The variables of the Gas Chromatography process

I have posted before on Gas Chromatography and its principles. 

  1. Gas Chromatography and why is it is so important to Pennsylvania DUI arrests
  2. Crimping a Headspace Vial in Gas Chromatography: How not putting the "lid on the jar" can lead to disaster in a DUI case
  3. A large problem in Gas Chromatography: No uniform standard for GC run position or composition

As I have written before:

As headspace gas chromatography (as opposed to direct injection) is based upon Henry’s law. Henry’s Law states that at a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid. Or stated differently, an equivalent way of stating the law is that the solubility of a gas in a liquid at a particular temperature is proportional to the pressure of that gas above the liquid. Headspace gas chromatography requires a closed system (i.e. no pressure leaking from the gaseous phase). As a result if the crimping of the headspace vial (which is typically a manual process) is not complete, then it is not a closed system. Hence, without assurances that the crimping is properly done, there is a large possible source of error as Henry’s Law is violated. It is indeed the entire principle upon which Headspace Gas Chromatography is based.

Henry's Law depends upon several key variables In the entire apparatus reamin constant throughout the run to work.  These are:

  • Flow/pressure rate
  • Temperature of the headspace vial incubation oven
  • Temperature of the oven
  • Injection port temperature

If any of the variables change and there is a "cold spot" or a pressure dip, then Henry's Law is violated.  The ultimate alleged and reported result is not accurate.  It is an isothermal process when Headspace Gas Chromatography with Flame Ionization Detector is used in ETOH determination.  But guess what is not recorded and reported at all times during the run of the analytical device? 

  • Flow/pressure rate
  • Temperature of the headspace vial incubation oven
  • Temperature of the oven
  • Injection port temperature

Interesting, huh?  In the Courtroom, we must not guess; we must not accept assertions based upon faith. it's not Amen. But rather, data, facts and proof.

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

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Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

 

Defending DUI Drug Cases: Part 3 from PA DUI attorney Justin J. McShane

Pennsylvania DUI attorney Justin J. McShane, Esq. presents his lecture "Defending DUI Drug Cases" in Hartford, CT in December 2009. In Part 3: "Pharmacology," expert DUI Attorney McShane explains the differences, both in testing procedure and impairment determination, between DUI Alcohol and DUI Drug cases. The McShane Firm is the premiere DUI/DWI law firm in Harrisburg, PA. For more information, visit themcshanefirm.com.

 

 


-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

If he was an analytical chemist or a DUI defense attorney he would say "Show me the separation!!"

Who can forget Cuba Gooding Junior in the movie Jerry McGuire shouting "SHOW ME THE MONEY!"???

If he was an analytical chemist or a DUI defense attorney facing a purported result from a Headspace Gas Chromatograph with a Flame Ionization Detector, he would yell:

 

"SHOW ME THE SEPARATION!!!!!!" 

 

Well, that is one of the things that a good criminal defense attorney who specializes in defending the citizen among us who has been accused of a DUI should always demand whenever there is a reported result from a chromatographic process. 

Why?

As I posted before in Gas Chromatography and why is it is so important to Pennsylvania DUI arrests:

Chromatography is strictly and simply speaking "separation science". It is the study of how an analyst can take a complex matrix (compound) and separate it out into its component parts.

If you can't prove separation between like analytes, then your result means nothing.

Much like I posted before "A large problem in Gas Chromatography: No uniform standard for GC run position or composition".  There is also no uniform nomenclature for what this is called.

I have seen it called:

  • Harrisburg DUI Lawyer verifier and resolution chromatogramResolution Control Standard
  • Separation chromatogram
  • Matrix chromatogram
  • some don't call it anything at all (because they don't do it)

For ETOH determinations at a minimum we need to see this proof of separation for from standards that are NIST certified values or comprised of USP grade materials (see generally:  Metrology in DUI prosecution for the importance of these concepts):

  1. acetaldehyde
  2. acetone
  3. acetonitrile
  4. ethanol
  5. ethyl acetate
  6. isopropanol
  7. methanol
  8. methyl ethyl ketone
  9. butanol

 Below is an example of just such a type of proof:

Harrisburg DUI Lawyer verifier and resolution chromatogram2

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

Police Oppose Anti-lying Policy

Should a police officer have to be ordered to tell the truth?

