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This report has not been published by the U.S. Department of Justice.
To provide better customer service, NCJRS has made this Federally-
funded grant final report available electronically in addition to
traditional paper copies.
Submitted to
National Institute of Justice
By
Washington State Patrol Crime Laboratory Division
Goal 1 was achieved with the development of a dynamic coating CE method using CElixirOATM
8.2 to separate inorganic anions including: acetate, azide, bromide, carbonate, chlorate, chloride,
fluoride, hypophosphate, iodide, nitrate, nitrite, perchlorate, phosphate, phosphite, sulfate,
sulfite, and thiocyanate. The developed method is capable of detecting these anions down to
between 10 and 30 ppm and with a percent relative standard deviation for normalized migration
times of less than 0.1%. This method was used to differentiate samples from various
methamphetamine manufacturing methods for the purpose of identifying the manufacturing
process that was utilized.
Goal 2 was accomplished in three primary ways. First, the phosphorus chemistry in the
hydriodic acid method of methamphetamine manufacture was elucidated using the CE anion
method (developed in Goal 1) and GC/MS analysis for organic species. Equations were
developed to allow the chemist to predict starting materials based on the analysis of post-reaction
materials. Using predicted, optimized reaction stoichiometry, methamphetamine was
manufactured in less than 15 minutes. Second, methamphetamine was manufactured in a “One-
Pot” environment using the in-situ generation of ammonia from fertilizer and lye combined with
an alkali metal and pseudoephedrine in a single reaction vessel. Third, pseudoephedrine was
demonstrated to be recoverable from multi-ingredient, liquid, and/or softgel over-the-counter
(OTC) medications using commonly available extraction methods. These same OTC
medications were shown to be converted to methamphetamine using the “One-Pot” method of
manufacture.
Goal 3 included the publication of six papers, production of eight training videos, and oral
presentations of results at twenty meetings with forensic scientists, clandestine laboratory
responders, law enforcement officials, community leaders, legislators and user agency personnel.
In addition, the CE methods have been successfully implemented in other crime laboratories
within the Washington State Patrol Crime Laboratory Division.
NIJ grant 2003-LT-BX-K004 Final Report
Submitted to
National Institute of Justice
By
Washington State Patrol Crime Laboratory Division
This summary details the ways in which these goals were accomplished.
Goal 1 – Capillary Electrophoresis Methods for Inorganic Ion Analysis of Samples from
Clandestinely Manufactured Methamphetamine
Flexible inorganic ion analysis techniques can be used to provide valuable data in the analysis of
samples from clandestine methamphetamine manufacturing sites. Variations within a specific
class of manufacturing methods can be difficult to differentiate without evaluating all of the
chemical species present. Two primary achievements in using capillary electrophoresis for this
purpose were accomplished.
1) Several capillary electrophoresis (CE) anion methods were evaluated for their suitability in
the analysis of clandestine laboratory samples 1-4. One specific goal was to find an
analytical approach for identifying the various phosphorus oxyacids (hypophosphorous
acid, phosphorous acid and phosphoric acid). The best results were obtained using
modifications made to a commercially available dynamic coating CE anion analysis kit,
CElixirOATM 8.2 (Microsolv Technology Corp, Longbranch, NJ). To achieve the desired
results, modifications were made to this kit including lowering the run temperature to 15°C
and utilizing an acid flush of the column between runs. These modifications succeeded in
creating a method that provides robust, reproducible results for the analysis a number of
forensically significant anions. The anions that were resolved using this method included:
acetate, azide, bromide, carbonate, chlorate, chloride, fluoride, hypophosphate, iodide,
nitrate, nitrite, perchlorate, phosphate, phosphite, sulfate, sulfite, and thiocyanate. The
developed method is capable of detecting these anions down to between 10 and 30 ppm
and with a percent relative standard deviation for normalized migration times of less than
0.1%. A separation of 100 ppm standards is shown in Exhibit 1. This concentration range
is useful for the analysis of samples from clandestine laboratories when they are diluted
appropriately. Lowering the temperature to 15°C improved resolution for some closely
migrating species (e.g. iodide and chloride). While the acid flush modification to the
method alleviated a problem with severe phosphate peak tailing that had been observed
initially. The peak tailing is believed to be from adsorption of phosphate in the system.
