# Department of Pesticide Regulation

Mary-Ann Warmerdam Director Arnold Schwarzenegger Governor

1001 I Street • P.O. Box 4015 • Sacramento, California 95812-4015 • www.cdpr.ca.gov

A Department of the California Environmental Protection Agency October 26, 2006

TO: Interested Parties

SUBJECT: 2006 UPDATE OF VOLA TILE ORGANIC COMP OUND EMISSION INVENTORY

The Department of Pesticide Regulation (DPR) has complete d the annual volatile organic compound (VOC) emission inventory based on the 2004 pesticide use data for five nonattainment areas in California. These areas are designated as being nonattainment for the federal one-hour ambient air quality standard fo r ozone. DPR prepared th e inventory as part of its commitment to reduce pesticide VOC emissions under the 1994 State Implementation Plan (SIP) for agricultural and commercial structural pesticides.

DPR has continued efforts to improve the ac curacy of the emission inventory and the 2004 inventory reflects these efforts. The most si gnificant improvement was the replacement of pesticide product default assumptions with pr oduct specific data. In February 2005, DPR required the submission of thermogravimetric an alysis data for several hundred pesticide products. Currently, thermogravimetric analysis is the most accurate method for estimating the VOC content of pesticide products. DPR received, ev aluated, and incorporated the data for all applicable years of the inventory.

As expected, the 2004 pesticide VOC emission i nventory mirrors the 2004 pesticide use report that showed decreases for two areas and increase s for the other areas compared to 2003. For the Sacramento Metropolitan and South Coast nonattainment areas, the 2004 pesticide VOC emission inventory continues to meet the targ ets of the 1994 SIP. The pesticide VOC emission inventory for the San Joaquin Valley, Ventura, and Southeast Desert nonattainment areas does not meet the targets. Additionally, in 2006, a court ordered DPR to achieve a 20 percent VOC reduction from 1991 levels in all nonattainment areas through regulation that must be adopted by 2008. The ruling is on appeal. However, we are taking regulatory steps to achieve our 1994 SIP commitments and comply with the court order.

Bringing the San Joaquin Valley nonattainment area into compliance with our obligations is our highest priority. For several ye ars, the pesticide VOC emissi on inventory trend for the San Joaquin Valley showed considerable and steady progress toward meeting the reduction goal, and was met in 2001. However, pestic ide VOC emissions have increased for the last three years in the San Joaquin Valley and are cu rrently above the reduction goal. For the past three years, DPR has begun the process of identify ing regulatory measures to bri ng the pesticide VOC emissions into compliance with the goals. In 2005, DPR issued a notice to pesticide registrants of productsInterested Parties October 26, 2006 Page 2

that contained a high amount of VOCs requiring a plan to reformulate below 20 percent. The notice involved over 700 pesticide pr oducts and will be completed soon.

In May 2006, DPR launched a comprehensive initi ative to improve air quality by additional regulation of pesticides. The Pesticide Air Initiati ve will involve a regulatory framework that will enhance DPR’s commitment to reduce VOC emissions from agricultural and commercial structural pesticides in nonattainment areas, as outlined in the 1994 SIP. DPR’s emphasis on reducing VOC emissions from pesticides will also be done in a way that reduces pesticide toxic risk and drift.

Our primary focus for reducing pesticide VOC emissions will be based on a reduction in VOC emissions from traditional pesticide applications and a shift in pest control practices. To achieve these two goals, DPR will reduce emissions from fumigants (which currently account for about one-fourth of all pesticide pounds applied annually) and complete the reformulation reevaluation process for pesticide products. Regu lations to reduce emissions from fumigants will be in place by the end of 2007.

More information on VOCs and DPR’s Pesticide Air Initiative is available at <http://www.cdpr.ca.gov/docs/empm/ehap.htm>.

