APPENDICES Ambient Air Monitoring for Chloropicrin and Breakdown Products of Metam Sodium - in Monterey and Santa Cruz Counties Fall 2001 Prepared by Operations Planning and Assessment Section Quality Management Branch Monitoring and Laboratory Division Project No. POI-004 December 23,2003 TABLE OF CONTENTS (Appendices) Appendix....... .. . /.......a I Protocol fothr e Ambient Air Monitoring for Methyl Bromide, 1,3-Dichloropropene, Chlororpicrin and Breakdown Products of Metam Sodium in Kern, Monterey and Santa Cruz Counties During Summary/Fall, 2001 .............................................. 1-12 II Air Sampling Cartridge Method Development and Analytical Results for Ambient Monitoring in Monterey and Santa CruzC ounties ............................................ 13-68 Ill Field Data Sheets for MIC ................................................................................ 69-84 IV Field Data Sheets for Chloropicrin. ................................................................... 85-99 V Field Data Sheets for MlTC and 1,3-Dichloropropene ................................. 100-114 VI Pesticide Ambient Sampling Procedures for Adsorbent Tubes .................... 11 5-11 7 VI1 Use information and Air Monitoring Recommendations for Field Fumigations with the Pesticide Active Ingredients 1,3-Dichloropropene, Chloropicrin, Metam Sodium, and Methly Bromide ....................................................................... 11 8-16 3 Vlll 1,3-Dichloropropene Cartridge Results ........................................................ 164-177 APPENDIX I Protocol for the Ambient Air Monitoring For Methyl Bromide, 1,3-Dichloropropene, Chloropicrin and Breakdown Products of Metam Sodium In Kern, Monterey and Santa Cruz Counties During Summary/Fall, 2001 State of California California Environmental Protection Agency AIR RESOURCES BOARD Protocol for the AmbienAtir Monitoring for Methyl Bromide, I,3-Dichloropropene, Chloropicrin and Breakdown Products of Metam Sodium In Kern, Monterey and SantaC ruz Counties During'SummerlFall,2001 Prepared by. Operations Planning and Assessment Section Quality Management Branch Monitoring and Laboratory Division Date: June 26, 2001 APPROVED: Quality.Management Branch Air Quality Surveillance Branch n Micxael Poore, Chief gnbtte Brooks,%ief Northern Laboratory Branch Measures Branch Source Division Monitoring and Labora&@hvision This protocol has been reviewed by the staff of the California Air Resources Board and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Air Resources Board, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. 000001 TABLE OF CONTENTS I. INTRODUCTION...................................................................................................... 1 II. SAMPLING ............................................................................................................... 2 CHLOROPICRIN, MIC AND MITC SAMPLING........................................................ 2 METHYL BROMIDE AND I,3-DICHLOROPROPENE. SAMPLING. ......................... 3 AMBIENT MONITORING. ......................................................................................... 4 Ill. ANALYSIS ................................................................................................................ 5 IV. QUALITY ASSURANCE ........................................................................................... 6 V. PERSONNEL............................................................................................................ 