The acid flush between runs removes any adsorbed materials. The recommended analysis
parameters are shown in Exhibit 2. Anion analysis for iodide, hypophosphite, phosphite,
and phosphate can be used to assist in the determination of which phosphorus – iodine
methamphetamine manufacturing method was used. This method was successfully
NIJ grant 2003-LT-BX-K004 Final Report
The CE anion method developed during this project was also used to evaluate samples
from other methamphetamine manufacturing methods. The determination of sulfate and/or
nitrate can be useful in identifying what type of ammonium salt was used to generate
liquefied ammonia for the alkali metal – liquefied ammonia methamphetamine
manufacturing method.
In addition to the utility of this method for the analysis of samples from clandestine drug
manufacturing cases, the developed CE anion analysis method is being used in other areas
of forensic analysis within the WSP CLD including: explosives cases, poisoning cases and
other chemistry cases involving inorganic anions.
NIJ grant 2003-LT-BX-K004 Final Report
Instrument Conditions
Cassette Temperature 15°C
Capillary 50 μM Inside diameter fused silica capillary, 80.5 cm actual length,
72 cm Effective length‡
Stacking Injection 50 mbar, 2 Seconds, sample vial to run buffer (7)
10 mbar, 2 Seconds, water (9) to run buffer (7)
Run Buffers Inlet vial (6), Outlet vial (7)
Run Voltage 30 kV, Negative polarity
Run Time 11 Minutes (approximately 22 minutes including preconditioning)
Detection Monitor at 233 nm, 20 nm bandwidth, no reference§
* Vial positions are included for subsequent reference, though the required buffers could be placed
in any location so long as the method is adjusted accordingly.
† The instrument’s standard flush pressure is used and will displace the volume of the capillary
from the injection vial to the detector in approximately 90 seconds.
‡ This column dimension is commercially available or can be cut from a spool of capillary at a
reduced cost. Capillary lengths of 64.5 cm were also found to provide acceptable results.
§ Other wavelengths may be useful for the detection of absorbing species, so it is recommended
that the entire spectrum be saved.
2) Existing commercial CE methods for the analysis of inorganic cations were evaluated for
their suitability in the analysis of clandestine laboratory samples. Two commercial CE
NIJ grant 2003-LT-BX-K004 Final Report
cations methods (from Agilent Technologies 5 and Waters Corporation 6) provide good
separation for ammonium, potassium, sodium, calcium, magnesium and lithium.
However, cations of iron, barium, zinc, nickel, and strontium tend to migrate in a very
narrow range close to the migration range of lithium. The addition of an organic modifier
(methanol or acetonitrile) to the CE run buffer of either commercial kit examined
improved the resolution of these cations listed above. Some organic cations (such as
methamphetamine, pseudoephedrine and ephedrine) are also resolved using these standard
commercial methods; however, the addition of the organic modifier did not improve
resolution of any of the organic amines examined. An example of the types of data
obtained is shown in Exhibit 3. Additional research is still needed to optimize these
methods; however, valuable information about the cationic species in clandestine
methamphetamine manufacturing samples is readily obtained using the current state of
technology. Cation analysis was demonstrated to be useful in providing data to confirm
the type of alkali metal and presence of ammonia in the alkali metal – liquefied ammonia
method of methamphetamine manufacture.
