FINAL REPORT

Meth Labs Sampling: Air and HVAC Systems Minnesota Pollution Control Agency CFMS No. A-79651

Report prepared by: Peter C. Raynor and Tricia Carmody

University of Minnesota Division of Environmental Health Sciences

Mayo Mail Code 807, 420 Delaware Street SE Minneapolis, MN 55455

Report submitted to: Kate Gaynor

Minnesota Pollution Control Agency 520 Lafayette Road

St. Paul, MN 55155-4194

September 29, 2006

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TABLE OF CONTENTS Background......................................................................................................................................3 Work Plan ........................................................................................................................................4 Literature Review on Airborne Methamphetamine Sampling.........................................................6 Proposed Sampling Methods ...........................................................................................................8 Air Sampling........................................................................................................................8 HVAC System Wipe Sampling ...........................................................................................8 Method Validation ...........................................................................................................................9 Methamphetamine Base Apparatus and Procedures............................................................9 Methamphetamine HCl Apparatus and Procedures...........................................................11 Sample Extraction Procedures ...........................................................................................13 Methamphetamine Base Results and Discussion...............................................................13 Methamphetamine HCl Results and Discussion................................................................14 Draft Manuscript................................................................................................................15 Sampling in Former Methamphetamine Labs................................................................................15 Eden Prairie Site ................................................................................................................16 St. Peter Site.......................................................................................................................18 Conclusions....................................................................................................................................19 References......................................................................................................................................21 Appendix........................................................................................................................................23

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BACKGROUND Methamphetamine, or "meth" for short, is an addictive stimulant drug that activates the brain (NIDA, 2005). Central nervous system effects from meth use include increased wakefulness, increased physical activity, decreased appetite, increased respiration, hyperthermia, and euphoria. Other effects include irritability, insomnia, confusion, tremors, convulsions, anxiety, paranoia, and aggressiveness. Methamphetamine causes increased heart rate and blood pressure which may damage blood vessels in the brain, producing strokes. Federal surveys indicate that 12.3 million Americans age 12 or older have tried meth at least once. Methamphetamine has been used in the medical field in small doses for the treatment of narcolepsy, attention deficit disorder (ADD), and obesity (NIDA, 2002). The effective dose per pill is 5 mg methamphetamine. For treating ADD, the dose is 20-25 mg/day. For obesity, the dose is one tablet prior to each meal (Medical Economics, 2003). Illegally, methamphetamine can be smoked, snorted, orally ingested, or injected. Smoking or injecting causes a different form of high than snorting or oral ingestion. The high from smoking or injecting is an intense rush about 3 to 5 minutes after taking the drug, whereas oral ingestion or snorting creates a high with no rush 15 to 20 minutes after taking the drug. Because of this, more than one form of taking the drug may be employed at one time, and users are likely to binge (NIDA, 2002). Methamphetamine is believed to damage the dopamine-producing cells in the brain, and can cause hypothermia, paranoid hallucinations, stroke, and weight loss (NIDA, 2002). The societal effects of methamphetamine use in Minnesota have been documented in the Star Tribune. Minnesota was the state with the greatest increase in prison population from June 30, 2003 to June 30, 2004, a statistic attributed partially to increased convictions for methamphetamine production, sales, and use (Xiong, 2005). Dakota County meth cases rose from only a few in 2001 to 446 in 2004 (Adams, 2005). Persons high on methamphetamine have committed crimes such as homicide, vehicular homicide, and bank robbery. Treatment of meth users brings additional patients into emergency rooms and mental health services that already have trouble meeting the needs of all patients (Phelps, 2005). In addition, these patients are frequently difficult for clinicians to treat because of their agitation, paranoia, and aggressiveness. Meth producers and users are found in the Twin Cities and other urban areas, suburbs, and rural communities. The annual public costs associated with methamphetamine abuse in Minnesota were estimated at $130 million for 2004 (Phelps, 2005). Methamphetamine can be produced in several ways; all involve chemicals that, until recently, were readily available to the public. Producers set up clandestine labs, often for making the drug for their own use, in homes, apartments, hotels, and even cars. As many as 34 different chemicals may be used in methamphetamine production (Scott and Dedel, 2002). The most common include ephedrine, pseudoephedrine, phenylpropanolamine, red phosphorous, iodine, hydrochloric acid, ether, hydriodic acid, and anhydrous ammonia. Many of these chemicals are explosive or corrosive and have the potential for acute toxicity. During the production or "cooking" process, exposures to airborne hydrochloric acid (HCl), iodine, and volatile organic compounds occur (Martyny et al., 2005a). In addition, airborne exposures to both methamphetamine base, a liquid, and methamphetamine HCl, the solid salt form that is taken as the illicit drug, can occur during and after the cook. Methamphetamine HCl will be present as

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small solid particles that can float throughout a home and be inhaled or deposit on surfaces and furnishings. The base is a semi-volatile material, meaning it can exist in both the liquid and vapor phases simultaneously. Thus, meth base may be present as vapor molecules or small liquid droplets that can disperse throughout a residence and be inhaled or settle or adsorb to surfaces. The number of illegal labs manufacturing methamphetamine has been on the rise. In 1993, approximately 200 labs nationally were seized by authorities, compared to over 10,000 in 2003 and about 15,000 in 2004 (Gorden et al., 2005). In Minnesota, law enforcement agencies seized between 400 and 500 methamphetamine laboratories in 2003, up from about 100 in 2000 (Levy, 2005). However, with the implementation of legislation in 2005 restricting sales of decongestants containing ephedrine and pseudoephedrine, the most common precursors for meth, the number of laboratory seizures has decreased noticeably, although not completely. When a methamphetamine lab is seized by authorities, gross contamination including chemicals and the cooking apparatus is removed and the structure is usually allowed to ventilate (Hannon, 2005). During this period, law enforcement officials, hazardous waste teams, and public health officers may be exposed to hazardous chemicals, including residual meth base and meth HCl. After the most hazardous chemicals like iodine, hydrochloric acid, ether, hydriodic acid, and anhydrous ammonia have been removed, the building owner is required to ensure that residual methamphetamine is at low enough levels for the building to be safe before it is reoccupied. Residual methamphetamine poses potential exposures for workers remediating a former clandestine lab. In addition, future residents face potential exposures if the clean-up is insufficient. The Minnesota Department of Health (MDH), in conjunction with the Minnesota Pollution Control Agency (MPCA), has issued cleanup guidance for remediation of properties formerly housing methamphetamine production. The guidance states that surfaces containing more than 10 µg/ft2 of methamphetamine in any form must be decontaminated (MDH/MPCA, 2006). As the document is careful to point out, this figure is not based on any known relationship to health effects. In fact, it merely represents an approximate limit of detection for methamphetamine with 1980's-vintage analytical techniques. No data exist to relate the level of contamination on surfaces in a former lab to the inhalation exposures to which workers or residents in these structures could be exposed. This is a serious flaw in the guidance for ensuring the health and safety of occupants of former clandestine meth labs. WORK PLAN MDH and MPCA personnel have used unvalidated sampling techniques to try to measure airborne methamphetamine levels in former labs. Although they were able to detect some airborne meth, they were uncertain if they were capturing it all and how to interpret the values they obtained. Therefore, MPCA, represented by Ms. Kate Gaynor and Mr. Stephen Lee, contracted with the authors to assist them in developing, validating, and demonstrating a method to sample and analyze airborne meth concentrations in former clandestine labs with the hope that such a method will lead to more relevant guidance on the levels to which former clandestine meth labs need to be cleaned to ensure that future occupants are not harmed. The work plan in the contract specified the following tasks:

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1. A literature review regarding chemical properties of methamphetamine and sampling protocols for methamphetamine will be completed with the first month of the contract. The review will be sent to MPCA personnel.

2. Air and HVAC system sampling methods shall be proposed within the first month of the contract. Analytical methods will be selected in consultation with Minnesota Department of Health Public Health (MDH PH) lab personnel. The proposed methods will be reported to MPCA personnel and their suggestions will be incorporated into the final methods.

3. In months 2-3 of the contract, sampling and analytical methods will be validated by measuring meth concentrations in a controlled atmosphere. A report on the results of the validation study will be sent to MPCA personnel at the end of the third month. Necessary changes to sampling and analytical techniques will be made at this time.

4. As soon as each former lab to be used in the study becomes available, a date will be set to conduct the area sampling. This sampling will occur in at least three labs, each requiring an 8 hr day with possibility of returning to the site for follow up. Air sampling at each lab will include these four scenarios:

• Quiescent air sampling • Air sampling during walking activity • Air sampling while cleanup activities are occurring • Air sampling while the furnace is both operating and not operating

Samples will be delivered to the MDH PH lab within 24 hours of sampling. Sampling will help determine:

• How much meth residue is found in the air at a former meth lab structure. • Whether meth residue is present in the structure in vapor or aerosol form. • If the HVAC system serves as vector to redistribute meth residue in a former

meth lab structure. 5. At each sampling location, a wipe sampling study of the HVAC system will be

conducted. Wipe samples will be taken initially, after running the furnace for 24-48 hrs, and before and after an industrial cleaning. Samples will be delivered to the MDH PH lab within 24 hours of sampling. This sampling will determine:

• If the HVAC system serves as vector to redistribute meth residue in a former meth lab structure

• Determine whether HVAC system cleaning using standard methods results in significant redistribution of meth with the structure

• Determine how much meth residue remains in the air after vent system cleaning is completed in a former meth lab structure.

If the sampling location remains available, a coating study will be completed to determine if industrial coatings prevent any residual methamphetamine in the HVAC system from redistribution.

6. If a former meth lab with sufficient contamination can be located, the particle size distribution associated with meth residue in the lab structure shall be determined using area sampling and an Andersen cascade impactor.

7. For each site, the researchers will prepare a summary report for MPCA on the methamphetamine concentrations measured at that site within two weeks of the completion of sampling. After sampling at the third and each subsequent lab, statistical comparisons among all the labs evaluated to that point will be included in the report.

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8. A formal final report should be issued to the MPCA by the end of the contract, September 30, 2006. The report will include a draft manuscript for submission to a per-reviewed journal for consideration by possible co-authors from MPCA and MDH.

Aims 1, 2, and 3 were completed successfully. Aims 4 and 5 were completed only partially because of MPCA's inability to identify former meth labs in which research could be performed. One of the main reasons for the lack of availability of labs is the reduced number of clandestine labs seized by law enforcement, most likely due to the 2005 legislation restricting sales of methamphetamine precursors. Aim 6 was never attempted because only very low concentrations of particle-associated methamphetamine were found at sites tested. Aim 7 has been completed for the labs evaluated. This report fulfills Aim 8. In summary, the researchers have completed all elements of the work plan to the extent possible given limitations on the availability of former clandestine laboratories. LITERATURE REVIEW ON AIRBORNE METHAMPHETAMINE SAMPLING No peer-reviewed literature has been published on the sampling of methamphetamine in air in any of its forms. Dr. John Martyny and co-workers at the National Jewish Hospital and Research Center in Denver have self-published a series of reports (Martyny et al., 2004a; 2004b; 2005b) on contaminants measured in air sampled during and immediately after production of methamphetamine by several methods. Their work is summarized below. The first study (Martyny et al., 2004a) was conducted to determine the primary chemical exposures of concern. The authors took air samples for analysis of hydrocarbons, phosphine, inorganic acids, iodine, metals, and methamphetamine during a red phosphorus method cook. Hydrocarbons were collected using summa canisters as well as carbo-trap tubes. Phosphine and inorganic acid samples were collected on silica gel tubes, iodine samples on standard charcoal tubes, metals on cellulose ester membrane filters, and methamphetamine on 37 mm sulfuric acid treated glass fiber filters. The sampling was performed over the final 200 minutes of the cook. Methamphetamine was analyzed in samples taken during the cooking and filtering/salting out phases of the cook and concentrations were reported. Methamphetamine was found at concentrations of 5.5 and 4.2 mg/m3 during the filtering/salting out phase, but was not detected during the cooking phase itself. Such high concentrations were deemed to be of great concern; they are similar to threshold limit values listed by the American Conference of Governmental Industrial Hygienists (ACGIH, 2003) for airborne exposure to other amines such as ethanolamine, diethanolamine, and triethanolamine. Martyny et al. (2004b) sampled air for methamphetamine during an anhydrous ammonia method cook again in the area of the cook, collecting samples on a 37 mm glass fiber filters with 37mm glass fiber filter backup pads. They desorbed the filters using sulfuric acid and analyzed the solution using a gas chromatograph with a mass spectrometer detector (GC/MS). Samples were collected in the cooking area, in a distant room, and as a personal sample on the cook during both the pre-salting phase and the salting phase. Methamphetamine was found in low but measurable quantities during the pre-salting out phase (2.4 to 42 µg/m3) and in higher levels during the salting out phase (12 to 680 µg/m3). Detectable concentrations were found in all three locations.

