulations (3 CCR) , section 6452.4 which requires the Director of Department of Pesticide Regulation (DPR) to issue an annual emissions inventory report for the Sacramento Metro, San Joaquin Valley, South Coast, Southeast Desert, and Ventura ozone nonattainment areas (NAAs) . This report presents data reported to or produced by DPR from May 1, 2010, to October 31, 2010, the peak ozone season in California. In addition, data from the same months in 1990 are included for baseline comparisons, and from 2007, 2008 and 2009 for trend analysis.

Background

Under the federal Clean Air Act, California must meet national standards for air borne pollutants and must specify how it plans to achieve these goals in a federally approved State Implementation Plan (SIP). Five regions in California

– the Sacramento Metro area, the San Joaquin Valley, the Southeast Desert region, Ventura County and t he South Coast area

- exceed federal ozone standards and are therefore designated NAAs. SIPs require the control of emissions of nitrogen oxides and volatile organic compounds (VOCs) because they are precursors to ozone. Under California’s SIP, approved by the U.S. Environmental Protection Agency (U.S. E PA ) in 1997, DPR must track and control VOC emissions from pesticide products used in agriculture and by commercial structural applicators in these five NAAs. Under the SIP, California is expected to reduce pesticide VOCs by 12 percent in the San Joaquin Valley and 20 percent in the other four NAAs, compared to 1990 levels.

DPR’s VOC emission inventory database includes only pesticide applications that are made between May 1 and October 31, the peak ozone season in California. The database is updated when annual pesticide use report data from the previous year becomes available, and contains data for every year since 1990. Each year contains about 2.5 million pesticide use records (PUR) and emission potential (EP) values for approximately 5,000 products. The EP is that fraction of a product that is assumed to contribute to atmospheric VOCs.

Beginning in 2008 DPR adopted regulations to reduce VOC emissions from fumigant pesticides. Section 6452.2 , 3 CCR, inclu des specific emission target levels (VOC regulation benchmarks) for each of the five NAAs, equivalent to the SIP obligation of a 12 percent or 20 percent reduction. The regulations reduce VOC emissions by requiring low- emission fumigation methods in certai n NAAs. In all NAAs but Ventura, if, in spite of these application method requirements, pesticide VOC emissions exceed 95 percent of the benchmark for a NAA, DPR will, as specified by the regulations, ensure that the benchmark is achieved by establishing a fumigant limit

. A fumigant limit is required at least through 2012 in Ventura. The fumigant limit is determined by subtracting the estimated nonfumigant emissions from the regulatory benchmark, basing the nonfumigant emissions estimate on VOC emission inventory data from previous years.3 Report Summary

VOC emissions in all five nonattainment areas increased in 2010, but in compliance with the SIP goals and below the VOC regulation benchmarks.

• Sacramento Metro NAA: VOC emissions decreased between 2006 and 2008, increased by

less than one percent in 2009 and a fu r ther 1 2 percent in 2010. Pesticide VOC emissions in

2010 were 62 percent lower than the 1990 base year and remain well in compliance with the SIP goal and the VOC regulation benchmark. In 2010, 91 percent of emissions were derived from nonfumigant s.

• San Joaquin Valley NAA: VOC emissions decreased between 2006 and 2009 and then

in creased by approximately 2 5 percent in 2010. Pesticide VOC emissions in 2010 were 18

percent lower than the 1990 base year and comply with the SIP goal and VOC regulation

benchmark. T hree

- quarters of pesticide emissions are derived from nonfumigant s.

• Southeast Desert NAA: VOC emissions increased from 2006 to 2007, but then decreased in

2008 and 2009. There was an increase of more than twice the amount of p esticide VOC

emissions from 2009 to 2010, but emissions in 2010 were 60 percent lower than the 1990 base year and comply with the SIP goal and VOC regulation benchmark. Emissions f rom fumigants account for more than one half of the total.

• Ventura NAA: The SIP goal and VOC regulation benchmark is phased in over several years

for this NAA. VOC emissions increased in 20 10 but continue to meet the SIP goal for 20 10 as well as the final goal to be met beginning in 2012. Pesticide VOC emissions in 20 10

were 31 percent lower than the 1990 base year. Eighty

- two percent (82 %) of emissions are derived from fumigants.

• South Coast NAA: VOC emissions in creased in 2010 by more than 40 percent compared to

2009 but remain well below the emission targets. Pesticide VOC emissions in 20 10 were 84 percent lower than the 1990 base year. More than t hree quarters of emissions are derived from nonfumigants

Section 6452.3 requires a 45-day public comment period of the draft report. C omments that were received during the comment period (November 17, 2011 – January 3 , 2012) are included in Appendix 4.4 Abbreviations and Definitions

AI Active Ingredient

APCD Air Pollution Control District

AMAF Application Method Adjustment Factor

ARB California Air Resources Board

EP Emission Potential

GIS Geographic Information System

MUF Method Use Fraction

NAA nonattainment area

PUR pesticide use report

SIP state implementation plan

TGA thermogravimetric analysis tpd tons per day

VOC Volatile Organic Chemical

ACKNOWLEDGEMENTS

The authors wish to thank the reviewers whose unique perspectives and experiences helped ensure the accuracy and readability of this report. We gratefully acknowledge the staff of DPR and cooperating federal, state, local, and private agencies for contributing to the database.

DISCLAIMER

The mention of commercial products, their source, or their use in this report is not to be

construed as either an actual or implied endorsement of such product.5 TABLE OF CONTENTS

EXECUTIVE SUMMARY

Preface..................................................................................... 2 Background............................................................................... 2 Report Summary......................................................................... 3

Abbreviations and Definitions......................................................... 4

ACKNOWLEDGEMENTS

................................................................... 4

DISCLAIMER

................................................................................... 4

LIST OF TABLES

.............................................................................. 6

LIST OF FIGURES

............................................................................. 8

OVERVIEW

Introduction............................................................................... 9

Nonattainment Area Goals.............................................................. 12 Procedure For Calculating Unadjusted and Adjusted VOC Emissions........... 12

Data Revisions...............................................................

............. 14

VOLATILE ORGANIC COMPOUND INVENTORY RESULTS

................... 16

Sacramento Metro Area

- NAA 1.............................................

......... 2 3 San Joaquin Valley

- NAA 2........................................................... 2 7

Southeast Desert

- NAA 3.............................................................. 31

Ventura

- NAA 4........................................................................ 3 5

South Coast

- NAA 5.................................................................. 3 9

PROJECTION OF 201 2 VOC EMISSIONS AND FUMIGANT LIMIT S

......... 4 3

REFERENCES

................................................................................... 4 5

APPENDIX 1

a. SUMMARY OF APPLICATION METHOD ADJUSTMENT FACTORS

AND METHOD USE FRACTIONS

b. FIELD FUMIGATION METHODS (FFM), FFM CODE FOR PESTICIDE USE REPORTING, AND EMISSION RATINGS

APPENDIX 2

– SUMMARY OF UNADJUSTED PESTICIDE VOC EMISSIONS

APPENDIX 3

– SUMMARY OF ADJUSTED PESTICIDE VOC EMISSIONS

APPENDIX 4

– COMMENTS ON THE DRAFT REPORT AND RESPONSES6 LIST OF TABLES

Table 1. Key information included in pesticide use reports that form the basis of DPR’s VOC emission inventory.................................................... 10

Table 2. A listing of counties wholly or partially within nonattainment areas in

California.............................................................................. 12

Table 3. Nonattainment Area Goals for 2008

– 2012.................................... 12

Table 4. Revised application method adjustment fact ors Iemission ratings)......... 15

Table 5

. May

– October (ozone season) unadjusted and adjusted pesticide VOC emissions and goals.................................................................. 1 9

Table 6 a

. May

– October (ozone season) adjusted fumigant and nonfumigant pesticide VOC emissions............................................................ 1 9

Table 6b

. May

– October (ozone season) unadjusted fumigant and nonfumigant pesticide VOC emissions............................................................ 20

Table 6 c

. May

- October (ozone season) nonfumigant pesticide VOC emissions derived from Emulsifiable Concentrate formulations (ECs) and all

Others.

.................................................................................. 21

Table 7. Top ten primary active ingredients contributing to 20 10 May

- October

ozone season adjusted VOC emissions in NAA 1, the Sacramento Metro

Area..................................................................... 2 4

Table 8. Top ten pesticide application sites contributing to 20 10 May

- October

ozone season unadjusted VOC emissions in NAA 1............................. 2 5

Table 9. Unadjusted 20 10 May

– October VOC emissions in NAA1 by ARB emission inventory classification (tons per day, tpd)............................. 2 6

Table 10. Top ten primary active ingredients contributing to 20 10 May

- October

ozone season adjusted VOC emissions in NAA 2, the San Joaquin Valley... 2 8

Table 11. Top ten pesticide application sites contributing to 20 10 May

- October

ozone season unadjusted VOC emissions in NAA 2............................. 2 9

Table 12. Unadjusted 20 10 May

– October VOC emissions in NAA 2 by ARB emission inventory classification (tons per day, tpd)............................ 30

Table 13. Top ten primary active ingredients contributing to 20 10 May

- October

ozone season adjusted VOC emissions in NAA 3, the Southeast Desert...

