Development of Medicinal Marijuana Testing in New Jersey

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Development of Medicinal Marijuana Testing in New Jersey Tina Fan, Ph.D. Program Manager, CT Lab New Jersey Department of Health, PHEL-ECLS APHL Annual Conference Indianapolis, IN May 18-21, 2015

NJ Medicinal Marijuana Program (MMP) The New Jersey Compassionate Use Medical Marijuana Act (Senate Bill, No. 119, the Act, N.J.S.A. 26:6I-1 et seq) was signed into law on January 18, 2010. The (NJDOH) Medicinal Marijuana Program was established to implement the law, develop and enforce the regulations. NJ PHEL-ECLS started the Marijuana Testing Project in June 2012.

Project Goals To comply with the Law Potency compliance of < 10 % Delta-9-Tetrahydrocannabinol (Δ- 9-THC) Free of pesticides, toxic heavy metals, and mycotoxins To establish reliable test methods Establish an accurate, sensitive, cost effective, rugged, defensible test method for medicinal marijuana with a shortest specimen turn around time.

Implementation Protocols for a Test Method Select target analytes Select analytical instrument HPLC-DAD, ICPMS, and HPLC-Fluorescence Detection Provide personnel training Develop the test method Validate the test method Selectivity, Precision Accuracy, Representation (sample size), Completeness, Comparability, Sensitivity Establish SOPs Establish reporting system Implement the test method

Analysis of Marijuana for Cannabinoids Using HPLC-DAD* Method Target Analytes Cannabidiol (CBD) Cannabidiolic acid (CBDA) Cannabigerollic acid (CBGA) Cannabigerol (CBG) Cannabinol (CBN) Delta-8-terahydrocannabinol (Δ-8-THC) Delta-9-Tetrahydrocannabinol (Δ-9-THC) Tetrahydocannabinolic acid (THCA) HEAT Note: THCA ------>Δ-9-THC *High Pressure Liquid Chromatography Diode Array Detector

Sample Processing and Analysis Method for Cannabinoids 0.2 gram MM Ground individual or a composite cultivar Extraction and centrifugation Filtration and preparation of appropriate dilutions Evaporation, reconstitution, addition of internal standard, mix and inject Analysis by High Pressure Liquid Chromatography Diode Array Detector Note: % of batch weight per cultivar: 1-5%; ~2.5 g/sample

Summary of Method Evaluation Results for Cannabinoids Analysis Calibration range : 0.25 50 µg/ml (v) (0.005 1% by sample wt) Coefficient of Determination (R 2 ): 0.995 Method Precision (%RSD) : 5-12 % Accuracy (%Recovery for % Δ-9-THC ): 105 ± 12.5% (spiked Medical Marijuana samples) Note: Allowable RSDs on sample duplicates : <30% Allowable Matrix Spikes Recoveries: 70% - 130% Detection Limit : 0.25 µg/ml (v) (50 µg/g by wt)

Elemental Analysis on Medicinal Marijuana Target Analytes Arsenic Cadmium Chromium Iron Lead Manganese Mercury Nickel Selenium Zinc

Sample Processing and Analysis of Metals in MM Using ICP-MS 0.1 gram MM Cultivar Composite Addition of Nitric Acid and Hydrogen Peroxide Hot Block Digestion Decant or Filter Digestate Supernatant QA/QC Internal Standards Laboratory Reagent Blank Calibration Verification at 3 levels Sample Duplicate Matrix Spike/Matrix Spike Duplicate Analysis by ICP-MS in Standard Mode

Summary of Elemental Method Evaluations Method Precision (%RSD) : 1.2% - 7.2% (< ±30%) Accuracy (%Recovery on Matrix Spikes): 85% - 114% (< ±30%) Linearity Concentration Range: 0.2-5 mg/g (± 25%) Detection Limits: 0.2 5.0 mg/g

Analysis of Pesticides in MM by GC-MS Chemical Class Example Pesticides Use Organophosphates Diazinon, Insecticide Phosmet Dichlorovos Insecticide Insecticide Pyrethroids Resmethrin Insecticide, Repellent Pyrethrin Insecticide, Repellent Allethrin Insecticide, Repellent Carbamates Terbucarb Insecticide Fenunucarb Insecticide Avermectins Abamectin (Avid ) Insecticide, Anthelmintic Thiabendazoles Thiabendazole Parasiticide Miscellaneous Atrazine Herbicide Bifenazate Acaricide Bromocil Herbicide Chlorpropham Growth Regulator Fenarimol Fungicide Pyrimethanil Fungicide Metribuzin Fungicide *Note: A total of 83 commonly used pesticides were tested but currently 56 are incorporated into method.