7 ATTACHMENTS I. QUALITY ASSURANCE PLAN FOR PESTICIDE AIR MONITORING II. STANDARD OPERATING PROCEDUREFOR THE SAMPLING AND ANALYSIS OF BROMOMETHANE, AND TELONEB Y GClMS USING A VARIAN CRYOGENIC SAMPLER AND SILCOTM6 LITER CANISTERS Ill. STANDARD OPERATING PROCEDURE, SAMPLINGA ND ANALYSIS OF BROMOMETHANE IN SlLCO CANISTERS IV. STANDARD OPERATING PROCEDURE, SAMPLING ANDA NALYSIS OF 1,3-DICHLOROPROPENE (TELONE) AND METHYL ISOTHIOCYANATE (MITC) IN APPLICATION AND AMBIENT AIRU SING GAS CHROMATOGRAPHYlMASS SELECTIVE DETECTOR V. STANDARD OPERATING PROCEDURE SAMPLINGA ND ANALYSIS OF METHYL ISOCYANATE IN APPLICATION AND AMBIENT AIR USING HIGH PERFORMANCE LIQUID CHROMATOGRAPHY WITH A FLUORESCENCE DETECTOR i 000002 VI.STANDARDOPERATING PROCEDURE SAMPLINGA ND ANALYSIS OF TRICHLORONITROMETHANE (CHLOROPICRIN) IN APPLICATION AND AMBIENT AIR USING GAS CHROMATOGRAPHYlMASSS ELECTIVE DETECTOR VII. PESTICIDE AMBIENTS AMPLINGPROCEDURES FOR CANISTERS VIII. PESTICIDE AMBIENT SAMPLINGPROCEDURESFOR ADSORBENT TUBES IX. CANISTER FIELD-LOGS HEET ANDCANISTERFIELD DATA SHEET X. ADSORBENT TUBE SAMPLING FIELD LOG SHEET .. 11 Protocol for the Ambient Air Monitoring for Methyl Bromide,I,3-Dichloropropene, Chloropicrin and Breakdown Productsof Metam Sodium In Kern, Monterey and Santa Cruz Counties During SummerlFall,2001 I. ‘Introduction At the request of theC alifornia Department of Pesticide Regulation (DPR) (June 28,2000 Memorandum, Helliker to Lloyd), the Air Resources Board (ARB) staff will conduct ambient air monitoring for the pesticides methyl bromide, 1,3-dichloropropene (Telone), chloropicrin and two breakdown products of metam sodium (methyl isothiocyanate and methyl isocyanate). Monitoring will occur in Kern County over an eight week ambient monitoring period, tentatively scheduled from June 30, 2001 to August 30, 2001 and also in Monterey and Santa Cruz Counties over an eight week ambient monitoring period, tentatively scheduled from September IO, 2001 to November 8,2001. This is the second consecutive year theD PR has requested monitoring for methyl bromide and 1,3-dichloropropene at these locations. This monitoring will be done to fulfill the requirements of AB I80713219 (Food and Agricultural Code, Division 7, Chapter 3, Article 1.5) which requires the ARB ”to document the level ofa irborne emissions.. .of pesticides which may bedetermined to ...” pose a present or potential hazard when requested by the DPR. Monitoring is being conducted to coincide with the primary use of these fumigants prior to plantingc arrots in Kern County and prior to planting strawberries in Monterey and SantaC ruz Counties. The sampling and analysis will follow the procedures outlined in this protocol as well as the quality assurance guidelines described in the “Quality Assurance Plan for Pesticide Air Monitoring” (May 11, 1999 version)(Attachment I). The draft method, ‘Standard Operating Procedures for the Sampling and Analysis of Bromomethane and Telone by GC1MS using a Varian Cryogenic Sampler and SilcoTM Canisters,” is included as Attachment II (May 2001 Version). This method will be used as the primary analysis method for methyl bromide (bromomethane) and 1,3- dichloropropene. Samples with concentrations above the calibration range of the primary method will be analyzed on a secondary method, “Standard Operating Procedure Sampling and Analysis of Bromomethane In Silco Canisters”, included as Attachment 111. The draft ARB method, “Standard Operating Procedure, Sampling and Analysis of 1,3-dichloropropene (Telone) and Methyl lsothiocyanate (MITC) in Application and Ambient Air using Gas Chromatography/Mass Selective Detector (06/25101 Version),” is enclosed as Attachment IV. The draft ARB method, “Standard Operating Procedure, Sampling and Analysis of 1 Methyl Isocyanate inA pplication and Ambient Air using High Performance Liquid Chromatography with a Fluorescence Detector (06/25/01 Version),” is enclosed as Attachment V. The draft ARB method, “Standard Operating Procedure, Sampling and Analysis of Trichloronitromethane (Chloropicrin) in Application and Ambient Air using Gas ChromatographylMass Selective Detector (06/25/01 Version),’’ is enclosed as Attachment VI. II. Samplinq The collection media used for monitoring of methyl bromide and I,3-dichloropropene will’involve SilcosteelBc anister sampling. The media used for chloropicrin will be XAD-4 sampling cartridges. The media used for methyl isocyanate (MIC) will be XAD-7’ sampling cartridges. The media used for methyl isothiocyanate (MITC) will be charcoal sampling cartridges (1,3-dichloropropene