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Martyny et al. (2005b) again took airborne methamphetamine samples, during a hypophosphorous/phosphorous flake method cook, in the cook area and in adjacent rooms. Samples were collected on 37 mm acid-treated glass fiber filters at a flow rate of 2 L/min. This study is similar to those published earlier (Martyny et al. 2004a; 2004b); the main difference is the method of methamphetamine production. Time of sampling was listed in this study for the two cooks. During cook #1, sampling lasted 204-210 minutes for the pre-salting out filter and 55 minutes for the salting out phase filter. Although some meth was detected in the pre-salting out phase, concentrations were 3-4 orders of magnitude lower than concentrations of 960 to 4,000 µg/m3 measured during the salting out phase. Air near cook #2 was sampled for 121-125 minutes during the pre-salting out phase. During cook #2, the investigators ran a 66-minute cook site sample for the salting out phase; no remote room samples were taken for this cook. Again, methamphetamine concentrations during the pre-salting out phase were 3-4 orders of magnitude lower than the 680 µg/m3 observed during the salting out phase. Martyny et al. (2005a) sampled the air for methamphetamine during a cook as well as 24 hours after a cook had been completed. This study also investigated the ability of methamphetamine to be re-suspended in air due to no-, medium- and high-level activities preformed in the structure such as vacuuming, moving furniture, and walking. Another goal of the study was to determine an aerosol size distribution of the methamphetamine. Total airborne methamphetamine was collected on acid-treated 37 mm glass fiber filters at a flow rate of 2 L/min. Respirable methamphetamine samples were collected onto a 37 mm acid-treated glass fiber filter using a SKC aluminum cyclone at a flow rate of 2.5 L/min. Size selective methamphetamine aerosol samples were collected on three stages (>2.5 µm, 2.5-1 µm, and <1 µm) of a Sioutas Personal Cascade Impactor with 25 mm acid-treated glass fiber filters at a flow rate of 9 L/min. The study was conducted over two days. Two cooks were conducted on the first day, each approximately 4 hours long. On the second day, air samples were taken at ‘no activity’, 13 hours after the second cook, then medium level activity including walking and opening cabinet doors at 16 hours, and during high activity levels including vacuuming and fluffing pillows at 18 hours. The study found total airborne methamphetamine concentrations ranging from 99 to 760 µg/m3 during the cooks on the first day and respirable concentrations ranging from 97 to 780 µg/m3. On the second day, total airborne methamphetamine levels were 70 µg/m3 during no activity periods, 170 µg/m3 during medium activity and 210 µg/m3 during heavy activity periods. In all situations, the vast majority of methamphetamine was found to be associated with particles smaller than 1 µm in aerodynamic diameter. Another study simulated smoking of methamphetamine in four ‘smokes’ with 91% pure methamphetamine (Martyny et al., 2004c). Normal ‘street’ meth is typically 50% pure. The first two tests were performed with 100 mg of methamphetamine in a pipe. The third was done with 250 mg of the meth in a pipe. The fourth was conducted with 2000 mg of meth on a hot plate. Air samples were taken using 37 mm acid-treated glass fiber filters at a flow rate of 2 L/min, similar to their other studies. The first two smokes collected airborne meth at amounts between 300 and 520 µg/m3. The third smoke created airborne meth levels of 1,600 µg/m3. The fourth smoke had airborne levels of 1,200 µg/m3. The typical ‘hit’ when using illegal meth in this manner is 100 mg. Cook et al. (1993) found that, when smoked at temperatures higher than 300

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°F, 50% of the methamphetamine will be volatilized from the pipe into the air. Additionally, this study found that of the 50% aerosolized, 90% was taken into the body. All of these studies sampled airborne methamphetamine solely with 37 mm acid-treated glass fiber filters. No studies have examined the possibility of methamphetamine being in the vapor phase, or sampled for methamphetamine vapor. Another concern in former methamphetamine labs is the heating, ventilating and air conditioning (HVAC) systems. No studies have been conducted to determine if meth deposits in these systems, or if these systems can re-suspend meth particles the way that vacuuming, walking, and other activities have been shown to (Martyny et al., 2005a). PROPOSED SAMPLING METHODS Air Sampling The proposed air sampling method seeks to collect both the aerosol and vapor phases of methamphetamine that may be present in an environment and to distinguish between the phases. The method collects particles with associated methamphetamine, both meth base and meth HCl, and methamphetamine vapor, presumably all meth base. The sampling train is comprised of a 37-mm 2-piece clear styrene cassette (Cat. No. 225-2050LF, SKC Inc., Eighty Four, PA) holding a glass fiber filter (Cat No. 225-709, SKC Inc.) followed by an acid-treated silica gel sorbent tube (Cat No. 226-42, SKC Inc.) connected to a personal sampling pump operating at 1.5 L/min. That flow should be calibrated before each sampling run using a bubble meter or another standard calibrating device. Tubing connecting the filter and sorbent tube should be Teflon-lined to prevent adsorption of methamphetamine into unlined plastic. HVAC System Wipe Sampling The proposed methodology is to use the same procedure listed in Appendix C.1 of the Minnesota Clandestine Drug Lab General Cleanup Guidance (MDH/MPCA, 2006). In short, the procedure calls for the use of a single 3" x 3" general use gauze sponge or sampling wipe wetted with 2 mL of methanol just before sampling to wipe a 6" x 6" sample area. The person performing the sampling is required to wear a new pair of nitrile gloves for each sampling and to limit the handling of wipers to avoid contamination. The wiping should be conducted in a tight Z pattern within the measured 6” x 6” area. Because methanol will evaporate to dryness, lessening the ability to pickup meth, the sample should be taken within 5 seconds. The wipe sample is placed back into a holding jar and the lid closed immediately after wiping. The 6" x 6" area can often be wiped using a template with the opening laid over the area of interest. Methamphetamine loading on a surface can then be reported in units of µg/ft2. On the interior of HVAC systems, finding a 6" x 6" surface can be difficult. If an equivalent area can be found, 3" x 12" for example, that area may be substituted. If a precise area can not be determined, results should be reported only in units of µg.

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METHOD VALIDATION Two test systems were developed, one for determining efficiency of air sampling for meth base and one for meth HCl. Samples were collected with the proposed sampling train described above using an Air Check 2000 personal sampling pump (SKC Inc., Eighty Four, PA). All trials were completed within a laboratory hood at the Minnesota Department of Health's Public Health Laboratory with the help and cooperation of Dr. Marty Bevan and Dr. Paul Swedenborg. Temperature remained between 19.5 and 21 °C during all experiments; ambient pressure ranged between 735 and 748 mm Hg. Methamphetamine Base Apparatus and Procedures Based on its volatility, airborne meth base will typically exist as a vapor in former labs being sampled. A test system, see Figures 1 and 2, was created based on the semi-volatile nature of methamphetamine base. Air was drawn into the apparatus though a HEPA filter (Pall Gelman,

East Hills, NY) to remove any particulate matter and the through a 38.1 cm length of 1.27 cm diameter Teflon-lined PVC tubing. Initial trials had the meth dissolved in methanol and placed the solution inside a small glass vial at the bottom of a 1,000 mL gas scrubbing bottle with the sampling train attached through 10.2 cm of 1.27 cm diameter Teflon-lined tubing. The large size of the scrubbing bottle and the depth of the vial prevented the methamphetamine from volatilizing within a reasonable time period, and recovery from this system was less than 20 % on the filter and sorbent tube. Changing to a 2.54 cm diameter watch glass aided in the volatilization of the meth base. Replacing the 1,000 mL gas scrubbing bottle with a 250 mL gas scrubbing bottle with the sampling train attached by 0.95 cm diameter Teflon-lined tubing helped increase the turnover of air in the system, leading to higher rates of evaporation. The sampling pump was connected to the silica gel sorbent tube using a 61.0 cm length of 0.64 cm PVC tubing. Teflon-lined tubing was not used here because no meth should be present downstream from the samplers. A series of three time trials were completed to determine how long experiments needed to run to recover as much of the meth base released into the apparatus as

Sampling pump

HEPA filter

Teflon-lined tubing

Glass chamber

Watch glass or vial

37-mm glass fiber filter Silica gel

sorbent tube

Air In

FIGURE 1. Meth base test apparatus.

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possible. Running the test for 30 minutes had equivalent recovery to trials run for longer times, so a 30 minute test period was established. A set mass of analytical grade meth base in methanol (Cambridge Isotopes, Andover, MA) was placed on a watch glass at the bottom of the gas scrubbing bottle (Kimble-Kontes, Vineland, NJ) and allowed to volatilize. Before each day’s testing, the gas scrubbing bottle was wiped with a swab wetted with methanol and rinsed with 15 mL of methanol. The rinsate was analyzed with the day’s samples to determine if any residual meth was present that morning in the sampling chamber. The methamphetamine was sampled with the proposed sampling train, with the exception that initial tests were conducted with an aluminum cassette rather than styrene ones due to concerns about vapor absorption into the styrene. The cassette and tube were connected by a small piece of 0.61 cm Teflon tubing that was attached to the back of the cassette. The silica gel tube slid inside the Teflon tubing to be flush with the opening of the cassette. The silica gel tube fit snugly enough so that no leakage could occur. Because the aluminum cassette was open-faced, a method was needed to connect the cassette to the tubing. Therefore, an aluminum cyclone was attached to the front of the cassette and air was drawn into the bottom of the cyclone and through the cassette. The normal entrance slit on the side of the cyclone was covered with Teflon-lined tubing in a snug fit to prevent undesired air flow into the system. A list of trials using the methamphetamine base system is shown in Table 1. The first sets of trials aimed at finalizing the glassware, watch glass, and time of experiment were conducted with

FIGURE 2. Meth base test apparatus with aluminum filter holder and cyclone entry.

TABLE 1. Samples taken with methamphetamine base system

Material TestedInitial Mass (µg) Mass Holder Filter Holder

Chamber Size (mL)

Number of Replicates

Meth Base 100 Glass Vial Aluminum 1000 3Meth Base 100 Watch Glass Aluminum 1000 5Meth Base 100 Watch Glass Aluminum 250 3Meth Base 100 Watch Glass Plastic 250 3Meth Base 10 Watch Glass Plastic 250 4Meth Base 3 Watch Glass Plastic 250 2Meth Base 1 Watch Glass Plastic 250 4Meth Base 0.1 Watch Glass Plastic 250 2Meth HCl 10 Watch Glass Plastic 250 2

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the aluminum cassette holder, pictured in Figure 2. Once recovery from this system was determined, the aluminum cassette and cyclone were replaced by a disposable 37-mm closed-face cassette to determine recovery from the new system. A comparison of the aluminum cassette efficiencies to those of the plastic cassette was conducted to determine if meth base adsorbed to the plastic of the disposable cassette. Validation trials began using 100 µg of meth in 100 µL of methanol, and once the method could be evaluated for that quantity, dilutions of 10 µg, 3 µg, 1 µg and 0.1 µg in 100 µL of methanol were run for the same length of time. Samples were extracted and analyzed using the procedures described below. Methamphetamine HCl Apparatus and Procedures Once the sampling procedure was validated for methamphetamine base, a set of trials was run in the meth base system with analytical grade methamphetamine HCl (Cambridge Isotopes Andover, MA) to determine if the methamphetamine HCl would volatilize at all. A solution of 10 µg of meth HCl in 100 µL of methanol was placed on the watch glass and allowed to evaporate for 30 minutes while the system was running. After data from these tests indicated that all meth HCl remained on the watch glass, the apparatus described below was built to validate the proposed airborne sampling method for meth HCl. A test system, see Figures 3 and 4, was devised based on the logic that non-volatile methamphetamine HCl should remain associated with particles in an airborne state. A Collison-type nebulizer (BGI Inc., Waltham, MA) was used to aerosolize a 5 mL solution of meth HCl in methanol. Pressurized laboratory-grade nitrogen was fed to the nebulizer rather than compressed air to minimize as much as possible the entry of additional particles into the system. A solenoid

valve and timer were used to control the amount of aerosol that the nebulizer released into the system. Operating the nebulizer for 2 seconds on and 6 seconds off consumed the 5 mL solution of meth HCl while providing approximately 40 L of air for sampling. The ratio between the time the solenoid was open and closed was determined to optimize aerosolization of the

Sampling pump at 1.5 L/min

Timer repeats 2 sec on and 6 sec off

Solenoid

To vacuum line w/ needle valve at 9 L/min

To Nitrogen gas

Open to air; Air In

Teflon-lined Tubing

37-mm glass fiber filter

Silica gel sorbent tube

Nebulizer system

FIGURE 3. Meth HCl test apparatus.

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methamphetamine. Leaving the nebulizer on for more than 2 seconds at a time caused the meth in methanol to be aerosolized too quickly; allowing longer than 6 seconds between bursts caused much of the methanol to volatilize without aid of the nebulizer leaving the meth HCl in the nebulizer jar. While the solenoid was open and the nebulizer was running, the flow from the nebulizer was greater than that of the sampling pump. This led to the need to create a coupling system with a secondary flow and make up air. A four-way brass coupling system of 1.27 cm interior diameter was built and connected to the outflow of the nebulizer to create three additional ports to the system. One port allowed

connection of the sampling train attached with 7.6 cm of 0.64 cm diameter Teflon-lined tubing. The personal sampling pump pulled air through the sampling train at 1.5 L/min. A glass fiber filter in a 37 mm clear styrene cassette was followed by a silica gel sorbent tube attached in the same manner as the meth base system. To a second port, a vacuum line was attached to the

coupling and operated at 9 L/min to prevent methamphetamine from being released into the hood through the the third port while the nebulizer was running. A disposable 37mm cassette with glass fiber filter was used to collect methamphetamine and prevent it from entering the hood’s vacuum system. A field rotometer with a needle valve was used to monitor the flow through the vacuum port. The third connection was left open through 22.9 cm of 1.27 cm diameter tubing to the hood environment to provide makeup air to the system when pressurized nitrogen was not being fed to the nebulizer. Sampling was completed when all liquid in the nebulizer had volatilized, which was after about 40 L of air passed through the filter and sorbent tube. Table 2 describes the samples taken using the methamphetamine HCl system. Before each day’s trials, 5 mL of methanol were added to the nebulizer and run as a blank to determine if there was any residual methamphetamine in the nebulizer system after cleaning. Trials began using 700 µg of meth HCl in 4,300 µL methanol for a total of 5 mL. This amount was chosen based on the flow rates of the personal sampling pump and the vacuum pump. If all the meth were to

FIGURE 4. Meth HCl test apparatus with four way connection for combining and splitting flows.