Sample Processing and Analysis of Pesticides in MM Using GC-MS 0.5 gram MM Cultivar Composite QuEChERS Extract and Centrifuge Extract Cleanup QA/QC Parameters Precision Accuracy Sensitivity Dilution and addition of Internal Standard Inject, PTV-GC-MS (SCAN) Analysis

Summary of Method Evaluation Results for Pesticides* Method Precision (%RSD): < 25% Accuracy (%Recovery): 80-115% Linearity (Concentration Range 50-2000 ppb): Coefficient of Determination (R 2 ) > 0.995 Method Detection Limit: 2.5 µg/g *Number of Pesticides (n = 56) *

Mycotoxin Analysis in MM by HPLC- Fluorescence Detection NJDA cooperates with NJ Department of Health to perform Mycotoxins analyses for medical marijuana plant materials The tests are aflatoxins (B1, B2, G1, and G2) and Ochratoxin A High Performance Liquid Chromatograph with fluorescence detection 1 4

Mycotoxins Determination Method for Medical Marijuana Weigh 0.25 g Add extraction solution Vortex for 3 minutes Centrifuge for 10 minutes Transfer supernant into sample reservoir Drive out at the end Vortex the elution Diluted with MQ H 2 0 Vortex the diluted elution Inject on HPLC - fluorescence detection for analysis 1 5

Summary of Method Evaluation Results for Mycotoxin Coefficient of Determination (R 2 ) 0.995 %Recovery (spiked on matrix): 82-95% Precision (RSD % ) 5% Detection Limit : 0.143 0.357 ng/g 3000 Conc. (ng/ml) 3500 Response 2500 2000 1500 1000 500 Aflatoxin G1 0 0 2 4 1 6

Summary Results of Cannabinoids Analysis (%wt) (October 2012 April 2015) Analyte N Median Min Max %Detected DL CBD 283 ND ND 2.130 27.9 0.012 CBDA 283 0.025 ND 17.59 79.5 0.012 CBG 283 0.050 ND 0.303 77.7 0.012 CBGA 283 0.299 ND 1.856 98.2 0.012 CBN 283 ND ND 0.125 24.4 0.012 Δ-8-THC 283 ND ND 0.282 12.7 0.012 Δ-9-THC 283 0.446 ND 3.789 99.6 0.012 THCA 283 14.7 0.396 34.2 100 0.012

Summary Results of Metals Analysis (µg/g) (October 2012 April 2015) Analytes N Median Min Max %Detected DL Arsenic 49 ND ND 1.00 0 1.0 Cadmium 49 ND ND 0.89 26.5 0.2 Chromium 49 2.0 ND 2.1 0 4.0 Iron 49 211 94.9 493 100 5.0 Lead 49 0.10 ND 0.29 14.3 0.2 Manganese 49 228 70.3 443 100 0.2 Mercury 49 ND ND 0.43 6.1 0.5 Nickel 49 ND ND 1.3 26.5 0.5 Selenium 49 ND ND 2.0 10.2 1.0 Zinc 49 113 52.6 239 100 5.0

Summary Results of Mycotoxins Analysis (ng/g) (October 2012 April 2015) Analyte N Median Min Max % Detected DL Aflatoxin 47 ND ND 2.3 2 1.0 Ochratoxin 47 ND ND 0.21 2 0.18

Major Challenges Administrative and Regulatory Perspective Staff Funding Time line Supply - DEA license, standards availability, sample collection, submission and receipt procedures No official reference values for pesticides, heavy metals or mycotoxins acceptance levels for the MM products in US.

Major Challenges-cont Technical Perspective Complex marijuana matrix Interference in pesticide and metal analyses Contamination of the analytical system Limited testing materials No SRM or PT samples Lack of partnership on MM analysis Difficulty in comparison among the results obtained from different analytical methods

Future Plan Development of a test method for pesticides analysis using Mass Quadrupole Time of Flight (TOF) Liquid Chromatography Mass Spectrometry (Q-TOF LC/MS). increase sensitivity; increase capacity & capability Develop a test method for the measurement of microbial contaminants in MM. Develop a test method for MM edible forms. Establishment of national standardized testing procedures for the analysis of MM. Establishment of national acceptable limits for target analytes Transition from a routine testing laboratory to a regulatory laboratory

Acknowledgements PHEL-NJDOH Christopher Rinn Onesia Bishop, Ph.D. Bahman Parsa, Ph.D. Sherman Hom, Ph.D. --CT Lab Floyd Genicola (retired) Bhupendra Patel, Ph.D. Daniel Wene --Inorganic lab Douglas R Haltmeier Shawn O Leary Eric Bind PHEL-NJDOH --Data Management Robert Servis Rafael Pietri-Pietri --QA Evan Cadoff (retired) Sharon Robinson Martha Smith Email: tina.fan@doh.state.nj.us Phone: (609) 530-2803 NJDOH MM Program Office John O Brien (retired) Jim Baracia Kevin Healey Dave Hodges Fredrick Loblein NJDA, Plant Industry Carl Schulze (retired) Yong Pu, Ph.D. Grace McMackin Marcello Mangano