results from the charcoal samples will also be reported). Individual samples will be ,collectedf or 24-hour periods. For pesticide ambient monitoring conducted in 2000, 24-hour samples were collected four days per week, Monday through Friday. However, for the 2001 monitoring the DPR has requested that: “At each site, 4 samples per week should be collected randomly over the full seven-day week during the sampling period”. To accommodate this request the sampling schedule will be arranged, generally in groups of four consecutive sampling periods separated by one, two or three off-days, to add sampling days during most of the weekends during the eight week monitoring studies. Caution should be used during field monitoring, transportation, storage, and lab analysis to minimize exposure of samples to sunlight in order to prevent photo degradation of chloropicrin, MIC and MITC. Chloropicrin, MIC and MITC Sampling: The sampling methods for three of the compounds require passing measured quantities of ambient air through adsorbent sampling tubes. For chloroticrin, thetu bes are 8 mm x150 mm, XAD-4, with 400 mg in the primary section, and 200 mg.in the secondary section (SKC special order). For MIC, the tubes are 6mm x 90m m, XAD-7, 1-(2-pyridyl)piperazine coated, with 80 mg in the primary section, and 40 mg in the secondary section (Supelco special order). Two tubes will be used in sequence for the MIC sampling. For MITC, the tubes are 8 mm x 110 mm, coconut shell charcoal with 400 mg in thep rimary section, and 200 mg int he secondary section (SKC catalogue #226-09). (The coconut base charcoal tube samples will also be analyzed for 1,3-dichloropropene to be comparedw ith the canister results). Sample collection forc hloropicrin is at a flow rate of 90 standard cubic centimeters per 2 000005 minute (sccpm); at 75 sccpm for MIC; and at 2.5 standardli ters per minute (slpm) for MITC. All samples are 24 hours in duration. Subsequent to sampling, the tubes are capped, labeled, placed in a culture tube and stored and transported to the ARB laboratory in Sacramento in an insulated container with dry ice. The DPR recommended target 24-hour estimated quantitation limits (EQLs) were 0.1 ug/m3, 0.05 ug/m3 and 0.5 ug/m3f or chloropicrin, MIC, and MITC, respectively. The ARB 24-hour EQLs are 0.15 ug/m3, 0.42 ug/m3 and 0.18 ug/m3f or chloropicrin, MIC, and MITC, respectively. The MIC EQL is approximately 8 times higher than requested. The DPR directed that the monitoring for MIC should be conducted as planned even with the higher than requested quantitation limit. Each sample train consists of an adsorbent tube, Teflon fittings and tubing, rainlsun shield, rotameter, train support and a 115 volt AC vacuum pump (Figure 1). Tubes are prepared for use by breaking off the sealed glass end and immediately inserting the tube into the Teflon fitting. The tubes are oriented in the sample train according to a small arrow printed on the side indicating the direction of flow. A 0-5 Ipm rotameter is used to control sample flow for the MITC sampling and 0-240 ccpm rotameters will be used to control the flow for the chloropicrin and MIC sampling. The flow rates will be set using ac alibrated digital mass flow meter (MFM) before the start of each sampling period. A MFM scaled from 0-5 slpm is used for MITC and a 0-100 sccpm MFM is used for the chloropicrin and MIC samplers. The flow rate is also checked and recorded, using the MFM, at the end of each sampling period. Samplers will be leak checked prior to each sampling period with the sampling tubes installed. Any change in flow rates will be recorded in the field'logbook. The pesticide ambient sampling procedures for adsorbent tubes are attached as AttachmentVIII. The adsorbent tube sampling field log sheet is enclosed as Attachment X. Methyl Bromide (MeBr) and 1,3-Dichloropropene Sampling Integrated ambient air samples will be collected using passive air sampling into evacuated six liter, SilcosteelB canisters (from Restec Corporation). The flow rate of 3 sccpm will