A 0 Pseudoephedrine
-1 Methamphetamine
Ephedrine
mAU
-2
-3
-4
-5
NH4+ Na+ Ca2+ Mg2+ Li+
-6
K+
-7
2 3 4 5 6
-15
B -16
Zn+ Ni2+
NH4+ Methamphetamine
mAU
-17
Pseudoephedrine
K+ Ephedrine
-18
Na+
Ca2+
-19 Li+ Ba2+
Sr2+
-20
2.5 3.5 4.5 5.5 6.5 7.5
0
C -2.5 Zn+
Fe2+
mAU
-5
-7.5
Sr2+
NH4+ Na+ Methamphetamine Pseudoephedrine
K+ Ba2+Li+ Ni2+
Ca2+ Mg2+ Ephedrine
-15
-17.5
2 3 4 5 6 7
Time (minutes)
A – 100 millimolar standards, Capillary: 75 micron i.d., 64.5 centimeters long (56 centimeters to detection
window), Agilent cation buffer, no organic modifier, detection – diode array UV monitored at 200
nanometers, temperature – 25°C.
B – 100 millimolar standards, Capillary: 75 micron i.d., 64.5 centimeters long (56 centimeters to detection
window), Agilent cation buffer, 10% acetonitrile modifier, detection – diode array UV monitored at 200
nanometers, temperature – 20°C.
C – 100 millimolar standards (ammonium at 200 millimolar), Capillary: 75 micron i.d., 64.5 centimeters
long (56 centimeters to detection window), Waters IonSelectTM Low Mobility Cation Electrolyte, 10%
acetonitrile modifier, detection – diode array UV monitored at 240 nanometers with a 214 nanometer
reference, temperature – 25°C.
NIJ grant 2003-LT-BX-K004 Final Report
The data from each of the reactions was used to confirm mechanistic pathways and show
the interconnections between all four variations. Exhibit 5 shows the relationships
between the various phosphorus containing reducing agents and the final product
phosphate.
NIJ grant 2003-LT-BX-K004 Final Report
Red Phosphorus
POS 0
Phosphite
POS +3
Phosphate
POS +5
A graphical schematic of likely oxidation pathways for common phosphorus-containing reducing agents in the
presence of water and iodine. The oxidation state assigned to the phosphorus atom (POS) is shown below each
species, illustrating the reactions that include oxidation of the phosphorus atom.
The data also was used to develop a detailed set of equations to describe the processes.
Net reaction equations for the four reactions are shown in Exhibit 6.
These equations show the appropriate stoichiometric balance of reactants for the efficient
manufacture of methamphetamine. Methamphetamine was manufactured in under 15
minutes using conditions that the equations predict to be optimal8, thus demonstrating that
methamphetamine manufacture can be done rapidly using these processes if the reaction
conditions are appropriately controlled. These equations can be used to calculate
NIJ grant 2003-LT-BX-K004 Final Report
relationships between the quantities of reactants used and the quantities of products
produced9. This allows the chemist to evaluate sample data to assist in the determination
of which manufacturing process was used. CE data obtained from case samples was
evaluated using the relationships described above. Exhibit 7 lists some of the conclusions
that can be determined from this data.