... 3 2

Table 14. Top ten pesticide application sites contributing to 20 10 May

- October

ozone season unadjusted VOC emissions in NAA 3............................. 3 3

Table 15. Unadjusted 20 10 May

– October VOC emissions in NAA 3 by ARB emission inventory classification (tons per day, tpd)............................. 3 4

Table 16. Top ten primary active ingredients contributing to 20 10 May

- October

ozone season adjusted VOC emissions in NAA 4, Ventura..................... 3 6

Table 17. Top ten pesticide application sites contributing to 20 10 May

- October

ozone season unadjusted VOC emissions in NAA 4............................. 3 7

Table 18. Unadjusted 20 10 May

– October VOC emissions in NAA 4 by ARB emission inventory classification (tons per da y, tpd)............................. 3 8

Table 19. Top ten primary active ingredients contributing to 20 10 May

- October

ozone season adjusted VOC emissions in NAA 5, South Coast............... 40

Table 20. Top ten pesticide application sites contributing to 20 10 May

- October

ozone season unadjusted VOC emissions in NAA 5............................. 417 Table 21. Unadjusted 2010 May

– October VOC emissions in NAA 5 by ARB emission inventory classification (tons per day, tpd)............................. 42

Table 22. Fumigant limit triggers and 20 10 pesticide VOC

emissions...............

............................................................... 43

Table 23

. May

– October (ozone season) nonfumigant pesticide VOC emissions... 44

Table 24

. P rojection for 201 2 NAA 4 VOC emissions. The 201 2 fumigant emission limit was determined by subtracting the forecast 201 2 nonfumigant emissions from the SIP goal and VOC regulation benchmark (Tao, 20 1 1 ).

. ................................................ .......................... 448 LIST OF FIGURES Figure 1. Federal nonattainment areas affected by California Regulations to reduce emissions from fumigant pesticides....................................... 11 Figure 2. Annual unadjusted ozone season pesticide VOC emissions by NAA

from 1990 to 20 10 , inclusive........................................................ 1 8 Figure 3. Annual ozone season pesticide VOC emissions by NAA. These figures

show adjusted emissions and SIP goals (reductions from 1990 emissions)... 2 2 Figure 4. Pesticide VOC emissions for the Sacramento Metro NAA, May

– October...............................................................................

. 2 4 Figure 5. Changes in adjusted emissions of selected AIs in the Sacramento Metro

NAA from 200 7 to 20 10

............................................................. 2 5 Figure 6. Changes in unadjusted emissions from selected commodities/sites in the

Sacramento Metro NAA from 200 7 to 20 10

............ .......................... 2 6 Figure 7. Pesticide VOC emissions for the San Joaquin Valley NAA, May

– October................................................................................. 2 8 Figure 8. Changes in adjusted emissions of selected AIs in the San Joaquin Valley

NAA from 200 7 to 20 10

............................................................. 2 9 Figure 9. Changes in unadjusted emissions from selected commodities/sites in the San Joaquin Valley NAA from 200 7 to 20 10

..................................... 30 Figure 10. Pesticide VOC emissions for the Southeast Desert NAA, May

– October............................................................................... 3 2 Figure 11. Changes in adjusted emissions of selected AIs in the Southeast Desert

NAA from 200 7 to 20 10

............................................................. 3 3 Figure 12. Changes in unadjusted emissions from selected commodities/sites in

the Southeast Desert NAA from 200 7 to 20 10

.................................... 3 4 Figure 13. Pesticide VOC emissions fo r the Ventura NAA, May

– October.

.......... 3 6 Figure 14. Changes in adjusted emissions of selected AIs in the Ventura NAA

from 200 7 to 20 10

..................................................................... 3 7 Figure 15. Changes in unadjusted emissions from selected commodities/sites in

the Ventura NAA from 200 7 to 20 10

.............................................. 3 8 Figure 16. Pesticide VOC emissions for th e South Coast NAA, May

– October.

......... ....................................................................... 40 Figure 17. Changes in adjusted emissions of selected AIs in the South Coast NAA

from 200 7 to 20 10

..................................................................... 41 Figure 18. Changes in unadjusted emissions from selected commodities/sites in

the South Coast NAA from 200 7 to 20 10

.......................................... 429 OVERVIEW

Introduction

The State Implementation Plan (SIP) for pesticides requires the California Department of Pesticide Regulation (DPR) to develop and maintain an emission inventory to track pesticide Volatile Organic Chemical (VOC) emissions an d to reduce emiss ions by 20 per cent from a base year in four out of five California nonattainment areas (NAA), and by 12 percent in the

fifth NAA. These five NAAs are defined as areas that do not meet the National Ambient Air Quality Standards for ozone as designated in th e Clean Air Act. The scope of the VOC inventory allows DPR to estimate VOC emissions from agricultural and commercial structural pesticide applications within the state. To do this DPR calculates emissions for each year beginning with 1990, and updates the se calculations annually based on most recent data. The inventory focuses on the peak ozone period between May 1 and October 31 for each year.

The VOC emission inventory is estimated based on pesticide use reports (PURs) that are collected by DPR. The inv entory includes applications that are made for agricultural and structural use as defined by law. Included are all applications with the exception of home use, industrial use, institutional use, applications made for vector control purposes and veterinarian uses. Production agricultural use covers applications to approximately 400 commodities/crops.

Non -production agricultural use includes applications to approx imately 20 sites including cemeteries, golf courses, parks, rights of way, etc. Structural use in cludes all applications by structural pest control businesses, regardless of site treated.

The key pesticide use report data used to calculate VOC emissions is given in Table 1. There are seven counties that are partially within NAAs. Because the location s of non -production agricultural and non-agricultural applications are only given down to the county level, these types of applications need to be allocated to the portions of those seven counties so that their contribution to NAA emissions can be accurately determined. Using a Geographic Information System (GIS) and surrogate data such as population, roadways, waterways and power lines, proportional estimates have been derived for structural and rights-of- way applications. Commodity fumigations are allocat ed based on information provided by the California County Agricultural Commissioners.10 Table 1. Key information included in pesticide use reports that form the basis of DPR’s VOC emission inventory.

Information Production Agriculture Report

(Each Application) Non

- Production Agriculture Report and Non Agricultural Reports
(Monthly Summary of Applications) Product Applied Yes Yes Crop/Site Treated Yes Yes Amount Applied Yes

– each application Monthly Total Date Applied Date and Time Month Application Method Yes No

Acres/Units Treated Yes Monthly Total Location of Application Township/Range/Section County Fumigant Method Code Yes* No
* fumigant use reports only

California’s five ozone NAAs included in the pesticide VOC emission inventory are Sacramento Metro (1), San Joaquin Valley (2), Southeast Desert (3), Ventura (4), and South Coast (5). The boundaries of these NAAs, as defined by CFR 40 Part 81 and a listing of

counties that fall within the boundaries are shown in Figure 1 and Table 2, respectively.

In January 2008, DPR adopted 3 CCR section 6452.3 requiring an annual VOC emissions inventory report that includes the following information:

• report total agricultural and structural pestic ide VOC emissions for the previous years,

• evaluate compliance with SIP goals (benchmarks specified in section 6452.2),

• establish fumigant emission limits for the upcoming year if necessary, according to section 6452.2, and

• establish an emission rating (or application method adjustment factor, the percentage of fumigant applied emitted to air) for each fumigation method

Section 6452.3 also requires a 45-day public comment period of the draft report. This report contains all of the information specified above, including emission estimates for 1990–2010 and fumigant limits for 20 12.11 Figure 1. Federal nonattainment areas affected by California Regulations to reduce emissions from fumigant pesticides.12 Table 2. A listing of counties wholly or partially within nonattainment areas in California.

NAA Counties within the NAA

1

– Sacramento Metro All of Sacramento, Yolo

Parts of Sutter, Solano, Placer, El Dorado

2

– San Joaquin Valley All of Fresno, Kings, Madera, Merced, San Joaquin, Stanislaus, Tulare

Western Part of Kern

3

– Southeast Desert Parts of Los Angeles, San Bernardino, Riverside

4

– Ventura All of Ventura

5

– South Coast All of Orange

Western Parts of Los Angeles, San Bernardino, Riverside

Nonattainment Area Goals

The emissions in DPR’s VOC inventory are compared to NAA goals listed in Table 3, which

are described in California’s original 1994 SIP (62 Fed. Reg. at 1170, 1997) and Appendix H to the 2007 SIP (73 Fed. Reg. 41277, 2008). These “SIP goals” are a 20 percent reduction from 1990 for the Sacramento Metro, Southeast Desert, and South Coast NAAs; a 12 percent reduction from 1990 for the San Joaquin Valley NAA; and a phase-in of the reductions for the Ventura NAA, with a final reduction for Ventura of 20 percent from 1990 by 2012.

Table 3. Nonattainment Area Goals for 2008 – 2012.