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volatilize with a 6:1 ratio between the flow rates, 100 µg of meth would flow toward the sampling train and 600 µg would pass toward the vacuum. Once the method could be validated at that quantity, dilutions of 350 µg and 175 µg in 5 mL of methanol were run for the same length of time. Samples were extracted and analyzed using the procedure described next. Sample Extraction Procedure Methamphetamine was extracted from the sample media with methanol and analyzed via liquid chromatography and mass spectroscopy (Model 1100 LC-MSD, Agilent, Wilmington , DE). For methamphetamine base, the watch glass was scrubbed with a swab wetted with methanol and then rinsed with 15 mL of methanol. The 15 mL methanol with the swab in had 2 µg internal standard (ISTD) added to it and was analyzed. For the methamphetamine HCl, the inside of the nebulizer bottle was scrubbed with a swab wetted with methanol and rinsed with 15 mL of methanol. Afterwards, 2 µg ISTD were added and the extract from the swab and 15 mL of methanol was analyzed. For both types of experiments, the filter was removed from the cartridge and 15 mL of methanol along with 2 µg ISTD were added for extraction. The silica gel sorbent tube was cracked and all silica gel and glass fiber spacers from the tube were placed together in a jar with 15 mL of methanol and 2 µg of internal standard for extraction and analysis. Preliminary tests determined that for the purposes of validating the methods, the breakthrough section of the silica gel tube could be analyzed with the front section, rather than performing separate extractions and analyses. The Agilent 1100 LC-MSD system includes a binary pump, vacuum degasser, autosampler, thermostatted column compartment, and diode-array detector with a single quadrupole mass spectrometer. The column has a Restek Allure Basix - 3 µm, 50 x 3.2 mm; with a Restek Trident Direct in-line Allure Basix guard column running at ambient temperature for 4.5 minutes per sample. The mobile phase used was 90% 10 mM ammonium formate (NH4O2CH) and 10% acetonitrile. The mass spectrometer used selected ion monitoring (SIM) for mass at 150 and 159. Ionization mode was ESI positive. The quantitation was based on the ISTD added to each sample. Quality controls and unknown sample concentrations were calculated by comparing against the internal standard and plotting against a standard curve using the following equation:

Sample Conc. (µg/smpl) = ISTD Conc. * [(Sample Area /ISTD Area) - Intercept]/Slope Methamphetamine Base Results and Discussion Table 3 shows the spike amount for each set of trials for meth base in relation to the percent recovery and the standard deviation for the filter, sorbent tube, watch glass, and sum of all three. The percent error and absolute mass not recovered are also shown. When 100 µg of meth base were placed in the system, recovery from the filter and sorbent was 97.3 % with 0.98 µg (approximately 1 %) remaining on the watch glass. Standard deviation was about 2 µg for each sampling medium, and error was 1.7 % overall. The first dilution, 10 µg, had 7.29 µg recovered, a standard deviation of 1.55 µg on the filter, and nothing on the sorbent tube. Meth remaining on the watch glass was 1.66 µg (17 %) with a standard deviation of 0.8 µg. All dilutions below 10 µg of meth base showed recoveries on the glass fiber filter only. As the amount of methamphetamine added to the system decreased, so did percent recovery. The percent error for

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the total mass recovered was quite low for 100 µg, but increased through the dilutions. The proportion of mass remaining on the watch glass in relation to the amount added also increased. The results indicate that methamphetamine base was volatile or semi-volatile because it moved readily from the test chamber to the sampling train with no mechanical aide such as the nebulizer used in the meth HCl system. Recovery was near 100 % for when 100 µg of meth base was added to the system, but lesss when smaller quantities were added due to losses to glassware surfaces. As the amount of meth added to the system decreased, the percentage of meth remaining on the watch glass increased. The absolute mass not recovered as a percentage of the total mass also increased as the amount of meth added to the system decreased. Only 2 % of the mass added to the system at 100 µg was not recovered, compared to 36% when 1 µg was added. This methamphetamine was probably lost to glassware surfaces. When blank samples were run after tests with 100 µg of meth base for 30 minutes with a dry watch glass, between 0.05 and 0.13 µg of meth were found in the system as residuals. This residual presumably volatilized over time from glassware surfaces. As 0.13 µg is 13% of the mass added in the 1 µg dilution, this finding could explain the fate of some of the methamphetamine not accounted for in Table 3. Sampling times influenced where methamphetamine was found within the sampling train. During longer tests, more of the total recovery of meth base was on the sorbent tube rather than on the filter. As the amount of meth base was decreased in the system, more of the meth was measured on the filter and not in the sorbent tube where it was expected as a semi-volatile vapor. The meth base may be able to pass only to the sorbent tube after the surfaces of the glass fibers in the filter are saturated with adsorbed meth base. Methamphetamine HCl Results and Discussion Table 4 shows the spike amount for each set of trials with meth HCl in relation to the percent recovered on the glass fiber filter and sorbent tube of the sampling train, the glass fiber filter of the vacuum line, the bottle rinse, and the total recovery as well as the standard deviations. When 700 µg of meth HCl were added to the system, 35.2 µg were recovered on the sampling train filter and 241.2 µg were collected on the vacuum filter with standard deviations of 2.05 µg and 36.5 µg respectively. This is a 6.85:1 ratio. The ratio for 350 µg was 7.1:1 and for 175 µg the ratio was 7.26:1. These figures are slightly higher than the expected ratio of 6:1. No mass was collected in the sorbent tube for any spike amount. The first trials with methamphetamine HCl were done in the meth base system to test the hypothesis that meth HCl, being a salt, is not volatile on its own. When a solution of 10 µg of

TABLE 3. Methamphetamine base results.

Spike Amount, µg

37-mm glass fiber filter

silica gel sorbent tube watch glass total

Absolute Mass Not Accounted For % error

100 47.99 (2.7) 49.30 (2.06) 0.98 (0.11) 98.27 (3.77) -1.73 -1.7310 7.29 (1.55) 0.00 (0.00) 1.66 (0.8) 8.94 (1.42) -1.06 -10.63 1.39 (0.44) 0.00 (0.00) 0.94 (0.37) 2.33 (0.07) -0.67 -22.331 0.19 (0.13) 0.00 (0.00) 0.45 (0.11) 0.64 (0.09) -0.36 -36

15

meth HCl in 100 µL of methanol was placed on the watch glass and the system was run for 30 minutes, no meth was detected in the filter or sorbent tube samples. This indicated that meth HCl is not volatile and will only be present when airborne in particles. In the nebulizer system, all meth HCl was collected on the glass fiber filter. Based on the air flows through the sampling train and the vacuum, a ratio of about 6 to 1 was expected for meth recovery. The ratio of the meth HCl collected between the sampling filter and the vacuum filter ranged from 6.3:1 to 7.6:1. Some of this difference may be due to the flow of the vacuum. This flow rate was controlled by a needle valve and measured by a field rotometer. The rotometer did show slight variations during sampling, suggesting substantial variation in the flow rates during the short 2 s on/6 s off cycle times for the timer operating the nebulizer. Percent error for the total system at each dilution level remained low, but increased with greater dilution. Based on the amount of meth collected in a bottle rinse compared to the samplers at the end of each sampling run, about 40 % of the meth HCl added to the system was aerosolized. This percentage might have been adjusted by changing the amount of liquid in the nebulizer or by changing the on/off settings of the solenoid. When the bottle was rinsed and a blank run between days of sampling, between 2 and 20 µg meth HCl remained in the nebulizer bottle even after cleaning. This may have implications to future studies. If research were contemplated on the efficiency of cleaning contaminated surfaces, especially glassware, the information here supports the notion that some cleaning solutions fail to remove deposited methamphetamine HCl effectively. Further cleaning studies may wish to evaluate the efficiency of differing solvents on reducing or eliminating the residual methamphetamine from the system. Although 100% of the meth base and meth HCl were not recovered during all of the tests, this does not pose a problem for using this method in the field. Most of the losses occurred in the test apparatus for both the meth base and meth HCl systems, which would not be an obstacle in the field. Draft Manuscript A draft manuscript for possible submission to a research journal has been prepared. It will be reviewed with MPCA and MDH personnel to determine revisions and additions that should be made prior to sending it to a journal. The draft manuscript is attached in the Appendix. SAMPLING IN FORMER METHAMPHETAMINE LABS Sampling was conducted using the methods developed and validated in the laboratory in two former clandestine methamphetamine labs. The results for each site are presented below.

TABLE 4. Methamphetamine HCl results

Spike Amount, µg

37-mm glass fiber filter, pump

silica gel sorbent tube, pump

37-mm glass fiber filter, vacuum Bottle Rinse total % error

700 35.23 (2.05) 0.00 (0.00) 241.24 (36.48) 470.3 (134.47) 712.8 (163.47) 1.83350 19.22 (1.79) 0.00 (0.00) 136.16 (31.27) 189.12 (6.46) 342.50 (26.59) -2.14175 10.33 (0.51) 0.00 (0.00) 74.97 (12.48) 100.84 (16.79) 186.14 (4.82) 6.37

Meth HCl Average Mass and (Standard Deviation) per Sampling Media, µg

16

Eden Prairie Site A two-level townhouse in Eden Prairie formerly housed a meth lab before the current residents purchased the property. The property changed hands approximately three years before sampling for this study occurred and the unit has been cleaned and renovated in part. The home has served as a site for MPCA and MDH studies on several prior occasions. This site was selected to help determine if any residual methamphetamine is still airborne or deposited on interior surfaces of the home HVAC system after the three years of occupancy and renovations. Air sampling was performed at two upstairs and two downstairs locations. Pumps ran for six hours at 1.5 L/min using the proposed sampling train described previously: a 37-mm glass fiber filter in a clear styrene cassette followed by a silica gel sorbent tube. Table 5 lists the sampling locations and methamphetamine found in the samples taken at each location. TABLE 5: Quantities of methamphetamine found in air samples taken at Eden Prairie site. IDs include filter samples (F) and sorbent tube samples (T).

Sample # Time Volume Field ID Description Meth Amount (µg)1 360 min 540 L Living room (F) Ontop of speaker by stairway 02 360 min 540 L Living room (T) Ontop of speaker by stairway 03 360 min 540 L Bedroom (F) Table next to dresser by vent 04 360 min 540 L Bedroom (T) Table next to dresser by vent 05 360 min 540 L Fireplace (F) Mantle of fireplace, right hand side, by desk 06 360 min 540 L Fireplace (T) Mantle of fireplace, right hand side, by desk 07 360 min 540 L Bar (F) Right side of Bar, on top of speaker 08 360 min 540 L Bar (T) Right side of Bar, on top of speaker 09 360 min 540 L Upstairs blnk (F) Coffee table, blank 0

10 360 min 540 L Downstairs blnk (F) Left side of mantle of fireplace, blank 011 361 min 541 L Upstairs blnk (T) Coffee table, blank 012 362 min 542 L Downstairs blnk (T) Left side of mantle of fireplace, blank 0

The sampling locations were chosen based on airborne hits from previous sampling, and from locations of higher quantities of meth found in wipe samples prior to previous cleanup efforts. Upstairs sampling locations included the speaker by the vent in the family room approximately 2.5 feet off the floor (a former air sampling location) and the first bedroom down the hallway on the left, again near the vent and about 15 inches off the floor. Downstairs sampling included the mantle of the fireplace about 5 feet off the floor and the wet bar about 4 feet off the floor. The fireplace has been encapsulated and the drop ceiling tiles changed since the last air sampling event. Results of the sampling indicated that no detectable amount of airborne methamphetamine was measured at the site. The team also conducted wipe sampling in the vents of the HVAC system at the Eden Prairie site. The purpose of this activity was to determine if residual methamphetamine was present on the interior surfaces of the HVAC duct work after three years of occupancy subsequent to the home housing a clandestine meth lab.

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Wipe sampling was performed within all supply and return vents in each room save one register in the first bedroom on the left because it was inaccessible without moving furniture out of the room. Where possible, a 6" x 6" area was sampled with the help of a template. However, some vents were not amenable to use of the template. Results are presented in Table 6 grouped by room. Data are reported in µg/sample and µg/ft2, if the template could be used. Results are highest in (1) the cold air return plenum in the heating system downstream from the filter, (2) the cold air return in the master bedroom, and (3) the cold air returns in the living room. TABLE 6: Quantities of methamphetamine found in air samples taken at Eden Prairie site. IDs include filter samples (F) and sorbent tube samples (T).