CE Results Interpretation
no significant phosphorous • red phosphorus with glues remaining on the surface
anions observed preventing oxidation (may show slow reaction rates as a
result, data not shown)
• freshly washed or extracted red phosphorus that has not had
time to oxidize
Other Anionic Species
Chloride ions • counter ion from precursor materials
• muriatic acid added to the reaction or used in a prior process
(e.g. from the precipitation of iodine from tincture)
Sulfate ions • counter ion from precursor material
• sulfuric acid added to the reaction or used in a prior process
(e.g. from the precipitation of iodine from tincture)
Carbonate ions • absorbed carbon dioxide (typical for highly basic pH
reaction materials – usually from the addition of NaOH)
2) Successful experiments were conducted that demonstrated the viability of a new variation
on the alkali metal – liquefied ammonia method of methamphetamine manufacture10. This
variation is termed the “‘One-Pot’ method of manufacture” because all of the reaction
materials are combined in a single reaction vessel. The variation involves the in-situ
generation of ammonia from an ammonium salt and sodium hydroxide11. The generated
ammonia is captured in a suitable organic solvent to which an alkali metal (e.g. sodium or
lithium) has been added. Ephedrine placed in the reaction vessel is converted to
methamphetamine in a single reaction step. The experiments were conducted
demonstrating that various ammonium salts (e.g. ammonium sulfate, ammonium nitrate
etc.) can be used with the “One-Pot” method, and that ephedrine does not need to be
purified prior to use in the experiment. Additional experiments also showed that other
alkali metals could be used as well. CE cation analyses of materials from these reactions
show high concentrations of sodium (from the sodium hydroxide) in addition to
ammonium and lithium. CE anion analysis will typically show the ammonium salt counter
ion (e.g. nitrate, sulfate, phosphate etc.) and any counter ions for pseudoephedrine and any
other tablet ingredients (e.g. chloride, sulfate, bromide, etc.).
3) Pseudoephedrine is a highly popular precursor for the manufacture of methamphetamine
and often is obtained from commercial over-the-counter (OTC) cold and/or allergy
preparations. Legislative restrictions on OTC pseudoephedrine preparations are being
implemented and vary from state to state12. Some pharmaceutical industry representatives
have insisted that multi-ingredient, liquid and/or softgel preparations are not suitable for
use in methamphetamine manufacture13. As a result, many jurisdictions have chosen to
exempt these preparations from control14. Experiments were undertaken to determine the
viability of these exempt preparations in the manufacture of methamphetamine. Three sets
of experiments were conducted:
a. A series of extraction techniques were applied to five representative multi-
ingredient, liquid and softgel OTC pseudoephedrine preparations to determine if
pseudoephedrine could be extracted from the other pharmaceutical ingredients15.
Simple, readily available extraction methods were shown to be successful in the
isolation of pseudoephedrine from the five OTC products examined.
NIJ grant 2003-LT-BX-K004 Final Report
The final goal of the project was to disseminate the results of the research in a manner that would
provide practical and beneficial information to a number of different audiences. Three general
groups of people were initially targeted as the recipients of the research results. These were:
1. Forensic chemists directly involved in the analysis of samples and interpretation of data
obtained from clandestine laboratories;
2. Clandestine laboratory scene responders responsible for scene interpretation, safety, and
sample collection at clandestine laboratory scenes. These may include forensic chemists,
clandestine laboratory trained law enforcement officers and others;
3. User agency personnel including law enforcement officers, evidence officers, prosecutors,
defense attorneys, emergency response personnel, health department personnel, and other
individuals directly or indirectly involved in clandestine laboratory work. Although not
originally identified as belonging to this last group, it was found necessary to provide
information concerning this project to legislators and other regulatory personnel.
Dissemination of the grant project results to the groups listed above has been done through written
papers, training videos (produced in cooperation with the Snohomish Regional Drug Task Force
and Detective Shawn Sheridan), professional meeting presentations, formal and informal training
sessions, and legislative testimony17. Exhibits 8, 9 and 10 below list the products that have been
generated as a result of the work done on this grant. In addition, numerous requests have been
received for copies of the videos and the executive summary on the multi-ingredient tablet
extraction results.
Acknowledgements
The authors would like to thank the following people for their contributions to this project. Much
of the practical street level drug intelligence data (including recipes and manufacturing trends)
were provided by Detective Shawn Sheridan of the Snohomish Regional Drug Task Force. He
was also responsible for shooting, producing and editing the videos that were put together during
this project. Mr. Ira Lurie, DEA Special Testing, Sterling, VA provided valuable assistance with
the CE methods development work. Mr. Jeff Jagmin (WSP Crime Lab, Tacoma) and Mr. Martin
McDermot (WSP Crime Lab, Seattle) also assisted with the implementation of the new CE anion
method in other laboratories. A special thanks to Mr. Larry Pederson of the Greeley-Weld County
Forensic Laboratory, Greeley, CO, who graciously provided adjudicated case samples for
evaluation using the methods developed during this project. Ms. Drexie Malone (WSP Crime Lab
Librarian) provided extensive assistance with literature searches. The authors would also like to
acknowledge the support of the Washington State Patrol and the many individuals within the
organization that supported this project and made it a success.