NAA SIP Goal (tons/day)

200 8 - 2012

1

– Sacramento Metro 2.2

2

– San Joaquin Valley 18.1

3

– Southeast Desert 0.92

4

– Ventura 2008 2009 2010 2011 2012

4.3 4.0 3.6 3.3 3.0

5

– South Coast 8.7

Procedure for Calculating Unadjusted and Adjusted VOC Emissions

Prior to 2008, DPR reported an unadjusted emission inventory that assumed the entire volatile portion of a fumigant product eventually volatilizes, contributing to atmospheric VOCloadings. However, several dozen field studies have shown that actual emissions from soilapplied fumigants such as methyl bromide vary by applicatio n method and are generally less than 100 percent. DPR has developed an adjustment procedure to account for the effect of application method on reducing fumigant VOC emissions.13 The unadjusted inventory is based on the premise that the VOC emission from a s ingle application of fumigant or nonfumigant product is equal to the amount used times the Emission Potential (EP) (Spurlock, 2002; 2006).

emission = lbs of product used x EP

In the adjusted inventory the emission from a single application of a fumigant active ingredient (AI) is reduced by an additional factor called the Application Method Adjustment Factor (AMAF), also referred to as the emission rating. AMAFs have been determined from field study data and are AI and application method specific (Barry et al., 2007). Since the AMAFs are based on field measured data for specific application methods and fumigants, they yield more refined estimates of fumigant VOC emissions than the previous unadjusted emission

estimates

emission = lbs of product used x EP x AMAF

In the adjusted inventory, nonfumigant product emissions are not currently adjusted for application method or other field factors due to a lack of data to support such adjustments. Consequently their emissions are calculated using the same procedure as the unadjusted inventory.

Usually there are several different types of application methods used for a particular fumigant in any particular NAA. Each method of use (e.g. drip, sprinkler, shank, tarp, etc.) represents a

fraction of the total number of methods used and is referred to as the Method Use Fraction (MUF). The sum of all MUFs for any particular (NAA/fumigant AI) combination is one. Use practices change over time so that different MUF s are used for the baseline year (1990) as opposed to more recent inventory years. For 2007 and earlier ye ars, MUF s are determined in a number of different ways. For 1,3-dichloropropene the MUF s are determined from use data collected by the registrant in support of DPR’s township application caps; for metam sodium and metam potassium grower/applicator surveys were conducted to determine types of applications for different crops and areas. Methyl bromide and chloropicrin MUF s are based on expert opinion and regulatory history. Finally, MUF s for dazomet and sodium tetrathiocarbonate equal one because the AMAF s fo r each of these two fumigants are constant, independent of application method. A detailed discussion of how MUF and AMAFs were determined is given by Barry et al (2007).

The 2008 VOC regulations included a change to pesticide use reports that requires recording the specific application method for each fumigation within NAAs. The MUFs for 2008 and later years are calculated using the fumigation method documented in pesticide use reports rather than the surrogate data described above. The use of a fumigant code to identify the fumigant application method in the pesticide use report was implemented in 2009 ( Ibewiro

, 2008). For all NAAs combined, approximately six percent of the pesticide use reports for 2010 are missing the identification of the application m ethod (fumigant code). In these cases, DPR14 used a conservative approach by assum ing that the application method with the highest AMAF allowed by the regulations for that fumigant was used. Field fumigation methods (FFM), FFM

codes for p esticide u se reporting, and corresponding e mission ratings , and the AMAFs and method use fractions for 1990, 2005, 2006, 2007 and 2008 in each of the NAAs are included in the appendix of this document (Tables A1 – 1 to A1 – 27, Appendix 1B).

In addition to the VOC emissions derived from fumigant active ingredients, inert ingredients for products that contain chloropicrin, methyl bromide, 1,3-dichloropropene and methyl iodide

are assumed to be volatile and are included in the inventory calculations. For the highest use products containing those fumigants, DPR analyzes their confidential statements of formula to determine the composition of inerts and decides whether those inerts are nonvolatile. Inert ingredients used in products containing metam sodium, metam potassium, sodium

tetrathiocarbonate and dazomet are non -volatile and so do not contribute to the emission potential of these products.

VOC emissions were calculated for each NAA and summed according to primary active ingredient, application site, and emission ca tegory as defined by the Air Resources Board (ARB). The primary active ingredient is defined as the pesticide active ingredient present at the highest percentage in a product. If a pesticide product contains 20 percent of active ingredient “A” and 10 perce nt of active ingredient “B”, all estimated emissions from that product are assigned to the primary active ingredient “A”. This approach prevents “double-counting” of emissions from products containing two active ingredients.

Both unadjusted and adjusted emission inventory data for the top ten primary active ingredients contributing to May-October ozone in 2007, 2008 and 2009 are included in this report

. Appendix 2 contains summaries of emissions attributable to specific application sites (or commodities). These summary data are provided only for unadjusted emissions because it is not possible to allocate adjusted emissions to specific application sites with the currently

available data.

ARB defines four VOC emission categories: methyl bromide emissions from agricultural applications, non- methyl bromide emissions from agricultural applications, methyl bromide emissions from structural applications, and non- methyl bromide emissions from structural applications. Emission s were calculated for the May

– October ozone season, and are reported as U.S. tons per day (tpd).

Data Revisions

DPR continually evaluates pesticide use report data, EP values, MUFs , and AMAF s to ensure the VOC inventory includes the most reliable data. Since the last annual report, DPR has completed review of several studies conducted under contract to ARB (Johnson 2011). These

studies evaluated 1,3-dichloropropene deep-shank injection fumigation methods that included five post- fumigation water treatments and a composted green wast e soil amendment. Based on these studies, DPR has established the AMAFs shown in Table 4. However, neither of these fumigation methods may be commercially feasible due to the high cost. Fumigation method codes will be assigned if and when these methods are used.15 Table 4

. Revised application method adjustment factors (emission ratings)

Method Description Fumigation

Method Code Original AMAF (%) Revised AMAF (%)

1,3- D, deep

- shank w/ 5 water treatments None None 15

1,3- D deep shank w/ green waste None None 5

VOC emissions from inert ingredients in glyphosate products have increased in the last few years in several NAAs. Most if not a ll of the increase in emissions was due to Roundup

Powermax Herbicide , first registered in 2007 . Due to a lack of thermogravimetric analysis data,

at that time DPR assigned an EP of 35.28 percent for this product. Most other glyphosate products have EPs of 0 to 6 percent. DPR then requested EP data from the product registrant, and has subsequently received, reviewed and approved that data that shows an EP of 0 percent for that product. Consequently the 2008 and 2009 inventories have been updated based on this

new information.

DPR recently adopted a new procedure for estimating emission potentials (EP) of selected product s with v ery high use when thermogravime tric analysis data are not available. That method is based on analysis of product confidential statements of formula as described by Oros and Spurlock (2011).

DPR has proposed a SIP revision with a commitment to ensure pesticide VOC emissions do not exceed 18.1 tons/day in the San Joaquin Valley NAA , equivalent to a 12 percent reduction from 1990 (Table 3). DPR will use the emissions estimation methodology descri bed in this report to meet the SIP commitment. Emission ratings for application methods that were used in 1990 will not be modified, absent a SIP revision. Similarly, regarding nonfumigant pesticides, DPR will not revise the emission potentials of formulations that were used in the base year,

absent a SIP revis ion.16 VOLATILE ORGANIC COMPOUND INVENTORY RESULTS

The main text of this report summarizes the pesticide VOC emission inventory data for 20 10 only. Adjusted and unadjusted emission data for 2007, 2008 and 2009, and unadjusted data for 2010 are summarized in Appendices 2 and 3. Previous inventory memos and the 2007, 2008

and 2009 report s included a summary of pesticide VOC emissions by commodity/site. At this time it is not possible to determine the breakdown of adjusted emissions by commodity, so only

the unadjusted emissions are shown by commodity. Tables for emissions calculated for active ingredients (adjusted and unadjusted) and application sites (unadjusted) contain information for the top ten contributors only.

Figure 2 illustrates the changes in unadjusted VOC emissions from 1990 to 2010 . These values

are unadjusted and so do not take in to consideration MUFs and AMAFs that can only be applied to emissions in 2004 through 2010, and 1990. The figure is useful in that it compares emissions for the entire history of the inventory and shows trends in five NAAs

.

Tables 5 and 6a and Figure 3 summarize the adjusted pesticide VOC emissions for 2004 through 2010, and compare them to the SIP goals that based a percentage reduction from the 1990. Table 6b compares the unadjusted and adjusted fumigant VOC emissions for 2004 through 2010. Table 6c shows the amount of emissions that resulted from nonfumigant products with emulsifiable concentrate formulations compared to all other formulations. The emissions in the base year are also included to reflect the long term decrease or increase.

Generall y, what the tables and figure show can be summarized as follows:

• Adjusted emissions in 2010 in the Sacramento Metro (1) reversed the decline of 2006 to 2009 and increased to above 1 ton per day (1.061 tpd). Nonfumigant s represented 91 percent of the total, the latter remaining well below the SIP goal. Fifty

- three percent (0.509 tpd) of nonfumigant emissions were derived from products with emulsifiable

concentrate formulations.