be set using a battery operated mass flow meter. The sampling system will be operated continuously for 24 hours with the exact operating interval recorded on the log and field data sheets (see Attachment IX). The canister vacuum reading will be recorded at the start and end of each sampling period using the -30 to 0 inHg gauge on the passive sampler. The start and end canister vacuumr eadings will be approximately -30 inHg and -8 inHg, respectively. The canister vacuum reading will also be measured using a more accurate gauge in thel ab before and after transport to/from the field. The laboratory gauge readings will be used to calculate the sample volume collected. The 3 sccpm sampling rate will yield a sample volume of 4.32li ters over the 24 hour sampling period. The EQL for MeBr is 0.036 ug/m3 (target EQL was 0.4 ug/m3)a nd the EQLs for cis and trans 1,3-dichloroproP ene are 0.015 and 0.03 ug/m3, respectively (target EQL for Telone was 0.01 uglm ). 3 The critical orifice flow controllers (Silcosteel treated Veriflo SC423XL) will be attached to the valve fitting on thec anister using a Silcosteel treated swagelock connector (Figure 2). A six foot section of 1/8 inch O.D, Silcosteel tubing will be attached tot he inlet end of an in-line, 7 micron filter, which will be attached tot he inlet end of the flow controller. The inlet end of the tubing will be bent into a U shape (to prevent rain from entering) and supported about six feet above the building roof tops for the'ambient monitoring. At the end of each sampling period, the canisters will be placed ins hipping contai,ners, with a sample identificationlchaino f custody sheet, and will be shipped as soon as reasonably possible to the ARB Monitoring and Laboratory Division laboratory for analysis. The samples will be stored at ambient laboratory temperature prior to analysis. When using a criticaolrifice flow restrictor for passive integrated sampling, the potential decrease in flow rate as the vacuum in the canister changes must be taken into account. This condition is resolved by using the Veriflo SC423XL flow controller. The controller uses a metald iaphram downstream of the critical orifice to regulate thef low as the pressure the canister changes. It is capable of maintaining a continuous low flow with vacuum ranges from -29.9 to approximately -5 inHg. The in-line filterp revents particles from entering the critical orifice tohfe flow controller, which could clog the critical orifice and affectt he flow through the controller. The outside temperaturec an also affect the flow rate. For example, there could be an approximately six percent flow drop when the temperaturec hanges from 80 OF to 125 (according to manufacturer's O F specifications). The pesticide ambient sampling procedures for canisters are enclosed as Attachment VII. The canister sampling field log sheet and canister data sheet are enclosed as Attachment IX. These forms will be used to record start and stop times, start and stop vacuum readings, sample identifications, weather conditions, sampler's initials and any other significant data. Ambient Monitoring The DPR has directed that monitoring site selection in Kern County should focus on 1,3-dichloropropene and metam sodium, but that samples be collected and analyzed for all five compounds. The historical use patterns for 1,3-dichloropropene and metam sodium suggest that monitoring should occur over a two-month period duringJ uly and August in Kern County. As was done in 2000, five sampling sites will be selected in relatively high-population areas or in areas frequented by people. At each site, a target of 32 discrete 24-hour sampling periods will be monitored during the study. Collocated (field duplicate) samplesw ill be collected for Iday/week at each sampling location. The DPR has directed that monitoring site selection in Monterey and Santa Cruz Counties should focus onm ethyl bromide and chloropicrin, but that samples be collected and analyzed for all five compounds. In Monterey and Santa Cruz Counties, ' 4 OOOOQ"?