Police lie about DUIMy office and I have litigated thousands of DUI and criminal cases all over Pennsylvania.  In this time I have met hundreds of Pennsylvania police officers.  In my opinion, most are very sincere in trying to perform their sworn duties with integrity.  However, some are not so honorable.  A few outright lie.  In many criminal matters, especially DUI, the police officer’s opinion and testimony is a main part of the case against the citizen accused.  When an officer is “fudging the details” or outright lying, this presents a huge problem for truth and justice which is the supposed currency of our courts.  It is very sad to say, but the actual confirmation of police officers not telling the truth is unfortunately much more common than you might think.  With dashcameras in patrol cars, the difference between truthful testimony and hyperbole to “win” a case can be discovered and exposed. 

To illustrate this, here is a recent story out of Boston.

Edward Davis defies cops’ union with his anti-lying edict

Bucking anticipated union opposition, Boston Police Commissioner Edward Davis decreed yesterday that any officer caught lying on the job, in court testimony or to the department’s Internal Affairs unit would be fired.

Think about this for a second.  Lying has become such big issue that the Police Commissioner had to issue a new policy banning lying and penalizing it with automatic termination.  What's even more disturbing is that the Police Union is opposing these sanctions as being too strict.  This is absolutely outrageous.  A police officer lying is a very serious transgression.  Take this scenario.  A person is accused of a DUI and is convicted due to tainted evidence and a lying police officer.  That person faces license suspension, fines and even jail time for a crime they didn't commit.  They lose their job, their integrity, and their self-esteem- and the police officer shrugs it off as a “white lie”.  That's not fair.

Lying police officers have no place in law enforcement.  If they lie they cannot be trusted to uphold the law.  I wholeheartedly support Commissioner Davis' one-strike-and-you're-out policy and wish Pennsylvania would enact a similar policy.  Police should be trustworthy and uphold the law by following the law and reporting the truth.

 

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification through NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

The Carry-over Effect: Lack of Blanks between tests leads to false positive or inflated BAC results

Harrisburg DUI Lawyer false BAC resultImagine. You go into your doctor’s office for a routine physical. As part of that routine physical, the doctor takes your blood. You come back two weeks later where the doctor delivers the single worst sentence you have ever heard in your life: “I’m sorry but you have cancer.” Then comes ever worse news from the doctor when the doctor says: “You have one possible chance at living. You have to undergo radical chemotherapy and a bone marrow transplant immediately.” You are shocked. You are young. You feel healthy. There is no family history of cancer.


After you recover as much as you can from the initial shock, you ask the doctor: “How do you know?” The doctor tells you that your blood sample that the doctor took two weeks ago was sent to the lab for routine testing using a test called a Complete Blood Count (CBC) examining your blood contents along with many other people from his practice. The doctor informs you that based upon the test run you have an abnormally high White Blood Cell Count (WBC) which is indicative of malignancy. You are floored. Still in disbelief, he shows you the result. As the doctor hands you the result, the doctor explains to you that at this lab, the lab runs a bunch of CBC tests right in a row using the same single testing instrument. That as a cost and time saving measure, the lab does not perform tests in-between each of his patient tests to make sure the device is clear thus making sure each test is only a report unique to that particular test and not due to the previous test.
 

While looking at the result, you note that your sample was labeled as sample 14 meaning that there were 13 others tested before yours. You ask the doctor about that. He pulls out his other reports and discovers that immediately before your test, there was a test done of his other patient who was unfortunately in Stage III or terminal end stage of cancer but who is still fighting with a superhigh WBC result. The doctor tells you about this other patient’s results and condition. The doctor gets a visible frown on his face. Despite all of this information, the doctor still tries to schedule the chemotherapy and the bone marrow transplant.
 

You have got to be thinking to yourself…no way. I would not undergo all of that based upon the way the tests were performed. That’s crazy.

Well, exactly that type of testing and evidence is what happens in Court every day and all day long in DUI and DUI Drug cases in the United States. It is reckless and shameful.
 

When you are accused of a crime that is almost entirely based on a numeric value, which is essentially what occurs in a prosecution based strictly on a reported Blood Alcohol Content result or a DUI Drugs case, we all want to be sure that the result is accurate, precise, repeatable, reliable, traceable, reproducible, robust and true being unique to that individual accused and that individual accused alone. However, as we discussed before "A large problem in Gas Chromatography: No uniform standard for GC run position or composition", namely there is no order or reason as to what goes into the autosampler carousel and in what order the samples go into the autosampler.
 