• Emissions in the South Coast NAA (5) increased by 42 percen t over 2009 values but

remain well below the SIP goal. More than three quarters of the total adjusted VOC

emissions came from non -fumigants (1.359 tpd), of which less than one third are attributable to products with emulsifiable concentrate formulations

.

• In 2010, fumigants accounted for more than half of VOC emissions in the Southeast Desert (3), up s ignificantly from 2009. Total VOC emissions in 20 10 in creased by more

than 60 percent from 2009 but continue to meet the SIP goal.

• 2010 VOC emissions in the Ve ntura NAA (4) increased by 0. 518 tpd from the previous year but continue to meet the regulatory goal for 2010, 2011and 2012. Eighty two percent of emissions ca me from fumigants.

• In the San Joaquin Valley NAA (2), nonfumigants accounted for three quarters o f the

total VOC emissions in 20 10 . In this NAA, VOC e missions in creased from 200 9 to 2010 by about 24 percent, but continue to be below the SIP goal by 1. 263 tpd, and 2010 emissions were approximately the average level of 2004 -2009. Nonfumigant emissions from products with emulsifiable concentrate formulations accounted for almost half of the total VOC emissions for this NAA and 64 percent of emissions from nonfumigants.17 Pesticide use varies from year to year depending on many factors, including weather, pest problems, economics and types of crops planted. Increases and decreases in pesticide use from one year to the next or in the span of a few years do not necessarily indicate a trend. Such

variances are and will continue to be a normal occurr ence. For example, extremely heavy rains result in excessive weeds, thus more pesticides may be used; drought conditions may result in fewer planted acres, thus less pesticide may be used. A more detailed explanation of pesticide use patterns is given in D PR’s annual summary of pesticide use reports available at: http://www.cdpr.ca.gov/docs/pur/pur10rep/chmrpt10.pdf

.

While emissions increased in 2010, DPR, growers, registrants, and othe rs have taken steps to reduce VOC emissions. In the last few years, DPR has registered several reformulated products with lower EPs, including products containing chlorpyrifos and abamectin that are major VOC contributors in the San Joaquin Valley. Many gr owers are switching to the reformulated products. For example, the reformulated chlopyrifos product with a lower EP was registered in 2008, and it was the chlorpyrifos product with the highest use in the San Joaquin Valley during

2010. DPR is drafting regu lations to address nonfumigant VOC emissions for the San Joaquin Valley, so this trend should continue.18 Figure 2. Annual unadjusted ozone season pesticide VOC emissions by NAA from 1990 to 2010, inclusive.

NAA 1 Sacramento Metropolitan

Year 1990 1993 1996 1999 2002 2005 2008 2011Emission Rate (tpd)

0 1 2 3 4 NAA 2 San Joaquin Valley

Year 1990 1993 1996 1999 2002 2005 2008 2011Emission Rtae (tpd)

0 10 20 30 40

NAA 3 Southeast Desert

Year 1990 1993 1996 1999 2002 2005 2008 2011Emission Rate (tpd)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 NAA 4 Ventura

Year 1990 1993 1996 1999 2002 2005 2008 2011Emission Rate (tpd)

0 2 4 6 8 10 12

NAA 5 South Coast

Year 1990 1993 1996 1999 2002 2005 2008 2011Emission Rate (tpd)

0 2 4 6 8 10 12Table 5. May –October (ozone season) adjusted pesticide VOC emissions and goals.

NAA 1990

Emissions (tons/day) SIP

Goal (tons/day) 2004

Emissions (tons/day) 2005

Emissions (tons/day) 2006

Emissions (tons/day) 2007

Emissions (tons/day) 2008

Emissions (tons/day) 2009

Emissions (tons/day) 2010

Emissions (tons/day)

1

– Sacramento Metro 2.7 84 2.2 1.235 1.239 1.354 1.050 0.938 0.946 1.061

2

– San Joaquin Valley 20. 517 18.1 17.322 20.740 21.305 17.164 14.5 43 13.484 16.837

3

– Southeast Desert 1.15 3 0.92 0.995 0.740 0.634 0.762 0.2 86 0.283 0.453

4

– Ventura 3.787 3.0 a 3.924 3.617 3.682 3.363 1.73 9 2.080 2.598

5

– South Coast 10.840 8. 7 1.922 1.969 1.482 1.487 1.283 1.220 1.734

a These numbers reflect the SIP goal for 2012 in Ventura, and do not reflect the phase in of reductions between 2008 and 2012.

Table 6a. May –October (ozone season) adjusted fumigant and nonfumigant pesticide VOC emissions.

NAA 1990

Emissions (tons/day) 2004

Emissions (tons/day) 2005

Emissions (tons/day) 2006

Emissions (tons/day) 2007

Emissions (tons/day) 2008

Emissions (tons/day) 200 9

Emissions (tons/day) 20 10

Emissions (tons/day)

1

– Sacramento Metro

0.384 (14%) 0.111 (9%) 0.085 (7%) 0.162 (12%) 0.189 (18%) 0.064 (7%) 0.133 (14%) 0.097 (9%) Fumigants
Nonfumigants 2.400 (86%) 1.124 (91%) 1.154 (93%) 1.192 (88%) 0.861 (82%) 0.8 73 (93%) 0.813 (86%) 0.965 (91%)

2

- San Joaquin Valley

5.536 (27%) 6.362 (37%) 6.910 (33%) 6.808 (32%) 6.123 (36%) 3.370 (23%) 3.424 (25%) 4.023 (24%) Fumigants
Nonfumigants 14.981 (73%) 10.960 (63%) 13.831 (67%) 14.498 (68%) 11.041 (64%) 11.1 7 3 (77%) 10.060 (75%) 12.814 (76%)

3

- Southeast Desert

0.840 (73%) 0.762 (77%) 0.474 (64%) 0.413 (65%) 0.575 (75%) 0.119 (4 2 %) 0.138 (49%) 0.272 (60%) Fumigants

Nonfumigants 0.313 (27%) 0.233 (23%) 0.266 (36%) 0.221 (35%) 0.187 (25%) 0.1 67 ( 58 %) 0.145 (51%) 0.181 (40%)

4

- Ventura

3.140 (83%) 3.302 (84%) 3.119 (86%) 3.175 (86%) 2.935 (87%) 1.252 (72%) 1.627 (78%) 2.122 (82%) Fumigants

Nonfumigants 0.647 (17%) 0.622 (16%) 0.497 (14%) 0.508 (14%) 0.428 (13%) 0.48 7 (28%) 0.453 (22%) 0.476 (18%)

5

– South Coast

9.372 (86%) 0.702 (37%) 0.594 (30%) 0.422 (28%) 0.411 (28%) 0.377 (29%) 0.297 (24%) 0.376 (22%) Fumigants
Nonfumigants 1.468 (14%) 1.220 (63%) 1.375 (70%) 1.060 (72%) 1.075 (72%) 0.9 06 (71%) 0.922 (76%) 1.359 (78%)20 Table 6b. May –October (ozone season) unadjusted and adjusted fumigant pesticide VOC emissions.

NAA 1990

Emissions (tons/day) 2004

Emissions (tons/day) 2005

Emissions (tons/day) 2006

Emissions (tons/day) 2007

Emissions (tons/day) 2008

Emissions (tons/day) 2009

Emissions (tons/day) 2010

Emissions (tons/day)

1

– Sacramento Metro

Unadjusted Fumigants 0.461 0.186 0.151 0.315 0.383 0.241 0.36 2 0.18 1

Adjusted Fumigants 0.384 0.111 0.085 0.162 0.189 0.064 0.133 0.097

2

- San Joaquin Valley

Unadjusted Fumigants 7.491 14.213 15.400 15.034 13.750 12.620 10. 559 12. 696

Adjusted Fumigants 5.536 6.362 6.910 6.808 6.123 3.370 3.42 4 4.02 3

3

- Southeast Desert

Unadjusted Fumigants 0.933 1.275 0.863 0.750 1.086 0.684 0.470 0.81 2

Adjusted Fumigants 0.840 0.762 0.474 0.413 0.575 0.119 0.138 0.272

4

- Ventura

Unadjusted Fumigants 3.909 8.916 8.841 9.113 8.658 6.543 6.345 8.844

Adjusted Fumigants 3.140 3.302 3.119 3.175 2.935 1.252 1.627 2.122

5

– South Coast

Unadjusted Fumigants 9.514 1.418 1.301 0.898 0.883 1.043 0.692 0.647

Adjusted Fumigants 9.372 0.702 0.594 0.422 0.411 0.377 0.297 0.37 621 Table 6c. May -October (ozone season) nonfumigant pesticide VOC emissions derived from Emulsifiable Concentrate formulations (ECs) and all Others. The adjusted and unadjusted VOC emissions for nonfumigants are the same.