Smpl # Field ID Sample ID Sample DescriptionMeth

(µg/smpl)Meth

(µg/sgft)3 CA plenum Dwnstrm filt Cold air plenum, downstream of filter, 6" x 6" 22.4 89.62 CA plenum Up PrevS Cold air plenum, upstream, over previous sampling, 6" x 6" 0.4 1.61 CA plenum Up NS Cold air plenum, upstream, to left of prior sampling, 6" x 6" 2.0 7.910 Supply Register SR-3 lower level, SR by bar, 6" x 6", horizontal round pipe bottom 10.7 42.99 Supply Register SR-2 lower level, SR by bar, 6" x 6", vertical 0.7 2.98 Supply Register SR-1 lower level, SR by fireplace, 6" x 6", vertical 4.7 18.719 0 SR-12 stair well, duct runs up, vertical, 6" x 6" 1.7 6.715 Supply Register SR-8 upper level, bath, vertical, 6" x 6" 2.7 10.77 Cold Air Return CAR-4 upper level, BR2, 6" x 6", horizontal 8.7 34.817 Supply Register SR-10 upper level, BR2, below window, diagonal, ug/sample 1.4 NA18 Supply Register SR-11 upper level, BR3, diagonal, 6" x 6" 1.7 7.112 Supply Register SR-5 upper level, floor below LR window, ug/sample, horizontal 3.2 NA14 Supply Register SR-7 upper level, kitchen wall, vertical, paper blocking air flow in summer 8.3 NA

14-Dup Supply Register SR-7 upper level, kitchen wall, vertical, paper blocking air flow in summer 8.3 NA4 Cold Air Return CAR-1 upper level, left, diagonal, ug/sample 20.8 NA

4-Dup Cold Air Return CAR-1 upper level, left, diagonal, ug/sample 20.9 NA13 Supply Register SR-6 upper level, LR, ug/sample, vertical 3.2 NA11 Supply Register SR-4 upper level, near slider, ug/sample, carpet fractions in dust, horizontal 4.2 NA5 Cold Air Return CAR-2 upper level, right, diagonal, ug/sample 15.5 NA6 Cold Air Return CAR-3 upper level, MBR, 6" x 6", horizontal 22.1 88.616 Supply Register SR-9 upper level, MBR, below window, ug/sample, horizontal 1.4 NA

The results show elevated levels of meth in the cold air returns in the master bedroom, bedroom 2, and the living room. The supply registers in the basement have high levels as well. The cold air returns have a lower velocity than the supply registers, possibly allowing the meth particles to have deposited more easily. The high results in the cold air return plenum in the heating unit downstream from the filter could be due to an absence of a filter or an improperly installed filter during the period when the meth was produced or that air bypassed an overloaded filter during that time. Detectable amounts of methamphetamine are present in the HVAC system of the Eden Prairie site. However, the air sampling did not detect any airborne methamphetamine, suggesting that the meth present in the HVAC system is not readily vaporized or aerosolized. However, sampling was performed at a time when neither the heating nor air conditioning systems were on in the home. Sampling during a time of the year when the heating or cooling system is in regular use might yield different results for airborne meth concentrations. The research team had several discussions with MPCA personnel about the value and ethics of having the duct systems in the home cleaned to remove any deposited meth. Because no evidence has suggested that the small quantities of meth found on the interior surfaces of the

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HVAC system is being volatilized or aerosolized, duct cleaning may not be warranted at this site. The largest concern is that the duct cleaning might cause transfer of meth onto living surfaces that have previously been cleaned or are otherwise free of deposited methamphetamine. In addition, after three years of occupancy, any meth that could be volatilized or aerosolized without being physically disturbed would likely have become airborne long ago. In short, leaving the ventilation system as is may be preferable to the risk of recontaminating the living areas of the home if the ducts are cleaned. This concern suggests that duct cleaning should be one of the first cleanup efforts undertaken at a recently seized meth lab. If repairs or renovations to the HVAC system at the Eden Prairie site are planned in the future, care should be taken to minimize the potential of exposures to dust in the system for those performing the repairs or renovations and for subsequent occupants. St. Peter Site The purpose of sampling at this site was to measure the concentration of airborne methamphetamine in the vapor and particle phases in a more recently seized property in St. Peter, MN that formerly housed a clandestine meth lab. Sampling pumps operating at 1.5 L/min drew air through sampling trains consisting of glass fiber filters (GFF) followed by acid-treated silica gel sorbent tubes (Sorbent). Samples were taken in the north and south ends of the attic, the basement near the furnace, and the kitchen on the counter to the right of the stove. Table 7 lists the sampling locations, the volume of air sampled at each location, and the methamphetamine results at those locations. Methamphetamine was found on only one of the sorbent tubes and at a low level, suggesting that volatilized meth base may be present at only barely detectable concentrations in the house. Detectible levels of methamphetamine were measured on the filters at all four locations, though the levels were low. TABLE 7: Quantities of methamphetamine found in air samples taken at St. Peter site. IDs include filter samples (GFF) and sorbent tube samples (Sorbent). The final two values are for field blanks.

Sample Sample Description Sample ID Smpl (L) µg/smpl µg/L DateSTP0001 attic, south end, chair near window 1-GFF 381.0000 0.11 3.00E-04 6/19/06STP0002 attic, south end, chair near window 1-Sorbent 381.0000 0.00 0.00E+00 6/19/06STP0003 basement, near furnace 2-GFF 462.0000 0.06 1.19E-04 6/19/06STP0004 basement, near furnace 2-Sorbent 462.0000 0.00 0.00E+00 6/19/06STP0005 kitchen, right of stove on counter 3-GFF 475.5000 0.17 3.47E-04 6/19/06

STP0005dup kitchen, right of stove on counter 3-GFF 475.5000 0.16 3.42E-04 6/19/06STP0006 kitchen, right of stove on counter 3-Sorbent 475.5000 0.02 3.73E-05 6/19/06STP0007 attic, north end, under vent 4-GFF 69.0000 0.05 7.09E-04 6/19/06STP0008 attic, north end, under vent 4-Sorbent 69.0000 0.00 0.00E+00 6/19/06STP0009 near pump 4 GFF 0.0000 DNR 6/19/06STP0010 near pump 4 Sorbent 0.0000 0.00 6/19/06

Report ValueMethamphetamine

Because most of the methamphetamine was located on the filters rather than in the sorbent tubes, most of the airborne methamphetamine present in the house is probably meth HCl rather than meth base. Sampling results were highest in the kitchen area, and lowest in the south end of the

19

attic and the basement. The pump at the north end of the attic malfunctioned, sampling only 69 L of air, much less than the rest of the pumps. Due to noise in the chemical analysis on such a small sample volume, more meth could possibly be present in this location than was actually measured. With assumptions, the potential dose of persons living in a home with the maximum concentration of meth found at the St. Peter site can be estimated. Assuming an averaged breathing rate of 15 L/min, higher than a typical resting rate for most people, and a 24 hour exposure to a meth concentration of 7.09 x 10-4 µg/L, the potential dose for meth would be about 15 µg/day. While neither the short-term nor long-term health effects of this inhaled dose are known, the estimated dose is more than three orders of magnitude lower than the therapeutic dose of methamphetamine once used for ADD (Medical Economics, 2003). Even several months after the last cook took place in this house, detectable levels of methamphetamine were present in the air. This house would be an excellent candidate for additional air sampling with light, moderate, and then heavy activity as detailed in the work plan. MPCA personnel tried to arrange further access to the St. Peter location for the research team, but were unable to make arrangements for sampling to take place during the contract period. CONCLUSIONS Airborne methamphetamine in both the vapor and particle phases can be sampled effectively. The method proposed in this report is to draw contaminated air at 1.5 L/min through a 37 mm clear styrene cassette containing a glass fiber filter followed by an acid-treated silica gel sorbent tube. Samples are then extracted using methanol and analyzed by liquid chromatography with a mass spectrometer detector to quantify methamphetamine. The base form of methamphetamine is a semi-volatile material capable of existing in the vapor and particle phases simultaneously. Laboratory tests with meth base demonstrated that this form is sampled by the filter to a small extent, but that the sorbent tube collects the bulk of meth base at higher concentrations. Moreover, results suggest that meth base captured by the filter can re-volatilize and transfer to the sorbent tube. Measurements with both aluminum and clear styrene filter cassettes indicated that meth base does not absorb to the clear styrene. As a result, the less expensive styrene cassettes are suitable for sampling. Methamphetamine HCl is a non-volatile substance that is associated with particles when released into air. Laboratory tests with meth HCl showed that this form of methamphetamine is sampled exclusively on the filter. The State of Minnesota publishes cleanup guidance for buildings formerly housing meth labs. That guidance provides a procedure for performing wipe sampling for surfaces potentially contaminated by methamphetamine. This procedure can be applied to sampling the interior surfaces of ventilation duct potentially contaminated with methamphetamine. The need to apply a 6" x 6" template to the interior surface of the duct may be the biggest drawback to the use of this methodology.

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The proposed methods were demonstrated in former clandestine meth labs. Measurements at a former lab that has been cleaned and renovated extensively in the three years since new owners occupied the space indicated that the site had no measurable airborne concentrations of methamphetamine in either the vapor or particle phases. However, the duct in the home had measurable levels of meth when evaluated by wipe sampling. Air sampling in a more recently seized former lab revealed measurable concentrations of methamphetamine. However, a potential dose from these levels of meth would be at least 1,000X smaller than the therapeutic dose of methamphetamine used at one time to treat Attention Deficit Disorder.

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REFERENCES ACGIH (2003). Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices. Cincinnati: American Conference of Governmental Industiral Hygienists, 206 pp. Adams J (2005). As meth takes hold across Twin Cities, crime follows. Star Tribune. p. 1A, Nov 22, 2005. Cook EC, Jeffcoat AR, Hill JM, Pugh DE, Patetta PK, Sadler BM, et al. (1993). Pharmacokinetics of Methamphetamine Self-Administered to Human Subjects by Smoking s-(+)-methamphetamine Hydrochloride. Drug Metabolism and Disposition, 24(4):717-723. Gorden, B et al. (2005). H.R. 798 The Methamphetamine Remediation Research Act of 2005. Introduced Feb. 15, 2005 to the U.S. House of Representatives. Hannan, D (2005). Meth labs – understanding exposure hazards and associated problems. Professional Safety, 50(6):24-31. Levy P (2005). New law is a bitter pill for makers of meth. Star Tribune. p. 1A, Nov 6, 2005. Martyny JW, Arbuckle SL, McCammon Jr. CS, Esswein EJ, Erb N (2004a). Chemical Exposures Associated with Clandestine Methamphetamine Laboratories. Denver: National Jewish Medical and Research Center. URL: http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny, JW Arbuckle, SL McCammon Jr. CS, Erb N (2004b). Chemical Exposures Associated with Clandestine Methamphetamine Laboratories using the anhydrous ammonia method of production. Denver: National Jewish Medical and Research Center. URL: http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny, JW Arbuckle SL, McCammon Jr. CS, Erb N (2004c). Methamphetamine contamination on environmental surfaces caused by simulated smoking of methamphetamine. Denver: National Jewish Medical and Research Center. URL: http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny JW, Erb N, Arbuckle SL, VanDyke MV (2005a). A 24-hour study to investigate chemical exposures associated with clandestine methamphetamine laboratories. Denver: National Jewish Medical and Research Center. URL: http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny JW, VanDyke MV, McCammon Jr. CS, Erb N, Arbuckle SL (2005b). Chemical Exposures Associated with Clandestine Methamphetamine Laboratories using the hypophosphorous and phosphorous flake method of production. Denver: National Jewish Medical and Research Center. URL: http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx

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MDH/MPCA (2006). Clandestine drug lab general cleanup guidance. Minnesota Department of Health and Minnesota Pollution Control Agency, St. Paul, MN, 60 pp. URL: http://www.health.state.mn.us/divs/eh/meth/lab/guidance0606.pdf Medical Economics, eds. (2003). Physicians Desk Reference, 57th ed. Montvale, NJ: Thomson Healthcare, pp. 441-442. NIDA (2002). Methamphetamine Abuse and Addiction (Research Report Series NIH Publication Number 02-4210). Bethesda: National Institute on Drug Abuse. NIDA (2005). NIDA Info Facts: Methamphetamine. National Institute on Drug Abuse, U.S. Department of Health and Human Services. Phelps D (2005). Meth's shared toll is growing. Star Tribune, p. 1A, Dec 27, 2005. Scott MS and Dedel K (2002). Clandestine drug labs. Problem-Oriented Guides for Police Series, No. 16, U.S. Department of Justice, Washington, DC, 54 pp. Xiong C (2005). State is no. 1 in prison growth. Star Tribune, p. 1A, Apr 25, 2005.

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APPENDIX

Draft manuscript for possible submission to academic journal: this manuscript was written by Tricia Carmody to fulfill her Plan B requirements for her MS degree in Environmental Health (Industrial Hygiene) at the University of Minnesota under the direction of Dr. Peter C. Raynor

24

Determination of an Air Sampling Protocol for Methamphetamine to be

used in Former Clandestine Laboratories

Tricia Carmody

University of Minnesota, Division of Environmental Health Sciences

Minneapolis, MN

Draft Plan B: 08/16/06

25

Abstract When illegal methamphetamine labs are discovered, the police remove hazardous chemicals, but

contamination from methamphetamine remains. The contamination may lead to airborne

methamphetamine exposures for law enforcement personnel, clean up and remediation workers,

and others.

Both methamphetamine base and methamphetamine HCl are concerns at former lab structures.

A sampling train was chosen based on the semi-volatile nature of methamphetamine base and the

aerosol nature of methamphetamine HCl. A 37-mm cassette holding a glass-fiber filter followed

by an acid-treated silica gel sorbent tube were connected to a personal sampling pump operating

at 1.5 L/min using Teflon lined tubing. This setup was tested to determine collection efficiency.

For methamphetamine base, a set mass was placed into a closed system and allowed to volatilize.

For methamphetamine HCl, an aerosol was generated using a nebulizer. Methamphetamine was

extracted from the samples with methanol and analyzed via liquid chromatography and mass

spectroscopy.

When 100 µg of meth base was placed in the system, recovery from the filter and sorbent was

measured between 93% and 101%. When 10 µg was placed in the system, only 51-76% was

recovered due to losses to glassware surfaces. In the meth HCl system, recovery was 94-101 %.

Whether the methamphetamine resided on the filter or the sorbent tube depended on the amount

added to the system and the duration of sampling. The tests demonstrated that the sampling

method is suitable for field work to measure airborne methamphetamine concentrations in former

clandestine laboratories.

26

Acknowledgments The author would like to thank Martin Bevan and Paul Swedenborg at the Minnesota Department of Health Public Health Lab for the use of the analytical equipment and hood space needed to perform these experiments, and Kate Gaynor and Stephen Lee at the Minnesota Pollution Control Agency for providing funding for this project.