Sincerely,

Paul H. Gosselin Chief Deputy Director (916) 445-4000

# Department of Pesticide Regulation

Mary-Ann Warmerdam Director 

### M E M O R A N D U M Arnold Schwarzenegger Governor

1001 I Street • P.O. Box 4015 • Sacramento, California 95812-4015 • www.cdpr.ca.gov

A Department of the California Environmental Protection Agency TO: John S. Sanders Branch Chief Environmental Monitoring Branch

FROM: Tamara L. Roush, Ph.D Original signed by Tamara Roush Environmental Research Scientist (916) 324-4279

DATE: October 24, 2006

SUBJECT: 2006 UPDATE TO THE PESTICIDE VOC INVENTORY: ESTIMATED EMISSIONS 1990-2004

I. OVERVIEW

This memorandum summarizes the Department of Pesticide Regulation’s (DPR’s) 2006 update of estimated pesticide volatile organic compound (VOC) emission data, with particular attention to May-October “ozone season” emissions in Cali fornia’s five non-attainment areas (NAAs). An electronic file containing de tailed statewide 1990-2004 data is available by download from DPR’s Web page at < http://www.cdpr.ca.gov/docs /pur/vocproj/vocmenu.htm > along with a variety of VOC documentation.

The 1990–2004 annual VOC inventories were recalcula ted and included three revisions to the procedures used in 2005 (Li and Spurlock 2005) . The revisions were 1) adding 11 application sites previously excluded from the VOC inventor y and excluding three sites previously included, 2) updating criteria used to id entify and exclude consumer produc ts, and 3) re-calculating the default emission potential for products containing sodium tetrathiocarbonate. These revisions are explained in greater detail in Spur lock (2006). Future changes that were not incorporated in this year’s calculations involve updates to default emi ssion potentials based on formulation codes and improved estimations of emission potentia ls based on data from field studies.

Additionally, the 1990 – 2004 VOC i nventories incorporate new em ission potential data for several hundred products. In February 2005, DPR reque sted thermogravimetric analysis data for several hundred pesticide products. Thermogravimet ric analysis is currently the most accurate method for estimating the VOC content of pestic ide products. DPR requested the data for most liquid products included in the inventory that had not been tested previously. The VOC emissions described here incorporate the thermogravimetric analysis data submitted, reviewed, and approved as of August 2006. The delay in p ublishing this annual report is due to time required to evaluate and incorporate the new data.

The 2004 VOC emissions reported are based on DPR’s 2004 pesticide use data, released in January 2006 (DPR, 2006). The NAA attainment goals discussed are those or iginally describedJohn S. Sanders October 24, 2006 Page 2

in the January 8, 1997, Federal Register, page 1170, Emission Reductions (Federal Register, 1997), as well as those described in the relief order issued Ap ril, 26, 2006, following the decision in El Comité Para Bienstar de Earlimart v. Helliker, 416 F. Supp. 2d 912, (E.D. Cal. 2006). Previously, the 1990 baseline was used to calc ulate the reduction goals of 12% in the San Joaquin Valley NAA and 20% in each of th e other NAAs. Under the court order, the 1991 base year is used, and the goal in each is 20%

. (Table 1). For simplicity and ease of comparison with previous reports, most of this document refers to the original goals that use 1990 as the base year and a 12% reduction for San Joaquin Valley.

TABLE 1: 1990 and 1991 May–October (ozone s eason) pesticide VOC emissions and goal emission rates in NAAs 1–5 reported as tons of total organic gases per day (tpd).

Original Court Order

NAA 1990 emissions (tpd) Goal emissions (tpd) Goal Year 1991 emissions (tpd) Goal emissions (tpd) 1 - Sacramento Metropolitan 2.876 2.301 2005 3.134 2.507 2 - San Joaquin Valley 22.604 19.892 1999 22.258 17.806
3 - Southeast Desert 1.241 0.993 2007 0.838 0.670
4 - Ventura 4.524 3.619 2005 3.946 3.157
5 - South Coast 10.898 8.718 2010 5.210 4.168

II. 2004 VOC INVENTORY RESULTS BY NON-ATTAINMENT AREA (NAA)

The 2004 VOC emissions were calculated for each non-attainment area and summed according to primary active ingredient, applicat ion site, and emission category as defined by the Air Resources Board (ARB). The primary activ e ingredient is defined as the pesticidal active ingredient present at th e highest percentage in a pr oduct. If a pesticide product contains 20 percent of active i ngredient “A” and 10 percent of active ingredient “B”, all estimated emissions from that product are assi gned to the primary active ingredient “A”. This approach prevents “double-counting” of emissions from products containing two active ingredients. The Air Resources Board defi nes four VOC emission categories: methyl bromide emissions from agricultural applic ations, non-methyl bromide emissions from agricultural applications, methyl bromide emi ssions from structural applications, and non-methyl bromide emissions from structural applications. Emissions were calculated for May – October, the ozone season, and are reported as US tons of total organic gases per day (tpd).John S. Sanders October 24, 2006 Page 3