NAA 1990

Emissions (tons/day) 2004

Emissions (tons/day) 2005

Emissions (tons/day) 2006

Emissions (tons/day) 2007

Emissions (tons/day) 2008

Emissions (tons/day) 200 9

Emissions (tons/day) 20 10

Emissions (tons/day)

1

– Sacramento Metro

1.129 (47%) 0.534 (47%) 0.642 (56%) 0.640 (54%) 0.479 (56%) 0.522 (60%) 0.429 (53%) 0.509 (53%) ECs

Others 1.271 (53%) 0.590 (53%) 0.513 (44%) 0.552 (46%) 0.382 (44%) 0.351 (40%) 0.384 (47%) 0.456 (47%)

2

- San Joaquin Valley

12.162 (81%) 8.613 (79%) 10.199 (74%) 10.119 (70%) 7.618 (69%) 7.510 (67%) 6.350 (63%) 8.140 (64%) ECs

Others 2.819 (19%) 2.347 (21%) 3.632 (26%) 4.379 (30%) 3.423 (31%) 3.663 (33%) 3.710 (37%) 4.674 (36%)

3

- Southeast Desert

0.217 (69%) 0.150 (64%) 0.185 (69%) 0.131 (59%) 0.105 (56%) 0.089 (53%) 0.073 (50%) 0.092 (51%) ECs

Others 0.096 (31%) 0.083 (36%) 0.082 (31%) 0.091 (41%) 0.083 (44%) 0.078 (47%) 0.073 (50%) 0.089 (49%)

4

- Ventura

0.402 (62%) 0.263 (42%) 0.286 (58%) 0.272 (54%) 0.210 (49%) 0.237 (49%) 0.242 (53%) 0.240 (50%) ECs

Others 0.245 (38%) 0.360 (58%) 0.211 (42%) 0.236 (46%) 0.218 (51%) 0.250 (51%) 0.212 (47%) 0.236 (50%)

5

– South Coast

0.921 (63%) 0.647 (53%) 0.762 (55%) 0.514 (48%) 0.459 (43%) 0.339 (37%) 0.371 (40%) 0.415 (31%) ECs

Others 0.547 (37%) 0.573 (47%) 0.613 (45%) 0.546 (52%) 0.616 (57%) 0.567 (63%) 0.551 (60%) 0.944 (69%)22 Figure 3. Annual ozone season pesticide VOC emissions by NAA. These figures show adjusted emissions and SIP goals (reductions from 1990 emissions).

NAA 1 Sacramento Metropolitan

Year 1990 1995 2000 2005 2010 2015Emission Rate (tpd)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 NAA 2 San Joaquin Valley

Year 1990 1995 2000 2005 2010 2015Emission Rate (tpd)

0 5 10 15 20 25

NAA 3 Southeast Desert

Year 1990 1995 2000 2005 2010 2015Emission Rate (tpd)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 NAA 4 Ventura

Year 1990 1995 2000 2005 2010 2015Emission Rate (tpd)

0 1 2 3 4 5

NAA 5 South Coast

Year 1990 1995 2000 2005 2010 2015Emission Rate (tpd)

0 2 4 6 8 10 12



## • Adjusted Emissions

(1990, 2004, 2005, 2006, 2007, 2008, 2009 & 2010)

SIP Goals23 Sacramento Metro Area - NAA 1

The Sacramento Metro NAA (NAA 1) 20 10 adjusted emissions increased to above the levels of

the two previous years. Adjusted emissions in 200 7 were 1.050 tpd which decreased to 0.938 tpd in 2008, increased to 0.946 tpd in 2009, and increased again to 1.061 tpd in 2010. Fumigant emissions in creased from 18 p ercent in 2007 (0.189 tpd), were reduced to 7 percent (0. 064 tpd) in 2008, increased in 2009 to 0.133 tpd and decreased to 0.097 tpd in 2010. In 2010, 91 percent of emissions were attributable to nonfumigants, 53 percent (0.509 tpd ) of which were from products with emulsifiable concentrate formulations. Total adjusted VOC

emissions (1.061 tpd) continue to remain well below the SI P goal of 2.2 tpd . (Tables 6a, 6b, 6c, Figures 3, 4).

Emissions from chlorpyrifos use decreased to 0.086 tpd in 2009 and 0.076 tpd in 2010, the

latter accounting for over seven percent of the total emissions in 2010 (Table 7 ). Emissions from the use of 1,3-dichloropropene , which doubled from 2008 to 2009, decreased to 0.035 tpd in 2010 accounting for 3.43 percent of emissions, and emissions from methyl bromide use increased from 0.031 tpd in 2009 to 0.045 tpd in 2010. Emissions from bifenthrin, a pyrethroid

insecticide used on a range of crops

, have increased every year from 0.0 25 tpd in 2007 to 0.120 tpd in 2010, as have emissions from trifluralin , which have tripled from 0.017 tpd in 2007 to 0.054 tpd in 2010. (Tables 7, A3 -1a to A3-1d, Figure 5 ).

In 2010 combined emissions from tomatoes and walnuts increased by approximately 0. 1 tpd (0.139 tpd in 2009 to 0.198 tpd in 2010, and 0.115 tpd in 2009 to 0.161 tpd in 2010, respectively). These two commodities/sites accounted for over 30 percent of the total emissions

in the Sacramento Metro Area NAA , with emissions from rice accounting f or an additional

18.0 2 percent, an increase from 0.192 tpd in 2009 to 0.206 tpd in 2010. Emissions from wine

grapes fell sharply from 0.177 tpd in 2009 to 0.055 tpd in 2010. It should be noted that in 2010

use of the category “soil application” as a site/commodity was substantially reduced from previous years. Correspondingly, emissions from this category fell from 0.128 tpd in 2009 to

less than 0.001 tpd in 2010. Th e “soil application” category is often used when a field is treated before a commodity has been planted. In 2010 it is most likely that the category has been replaced by more specific annual commodities such as tomatoes, sunflowers, strawberries, alfalfa, etc. (Tables 8, A2 -1 e to A2 -1h, Figure 6).

Since this NAA has complied with the SIP goal for several years, most provisions of the 2008 fumigant regulations do not apply. Therefore, the fumigant regulations had little or no impact

on emissions in this NAA.

Using the ARB emission inventory classification, emissions from structural applications of methyl bromide continue to be less than 0.001 tpd. A gricultural applications decreased from 0.062 tpd in 2007 to 0.035 tpd in 2009, but increased to 0.057 tpd in 2010. Non- methyl

bromide emissio ns f rom structural applications continue to decline from 0.066 tpd in 2007, 0.062 tpd in 2008 and 0.053 tpd in 2009, to 0.047 tpd in 2010 (Tables 9, A2 -1 i

- A2 -1l).24 Figure 4. Pesticide VOC emissions for the Sacramento Metro NAA, May

– October. Emissions

for each year are divided into fumigants, nonfumigants with emulsifiable concentrate

formulations (ECs) and other nonfumigants (Others) . Fumigant emissions are adjusted to account for fumigation method.

Table 7. Top ten primary active ingredie nts contributing to 2010 May

- October ozone season adjusted VOC emissions in NAA 1, the Sacramento Metro Area.

Primary AI Total Product Adjusted Emissions (tons/day) Percent of All NAA 1 May

– Oct 20 10 Adjusted Emissions

BIFENTHRIN 0.120 11.80

CHLORPYRIFOS 0.076 7.42

TRIFLURALIN 0.054 5.31

THIOBENCARB 0.048 4.68

METHYL BROMIDE 0.045 4.41

ABAMECTIN 0.042 4.14

PROPANIL 0.038 3.71

PENOXSULAM 0.037 3.63

1,3

- DICHLOROPROPENE 0.035 3.43

ETHALFLURALIN 0.030 2.99 0.0 0.5 1.0 1.5 2.0 2.5 3.0

1990 2006 2007 2008 2009 2010VOC Emissions (tons/day)

Fumigant Nonfumigant - ECs Nonfumigant - Others25 Figure 5. Changes in adjusted emissions of selected AIs in the Sacramento Metro NAA from

2007 to 2010.

Table 8. Top ten pesticide application sites contributing to 2010 May -October ozone season unadjusted VOC emissions in NAA 1.

Application Site Emissions (tons/da y) Percent of all NAA 1 May

– Oct 20 10 emissions

RICE 0.206 18.02

TOMATOES, FOR PROCESSING/CANNING 0.198 17.27

WALNUT 0.161 14.01

RIGHTS OF WAY 0.059 5.16

GRAPES, WINE 0.055 4.80

STRUCTURAL PEST CONTROL 0.046 4.06

LANDSCAPE MAINTENANCE 0.046 3.99

ALMOND 0.039 3.43

COMMODITY FUMIGATION 0.034 2.97

N

- OUTDR CONTAINER/FLD GRWN PLANTS 0.033 2.87 0.000 0.020 0.040 0.060 0.080 0.100 0.120 0.140

2007 2008 2009 2010VOC Emissions (tons/day)

CHLORPYRIFOS 1,3-DICHLOROPROPENE

METHYL BROMIDE BIFENTHRIN

TRIFLURALIN26 Figure 6. Changes in unadjusted emissions from selected commodities/sites in the Sacramento

Metro NAA from 2007 to 2010.

Table 9. Unadjusted 2010 May –October VOC emissions in NAA1 by ARB emission inventory classification (tons per day, tpd).