This lack of standardization, even within the same lab and even from run to run made by the same technician, and especially with the nearly absent use of blanks is one of the fundamental flaws of Gas Chromatography for ETOH or drugs of abuse testing in America. In my considered opinion and in the general scientific community (as opposed to the law enforcement community), it is the single largest and most basic systemic problem with the way that Gas Chromatography is practiced in forensic testing today.
 

With this post, I will explain how the lack of using a blank before and after each unknown sample run invites well-deserved scientific scrutiny and rightly calls into question the conclusory reported and alleged result in every single case.
 

But first some background:
 

What is a blank?
 

Simply and generally, in analytical chemistry a blank is a sample that is prepared using the same methods that an unknown would be prepared within the run simply without the unknown added.
 

Ok, let’s translate that. In our case of assaying an accused’s blood which contains an unknown amount of analyte of interest (e.g., drugs of abuse or ETOH) is typically prepared by diluting the sample by adding a known amount of internal standard which is typically n-propanol when the unknown looked for is ETOH. [Blogger’s note: in the future a detailed post will be used to examine the use and potential problems when internal standards are used]. When a blank is created, the same exact amount of n-propanol that is added to the accused’s blood is added to a sample jar (in our case a headspace vial) but with no blood added. In simpler terms, it is a virgin sample with only n-propanol added. As a result, as there is only n-propanol, there should only be one peak on the chromatogram which corresponds to n-propanol. The lack of any other peaks is where the name of “blank” comes from in the analytical world.
 

Harrisburg DUI Lawyer blank chromatogram carry over effect
(Pictured above:  a blank with only n-propanol)

 

Why is this important?

In a phrase “carry-over effect” in another phrase an inaccurate inflated reported Blood Alcohol Content. Simply put, a false Blood Alcohol Content result. Think of it as contamination.
 

In analytical chemistry, carry-over effect can be thought in terms of pick up. When a carry-over event occurs the sample “picks up” the analytes of interest from a previous sample. A carryover effect is an effect that "carries over" from one experimental condition to another. It is a form of contamination from one sample to another.

Carry over in gas chromatography analysis can come from three typical sources: first, autodiluting [Blogger’s note: an entire future post will be dedicated to this concept]; second, injector contamination [Blogger’s note: an entire future post will be dedicated to this concept]; and third, remaining analyte on the column.
 

Whether direct injection or an autosampler is used, without a blank inserted before and after an unknown, then there is no way of scientifically knowing the alleged reported result is unique to that particular sample.
 

Until this very basic systemic flaw is solved, then it cannot be responsibly and scientifically asserted that the reported result is unique to the unknown analysis and not carried over from another analysis.

Harrisburg DUI Lawyer carry-over effect in gas chromatography
  (Pictured above:  an over lay of chromatograpms where in green there is the electrical signal as detected by a Flame Ionization detector when a Resolution Control Standard or Separation chromatogram is generated and in black is the blank run)

It is so easy to solve, yet no one seems to care. You just insert a blank. I guess the forensic science community doesn’t care because the result doesn’t affect them.
 

As an illustration, I draw your attention to a past post as a concrete example for this discussion.  In "Highest reported BAC .708: I call Shenanigans", we discussed an extremely high reported BAC result.  Much like our cancer example, would you like to be the next test sample after that superhigh result?  I would think not.

How about we start doing things in a scientifically responsible manner and run blanks in-between unknowns????

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

Defending DUI Drug Cases: Part 2 from PA DUI attorney Justin J. McShane

Pennsylvania DUI attorney Justin J. McShane, Esq. presents his lecture "Defending DUI Drug Cases" in Hartford, CT in December 2009. In Part 2: "Drug Identification and Quantification," expert DUI Attorney McShane details the difference between impaired and metabolite states, and explains why "the numbers by themselves are meaningless or junk." The McShane Firm is the premiere DUI/DWI law firm in Harrisburg, PA. For more information, visit TheMcShaneFirm.com.

 

 


-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

A wakeup call: Independence in Crime Labs is not enough

Harrisburg DUI Lawyer blood testingWhile independence is necessary for any laboratory to insure against bias, it is just a start. Without meaningful double blind unannounced proficiency-based testing of every technician conducted by yet and another independent certified set of laboratory auditors, then it means nothing. We also need the technicians to be true credentialed scientists having graduated from brick and mortar post-secondary institutions employing the scientific method in the discipline that they are formally trained in and not testifying beyond beyond the scope of their expertise. Finally, to make it have any sort of testing scientific meaningful, the methods must be robust and internally and externally validated.