A. NAA 1, Sacramento Metropolitan Area

The emission rate in NAA 1 continues the decr easing trend seen since 2002 and is down 15.3% from the 2003 rate of 1.624 tpd. The 2004 le vel of 1.376 tpd is well below the 2005 goal emission rate of 2.301 tpd (Figure 1). Molin ate and thiobencarb, herbicides used on rice, contributed substantially to NAA 1 emissions (Tab le 2). The insecticide chlorpyrifos was the second highest contributor at 7.8% of the emissions. Rice was the highest contributing application site with 27.5% of emissions, followed by walnuts at 13.2% (Table 3). Products containing the fumigants 1,3-dichloropropene an d methyl bromide accounted for much of the emissions in NAA 1. Agricultural applications contri buted to 90.6% of the total emissions, with 85.6% comprised of non-methyl bromide agricultural applica tions (Table 4).

TABLE 2: Top ten primary active ingredient s contributing to 2004 May-October ozone season VOC emissions in NAA 1, the Sacramento Metropolitan Area.

Primary AI Total product emissions (tons/day) % of all NAA 1 May - Oct 2004 emissions

MOLINATE 0.198 14.4
CHLORPYRIFOS 0.108 7.8
THIOBENCARB 0.100 7.3 1,3-DICHLOROPROPENE 0.094 6.8
METHYL BROMIDE 0.068 5.0
CYPERMETHRIN 0.065 4.7
COPPER ETHANOLAMINE COMPLEXES, MIXED 0.055 4.0
TRIFLURALIN 0.050 3.6
PROPYLENE OXIDE 0.049 3.5
DIMETHOATE 0.047 3.4John S. Sanders October 24, 2006 Page 4

TABLE 3: Top ten pesticide application sites contributing to 2004 May-October ozone season VOC emissions in NAA 1.

Application site Emissions (tons/day) % of all NAA 1 May - Oct 2004 emissions

RICE 0.379 27.5
WALNUT 0.182 13.2
STRUCTURAL PEST CONTROL 0.130 9.4
PROCESSING TOMATOES 0.126 9.2
RIGHTS OF WAY 0.090 6.5
COMMODITY FUMIGATION 0.081 5.9
WINE GRAPE 0.071 5.2
ALFALFA 0.054 3.9
SOIL FUMIGATION / PREPLANT 0.037 2.7
LANDSCAPE MAINTENANCE 0.029 2.1

TABLE 4: 2004 May–October VOC emissions in NAA1 by ARB emission inventory classification (tons per day, tpd).

Agricultural applications Structural applications methyl bromide emissions 0.068 0.000 non-methyl bromide emissions 1.178 0.130

B. NAA 2, San Joaquin Valley

The 2004 ozone season NAA 2 emission rate of 25.648 tpd is slightly more than the 24.559 tpd found in 2003, and still greater than rates in 2002 and 2001. Furthermore, this exceeded the 1999 goal of 19.892 tpd by 28.9% (Figure 1) . Fumigants accounted for 54.2% of all emissions (Table 5), and carrots, almonds, and cotton were the top three application sites, contributing 38% to emissions (Table 6). Thes e are the same trends as those reported for 2002 and 2003. Almost all of 2004 NAA 2 VOC em issions (98.4%) were attributable to agricultural pesticide uses w ith the remaining 1.6% from co mmercial structural pesticide applications. Methyl bromide contributed only 10.6% to the agricultu ral applications and 3.2% to non-agricultural applications (Table 7).John S. Sanders October 24, 2006 Page 5

TABLE 5: Top ten primary active ingredient s contributing to 2004 May-October ozone season VOC emissions in NAA 2, the San Joaquin Valley.