27

Table of Contents Abstract ......................................................................................................................................... 25 Acknowledgments......................................................................................................................... 26 Table of Contents.......................................................................................................................... 27 Background................................................................................................................................... 28 Materials and Methods.................................................................................................................. 35

Methamphetamine Base............................................................................................................ 35 Methamphetamine HCl............................................................................................................. 37 Extraction Procedure................................................................................................................. 40

Results........................................................................................................................................... 41 Methamphetamine Base............................................................................................................ 41 Methamphetamine HCl............................................................................................................. 41

Discussion..................................................................................................................................... 42 Methamphetamine Base............................................................................................................ 42 Methamphetamine HCl............................................................................................................. 43

Suggested Further Work ............................................................................................................... 44 Conclusions................................................................................................................................... 45 Tables............................................................................................................................................ 48

Table 1: Samples taken with methamphetamine base system ............................................. 48 Table 2: Samples taken with methamphetamine HCl system.............................................. 48 Table 3. Methamphetamine base results.............................................................................. 48 Table 4. Methamphetamine HCl results .............................................................................. 48

Figures........................................................................................................................................... 49 Figure 1. Methamphetamine base system diagram.............................................................. 49 Figure 2. Photo of methamphetamine base system.............................................................. 49 Figure 3. Methamphetamine HCl system diagram .............................................................. 50 Figure 4. Photo of Methamphetamine HCl system.............................................................. 50

Appendix I. Methamphetamine Base Data .................................................................................. 51 1000 mL Chamber, Aluminum Cassette, glass vials, Trials 1-3 .......................................... 51 1000 mL Chamber, Aluminum Cassette, Watch Glass, Trials 4-8....................................... 52 250 mL Chamber, Disposable Cassette, 30 minutes, Trials 12-15....................................... 54 250 mL Chamber, Disposable Cassettes, Dilutions (.1 , 1, 10 µg) , Trials 16-21 ................ 55 250 mL Chamber, Disposable Cassette, Dilutions (1, 3, 10 µg), Trials 22-29..................... 56

Appendix II. Methamphetamine HCl Trials ................................................................................ 57 Meth HCl Trials in Meth Base system: 10 µg, 1 hr sampling ............................................. 57 Nebulizer System: 350 µg meth HCl, 40 L, Trials H – J...................................................... 59 Nebulizer System: 175 µg meth HCl, 40 L, Trials K – M.................................................... 60

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Background Use and abuse of methamphetamine, an addictive stimulant, has been on the rise in the United

States, especially since the 1980s. The drug can be manufactured in the home relatively easily

from commonly available products (NIDA, 2002). The National Household Survey on Drug

Abuse (2000) found that about 4 percent of the U.S. population, more than 8 million people, has

tried methamphetamine at some point in their lives. The number of illegal labs manufacturing

the drug has been on the rise. In 1993, approximately 200 labs were seized by authorities,

compared to over 10,000 in 2003 and about 15,000 in 2004 (Gorden et al., 2005).

Methamphetamine has been used in the medical field in small doses for the treatment of

narcolepsy, attention deficit disorder (ADD), and obesity (NIDA, 2002). The effective dose per

pill is 5 mg methamphetamine. For treating ADD, the dose is 20-25 mg/day. For obesity, the

dose is one tablet prior to each meal (Desoxyn, 2003). Illegally, methamphetamine can be

smoked, snorted, orally ingested, or injected. Smoking or injecting causes a different form of

high than snorting or oral ingestion. The high from smoking or injecting is an intense rush about

3-5 minutes after taking the drug, whereas oral ingestion or snorting creates a high with no rush

15 to 20 minutes after taking the drug. Because of this, more than one form of taking the drug

may be employed at one time, and users are likely to binge (NIDA, 2002).

Methamphetamine abuse has a great impact on both the user and society. Methamphetamine is

believed to damage the dopamine-producing cells in the brain, and can cause hypothermia,

paranoia hallucinations, stroke, and weight loss (NIDA, 2002). The capillary veins of a user can

atrophy, causing severe itching. Users feel as though they have bugs crawling in and on their

skin, and create sores on their arms, legs, and face from picking and scratching at these ‘bugs’

29

(NIDA, 2002). Abuse of methamphetamine takes its toll on public services, with approximately

13,500 drug-related episodes occurring in hospital emergency departments in 21 metropolitan

areas in 2000. Additionally, drug abuse treatment administrations in 2001 reported that

methamphetamine was one of the leading drugs of abuse (NIDA, 2002). Increased risk of

HIV/AIDS and hepatitis B and C transmission is likely to be associated with methamphetamine

abuse, especially in those areas of the country where injection is the primary method of abuse

(NIDA, 2002). Children are often found present at meth labs, and these children must be put into

foster care, burdening state systems. Children are often suffering from chemical/drug exposures

and require treatment.

Once a methamphetamine lab has been seized by authorities, gross contamination including

chemicals and cooking apparatus is removed and the structure is usually allowed to ventilate

(Hannon, 2005). Occupational exposures can occur to both emergency response personnel and

cleanup contractors as they remove the ‘ingredients’ needed to make meth and the waste

products created during cooking. Cooking meth requires extracting psuedoephedrine from

tablets by separating the active ingredient from the coating. There are various methods of

‘cooking’ the meth base. In Minnesota, the ‘Nazi’ method is most often seen at busts (Hannon,

2005). This method uses sodium or potassium metal, anhydrous ammonia, and lye to create

meth base. Another popular method is the ‘Red Phosphorus’ method using red phosphorus from

matchbooks and iodine to create the meth base. Other methods discovered include using

hypophosphorous acid or solid phosphorous flakes instead of red phosphorus (Martyny, 2005b).

An older method known as P-2-P used lead acetate and mercuric chloride to create the meth base

(Hannon, 2005). Once meth base has been created, the drug must be ‘salted out’ using rock or

30

table salt and sulfuric or other acid. This produces hydrogen chloride gas and this is bubbled

through the meth base to precipitate the drug. The ingredients can be flammable, corrosive,

dangerous when wet, or poisonous gasses. The precursors and their byproducts are occupational

hazards when cleaning a former meth lab. Inhalation of vapors can cause respiratory damage,

and contact with corrosives can cause skin burns, sometimes quite severe. Additionally, meth

users and cookers are known to booby trap their cook sites, creating additional hazards (Hannon,

2005).

No peer reviewed research has been published on measurement of airborne methamphetamine

concentrations during or after production. Recent non-peer reviewed studies (Martyny et al.,

2004a; 2004b; 2005b) have been completed to determine what chemicals are present and persist

during and after a cook. The first study (Martyny et al., 2004a) was conducted to determine the

primary chemical exposures of concern. The study took air samples for hydrocarbons,

phosphine, inorganic acids, iodine, metals and methamphetamine during a red phosphorus

method cook. Hydrocarbons were collected using summa canisters as well as carbo-trap tubes.

Levels were not found to be exceptionally high. Phosphine and inorganic acid samples were

collected on silica gel tubes, iodine samples on standard charcoal tubes, metals on cellulose ester

membrane filters, and methamphetamine on 37 mm sulfuric acid treated glass fiber filters.

Phosphine ranged from 0.17 mg/m3 to 4.84 mg/m3. The American Conference of Governmental

Industrial Hygienists (ACGIH) Threshold Limit Value (TLV) on an 8-hr time weighted average

for phosphine is 0.42 mg/m3 and the Short Term Exposure Limit (STEL) is 1.4 mg/m3 (ACGIH,

2006). Most inorganic acid levels were found to be non-detects. Only hydrogen chloride was

found in high levels, and only during cooking. Hydrogen chloride was sampled during the whole

31

cook, but was highest during the salting out phase, reaching levels of 56.2 mg/m3, much higher

than the OSHA Ceiling Limit of 3 mg/m3. The highest concentrations found were 4 times the

STEL. Iodine levels at red phosphorus cooks were collected using charcoal tubes, and ranged

from 0.07 to 37 mg/m3. The ACGIH Ceiling TLV for iodine is 1.0 mg/m3. Methamphetamine

was analyzed in samples taken during the cooking and filtering/salting out phases of the cook

and reported in µg/m3. Methamphetamine was sampled for the last 200 minutes of the cook and

detected at concentrations of 4200-5500 µg/m3 during the salting out phase, but not during the

cook itself.

Martyny et al. (2004b) sampled air for methamphetamine during an anhydrous ammonia method

cook again in the area of the cook, collecting samples on a 37 mm glass fiber filters (with 37mm

glass fiber filter backup pads). They desorbed the filters using sulfuric acid and analyzed the

solution using a gas chromatograph with a mass spectrometer detector (GC/MS). Samples were

collected in the cooking area, in a distant room, and as a personal sample on the cook during both

the pre-salting phase and the salting phase. Anhydrous ammonia was sampled using real time

samplers and found in levels from <66ppm to 410ppm depending on location of the sampler.

The ACGIH STEL for anhydrous ammonia is 35ppm. The National Institute of Occupational

Safety and Health (NIOSH) has a level of 300ppm as Immediately Dangerous to Life and Health

(IDLH). Cooking using the anhydrous ammonia method can create levels higher than this.

Hydrogen chloride was again sampled for, but levels were below current standards.

Methamphetamine was found in low but measurable quantities (2.4 to 42 µg/m3 ) during the pre-

salting out phase, and in higher levels (12 to 680 µg/m3 ) during the salting out phase.

32

Detectable concentrations were found in all three locations sampled, cook area, distant room

area, and personal sampling on the cook.

Martyny et al. (2005b) again took airborne methamphetamine samples, during a

hypophosphorous/phosphorous flake method cook, in the cook area and in adjacent rooms.

Samples were collected on 37 mm acid-treated glass fiber filters at a flow rate of 2 L/min. This

study is similar to those published earlier (Martyny et al., 2004a; 2004b); they vary the method

of methamphetamine production. Time of sampling was listed in this study for the two cooks.

During cook one, sampling lasted 204-210 minutes for the pre-salting out filter and 55 minutes

for the salting out phase filter. Although some meth was detected in the pre-salting out phase,

concentrations were <0.11 to 0.19 µg/m3, compared to concentrations of 680 to 4000 µg/m3

during the salting out phase. Cook #2 sampled for 121-125 minutes for the pre-salting out phase.

During cook #2 the investigators ran a 66-minute cook site sample for the salting out phase; no

remote room sample were taken for this cook. Again, methamphetamine concentrations during

the pre-salting out phase were 3-4 orders of magnitude lower than in the salting out phase.

Martyny et al.(2005a) sampled the air for methamphetamine during a cook as well as 24 hours

after a cook had been completed. This study also investigated the ability of methamphetamine to

be re-suspended in air due to no-, medium- and high-level activities performed in the structure

such as vacuuming, moving furniture, and walking. Another goal of the study was to determine

an aerosol size distribution of the methamphetamine. Total airborne methamphetamine was

collected on acid treated 37 mm glass fiber filters at a flow rate of 2 L/min. Respirable

methamphetamine samples were collected onto a 37 mm acid-treated glass fiber filter using a

33

SKC aluminum cyclone at a flow rate of 2.5 L/min. Aerosol size selective methamphetamine

samples were collected on three stages (>2.5 µm, 2.5-1 µm, and <1 µm) of a Sioutas Personal

Cascade Impactor with 25 mm acid treated glass fiber filters at a flow rate of 9 L/min. The study

was conducted over two days. Two cooks were conducted on the first day, each approximately 4

hours long. Total methamphetamine samples had concentrations near the cook at 520 µg/m3

during cook 1 and 760 µg/m3 during cook 2. In the remote sampling area, cook 1 had

concentrations of 990 µg/m3 and cook 2 had concentrations of 510 µg/m3. The level of respirable

airborne methamphetamine concentrations were very similar to the total airborne

methamphetamine results. Most particulate matter was found to be less than 1 µm in size. On

the second day, air samples were taken at ‘no activity’, 13 hrs after the second cook, then

medium level activity including walking and opening cabinet doors at 16 hours, and during high

activity levels including vacuuming and fluffing pillows at 18 hrs. Again total airborne

methamphetamine samples and respirable fraction samples had concentrations that were very

similar. The concentration during no activity was 70 µg/m3, during medium activity was 170

µg/m3, and during heavy activity was 210 µg/m3. The majority of the concentration from the

selective size samples during day two were consistent with day one; most of the

methamphetamine particles were smaller than 1 µm.

Another study simulated smoking of methamphetamine in four ‘smokes’ with 91% pure

methamphetamine (Martyny et al., 2004c) in a hotel room. Normal ‘street’ meth is typically

50% pure. The first two tests were performed with 100 mg of methamphetamine in a pipe. The

third was done with 250 mg of the meth in a pipe. The fourth was conducted with 2000 mg of

meth on a hot plate. Air samples were taken using 37 mm acid-treated glass fiber filters at a flow

34

rate of 2 L/min, similar to their other studies. Area air samples were taken at the smoke area, at a

table across the room, at the bathroom sink, and at the heater. The first two smokes collected

airborne meth at amounts between 300 and 520 µg/m3. The third smoke created airborne meth

levels of 1,600 µg/m3. The fourth smoke had airborne levels of 1,200 µg/m3. The typical ‘hit’

when using illegal meth in this manner is 100 mg. Cook et al. (1993) found that, when smoked

at temperatures higher than 300 degrees F, 50% of the methamphetamine will be volatilized from

the pipe into the air. Additionally, this study found that of the 50% aerosolized, the

pharmacokinetic bioavailability was 90%.

These studies determined the chemicals of concern during an illegal methamphetamine cook, and

the residual contamination left at a meth lab. Methamphetamine was sampled for both by wiping

surfaces and by airborne sampling. All of the previous studies, however, concentrated on

determining the airborne methamphetamine concentrations with 37 mm acid-treated glass fiber

filters. No studies have examined the possibility of methamphetamine being in the vapor phase,

or sampled for methamphetamine vapor. The objectives of this study were to determine

sampling methods for both meth HCl and meth base. Additionally, this study sought to

determine if meth HCl or base are present in the vapor form and will collect on a silica gel

sorbent tube placed in line with a 37 mm glass fiber filter. The study also aimed to determine if

there are losses during sampling due to adsorption onto internal surfaces of disposable 37 mm

plastic cassette holders as current field practice uses these cassettes to sample for

methamphetamine.

