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C): Gas Chromatography Mass Spectrometry (GCMS) Tests: 15/07/1999 - 15/09/1999

 

The following is an extract from the cross-examination of analyst Ballard:

Q: The conditions require a window of .2, now, without the curator standard the retention time for the 15 July experiment wouldn’t mean much for the retention time, would it?

A: The instrument I used on 5 July --

Q: 15 July.

A: On 15 July ‘99, the GCMS is - well, our laboratory and the one’s we worked on were never used with a window actually inserted.

 

1: Analyst Ballard performed a Gas Chromatography Mass Spectrometry test on 15/07/1999 on sample 991685, exhibit 157, and declared it a match for methcathinone when visually compared to the literature standard, exhibit 158. One problem in a visual match here was that the literature standard and the actual test were at different scales.

Analyst Ballard said;

“They are different scales but it is a matter of looking at one to the other and I mean it is simple to adjust to determine the difference in scale.”

The defense analyst said that a close inspection of ion abundances was at odds with analyst Ballard’s conclusions. The mass spectrum as shown in GCMS test results for sample 991685 did not comply with the manual and more importantly was inconsistent with the structure of methcathinone as exhibited in the microgram literature reference.

The AGAL manual states:

‘Individual compound identification: It should be done by comparison with reference spectrum, comparison may be done manually or using the table of relative ion abundances...’

Analyst Ballard’s GCMS test on sample 991685 was conducted prior to the availability of the curator’s standard and was compared visually to the microgram journal reference. The manual allows a 20% margin for the reference spectra - 10% if the curator’s standard is available. Both the trial judge and the jury were supplied with rulers in order to manually measure the differences between the sample and the reference spectra peaks. Even allowing a 30% margin, analyst Ballard’s tests were found to be 90% out on one ion alone other ions were out by considerably more, some well over 100%.

According to Dr Kibby under questioning by defense counsel:

Q: The relative abundance of the five most significant masses, what does that mean please?

A: The appearance of those ions is characteristic of a particular molecule. It relates to the energy of the bonds in the molecule in the way that molecule fragments when bombarded with high energy electrons. So it’s characteristic of a molecule. Different molecules give different ion intensities.

The following is a brief excerpt from the cross examination of analyst Ballard:

Q: Why calculate the relative ion intensities?

A: As I said, it is not often done. I can’t think of any occasion in the laboratory where myself or others I have worked with have actually done that. It is not procedure.

Defense analyst Kibby said that this should be a matter of grave concern for the citizens of NSW.

The defense analyst said that the data produced in this test made it impossible to identify sample 991685 as methcathinone and in fact indicates it is not methcathinone.

Analyst Ballard in his analysis included ions at 120, 147 and 148 which did not appear numbered on the X axis of his test results but did appear in the microgram reference for methcathinone and all three were at very low frequency. This analyst said that although not numbered in exhibit 157 those small peaks were visible at 120, 147 and 148 and on that basis all three ions were points of inclusion when compared with exhibit 157, the test result for sample 991685. However, he did not include the 115 ion, having a relative intensity of 1.8,one of many shown in exhibit 157 but not in the literature reference as a point of difference. His reasoning being that the computer doesn’t number all ions and although he couldn’t see the particular ion115 in his literature reference that didn’t mean it was not there.

Analyst Ballard disagreed that his analysis was subjective rather than objective and concluded that sample 991685, exhibit 157, was a match for methcathinone. The defense analyst testified that the 115 ion was inconsistent with the structure of methcathinone. Analyst Kibby said that from the data produced by analyst Ballard it was impossible to conclude that sample 991685 was methcathinone. In fact he went further in saying that the data indicates that the sample is not methcathinone.

It is important to note that this analyst used low resolution mass spectrometry which limits the data produced to being a whole number where as in high resolution mass spectrometry the instrument is more definitive in that it resolves the data to the decimal place. When looking at the Beynon Tables, described by Dr Kibby as a “text on organic compound identification by spectrometry”, and using as an example the 77 ion there are 13 possibilities for that ion. Low resolution spectrometry, as used by analyst Ballard, does not have the ability to identify which of the 13 possibilities is represented in the test result. Had high resolution spectrometry been used, the 77 ion would have been resolved to a decimal place and so identify with one of the 13 possibilities, e.g.

a) the first entry for the ion 77 in the table was HN2O3 and given that it has two nitrogens and three oxygens would not be consistent with methcathinone.

b) the last entry for the ion 77 in the table was C6H5 and given that it represents a benzene ring would be consistent with methcathinone.

The reasons for this analyst’s choice of low resolution mass spectrometry are unclear.

(Day 53, Pages 2860 - 2887)   (Day 77, Pages 4208- 4217)

 

2: On 15 September 1999, analyst Ballard ran a GCMS test on sample 991691 together with the mixed drug standard, the mixed drug standard did not contain methcathinone. This test became exhibit 159 and was compared with the literature reference 158. Again the relative ion intensities were outside the 20% criteria as stated in the manual. Further to that, there were several ions present in the literature standard not reflected in the sample 991691 and fragments at 115, 132 and 144 as shown in test results for 991691 were inconsistent with the methcathinone molecule and yet he maintained that they were a match.

The relative intensities of the ions, 42, 51, 56, 77 and 105 compared to the major ion 58 are different in exhibits 159 and 158, so different that Dr Kibby would reject them as being the same compound. Regarding his identification of caffeine, the defense analyst says these exhibits didn’t enable him to make a finding of caffeine. Analyst Ballard performed a visual exam only and Dr Kibby says even visually there is no match.






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