Primary AI Total product emissions (tons/day) % of all NAA 2 May - Oct 2004 emissions
METAM-SODIUM 5.749 22.4 1,3-DICHLOROPROPENE 4.887 19.1 CHLORPYRIFOS 2.856 11.1 METHYL BROMIDE 2.694 10.5 DIMETHOATE 0.570 2.2 OXYFLUORFEN 0.569 2.2POTASSIUM NMETHYLDITHIOCARBAMATE 0.565 2.2 GIBBERELLINS 0.515 2.1 ENDOSULFAN 0.515 2.0 ACROLEIN 0.454 1.8

TABLE 6: Top ten pesticide applicati on sites contributing to 2004 May-October ozone season VOC emissions in NAA 2.

Application site Emissions (tons/day) % of all NAA 2 May - Oct 2004 emissions
CARROT 3.952 15.4 ALMOND 3.113 12.1 COTTON 2.690 10.5 ORANGE 2.007 7.8 N URSERY OUTDR CONTAINER -FLD GRWN PLANTS 1.779 6.9 GRAPE 1.337 5.2 POTATO 0.985 3.8 WALNUT 0.838 3.3 RIGHTS OF WAY 0.654 2.6 PROCESSING TOMATOES 0.579 2.3
TABLE 7: 2004 May–October VOC emissions in NAA 2 by ARB emission inventory classification (tons per day, tpd).

Agricultural applications Structural applications methyl bromide emissions 2.681 0.013 non-methyl bromide emissions 22.563 0.391John S. Sanders October 24, 2006 Page 6

C. NAA 3, Southeast Desert

The 2004 NAA 3 ozone season VOC emissions of 1.506 have not changed much since 2003 (1.559 tpd). Emission rates for this region have generally increased since 1998 and are now 51.7% above the 2007 ozone season target of 0.993 tpd (Figure 1). The fumigants metam-sodium, methyl bromide, 1,3-dichloroprop ene, and chloropicrin were the top four contributing primary active ingredients, toge ther comprising 82.7% of the NAA 3 emissions (Table 8). Uncultivated agricultural areas acco unted for approximately one quarter of all emissions, followed by peppers, carr ots, and strawberries (Table 9). Agricultural applications contributed to 94.1% of all em issions. Methyl bromide was more widely used in NAA 3, accounting for 24.8% of emissions from the agricultural applications (Table 10).
TABLE 8: Top ten primary active ingredient s contributing to 2004 May-October ozone season VOC emissions in NAA 3, the Southeast Desert.

Primary AI Total product emissions (tons/day) % of all NAA 3 May - Oct 2004 emissions
METAM-SODIUM 0.835 55.5 METHYL BROMIDE 0.352 22.4 1,3-DICHLOROPROPENE 0.041 2.7 CHLOROPICRIN 0.031 2.1 PERMETHRIN 0.029 1.9 CHLORPYRIFOS 0.018 1.2 EPTC 0.015 1.0 MEFENOXAM 0.014 0.9 BENSULIDE 0.014 0.9 PENDIMETHALIN 0.011 0.7
TABLE 9: Top ten pesticide applicati on sites contributing to 2004 May-October ozone season VOC emissions in NAA 3.

Application site Emissions (tons/day) % of all NAA 3 May - Oct 2004 emissions UNCULTIVATED AGRICULTURAL AREAS* 0.378 25.1 PEPPERS, FRUITING 0.261 17.3 CARROT 0.181 12.0 STRAWBERRY 0.160 10.7 POTATO 0.128 8.5 STRUCTURAL PEST CONTROL 0.087 5.8 CANTALOUPE 0.053 3.5 TURF / SOD 0.039 2.6
CELERY 0.034 2.2 WATERMELON 0.028 1.8 * Treatment of an area prior to determining which crop will be planted.John S. Sanders October 24, 2006 Page 7

TABLE 10: 2004 May–October VOC emissions in NAA 3 by ARB emission inventory classification (tons per day, tpd).

D. NAA 4, Ventura

Ozone season emissions of 9.506 increased 24.7% over 2003, and exceeded the 2005 target of 3.619 tpd by 97.4% (Figure 1). As in NAA 3 and NAA 2, fumigants contributed to the majority of emissions (Table 11). Strawberry applications produced approximately three quarters of the emissions, and soil fumigations accounted for anothe r 10.5% (Table 12). Only 2.1% of NAA 4 emissions re sulted from commercial struct ural pesticide applications, and methyl bromide emissions comprised over half of the emissions from agricultural applications (Table 13).