35

Materials and Methods Two test procedures were developed, one for determining efficiency of collection of meth base,

and one for meth HCl. Both procedures sampled the two forms of meth using the same sampling

train: a 37-mm cassette holding a glass-fiber filter (SKC 225-709) followed by a silica gel

sorbent tube (SKC 226-42) were connected to an Air Check 2000 personal sampling pump

operating at 1.5 L/min (SKC, Eighty Four, PA). All tubing connecting the sampling train was

Teflon lined to prevent adsorption of methamphetamine into the plastic. This study started with

relatively high amounts of meth HCl and meth base and then proceeded through dilutions to

determine the effectiveness of the sampling method. All trials were completed within a hood

where temperature remained between 19.5 and 21 degrees C during all experiments and pressure

ranged between 735 and 748 mmHg.

Methamphetamine Base A closed system (Figure 1) was created based on the semi-volatile nature of methamphetamine

base. Air entering the system was drawn into the system though a HEPA filter (Pall Gelman,

East Hills, NY) to remove any particulate matter and 38.10 cm of 1.27 cm diameter Teflon lined

tubing. Methamphetamine base was assumed to be in the vapor form and that additional

particulate matter added to the system may cause the vapor to adhere to these particles as it

passed through the system, misrepresenting the actual nature of the meth base. Initial trials had

the meth in methanol placed inside a small glass vial at the bottom of a 1000 mL gas scrubbing

bottle attached to the sampling train through 10.16 cm of 1.27 cm diameter Teflon lined tubing.

The large size of the scrubbing bottle and the shape of the vial prevented the methamphetamine

from volatilizing within the time of the experiment, and recovery from this system was less than

36

20 percent on the filter and sorbent tube. Changing to a 2.54 cm diameter watch glass aided in

the volatilization of the meth base, and a 250 mL gas scrubbing bottle attached to the sampling

train with 0.95 cm diameter Teflon lined tubing helped increase the turnover of air in the system,

leading to higher rates of evaporation. The silica gel tube was attached to the sampling pump

with a 60.96 cm length of 0.64 cm PVC tubing. Teflon lined tubing was not used here because

no meth should be present downstream of the samplers. A series of three time trials were then

completed to determine how long the experiment needed to run to get maximum recovery of the

meth base. The personal sampling pump operating for thirty minutes had equivalent recovery to

trials run for longer times, so a thirty minute trial time was set.

A set mass of analytical grade meth base in methanol (Cambridge Isotopes Andover, MA) was

placed on a watch glass at the bottom of the gas scrubbing bottle (Kimble-Kontes, Vineland,

New Jersey ) and allowed to volatilize. Before each day’s experiment(s), the gas scrubbing

bottle was swabbed with a cue tip wetted with methanol and rinsed with 15 mL of methanol.

The rinsate was analyzed with the day’s samples to determine if there was any residual meth in

the sampling chamber. The methamphetamine was first collected on a glass fiber filter held by

an aluminum cassette in line with a silica gel sorbent tube. The cassette and tube were connected

by a small piece of 0.61 cm Teflon tubing that was attached to the back of the cassette. The

silica gel tube was then slid inside the Teflon tubing to be just flush with the opening of the

cassette. The silica gel tube fit snugly within the Teflon tubing and there were few losses to the

system from this route, as determined by the total recovery of the system. Because the aluminum

cassette was open-faced, a method was needed to connect the cassette to the tubing. Therefore,

an aluminum cyclone was attached to the front of the cassette and air was blown in the bottom of

37

the cyclone (so that it would follow a straight path) and through the cassette. The normal

entrance slit on the side of the cyclone was covered with Teflon lined tubing in a snug fit to

prevent leakage into the system.

A list of trials using the methamphetamine base system is shown in Table 1. The first sets of

trials including finalizing the glassware, watch glass, and time of experiment were conducted

with an aluminum cassette holder (shown in Figure 2). Once recovery from this system was

determined, the aluminum cassette and cyclone were replaced by a disposable 37-mm closed-

face cassette to determine recovery from the new system. A comparison of the aluminum

cassette efficiencies to those of the plastic cassette was conducted to determine if meth base

adsorbed to the plastic of the disposable cassette. Trials began using 100 µg of meth in methanol

(100 µL), and once the method could be validated at that quantity, dilutions of 10 µg, 3 µg, 1 µg

and 0.1 µg (all in 100 µL of solution) were run for the same length of time. Samples were

extracted and analyzed in the method described below.

Methamphetamine HCl Once the sampling procedure had been validated for methamphetamine base, an experiment was

devised to validate for methamphetamine HCl. First, a set of trials was run in the meth base

system (described above) with analytical grade methamphetamine HCl (Cambridge Isotopes

Andover, MA) to determine if the methamphetamine HCl would volatilize without the aid of a

nebulizer. Ten µg of meth HCl in methanol (100 µL total) were placed on the watch glass and

allowed to volatilize while the system was running for 30 minutes. When analysis of these data

38

showed that all meth HCl remained on the watch glass, the meth HCl system described below

was built to validate sampling methods for airborne meth HCl.

A closed system was devised based on the aerosol nature of methamphetamine HCl (Figures 3

and 4). A nebulizer (BGI, Inc., Waltham, MA) was used to aerosolize a 5 mL mixture of

methanol and methamphetamine HCl. Laboratory-grade nitrogen was inputted into the nebulizer

to prevent additional particles from entering the system. A solenoid valve and timer were used to

control the rate at which the nebulizer released aerosol into the system. It was determined that

operating the nebulizer for 2 seconds on and 6 seconds off provided approximately 40 L of air to

be sampled by the personal sampling pump. The length of time sampled was determined based

on the time it took for the methanol to volatilize without aid of the nebulizer. The ratio between

the time the solenoid was open and closed was determined to optimize aerosolization of the

methamphetamine. Leaving the nebulizer on for more than 2 seconds at a time caused the meth

in methanol to be aerosolized too quickly. Leaving more than 6 seconds between bursts caused

much of the methanol to volatilize without aid of the nebulizer, leaving the meth HCl in the

nebulizer jar. While the solenoid was open and the nebulizer was running, the flow from the

nebulizer was greater than that of the sampling pump. This led to the need to create a coupling

system with a secondary flow and make up air.

A four-way brass coupling system of 1.27 cm interior diameter was created and connected to the

outflow of the nebulizer to create three additional connections to the system. The first was the

sampling train attached with three inches of 0.64 cm diameter Teflon lined tubing. The personal

sampling pump pulled air through the system at 1.5 L/min through the sampling train. Because

39

the efficiency of the plastic cassette was determined to be equivalent to that of the aluminum in

the meth base trials, a disposable plastic 37 mm cassette was followed in line by a silica gel tube

attached in the same manner as the meth base system. In addition to the sampling train (above),

a vacuum was attached to the coupling and operated at 9 L/min to prevent methamphetamine

from being released into the hood through the open coupling while nebulizer was running. A

disposable 37mm cassette with glass fiber filter was used to collect methamphetamine and

prevent it from entering the hood’s vacuum system. A field rotometer with a pincer valve were

used to set flow rate through the vacuum. One side was left open to the hood environment to

provide makeup air with 22.86 cm of 1.27 cm. diameter tubing attached so that air did not flow

the wrong way when the nebulizer was not operating. Sampling was completed at about 40 L of

air sampled, when all liquid in the nebulizer had volatilized.

Table 2 describes the samples taken with the methamphetamine HCl system. Before each day’s

trials, 5 mL of methanol were added to the nebulizer and run as a blank to determine if there was

any residual methamphetamine in the nebulizer system after cleaning. Trials began using 700 µg

of meth HCl in 4300 µL methanol for a total of 5 mL. This amount was chosen based on the

flow rates of the personal sampling pump and the vacuum pump. If all the meth were to

volatilize with a 6:1 ratio between the flow rates, 100 µg of meth would flow towards the

sampling train, the same amount started with for the meth base experiments, and 600 µg would

flow towards the vacuum. Once the method could be validated at that quantity, dilutions of 350

µg in 5 mL solution and 175 µg in 5 mL solution run for the same length of time. Samples were

extracted and analyzed in the method listed below.

40

Extraction Procedure Methamphetamine was extracted from the sample media with methanol and analyzed via liquid

chromatography and mass spectroscopy on an Agilent 1100 LC-MSD. For methamphetamine

base, the watch glass was scrubbed with a cue tip wetted with methanol and then rinsed with 15

mL of methanol. The 15 mL methanol with the cue tip in had 2 µg internal standard added to it

and was analyzed. For the methamphetamine HCl, the inside of the nebulizer bottle was

scrubbed with a cue tip wetted with methanol and rinsed with 15 mL of methanol. 2 µg internal

standard (ISTD) was added and the cue tip and 15 mL of methanol were then analyzed. For both

methods, the filter was removed from the cartridge and 15 mL of methanol along with 2 µg

internal standard. The silica gel sorbent tube was cracked and all silica gel and glass fibers were

placed in a jar with 15 mL of methanol and 2 µg of internal standard to be analyzed. It was

determined that for the purposes of validating the methods, the breakthrough section of the silica

gel tube could be analyzed with the front section, rather than doing to separate extractions and

analyses.

The Agilent 1100 LC-MSD system includes a Binary Pump, Vacuum Degasser, Autosampler,

Thermostatted Column Compartment and a Diode-array Detector with a single quadrupole mass

spectrometer manufactured by Agilent (Wilmington, DE). The column has a Restek Allure

Basix - 3 µm, 50 x 3.2 mm; with a Restek Trident Direct in-line Allure Basix guard column

running at ambient temperature for 4.5 minutes per sample. The mobile phase used was 90% -

10 mM ammonium formate (NH4O2CH), 10% - Acetonitrile. The Mass Spectrometer used

selected ion monitoring (SIM) for mass at 150 and 159. Ionization mode was ESI positive. The

quantitation was based on the ISTD added to each sample. QC and unknown sample

concentration were calculated by comparing to internal standard and plotting against standard

41

curve using the following equation:

Smpl Conc. (µg/smpl) = ISTD Conc. * [(Smpl Area /ISTD Area) - Intercept] /Slope

Results

Methamphetamine Base Table 3 shows the spike amount for each set of trials for meth base in relation to the percent

recovery and the standard deviation for the filter, sorbent tube, the watch glass, and the total. The

percent error and absolute mass not recovered are also shown. When 100 µg of meth base was

placed in the system, recovery from the filter and sorbent was 97.3 % with 0.98 µg

(approximately 1 percent) remaining on the watch glass. Standard deviation was about 2 µg for

each sampling medium, and percent error was 1.7 overall. The first dilution, 10 µg, had 7.29 µg

recovered, standard deviation of 1.55 µg on the filter and nothing on the sorbent tube. Meth

remaining on the watch glass was 1.66 µg (17 percent) with a standard deviation of 0.8 µg. All

dilutions below 10 showed recoveries on the glass fiber filter only. As the amount of

methamphetamine added to the system decreased, so did percent recovery. The percent error for

the total mass recovered was quite low for 100 µg, but increased through the dilutions. The

proportion of mass remaining on the watch glass in relation to the amount added also increased.

Methamphetamine HCl Table 4 shows the spike amount for each set of trails for the meth HCl in relation to the percent

recovered on the glass fiber filter and sorbent tube of the sampling train, the glass fiber filter of

the vacuum line, the bottle rinse, and the total recovery as well as the standard deviation. When

700 µg were added to the system, 35.2 µg were recovered on the sampling train filter and 241.2

42

µg were collected on the vacuum filter with standard deviations of 2.05 µg and 36.5 µg

respectively. No mass was collected in the sorbent tube for any spike amount. This is a 6.85:1

ratio. The ratio for 350 µg was 7.1:1 and for 175 µg the ratio was 7.26:1. Percent error for the

total system at each dilution level remained quite low, but increased with smaller dilutions.

Discussion

Methamphetamine Base The methamphetamine base was determined to be volatile as it moved from the sampling

chamber to the sampling train with no mechanical aide (such as the nebulizer used in the meth

HCl system). Recovery was near 100 % for larger quantities, but less, due to losses to glassware

surfaces, when smaller quantities were added to the system. As the amount of meth added to the

system decreased, the percentage of meth remaining on the watch glass increased. The absolute

mass not recovered as a percentage of the total mass also increased as the amount of meth added

to the system decreased. Only 2 % of the mass added to the system at 100 µg was not recovered,

compared to 36% when 1 µg was added. This methamphetamine was probably lost to glass wear

surfaces. When a blank sample was run before the dilutions for 30 minutes, sampling train set

up with a dry watch glass added between 0.05 and 0.13 µg of meth were found in the system as

residuals. As 0.13 µg is 13% of the mass added in the 1 µg dilution, this could explain where

some of the unrecovered methamphetamine.

The difference between thirty minutes and longer sampling times was where methamphetamine

was collected within the sampling train; the longer the system ran, the higher percent of total

recovery of meth base was on the sorbent tube rather than on the filter. As the amount of meth

was decreased in the system, the meth was collected on the filter and not in the sorbent tube

43

where it was expected as a semi-volatile vapor. It could be that the meth base only moves to the

sorbent tube when the filter is saturated, or that for such small quantities of meth base, it would

take more than the 30 minutes provided to move from the glass fiber filter media to the silica gel

sorbent tube.

Methamphetamine HCl The first trials with methamphetamine HCl were done in the meth base system to test the

hypothesis that meth HCl is not volatile on its own, being a salt, even though it was dissolved in

methanol. 10 µg meth HCl in methanol (100 µL total solution) were placed on the watch glass

and the system was run for 30 minutes. This indicated that meth HCl is not volatile and will only

be present when airborne in a particle. Thus, the meth HCl had to be aerosolized for testing.