NIJ grant 2003-LT-BX-K004 Final Report
Knops, Lori A.; Northrop, David M.; Person, Eric C., "Capillary Forensic Chemists
Electrophoretic Analysis of Phosphorus Species in Clandestine
Laboratory Samples," Journal of Forensic Sciences, 51(1), 2006.
Heegel, Robert A., Knops, Lori A., Northrop, David M., and Person, Forensic Chemists
Eric C., “Abbreviated Reaction Times In the Red Phosphorus – Iodine
Manufacturing Method”, Journal Of The Clandestine Laboratory
Investigating Chemists Association, Volume 14 Number 3 – July
2004, p. 11.
Person, Eric C.; Knops, Lori A.; Northrop, David M.; Sheridan, Forensic Chemists
Shawn P., “ ‘One-Pot’ Methamphetamine Manufacture,” Journal of
Clandestine Laboratory Investigating Chemists Association, Volume
14, Number 2, April, 2005, pp. 14-15.
Northrop, David M.; Knops, Lori A.; Person, Eric C., Forensic Chemists
"Methamphetamine Manufacture From Cold and Allergy Medications
Containing Pseudoephedrine in Multi-ingredient, Liquid, and Softgel
Preparations," Journal of the Clandestine Laboratory Investigating
Chemists Association, Volume 15, Number 2, April, 2005, pp. 11-19.
Heegel, Robert A.; and Northrop, David M., “‛One-Pot’ Forensic Chemists
Methamphetamine Manufacture via the Lithium-Ammonia Method
with Multi-Ingredient, Liquid, and/or Soft-gel Pseudoephedrine
Preparations,” Submitted to Journal of the Clandestine Laboratory
Investigating Chemists Association, November, 2005, In Press
Person, Eric C.; Knops, Lori A.; Northrop, David M.; and Heegel, Forensic Chemists
Robert A.; “Phosphorus-Containing Reducing Agents:
A review of their chemistry and use in the manufacture of
methamphetamine and the significance of observed phosphate,
phosphite, and hypophosphite in clandestine laboratory casework,” to
be submitted to the Journal of the Clandestine Laboratory
Investigating Chemists Association, January 2006.
Northrop, David M.; Knops, Lori A.; Person, Eric C., Non – law
"Methamphetamine Manufacture From Cold and Allergy Medications enforcement
Containing Pseudoephedrine in Multi-ingredient, Liquid, and Softgel Personnel
Preparations," – Executive Summary
NIJ grant 2003-LT-BX-K004 Final Report
References
15. Northrop, David M.; Knops, Lori A.; Person, Eric C., "Methamphetamine Manufacture
From Cold and Allergy Medications Containing Pseudoephedrine in Multi-ingredient,
Liquid, and Softgel Preparations," Journal of the Clandestine Laboratory Investigating
Chemists Association 15(2), (April, 2005): 11-19.
16. Heegel, Robert A.; and Northrop, David M., “‛One-Pot’ Methamphetamine Manufacture
via the Lithium-Ammonia Method with Multi-Ingredient, Liquid, and/or Soft-gel
Pseudoephedrine Preparations,” Journal of the Clandestine Laboratory Investigating
Chemists Association, (November 2005): In Press.
17. Rose, Joseph, “House Panel Unanimous in Advancing Cold Pill Bill” The Oregonian (June
24, 2005). Retrieved November 3, 2005 from
http://www.oregonlive.com/news/oregonian/index.ssf?/base/front_page/111960743230484
0.xml&coll=7&=2 .