NAA 1 - 2010 Agricultural Applications Structural Applications

METHYL BROMIDE EMISSIONS 0.0 57 0.000

NON

- METHYL BROMIDE EMISSIONS 1.036 0.0 47 0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350

2007 2008 2009 2010VOC Emissions (tons/day)

RICE GRAPES, WINE

TOMATO, PROCESSING STRUCTURAL PEST CONTROL

WALNUT SOIL APPLICATION, PREPLANT27 San Joaquin Valley - NAA 2

Adjusted emissions in 2010 in creased from 13.484 tpd in 2009 to 16.837 tpd in 2010, a 24 percent increase . As with the 2009 emissions, the 2010 emissions are below the SIP goal of 18.1 tpd (Tables 6a, 6b, Figure 3, 7 ).

Nonfumigants continue to account for the largest portion of adjusted emissions, with more than 76 percent of the total in 2010 (12.814 tpd). Overall, nonfumigant emissions increased by 2.754 tpd (2 7 percent) in 2010, bringing emissions back to a level not seen since before 2007. In 2010, 64 percent of nonfumigant emissions was from products with emulsifiable concentrate formulations (8.140 tpd), an increase of 1.79 tpd from 2009 (Table 6c). The top emission contributor for 2007 through 2010 was the nonfumigant, chlorpyrifos, which accounted for 2.263 tpd in 2007, 2.221 tpd in 2008, 1.389 tpd in 2009 and 1.828 tpd in 2010. (Tables 10, A3

- 2a to A3-2d, Figure 7 ). In 2010 more than 25 percent of emissions from chlorpyrifos came from use on almonds, with another 55 percent of emissions from chlorpyrifos from the

combined use on cotton , oranges and alfalfa . Fumigant use on carrots, in the form of metamsodium, 1,3-dichloropropene and potassium N- methyldithiocarbamate, accounted for more than

98 percent of emissions from this commodity (Tables 11, A2 - 2e to A2-2h, Figure 9). Total adjusted e missions from metam -sodium increased from 1.120 tpd in 2009 to 1.148 tpd in 2010

from use on onions, head lettuce and tomatoes. Emissions from products containing bifenthrin

increased by alm ost 500 percent from 0.296 tpd in 2009 to 1.553 tpd in 20 10 , due in large part to increased use on almonds and pistachios (Figure 8).

Although the 2008 fumigant regulations continued to maintain lower emissions from fumigants, a djusted f umigant emissions in creased by 0.599 tpd (18 percent) between 200 9 and 2010. Use (unadjusted emissions) of fumigants in creased by 20 percent (Table 6b ). The increase in fumigant emissions is primarily due to increased product use overall, as the use of

low- emission fumigati on methods required by the 2008 regulations is now well established.

Using the ARB emission inventory classification, emissions from structural applications of methyl bromide de crease d significantly in 2010 going from 0.012 tpd in 2009 to less than 0.001 tpd in 2010 . Agricultural applications increased by approximately 15 percent from 0.908 tpd in 2009 to 1.044 tpd in 20 10 . Non- methyl bromide emissions from agricultural applications

in creased from 19.242 tpd in 2009 to 23.892 tpd in 2010, and structural applications in creased

from 0.190 tpd in 2009 to 0.239 tpd in 2010. (Tables 12, A2 -2 i to A2 -2l).28 Figure 7. Pesticide VOC emissions for the San Joaquin Valley NAA, May–October. Emissions for each year are divided into fumigants, nonfumigants with emuls ifiable concentrate formulations (ECs) and other nonfumigants (Others). Fumigant emissions are adjusted to account for fumigation method.

Table 10. Top ten primary active ingredients contributing to 2010 May -October ozone season adjusted VOC emissions in NAA 2, the San Joaquin Valley.

Primary AI Total Product Adjusted Emissions (tons/day) Percent of All NAA 2 May

– Oct 20 10 Adjusted Emissions

CHLORPYRIFOS 1.828 11.32

BIFENTHRIN 1.553 9.61

1,3

- DICHLOROPROPENE 1.488 9.21

METAM

- SODIUM 1.148 7.11

ABAMECTIN 1.064 6.58

OXYFLUORFEN 0.687 4.25

GIBBERELLINS 0.684 4.23

METHYL BROMIDE 0.581 3.60

GLYPHOSATE, ISOPROPYLAMINE SALT 0.459 2.84

POTASSIUM N

- METHYLDITHIOCARBAMATE 0.436 2.70 0.0 5.0 10.0 15.0 20.0 25.0

1990 2006 2007 2008 2009 2010VOC Emissions (tons/day)

Fumigant Nonfumigant - ECs Nonfumigant - Others29 Figure 8. Changes in adjusted emissions of selected AIs in the San Joaquin Valley NAA from

2007 to 2010.

Table 11. Top ten pesticide application sites contributing to 2010 May -October ozone season unadjusted VOC emissions in NAA 2.

Application Site Emissions (to ns/day) Percent of all NAA 2 May

– Oct 20 10 emissions

ALMOND 4.662 18.28

CARROTS 3.604 14.13

COTTON 1.605 6.29

SOIL APPLICATION, PREPLANT

- OUTDOOR 1.303 5.11

GRAPES 1.274 5.00

TOMATOES, FOR PROCESSING/CANNING 1.245 4.88

ORANGE 1.020 4.00

N

- OUTDR CONTAINER/FLD GRWN PLANTS 1.017 3.99

WALNUT 0.897 3.52

POTATO 0.872 3.42 0.000 1.000 2.000 3.000

2007 2008 2009 2010VOC Emissions (tons/day)

CHLORPYRIFOS 1,3-DICHLOROPROPENE

METAM-SODIUM METHYL BROMIDE

BIFENTHRIN GLYPHOSATE, ISOPROPYLAMINE SALT30 Figure 9. Changes in unadjusted emissions from selected commodities/sites in the San Joaquin Valley NAA from 200 7 to 2010.

Table 12. Unadjusted 2010 May –October VOC emissions in NAA 2 by ARB emission inventory classification (tons per day, tpd).

NAA 2 - 2010 Agricultural Applications Structural Applications

METHYL BROMIDE EMISSIONS 1.044 0.000

NON

- METHYL BROMIDE EMISSIONS 23. 892 0.2 39 0.000 0.500 1.000 1.500 2.000 2.500 3.000 3.500 4.000 4.500 5.000

2007 2008 2009 2010VOC Emissions (tons/day)

CARROT ALMOND COTTON TOMATO, PROCESSING31 Southeast Desert - NAA 3

In 2010 total adjusted emissions for the Southeast Desert increased from 0.283 tpd in 2009 to 0.453 tpd in 2010. The 2010 rate is well below the SIP go al of 0.92 tpd, (Tables 6a, 6b, Figure 3, 10).

Fumigants account ed for 60 percent of th e emissions in this NAA in 2010, increas ing to 0.272 tpd, almost double that of the previous year

. Metam -sodium continues to be the primary contributor, accounting for 35 percent of emissions in 2010 (0. 160 tpd), up from 0.074 tpd in

2009. Emissions from four other fumigants, chloropicrin, 1,3-dichloropropene, dazomet and methyl bromide accounted for an additional 22 percent of the total. Emissions from t he use of 1,3- dichloropropene increased from 0.001 tpd in 2009 to 0.038 tpd in 2010, while methyl bromide and dazomet declined (Tables 13, A3 -3a to A3 -3d, Figure 11 ). Approximately half of emissions from nonfumigant came from products with emulsifiable concentrate formulations (Table 6c). Unadjusted e missions from commodities during the ozone season in 201 0 was

varied

. Emissions from potatoes, peppers and strawberries increased, while those from carrots

and ornamental turf declined. The use of metam -sodium on peppers and watermelon correlates to the increase in emissions from this fumigant (Tables 14, A2 - 3d to A2 -3h, Figure 12).

The 2008 fumigant regulations caused a decrease in emissions in Southeast Desert NAA in 2009. However, fumigant emissions almost doubled between 2009 and 2010, from 0.138 tpd to 0.272 tpd. Approximately three

- quarters of the increased emissions were due to increased use, as indicated by the change in unadjusted and adjusted fumigant emissions shown in Table 6b. Fumigants accounted for almost two

- thirds of the pesticide emissions in 2010 for this NAA, but

accounted for less than hal f the emissions in 2009 (Figure 10)

.

Using the ARB emission inventory classification, emissions from structural applications of methyl bromide have been less than 0.001 tpd since 2005. A gricultural applications peaked at 0.286 tpd in 2007, and have since decreased to 0.012 tpd in 2010. These findings are consistent

with the trend found for the decline in use of methyl bromide on turf/sod. Non- methyl bromide emissions from agricultural applications increased by 88 percent fr om 0.494 tpd in 2009 to 0.930 tpd in 2010. Structural non- methyl bromide emissions also increased from 0.045 tpd in 2009 to 0.051 tpd in 20 10 (Tables 15, A2 -3 i to A2 -3l).32 Figure 10. Pesticide VOC emissions for the Southeast Desert NAA, May–October. Emissions for each year are divid ed into fumigants, nonfumigants with emulsifiable concentrate formulations (ECs) and other nonfumigants (Others). Fumigant emissions are adjusted to account for fumigation method.