 

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

There is no such thing as the presumption of innocence in DUI cases

Harrisburg DUI Lawyer false arrest presumption of innocenceThere’s no such thing as the presumption of innocence in modern day United States and Pennsylvania jury trials.

It’s a sad fact that it seems as if a person, especially accused of a DUI, has to prove themselves to be innocent through the course of trial proceedings rather than the proper burden being applied both in terms of production and persuasion in that the Government must provide sufficient proof that rises to the level of proof beyond a reasonable doubt in order for anyone to be convicted of any crime.

It seems as if, in DUI cases, it is totally rejected in favor of a person accused has to prove that he/she wasn’t driving drunk before a not guilty verdict is returned.

It’s simply illustrated by the everyday common sense fact that occurs when we are driving in our cars to and from wherever we are going. You might see a police car with a person in the back seemingly handcuffed behind the officer. When we take a look at that situation, for example when we are stopped at a stop light and the police car is next to us we look over at that person. 

Don’t we think to ourselves:  "I wonder what he/she did", instead of asking ourselves:  "Boy, I wonder if he/she did anything wrong."

That is a pretty sharp and useful illustration of how the presumption of innocence doesn’t necessarily apply and isn’t the default position. When we go to trial at The McShane Firm, which is quite frequently, we take a very hard stance and challenge jurors to apply the principles of not only the presumption of innocence but also that the Commonwealth has its burden of proof beyond a reasonable doubt along with all of the other Constitutional protections such as the right to remain silent and not to be forced to provide testimony against one’s self as granted to us by our wise forefathers both in the United States Constitution and the Bill of Rights.

 

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

DUI Witch Hunting

When I introduce myself as a Pennsylvania DUI lawyer to new people I get some mixed responses.  Many people who are probably well intentioned see this as absolutely abhorrent.  Then comes the inevitable question set in an offensive tone, “How do you defend THOSE people?”.   This leads into discussions about carnage on the road and the thousands of deaths annually caused by DUI drivers and the it typically devolves into how I feel about people who are accused of a DUI and through “smart lawyering” are acquitted to only later go on to either re-offend or hurt or kill someone.  My answer is to them is quite simple: “I defend them because you would not.”

Most of these people probably haven't sat down and given serious thought to this issue.  At the core of the issue lies the question, “Should a person accused of a DUI be allowed a truthful and honest defense in a court of law?”  Think about it, people accused of murder, rape, tax evasion, child molestation and a host of other crimes are allowed a fair trial and are permitted to present a truthful defense.  Why should it be any different for someone accused of a DUI?  In the United States, everyone has a right to a fair trial by jury.  Alleged murderers, tax cheats and drunk drivers included. 

Pennsylvania DUI witch huntEven with the right to counsel, there are a huge number of innocent people locked up in prison for crimes they did not commit.  My recent posts Putting Innocent People in Jail and the Pennsylvania DUI Innocence Project show how widespread this problem actually is.

Here's another question, “If we want to limit defenses and rights, what criteria would we use to determine who is entitled to a defense against their criminal charges?” Do you see where this is going? When we as a society start to sit down and cherry pick out who gets a defense and who doesn’t, it's a slippery slope that leads to us having a trial simply by accusation or a witch-hunt.  This is where the Salem Witch trials really come into play. There was no defense to being accused as a witch. Once you received that moniker that you’re a witch then you were condemned to death. I defend people who are accused of a DUI. I do so ethically and by providing the truth to jurors so they can make an informed decision not based solely upon limited data or solely based upon accusation.  I do this because every American has the right to be defended against their charges: DUI included.

 

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-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency

Defending DUI Drug Cases: Part 1 from PA DUI attorney Justin J. McShane

Pennsylvania DUI attorney Justin J. McShane, Esq. presents his lecture "Defending DUI Drug Cases" in Hartford, CT in December 2009. In this introduction, expert DUI Attorney McShane presents an overview of how DUI lawyers can use forensic science to successfully defend clients accused of DUI-D cases. The McShane Firm is the premiere DUI/DWI law firm in Harrisburg, PA. For more information, visit TheMcShaneFirm.com.

 

 


-Justin J. McShane, Esquire, Pennsylvania DUI Attorney

I am the highest rated DUI Attorney in PA as Rated by Avvo.com

You can follow me on Twitter, Facebook or Linkedin

Harrisburg DUI Lawyer Justin J McShane Esquire earns
criminal law certification throguh NBTA

Board Certified Criminal Trial Advocate
By the National Board of Trial Advocacy
A Pennsylvania Supreme Court Approved Agency