TABLE 11: Top ten primary active ingredient s contributing to 2004 May-October ozone season VOC emissions in NAA 4, Ventura.

Primary AI Total product emissions (tons/day) % of all NAA 4 May - Oct 2004 emissions
METHYL BROMIDE 4.855 51.1 1,3-DICHLOROPROPENE 2.524 26.5 CHLOROPICRIN 1.001 10.5 METAM-SODIUM 0.457 4.8 PIPERONYL BUTOXIDE 0.178 1.9 CHLORPYRIFOS 0.081 0.9 PETROLEUM OIL, UNCLASSIFIED 0.072 0.8 ABAMECTIN 0.028 0.3POTASSIUM NMETHYLDITHIOCARBAMATE 0.028 0.3 METALDEHYDE 0.024 0.3 Agricultural applications Structural applications methyl bromide emissions 0.352 0.000 non-methyl bromide emissions 1.066 0.088John S. Sanders October 24, 2006 Page 8

TABLE 12. Top ten pesticide appl ication sites contri buting to 2004 May-October ozone season VOC emissions in NAA 4.

Application site Emissions (tons/day) % of all NAA 4 May - Oct 2004 emissions
STRAWBERRY 7.060 74.3 SOIL FUMIGATION / PREPLANT 0.997 10.5
TOMATO 0.430 4.5 STRUCTURAL PEST CONTROL 0.198 2.1 LEMON 0.196 2.1 N URSERY OUTDR GRWN CUT FLWRS OR GREENS 0.098 1.0 UNCULTIVATED AGRICULTURAL AREAS 0.094 1.0 TURF / SOD 0.080 0.8
RASPBERRY 0.078 0.8 PEPPERS, FRUITING 0.061 0.6
TABLE 13: 2004 May–October VOC emissions in NAA 4 by ARB emission inventory classification (tons per day, tpd).

Agricultural applications Structural applications methyl bromide emissions 5.135 0.000 non-methyl bromide emissions 4.173 0.198

E. NAA 5, South Coast

At 2.615 tpd, VOC emissions in NAA 5 were sli ghtly lower than those in 2003 (Figure 1), and were far below the 2010 goal emissi on rate of 8.718 tpd. Methyl bromide, 1,3- dichloropropene, and chlor opicrin contributed to 51.7% of emissions (Table 14). Consequently, application sites based heavily on fumigations also accounted for almost all emission production (Table 15). Approximately one third each of emissions in NAA 5 were attributable to methyl bromid e agricultural uses, non-methyl bromide agricultural uses, and non-methyl bromide commercial structural uses (Table 16).John S. Sanders October 24, 2006 Page 9

TABLE 14: Top ten primary active ingredie nts contributing to 2004 May-October ozone season VOC emissions in NAA 5, South Coast.

Primary AI Total product emissions (tons/day) % of all NAA 5 May - Oct 2004 emissions
METHYL BROMIDE 0.881 33.7 PERMETHRIN 0.338 12.9 1,3-DICHLOROPROPENE 0.328 12.5 N -OCTYL BICYCLOHEPTENE DICARBOXIMIDE 0.174 6.7 CHLOROPICRIN 0.143 5.5 BIFENTHRIN 0.075 2.9 CHLORPYRIFOS 0.055 2.1 CYPERMETHRIN 0.049 1.9 PIPERONYL BUTOXIDE 0.046 1.8 CYFLUTHRIN 0.038 1.4

TABLE 15: Top ten pesticid e application sites contri buting to 2004 May-October ozone season VOC emissions in NAA 5.