In the nebulizer system, all meth HCl was collected on the glass fiber filter. This was the

expected location of collection. Based on the flow rates of the sample flow and the vacuum, a

ratio of about 6 to 1 was expected for meth recovery. The ratio of the meth HCl collected

between the pump filter and the vacuum filter ranges from 6.3:1 to 7.6:1. Some of this difference

could have to do with the flow of the vacuum. It was controlled by a pincer valve and measured

by a field rotometer. The rotometer did show slight variations during sampling.

Based on the amount of meth collected in a bottle rinse compared to the samplers at the end of

each sampling run, about 40 percent of the meth HCl added to the system is being aerosolized.

This percentage may be able to be adjusted by changing the amount of liquid in the nebulizer or

by changing the on/off settings of the solenoid. When the bottle was rinsed and a blank run

44

between days of sampling, 2 to 20 µg meth remained in the nebulizer bottle even after cleaning.

This may have implications to further studies. If a study were to be completed on the efficiency

of cleaning contaminated surfaces, especially glassware, this information would show that some

cleaning solutions leave a methamphetamine residue behind. Further cleaning studies may wish

to evaluate the efficiency of differing solvents on reducing or eliminating the methamphetamine

residue from the system.

Even though 100% of the meth base and meth HCl were not recovered during all of the

sampling, this does not pose a problem for using this method in the field. Many of the losses

occurred in the sampling system, i.e. the sampling chamber for both the meth base and meth HCl

system, which would not be a problem in the field.

Suggested Further Work For the methamphetamine base, it was determined that most losses in the dilutions of the meth

base experiments happened from losses to glassware surfaces including the spiked watch glass.

Repeating the methamphetamine base experiments with acid-treated glass fiber filters may be

useful, especially to see if there is better collection efficiency at the lower dilution rates. A

future study would be to run one of the dilution levels, perhaps 3 µg, for varying amounts of time

to determine if recovery on the filter media (versus the watch glass) increases, and if absolute

mass not recovered decreases.

For meth HCl, only 40 percent of the methamphetamine was aerosolized on the initial run of the

sampling train. Additional methanol could be added to the nebulizer in future trials to determine

if this aids in more meth being aerosolized.

45

After one day of trials, the glass nebulizer bottle was cleaned twice with bleach, washed by the

glass washer, and then the bottle rinse was analyzed for remaining methamphetamine. There

was methamphetamine still present in the bottle. Further research could be conducted to

determine which cleaning methods or materials reduce the amount of methamphetamine

remaining in the bottle.

Conclusions A system for methamphetamine base and one for methamphetamine HCl was created to validate

an air sampling protocol for methamphetamine in former clandestine labs. The meth base

system was designed as a passive system as meth base is semivolatile. Meth HCl was tested in

the meth base system to determine if a passive system could be used. Meth HCl was determined

to need an active generation system using a nebulizer to create an aerosol in order to validate the

sampling method. Tests showed that no losses occurred to the plastic 37-mm cassette as

compared to the aluminum cassette. Whether the methamphetamine base resided on the filter or

the sorbent tube depended on the amount added to the system and the duration of sampling.

Longer sampling times showed more meth base on the sorbent tube, whereas shorter sampling

had the ratio at about 50/50. It is believed that if the system was allowed to run longer, the meth

base would move through the glass fiber filter and remain in the silica gel sorbent tube. All meth

HCl was collected on the filter media with no breakthrough to the silica gel tube. In the field,

this could help to determine whether one is sampling simple meth HCl or both meth base and

HCl. The tests demonstrated that the sampling method is suitable for field work to measure

airborne methamphetamine concentrations in former clandestine laboratories.

46

References ACGIH. (2006). TLVs and BEIs. American Conference of Governmental Industrial Hygienists, publication no. 0106. Cincinnati, OH. Cook, Edgar C., Jeffcoat, A. Robert, Hill, Judith M., Pugh, Dorothy E., Patetta, Patricia K., Sadler, Brian M., et al. (1993). Pharmacokinetics of Methamphetamine Self-Administered to Human Subjects by Smoking s-(+)-methamphetamine Hydrochloride. Drug Metabolism and Disposition, 24(4), 717-723. Desoxyn. Physicians Desk Reference (57th ed.) (pp. 441-442). Montvale: Thomson Healthcare. Hannan, Dan. (2005). Meth labs – understanding exposure hazards and associated problems. Professional Safety, 50(6), 24-31. Gorden, B., et al. (2005). H.R. 798 The Methamphetamine Remediation Research Act of 2005. Introduced Feb. 15, 2005 to the U.S. House of Representatives. Martyny, John W., Arbuckle, Shawn L., McCammon, Charles S. Jr., Esswein, Eric J., Erb, Nicola. (2004a). Chemical Exposures Associated with Clandestine Methamphetamine Laboratories. Denver: National Jewish Medical and Research Center. http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny, John W., Arbuckle, Shawn L., McCammon, Charles S. Jr., Erb, Nicola. (2004b). Chemical Exposures Associated with Clandestine Methamphetamine Laboratories using the anhydrous ammonia method of production. Denver: National Jewish Medical and Research Center. http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny, John W., Arbuckle, Shawn L., McCammon, Charles S. Jr., Erb, Nicola. (2004c). Methamphetamine contamination on environmental surfaces caused by simulated smoking of methamphetamine. Denver: National Jewish Medical and Research Center. http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny, John W., Erb, Nicola, Arbuckle, Shawn L., VanDyke, Michael V. (2005a). A 24-hour study to investigate chemical exposures associated with clandestine methamphetamine laboratories. Denver: National Jewish Medical and Research Center. http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx Martyny, John W., VanDyke, Michael V., McCammon, Charles S. Jr., Erb, Nicola, Arbuckle, Shawn L. (2005b). Chemical Exposures Associated with Clandestine Methamphetamine Laboratories using the hypophosphorous and phosphorous flake method of production. Denver: National Jewish Medical and Research Center. http://www.nationaljewish.org/news/health-news/y2005/meth_research_results.aspx National Institute on Drug Abuse (NIDA). (2002). Methamphetamine Abuse and Addiction (Research Report Series NIH Publication Number 02-4210). Bethesda: National Institute on Drug Abuse.

47

Substance Abuse and Mental Health Services Administration (SAMHSA). (2000). Summary of findings from the 2000 National Household Survey on Drug Abuse. www.samhsa.gov

48

Tables Table 1: Samples taken with methamphetamine base system

Material TestedInitial Mass (µg) Mass Holder Filter Holder

Chamber Size (mL)

Number of Replicates

Meth Base 100 Glass Vial Aluminum 1000 3Meth Base 100 Watch Glass Aluminum 1000 5Meth Base 100 Watch Glass Aluminum 250 3Meth Base 100 Watch Glass Plastic 250 3Meth Base 10 Watch Glass Plastic 250 4Meth Base 3 Watch Glass Plastic 250 2Meth Base 1 Watch Glass Plastic 250 4Meth Base 0.1 Watch Glass Plastic 250 2Meth HCl 10 Watch Glass Plastic 250 2

Table 2: Samples taken with methamphetamine HCl system

Material Tested Initial Mass Filter Holder SystemNumber of Replicates

Meth HCl 700 Plastic Nebulizer 7Meth HCl 350 Plastic Nebulizer 3Meth HCl 175 Plastic Nebulizer 3

Table 3. Methamphetamine base results

Spike Amount, µg

37-mm glass fiber filter

silica gel sorbent tube watch glass total

Absolute Mass Not Accounted For % error

100 47.99 (2.7) 49.30 (2.06) 0.98 (0.11) 98.27 (3.77) -1.73 -1.7310 7.29 (1.55) 0.00 (0.00) 1.66 (0.8) 8.94 (1.42) -1.06 -10.63 1.39 (0.44) 0.00 (0.00) 0.94 (0.37) 2.33 (0.07) -0.67 -22.331 0.19 (0.13) 0.00 (0.00) 0.45 (0.11) 0.64 (0.09) -0.36 -36

Table 4. Methamphetamine HCl results

Spike Amount, µg

37-mm glass fiber filter, pump

silica gel sorbent tube, pump

37-mm glass fiber filter, vacuum Bottle Rinse total % error

700 35.23 (2.05) 0.00 (0.00) 241.24 (36.48) 470.3 (134.47) 712.8 (163.47) 1.83350 19.22 (1.79) 0.00 (0.00) 136.16 (31.27) 189.12 (6.46) 342.50 (26.59) -2.14175 10.33 (0.51) 0.00 (0.00) 74.97 (12.48) 100.84 (16.79) 186.14 (4.82) 6.37

Meth HCl Average Mass and (Standard Deviation) per Sampling Media, µg

49

Figures Figure 1. Methamphetamine base system diagram

Figure 2. Photo of methamphetamine base system

Sampling pump

HEPA filter

Teflon-lined tubing

Glass chamber

Watch glass or vial

37-mm glass fiber filter Silica gel

sorbent tube

Air In

50

Figure 3. Methamphetamine HCl system diagram

Figure 4. Photo of Methamphetamine HCl system

Sampling pump at 1.5 L/min

Timer repeats 2 sec on and 6 sec off

Solenoid

To vacuum line w/ needle valve at 9 L/min

To Nitrogen gas

Open to air; Air In

Teflon-lined Tubing

37-mm glass fiber filter

Silica gel sorbent tube

Nebulizer system

51

Appendix I. Methamphetamine Base Data 1000 mL Chamber, Aluminum Cassette, glass vials, Trials 1-3

Trial Sample Description

Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

1 First Trial, Glass Fiber Filter 0.10 0.1%1 First Trial, Acid Treated Silica Gel Tube 0.00 0.0%1 First Trial, Glass holding bottle 100.08 100.1%

System Total 100.0 100.17 100.2%

2 Second Trial, Glass Fiber Filter 0.13 0.1%2 Second Trial, Acid Treated Silica Gel Tube 0.00 0.0%2 Second Trial, Glass holding bottle 9.25 9.2%2 Second Trial, Glass holding bottle duplicate 9.23 9.2%2 Bottle Rinse; MeOH extraction w/ scrub 3.34 3.3%2 Stopper Rinse; MeOH extraction w/ scrub 0.53 0.5%2 Cyuclone Rinse; MeOH extraction w/ scrub 0.05 0.1%

System Total 100.0 13.29 13.3%

3 Third Trial, Glass Fiber Filter 2.02 2.0%3 Third Trial, Silica Gel Tube 0.00 0.0%3 Third Trial, Glass holding bottle 17.23 17.2%3 Third Trial, Glass holding bottle - Duplicate 17.23 17.2%

System Total 100.0 19.25 19.2%

3 Third Trial, Glass holding bottle outside system 100.0 0.99 1.0%System Total 100.0 0.99 1.0%

100.0

100.0

100.0

52

1000 mL Chamber, Aluminum Cassette, Watch Glass, Trials 4-8

Trial Sample Description

Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

4 Fourth Trial, Glass Fiber Filter 20.17 20.2%4 Fourth Trial, Silica Gel Tube 59.25 59.2%4 Fourth Trial, watch glass 1.20 1.2%4 Fourth Trial, watch glass - Duplicate 1.20 1.2%

System Total 100.0 80.62 80.6%

4 Fourth Trial, watch glass outside system 100.0 0.57 0.6%System Total 100.0 0.57 0.6%

5 Fifth Trial, Glass Fiber Filter 17.71 17.7%5 Fifth Trial, Silica Gel Tube 70.91 70.9%5 Fifth Trial, watch glass 0.89 0.9%

System Total 100.0 89.51 89.5%

5 Fifth Trial, watch glass outside system 100.0 0.48 0.5%System Total 100.0 0.48 0.5%

6 sixth trial, GFF 11.98 12.0%6 sixth trial, silica gel tube 16.40 16.4%6 sixth trial, silica gel duplicate 17.53 17.5%6 sixth trial, watchglass in system 1.34 1.3%

System Total 100.0 28.95 29.0%

6 sixth trial watchglass outside of system 100.0 9.65 9.7%System Total 100.0 9.65 9.7%

7 seventh trial, GFF 19.15 19.1%7 seventh trial, silica gel tube 4.51 4.5%7 seventh trial, selica gel duplicate 4.99 5.0%7 seventh trial, watchglass in system 0.94 0.9%

System Total 100.0 24.84 24.8%

7 seventh trial, watchglass outside of system 100.0 11.77 11.8%System Total 100.0 11.77 11.8%

8 watch glass, overnight blank check 0.10 N/A8 glass fiber filter, overnight blank check 3.41 N/A8 silica gel sorbent tube, overnight blank check 1.04 N/A

System Total 0.0 4.54 N/A

Blank

100.0

100.0

100.0

100.0

53

250 mL Chamber, Aluminum Cassette, time trials, Trials 9-11

Trial Sample Description

Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

9 Glass fiber filter, new glassware, 40 min 28.15 28.2%9 Sorbent Tube, new glassware, 40 min 65.24 65.2%9 Sorbent Tube, new glassware, 40 min - Dup 69.24 69.2%9 Watch glass in system, new glassware, 40 min 2.16 2.2%

System Total 100.0 97.55 97.5%

10 Glass fiber filter, new glassware, ~ 10 min 30.22 30.2%10 Sorbent Tube, new glassware, ~10 min 73.87 73.9%10 Watch glass in system, new glassware, ~10 min 1.66 1.7%

System Total 100.0 105.76 105.8%

11 GFF-60 minutes-trial eleven 20.03 20.0%11 silica gel tube-60 minutes-trial eleven 55.13 55.1%11 watchglass in system-trial eleven 3.31 3.3%

System Total 100.0 78.48 78.5%

11 15mL methanol rinse of cyclone-trial eleven 0.0 4.56 NASystem Total 0.0 4.56 NA