Table 13. Top ten primary active ingredients contributing to 2010 May -October ozone season adjusted VOC emissions in NAA 3, the Southeast Desert

Primary AI Total Product Adjusted Emissions (tons/day) Percent of All NAA 3 May

– Oct 20 10 Adjusted Emissions

METAM

- SODIUM 0.160 35.31

CHLOROPICRIN 0.038 8.34

1,3

- DICHLOROPROPENE 0.038 8.28

BENSULIDE 0.032 7.16

DAZOMET 0.012 2.75

METHYL BROMIDE 0.012 2.69

EPTC 0.011 2.54

GLYPHOSATE, ISOPROPYLAMINE SALT 0.010 2.28

GIBBERELLINS 0.010 2.22

CYFLUTHRIN 0.009 1.94 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

1990 2006 2007 2008 2009 2010VOC Emissions (tons/day)

Fumigant Nonfumigant - ECs Nonfumigant - Others33 Figure 11. Changes in adjusted emissions of selected AIs in the Southeast Desert NAA from

2007 to 2010.

Table 14. Top ten pesticide application sites contributing to 2010 May -October ozone season unadjusted VOC emissions in NAA 3.

Application Site Emissions (tons /day) Percent of all NAA 3 May

– Oct 20 10 emissions

PEPPERS 0.275 27.73

STRAWBERRY 0.149 14.97

CARROT S 0.087 8.72

WATERMELONS 0.079 7.94

LETTUCE, LEAF 0.056 5.64

UNCULTIVATED AGRICULTURAL AREAS * 0.053 5.32

STRUCTURAL PEST CONTROL 0.051 5.11

CAULIFLOWER 0.029 2.92

POTATO 0.028 2.81

GRAPES 0.027 2.68
* Treatment of an area prior to determining which crop will be planted. 0.000 0.100 0.200 0.300 0.400

2007 2008 2009 2010VOC Emissions (tons/day)

METAM-SODIUM METHYL BROMIDE 1,3-DICHLOROPROPENE DAZOMET34 Figure 12. Changes in unadjusted emissions from selected commodities/sites in the Southeast

Desert NAA from 200 7 to 2010.

Table 15. Unadjusted 2010 May –October VOC emissions in NAA 3 by ARB emission inventory classification (tons per day, tpd).

NAA 3 - 2010 Agricultural Applications Structural Applications

METHYL BROMIDE EMISSIONS 0. 0 12 0.000

NON

- METHYL BROMIDE EMISSIONS 0. 93 0 0.0 51 0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350

2007 2008 2009 2010VOC Emissions (tons/day)

PEPPERS ORNAMENTAL TURF POTATO

CARROT STRAWBERRY35 Ventura - NAA 4

Ozone season adjusted emissions in the Ventura NAA (NAA 4) in creased by 0.518 tpd from 2.080 tpd in 2009 to 2.598 tpd in 2010 (25 percent). E missions continued to meet the SIP goal for 2012 (3.0 tpd). ( Tables 6a, 6b, Figure 3, 13 ).

As in previous years, fumigants dominate the pe sticide inventory for this NAA. I n 2010 fumigants account ed for 82 percent of the emissions , up from 78 percent in 2009 and 72 percent in 2008. The most heavily used fumigants in NAA 4 in 2010 were chloropicrin, methyl bromide, and 1,3-dichloropropene, which together accounted for over 65 percent of emissions (Tables 16, A3

- 4a to A3 -4d, Figure 14). Emissions from 1,3-dichloropropene and chloro picrin

increased in 20 10 , while emissions from methyl bromide decline d slightly from 0.544 tpd in 2009 to 0.515 tpd in 2010, but were above emission levels in 2008 (0.277 tpd). In 2010 over 96 percent of chloropicrin emissions and over 89 percent of methyl bromide emissions came from applications to strawberries or “soil application/preplant”. It should be noted that the commodity/site description “soil fumigation/preplant” refers to applications that are made before the grower has made a decision about which commodity to plant. These sites may be re

identified at a later time as any number of commodities including strawberries, peppers, raspberries, herbs, etc., but it is beyond the scope of this inventory to be able to identify which

commodities these are. Other major commodities/sites in 2010 in clude raspberries, lemons,

and tomatoes . (Tables 17, A2 -4e to A2 -4h, Figure 15). In 2010 50 percent of nonfumigant emissions, which account for less than 20 percent of this NAA’s total adjusted emissions , were from products with emulsifiable concentrate formulations (0.240 tpd) (Table 6c).

Using the ARB emission inventory classification, emissions from structural applications were below 0.001 tpd in 2010. Emissions from a gricultural applications of methyl bromide de creased

from 1.134 tpd in 2009 to 1.073 tpd in 2010. These findings are consistent with the trend found for the use of methyl bromide to strawberries and soil fumigation/preplant . Non

- methyl bromide emissions from agricultural applications in creased from 5.160 tpd in 2009 to 7.634 tpd in 2010. Structural non- methyl bromide emissions were less than 0.0 25 tpd (Tables 18, A2

- 4 i to A2 -4l).36 Figure 13. Pesticide VOC emissions for the Ventura NAA, May–October. Emissions for each year are divided into fumigants, nonfumigants with e mulsifiable concentrate formulations (ECs) and other nonfumigants (Others). Fumigant emissions are adjusted to account for fumigation method.

Table 16. Top ten primary active ingredients contributing to 2010 May -October ozone season adjusted VOC emissions in NAA 4, Ventura.

Primary AI Total Product Adjusted Emissions (tons/day) Percent of All NAA 4 May

– Oct 20 10 Adjusted Emissions

CHLOROPICRIN 0.804 31.00

METHYL BROMIDE 0.515 19.88

1,3

- DICHLOROPROPENE 0.380 14.64

METAM

- SODIUM 0.056 2.18

CHLORPYRIFOS 0.043 1.64

MINERAL OIL 0.037 1.44

ABAMECTIN 0.036 1.38

PETROLEUM OIL, UNCLASSIFIED 0.029 1.11

OXAMYL 0.022 0.85

METALDEHYDE 0.021 0.80 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

1990 2006 2007 2008 2009 2010VOC Emissions (tons/day)

Fumigant Nonfumigant - ECs Nonfumigant - Others37 Figure 14. Changes in adjusted emissions of selected AIs in the Ventura NAA from 2006 to

2009.

Table 17. Top ten pesticide application sites contributing to 2010 May -October ozone season unadjusted VOC emissions in NAA 4.

Application Site Emissions (tons/day) Percent of all NAA 4 May

– Oct 20 10 emissions

STRAWBERRY 7.493 80.40

SOIL APPLICATION, PREPLANT

- OUTDOOR 0.981 10.53

RASPBERRY 0.160 1.72

LEMON 0.159 1.70

TOMATO 0.149 1.60

N

- OUTDR GRWN CUT FLWRS OR GREENS 0.085 0.92

PEPPERS 0.036 0.39

AVOCADO 0.033 0.35

STRUCTURAL PEST CONTROL 0.025 0.27

CELERY 0.024 0.25 0.000 0.200 0.400 0.600 0.800 1.000 1.200 1.400

2007 2008 2009 2010VOC Emissions (tons/day)

CHLOROPICRIN METHYL BROMIDE 1,3-DICHLOROPROPENE38 Figure 15. Changes in unadjusted emissions from selected commodities/sites in the Ventura

NAA from 200 7 to 2010.

Table 18. Unadjusted 2010 May –October VOC emissions in NAA 4 by ARB emission inventory classification (tons per day, tpd).

NAA 4 - 2010 Agricultural Applications Structural Applications

METHYL BROMIDE EMISSIONS 1. 134 0.000

NON

- METHYL BROMIDE EMISSIONS 7.6 34 0.0 25 0.000 1.000 2.000 3.000 4.000 5.000 6.000 7.000 8.000

2007 2008 2009 2010VOC Emissions (tons/day)

STRAWBERRY SOIL FUMIGATION/PREPLANT LEMON39 South Coast - NAA 5

In the South Coast NAA, adjusted emissions increased from 1.220 tpd in 2009 to 1.734 tpd in

2010 , well below the SIP goal of 8.7 tpd. In 2010 , e missions from nonfumigants accounted for more than 78 percent of the total for the South Coast NAA . Emissions from nonfumigants with emulsifiable concentrate formulations accounted for 0.415 tpd, which is 24 percent of the

nonattainment area’s total adjusted emissions (Tables 6a, 6b, 6c, Figure 3, 16 ).