Application site Emissions (tons/day) % of all NAA 5 May - Oct 2004 emissions
STRAWBERRY 1.099 42.0 STRUCTURAL PEST CONTROL 0.892 34.1 FUMIGATION, OTHER 0.176 6.7 LANDSCAPE MAINTENANCE 0.140 5.4 N URSERY OUTDR CONTAINER -FLD GRWN PLANTS 0.064 2.4 RIGHTS OF WAY 0.056 2.2 COMMODITY FUMIGATION 0.040 1.5 SOIL APPLICATION/PREPLANT 0.029 1.1 PEPPERS, FRUITING 0.022 0.8 FOOD PROCESSING/HANDLING PLANT/AREA (ALL / UNSPEC) 0.017 0.6
TABLE 16: 2004 May–October VOC emissions in NAA 5 by ARB emission inventory classification (tons per day, tpd).

Agricultural applications Structural applications methyl bromide emissions 0.876 0.005 non-methyl bromide emissions 0.845 0.889John S. Sanders October 24, 2006 Page 10

III. SUMMARY

NAA 1 (Sacramento Metropolitan) and NAA 5 (Sout h Coast) 2004 May-October emissions were the only two regions with emission rates below th eir respective attainment goals. Emission rates for NAA 1 and NAA 5 also were lower than those found in 2003. On the other hand NAA 2 (San Joaquin Valley) and NAA 4 (Ventura) produced higher emission rates in 2004 and exceeded their attainment goa ls. Although the emission rate in NAA 3 (Southeast Desert) decreased slightly in 2004, this rate is still we ll above its attainment goal. These trends hold regardless if 1990 or 1991 is used as the base year , or a 12% or 20% reduction goal is used for San Joaquin Valley. Fumigants were the major s ources of emissions in all regions except NAA 1; consequently unless these emissions are significantly re duced, NAA 2, NAA 3, and NAA 4 will continue to fa il to meet their goals.

IV. REFERENCES

Department of Pesticide Regulation. 2006. News Release 06-01: DPR releases 2004 pesticide use data; more nature-friendly chemicals gain favor

. available on-line:

< http://www.cdpr.ca.gov/docs/pressrls/2006/060124.htm > , verified September 5, 2006.

Eastern District of California. 2006. No. Civ. S-04-882 (E.D. Cal. filed April 6, 2006), enforcing El Comité Para el Bienestar de Earlimart v. Helliker , 416 F. Supp. 2d 912.

Federal Register, January 8, 1997. Volume 62, No. 5, p. 1170.

Li, L. Y. and F. Spurlock. 2005. April 5, 2005, me morandum to J. Sanders: January 2005 update to the Pesticide Volatile Organic Com pound Inventory: Estimated Emissions 1990—2003.

Spurlock, F. 2006. July 18, 2006, memorandum to J. Sanders: 2006 Revisions to Procedures for Estimating Volatile Organic Compound Emissions from Pesticides.

cc: Randy Segawa, Agriculture Program SupervisorJohn S. Sanders October 24, 2006 Page 11

Figure 1. Annual ozone season pesticide VOC emissions by NAA. For simplicity and ease of comparison with previous reports, these figures use 1990 as the base year and a 12% reduction for San Joaquin Valley

.

NAA 1 Sacramento Metropolitan

Year 1 9 9 0 1 9 9 2 1 9 9 4 1 9 9 6 1 9 9 8 2 0 0 0 2 0 0 2 2 0 0 4Emission rate (tpd)

1.0 1.5 2.0 2.5 3.0 3.5 4.0

VOC emissions Goal emission NAA 2 San Joaquin Valley

Year 1 9 9 0 1 9 9 2 1 9 9 4 1 9 9 6 1 9 9 8 2 0 0 0 2 0 0 2 2 0 0 4Emission rate (tpd)

15 20 25 30 35 40

NAA 3 Southeast Desert

Year 1 9 9 0 1 9 9 2 1 9 9 4 1 9 9 6 1 9 9 8 2 0 0 0 2 0 0 2 2 0 0 4Emission rate (tpd)

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 NAA 4 Ventura

Year 1 9 9 0 1 9 9 2 1 9 9 4 1 9 9 6 1 9 9 8 2 0 0 0 2 0 0 2 2 0 0 4Emission rate (tpd)

3 4 5 6 7 8 9 10

NAA 5 South Coast

Year 1 9 9 0 1 9 9 2 1 9 9 4 1 9 9 6 1 9 9 8 2 0 0 0 2 0 0 2 2 0 0 4Emission rate (tpd)

2 4 6 8 10 12