100.0

100.0

100.0

54

250 mL Chamber, Disposable Cassette, 30 minutes, Trials 12-15

Trial Sample Description

Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

12 GFF-30 min, disposible cartriage-trial twelve 45.70 45.7%12 silica gel tube-30 minutes-trial twelve 50.09 50.1%12 silica gel tube-30 minutes duplicate-trial twelve 49.64 49.6%12 watchglass in system-trial twelve 1.02 1.0%

System Total 100.0 96.58 96.6%

13 GFF-30 min, disposible cartriage-trial thirteen 45.72 45.7%13 silica gel tube-30 minutes-trial thirteen 47.07 47.1%13 watchglass in system-trial thirteen 1.05 1.1%

System Total 100.0 93.84 93.8%

14 GFF-30 min, disposible cartriage-trial fourteen 51.00 51.0%14 GFF duplicate - 30 min, disposible cartriage-trial fourteen 48.39 48.4%14 silica gel tube-30 minutes-trial fourteen 46.23 46.2%14 watchglass in system-trial fourteen 1.04 1.0%

System Total 100.0 96.97 97.0%

15 GFF-30 min delay analysis - trial fifteen 49.53 49.5%15 silica gel tube-30 min delay analysis - trial fifteen 51.88 51.9%15 watchglass in system-30 min delay analysis - trial fifteen 0.81 0.8%

System Total 100.0 102.22 102.2%

100.0

100.0

100.0

100.0

55

250 mL Chamber, Disposable Cassettes, Dilutions (.1 , 1, 10 µg) , Trials 16-21

Trial Sample Description

Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

16 GFF-30 min, dilutions, disposible cartriage-trial sixteen 0.26 258.7%16 silica gel tube, dilutions-30 minutes-trial sixteen 0.00 0.0%16 silica gel tube dilutions, -30 minutes duplicate-trial sixteen 0.00 0.0%16 watchglass in system, dilutions-trial sixteen 0.14 144.5%

System Total 0.1 0.40 403.1%

17 GFF-30 min, dilutions, disposible cartriage-trial seventeen 0.24 24.2%17 silica gel tube, dilutions-30 minutes-trial seventeen 0.00 0.0%17 watchglass in system, dilutions-trial seventeen 0.55 55.1%

System Total 1.0 0.79 79.2%

18 GFF-30 min, dilutions, disposible cartriage-trial eightteen 5.07 507.3%18 GFF dup, dilutions-30 min, disp. cartriage-trial eightteen 5.05 505.3%18 silica gel tube, dilutions-30 minutes-trial eightteen 0.00 0.0%18 watchglass in system, dilutions-trial eightteen 2.44 24.4%

System Total 10.0 7.51 75.1%

19 GFF-30 min, dilutions, disposible cartriage-trial nineteen 0.00 0.0%19 silica gel tube, dilutions-30 minutes-trial nineteen 0.00 0.0%19 silica gel tube dilutions, -30 minutes duplicate-trial nineteen 0.00 0.0%19 watchglass in system, dilutions-trial nineteen 0.12 12.0%

System Total 0.1 0.12 120.0%

20 GFF-30 min, dilutions, disposible cartriage-trial twenty 0.33 33.5%20 silica gel tube, dilutions-30 minutes-trial twenty 0.00 0.0%20 watchglass in system, dilutions-trial twenty 0.32 32.1%

System Total 1.0 0.66 65.6%

21 GFF-30 min, dilutions, disposible cartriage-trial twentyone 7.57 75.7%21 GFF dup., dilutions-30 min, disp. cartriage-trial twentyone 7.53 75.3%21 silica gel tube, dilutions-30 minutes-trial twentyone 0.00 0.0%21 watchglass in system, dilutions-trial twentyone 0.57 5.7%

System Total 10.0 8.12 81.2%

1.0

0.1

10.0

1.0

0.1

10.0

56

250 mL Chamber, Disposable Cassette, Dilutions (1, 3, 10 µg), Trials 22-29

Trial Sample DescriptionMeth Spiked

Amt (µg)Meth

(µg/smpl)Meth % Rcvry

22 GFF-30 min, dilutions, disposible cartriage-trial twentytwo 0.03 N/A22 silica gel tube, dilutions-30 minutes-trial twentytwo 0.00 N/A22 silica gel tube dilutions, -30 minutes duplicate-trial twentytwo 0.02 N/A

System Total 0.0 0.05 N/A

23 GFF-30 min, dilutions, disposible cartriage-trial twentythree 0.02 0.0223 duplicate GFF-30 min, dilutions, disposible cartriage-trial twentythree 0.02 0.0223 silica gel tube, dilutions-30 minutes-trial twentythree 0.00 0.0023 watchglass in system, dilutions-trial twentythree 0.55 0.55

System Total 1.0 0.57 0.57

24 GFF-30 min, dilutions, disposible cartriage-trial twentyfour 1.70 0.1724 silica gel tube, dilutions-30 minutes-trial twentyfour 0.00 0.0024 Watchglass dilutions, -30 minutes-trial twentyfour 0.68 0.07

System Total 3.0 2.38 0.79

25 GFF-30 min, dilutions, disposible cartriage-trial twentyfive 7.88 0.7925 silica gel tube, dilutions-30 minutes-trial twentyfive 0.00 0.0025 Watchglass dilutions, -30 minutes-trial twentyfive 1.62 0.16

System Total 10.0 9.50 0.95

26 GFF-30 min, dilutions, disposible cartriage-trial twentysix 0.11 N/A26 silica gel tube, dilutions-30 minutes-trial twentysix 0.00 N/A26 silica gel tube dilutions, -30 minutes duplicate-trial twentysix 0.02 N/A

System Total 0.0 0.13 N/A

27 GFF-30 min, dilutions, disposible cartriage-trial twentyseven 0.22 0.2227 duplicate GFF-30 min, dilutions, disposible cartriage-trial twentyseven 0.21 0.2127 silica gel tube, dilutions-30 minutes-trial twentyseven 0.00 0.0027 watchglass in system, dilutions-trial twentyseven 0.48 0.48

System Total 1.0 0.70 0.70

28 GFF-30 min, dilutions, disposible cartriage-trial twentyeight 1.08 0.1128 silica gel tube, dilutions-30 minutes-trial twentyeight 0.00 0.0028 Watchglass, dilutions, -30 minutes -trial twentyeight 1.20 0.12

System Total 3.0 2.28 0.76

29 GFF-30 min, dilutions, disposible cartriage-trial twentynine 8.65 0.8629 silica gel tube, dilutions-30 minutes-trial twentynine 0.02 0.0029 Watchglass, dilutions, -30 minutes -trial twentynine 2.02 0.20

System Total 10.0 10.69 1.07

10.0

3.0

0.0

1.0

3.0

10.0

0.0

1.0

57

Appendix II. Methamphetamine HCl Trials

Meth HCl Trials in Meth Base system: 10 µg, 1 hr sampling

Trial Sample Description Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

30 GFF-30 min blank, disposible cartriage-trial thirty 0.10 N/A30 silica gel tube,blank-30 minutes-trial thirty 0.00 N/A30 watchglass blank, -30 minutes-trial thirty 0.00 N/A

System Total 0.0 0.10 N/A

31 GFF-60-min Meth HCl, disposible cartriage-trial thirtyone 0.18 1.8%31 duplicate GFF-60 min, Meth HCl, disposible cartriage-trial thirtyone 0.17 1.7%31 silica gel tube, Meth HCl, 60 minutes-trial thirtyone 0.00 0.0%31 watchglass in system, Meth HCl-trial thirtyone 9.96 99.6%32 duplicate watchglass in system,Meth HCl-trial thirtyone 10.12 101.2%

System Total 10.0 10.13 101.3%

32 GFF-60-min Meth HCl, disposible cartriage-trial thirtytwo 0.19 1.9%32 silica gel tube, Meth HCl, 60 minutes-trial thirtytwo 0.00 0.0%32 Watchglass Meth HCL, -60 minutes-trial thirtytwo 10.49 104.9%

System Total 10.0 10.68 106.8%

0.0

10.0

10.0

58

Nebulizer System: 700 µg meth HCl, 40 L, Trials A-G

Trial Sample Description Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

A Pump GFF, disposible cartriage, Sample Run A 32.01 4.6%A Duplicate Pump GFF, disposible cartriage, Sample Run A 31.76 4.5%A Pump silica gel tube, Sample Run A 0.00 0.0%A Vacuum GFF, disposible cartriage, Sample Run A 206.72 29.5%A Nebulizer bottle rinse, 15 mL MeOH, Sample Run A 250.52 35.8%

System Total 700.0 489.12 69.9%

B Pump GFF, disposible cartriage, Sample Run B 35.23 5.0%B Pump silica gel tube, Sample Run B 0.00 0.0%B Vacuum GFF, disposible cartriage, Sample Run B 249.09 35.6%B Nebulizer bottle rinse, 15 mL MeOH, Sample Run B 389.34 55.6%

System Total 700.0 673.66 96.2%

C Pump GFF, disposible cartriage, Sample Run C 37.33 5.3%C Duplicate Pump GFF, disposible cartriage, Sample Run C 37.05 5.3%C Pump silica gel tube, Sample Run C 0.00 0.0%C Vacuum GFF, disposible cartriage, Sample Run C 244.74 35.0%C Nebulizer bottle rinse, 15 mL MeOH, Sample Run C 466.71 66.7%

System Total 700.0 748.64 106.9%

D Pump GFF, disposible cartriage, Sample Run D 37.52 5.4%D Pump silica gel tube, Sample Run D 0.00 0.0%D Vacuum GFF, disposible cartriage, Sample Run D 304.35 43.5%D Nebulizer bottle rinse, 15 mL MeOH, Sample Run D 620.22 88.6%

System Total 700.0 962.10 137.4%

E Pump GFF, disposible cartriage, Sample Run E - blank 0.81 N/AE Pump silica gel tube, Sample Run E-Blank 0.00 N/AE Vacuum GFF, disposible cartriage, Sample Run E - Blank 5.36 N/AE Nebulizer bottle rinse, 15 mL MeOH, Sample Run E - Blank 14.11 N/A

System Total 0.0 20.28 N/A

F Pump GFF, disposible cartriage, Sample Run F 34.54 4.9%F Duplicate Pump GFF, disposible cartriage, Sample Run F 34.28 4.9%F Pump silica gel tube, Sample Run F 0.02 0.0%F Vacuum GFF, disposible cartriage, Sample Run F 203.80 0.0%F Nebulizer bottle rinse, 15 mL MeOH, Sample Run F 571.38 81.6%

System Total 700.0 809.61 115.7%

G Pump GFF, disposible cartriage, Sample Run G 35.15 5.0%G Pump silica gel tube, Sample Run G 0.00 0.0%G Vacuum GFF, disposible cartriage, Sample Run G 238.75 34.1%G Nebulizer bottle rinse, 15 mL MeOH, Sample Run G 523.60 74.8%

System Total 700.0 797.50 113.9%

700.0

700.0

700.0

700.0

0.0

700.0

700.0

**Trial E a 30 minute blank to determine system contamination

59

Nebulizer System: 350 µg meth HCl, 40 L, Trials H – J

Trial Sample Description Meth Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

H bottle blank, 15 mL rinse, Sample Run H - blank 0.07 N/AH Pump GFF, disposible cartriage, Sample Run H - blank 0.08 N/AH Pump silica gel tube, Sample Run H-Blank 0.00 N/AH Vacuum GFF, disposible cartriage, Sample Run H - Blank 0.56 N/AH Nebulizer bottle rinse, 15 mL MeOH, Sample Run H - Blank 0.84 N/A

System Total 0.0 1.55 N/A

I Pump GFF, disposible cartriage, Sample Run I 18.07 5.2%I Duplicate Pump GFF, disposible cartriage, Sample Run I 17.84 5.1%I Pump silica gel tube, Sample Run I 0.00 0.0%I Vacuum GFF, disposible cartriage, Sample Run I 114.05 32.6%I Nebulizer bottle rinse, 15 mL MeOH, Sample Run I 191.69 54.8%

System Total 350.0 323.70 92.5%

J Pump GFF, disposible cartriage, Sample Run J 20.48 5.9%J Pump silica gel tube, Sample Run J 0.00 0.0%J Vacuum GFF, disposible cartriage, Sample Run J 158.27 0.0%J Nebulizer bottle rinse, 15 mL MeOH, Sample Run J 182.55 45.2%

System Total 350.0 361.30 103.2%

0.0

350.0

350.0

60

Nebulizer System: 175 µg meth HCl, 40 L, Trials K – M

Trial Sample DescriptionMeth

Spiked Amt (µg)

Meth (µg/smpl)

Meth % Rcvry

K bottle blank, 15 mL rinse, Sample Run K - blank 0.00 N/AK Pump GFF, disposible cartriage, Sample Run K - blank 0.33 N/AK Pump silica gel tube, Sample Run K-Blank 0.00 N/AK Vacuum GFF, disposible cartriage, Sample Run K - Blank 2.11 N/AK Nebulizer bottle rinse, 15 mL MeOH, Sample Run K - Blank 14.11 N/A

System Total 0.0 16.55 N/A

L Pump GFF, disposible cartriage, Sample Run L 10.75 8.1%L Duplicate Pump GFF, disposible cartriage, Sample Run L 10.63 6.1%L Pump silica gel tube, Sample Run L 0.00 6.1%L Vacuum GFF, disposible cartriage, Sample Run L 66.14 0.0%L Nebulizer bottle rinse, 15 mL MeOH, Sample Run L 112.71 37.8%

System Total 175.0 189.54 108.3%

M Pump GFF, disposible cartriage, Sample Run M 9.97 5.7%M Pump silica gel tube, Sample Run M 0.00 0.0%M Vacuum GFF, disposible cartriage, Sample Run M 83.79 47.9%M Nebulizer bottle rinse, 15 mL MeOH, Sample Run M 88.97 47.9%

System Total 175.0 182.72 104.4%

0.0

175.0

175.0