The fumigants methyl bromide, chloropicrin, and 1,3-dichloropropene, contributed to 18.86 percent of 20 10 adjusted emissions . Emissions from methyl bromide decreased from 200 9 by

0.005 tp d, but chloropicrin and 1,3-dichloropropene emissions increased from 0.058 tpd and 0.025 in 2009 to 0.106 and 0.071 tpd in 2010, respectively. Cyfluthrin and p ermethrin

, pyrethroid insecticide s used in structural pest control, landscape maintenance and on a wide range of nursery commodities, w ere the largest nonfumigant contributors to the adjusted inventory accounting for 28.04 percent (0. 265 tpd and 0.226 tpd, respectively) of emissions, up

from 0. 066 tpd and 0.203 tpd in 2009 (Tables 19, A3 -5a to A3 -5d, Figure 17 ). Limonene, an oil extracted from citrus that is used almost exclusively in structural pest control, de creased in emissions in 2010 (0.024 tpd), one third those from 2009 (0.070 tpd). Over seventy

- six percent
of emissions in NAA 5 came from fumi gant and nonfumigant use in structural pest control and

on strawberries, with landscape maintenance accounting for another 8.21 percent ( 0.165 tpd ). Emissions from dazomet, primarily used on rights-of-way, decreased from 0.037 tpd in 2009 to 0.021 tpd in 2010 to (Tables 20, A2 -5 e to A2 -5h, Figure 18).

Since this NAA has complied with the SIP goal for several years, most provisions of the 2008 fumigant regulations do not apply. Therefore, the fumigant regulations had little or no impact

on emissions in this NAA.

Using the ARB emission inventory classification, emissions from structural applications of methyl bromide remained at 0.002 tpd in 2010. Agricultural applications de creased from 0.227 tpd in 2009 to 0.189 tpd in 2010. Non- methyl bromide emissions from agricultural applications

in creased from 0. 655 tpd in 2009 to 0.757 tpd in 2010. Structural non- methyl bromide

emissions increased from 0.658 tpd in 2009 to 1.018 tpd in 2010 (Tables 21, A2 -5i to A2-5l).40 Figure 16. Pes ticide VOC emissions for the South Coast NAA, May– October. Emissions for each year are divided into fumigants, nonfumigants with emulsifiable concentrate formulations (ECs) and other nonfumigants (Others). Fumigant emissions are adjusted to account for fumigation method.

Table 19. Top ten primary active ingredients contributing to 2010 May -October ozone season adjusted VOC emissions in NAA 5, South Coast.

Primary AI Total Product Adjusted Emissions (tons/day) Percent of All NAA 5 May

– Oct 20 10 Adjusted Emissions

CYFLUTHRIN 0.265 15.27

PERMETHRIN 0.226 13.02

DISODIUM OCTABORATE TETRAHYDRATE 0.156 9.02

METHYL BROMIDE 0.149 8.62

CHLOROPICRIN 0.106 6.12

N

- OCTYL BICYCLOHEPTENE

DICARBOXIMIDE 0.087 5.01

1,3

- DICHLOROPROPENE 0.071 4.12

IMIDACLOPRID 0.067 3.88

PIPERONYL BUTOXIDE 0.054 3.11

BIFENTHRIN 0.041 2.39 0.0 2.0 4.0 6.0 8.0 10.0 12.0

1990 2006 2007 2008 2009 2010VOC Emissions (tons/day)

Fumigant Nonfumigant - ECs Nonfumigant - Others41 Figure 17. Changes in adjusted emissions of selected AIs in the South Coast NAA from 2007

to 2010.

Table 20. Top ten pesticide application sites contributing to 2010 May -October ozone season unadjusted VOC emissions in NAA 5.

Application Site Emissions (tons/day) Percent of all NAA 5 May

– Oct 20 10 emissions

STRUCTURAL PEST CONTROL 1.019 50.79

STRAWBERRY 0.512 25.52

LANDSCAPE MAINTENANCE 0.165 8.21

FUMIGATION, OTHER 0.085 4.23

N

- OUTDR GRWN CUT FLWRS OR GREENS 0.077 3.85

RIGHTS OF WAY 0.039 1.97

N

- OUTDR CONTAINER/FLD GRWN PLANTS 0.026 1.27

COMMODITY FUMIGATION 0.019 0.95

AVOCADO 0.008 0.42

ORANGE 0.008 0.41 0.000 0.100 0.200 0.300

2007 2008 2009 2010VOC Emissions (tons/day)

PERMETHRIN METHYL BROMIDE

1,3-DICHLOROPROPENE DISODIUM OCTABORATE TETRAHYDRATE

CHLOROPICRIN CYFLUTHRIN42 Figure 18. Changes in unadjusted emissions from selected commodities/sites in the South

Coast NAA from 2007 to 2010.

Table 21. Unadjusted 2010 May –October VOC emissions in NAA 5 by ARB emission inventory classification (tons per day, tpd).

NAA 5 - 2010 Agricultural Applications Structural Applications

METHYL BROMIDE EMISSIONS 0. 189 0.002

NON

- METHYL BROMIDE EMISSIONS 0. 75 7 1.018 0.000 0.200 0.400 0.600 0.800 1.000 1.200

2007 2008 2009 2010VOC Emissions (tons/day)

STRUCTURAL PEST CONTROL STRAWBERRY

LANDSCAPE MAINTENANCE COMMODITY FUMIGATION43 PROJECTION OF 201 2 VOC EMISSIONS AND FUMIGANT LIMIT S

DPR is required to limit VOC emissions of volatile organic compounds from pesticides in Ventura County during each annual May–October ozone season, and for the other NAAs if pesticide VOC emissions exceed 95 percent of the benchmarks specified in 3 CCR section 6452.2. As shown in Table 22, pesticide VOC emissions are less than 95 percent of the

benchmarks that trigger fumigant limits in the Sacramen to Metro, San Joaquin Valley,

Southeast Desert and South Coast NAAs

.

Table 22. Fumigant limit triggers and 20 10 pesticide VOC emissions.

NAA Benchmark and

SIP Goal (tons/day) Fumigant Limit Trigger (95% of Benchmark) (tons/day) 20 10

Emissions (tons/day)

1

– Sacramento Metro 2.2 2.1 1.0 61

2

– San Joaquin Valley 18.1 17.2 16. 837

3

– Southeast Desert 0.92 0.87 0.453

5

– South Coast 8.7 8.3 1.73 4

The maximum allowable annual ozone season pesticide VOC emissions (VOC MAX ) are defined in regulation 3 CCR, section 6452.2 . DPR limits emissions by restricting use of the highest VOC contributing pesticides. These are the fumigants methyl bromide, 1,3- dichloropropene, chloropicrin, metam-sodium, metam-potassium, dazomet and sodium tetrathiocarbonate. DPR calculates the maximum allowable fumigant emissions (VOC FUM )

as the difference between VOC MAX and projected nonfumigant pesticide emissions (VOC NF ) during the ozone season.

[1] NF MAX FUM VOC VOC VOC

− =

The allowable fumigant use is then calculated from VOC FUM using the most recent method use fractions and application method adjustment factors as originally described in Barry et al. (2007). This procedure is defined in regulation (3 CCR section 6452.2) and requ ires DPR to develop an estimate of nonfumigant emissions in advance of an upcoming ozone season. For 2012, the 2010 method use fraction data and the application method adjustment factors used to determine allowable fumigant use from VOC FUM are given in Appendix 1.

DPR developed a forecasting method to estimate Ventura NAA NOC NF based on a statistical time series analysis (Spurlock, 2009). The time series model is updated each year to include the most recent available pesticide use report data. After updati ng, the revised time series model is used to forecast nonfumigant emissions which, in turn, are used to calculate allowable fumigant emissions and fumigant use as described above. Table 23 compares 2004–2010 NAA 4 nonfumigant ozone seasons emissions, while Table 2 4 provides the forecast 2012 nonfumigant emissions and resultant allowable fumigant emissions based on the regulatory benchmark and the SIP goal

.44 Table 23. May –October (ozone season) nonfumigant pesticide VOC emissions and percent of total adjusted emissions.

NAA 2004

Emissions (tons/day) 2005

Emissions (tons/day) 2006

Emissions (tons/day) 2007

Emissions (tons/day) 2008

Emissions (tons/day) 2009

Emissions (tons/day) 2010

Emissions (tons/day) Mean

Percent of

Total

Emissions

4

– Ventura

Nonfumigant s 0.622 (16%) 0.497 (14%) 0.508 (14%) 0.42 8 (13%) 0.48 7 ( 2 8%) 0.4 53 (2 2 %) 0.47 6 ( 18% ) 1 8 %

Table 2 4. Projection for 2012 NAA 4 VOC emissions. The 2012 fumigant emission limit was determined by subtracting the forecast 2012 nonfumigant emissions from the SIP goal and VOC regulation benchmark (Tao, 2011 ).

Non

Attainment

Area SIP Goal and VOC Regulation

Benchmark (tons/day) Forecast 201 2 Nonfumigant

Emissions (tons/day) 201 2 Fumigant

Limit (tons/day) 201 2 Fumigant

Limit (pounds) 20 10 Adjusted Fumigant

Emissions (tons/day)

4

- Ventura 3. 0 a 0.440 2. 5 6 9 42

, 00 0 2.122

a The Ventura SIP Goal and VOC Regulation Benchmark for 20 12 is shown.45 REFERENCES

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Barry, T. 2008. September 28, 2008, memorandum to Randy Segawa: Development of SubChronic Air Concentration Estimates Associate d with Single Fumigant Application

.

Federal Register. 1997. January 8, 1997, page 1170, Emission Reductions.

Federal Register. 2008. July 18, 2008, page 41277, Revisions to the California State Implementation Plan; Pesticide Element; Ventura County.

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On

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