Archive for the ‘Miscellaneous’ Category

Liners Every Lab Should Own (in my opinion)

We often get asked in tech service which injection port liner we would recommend for a particular analysis. For this type of question, it would not be uncommon to receive different answers, as each person has had positive and negative experiences with different liner styles. As a result, the recommendations I provide below are based solely on my past experiences, and do not reflect those of the rest of the tech service group.

Because I used Agilent instruments with split/splitless injection ports for most of my career, I will only provide you the Restek liner catalog numbers designed for these instruments. If you are using another brand of GC, you should be able to determine if we have a similar liner for your particular instrument make/model.  Just click on this link Inlet Liners & Liner Supplies and look for “Instrument Manufacturer/Model” under the “Narrow Your Results” filter.

 

When doing split/splitless, or splitless injections, I usually recommend a single gooseneck liner (no wool). I have experienced efficient sample transfer when the capillary column is installed around 5-7mm from the tip of the compact ferrule. Depending upon the expansion volume of the solvent (or the volume of a gas sample), either a 2mmID or 4mmID should be selected. Our Solvent Expansion Calculator can help you determine the proper liner internal diameter (ID).

 

The liner below is Restek 23302.1 Sky® 4.0mm ID Single Taper Inlet Liner , which is typically the best choice for 1-2µL injections of non-polar solvents (like hexane), 0.5-1µL injections of polar solvents (like methanol), and gas injections approximately >250µL.

 

The liner below is Restek 23315.1 Sky® 2.0mm ID Single Taper Inlet Liner , which is typically the best choice for 1µL or less injections of non-polar solvents (with low expansion volumes), or gas injections less than approximately 250µL.

 

Do I ever recommend a wool-packed split/splitless liner? Sure I do, but only when analyzing very dirty samples, when increased surface area is needed to properly vaporize the sample/compounds, or when doing water injections. However, I personally never recommend water injections be done in split/splitless or splitless mode. I have been able to obtain better peak shapes and peak area count reproducibility using split mode.

 

When doing split injections, I usually recommend a Cyclosplitter liner like Restek 23312.1 (photo below) Sky® 4.0mm ID Cyclo Inlet Liner . I have found that this style of liner does a great job of vaporizing a sample through increased internal surface area and by introducing turbulence to the sample.

 

There is, however, one drawback with these liners; they are very difficult to clean. Therefore, if you have dirty samples, or those containing non-volatile residue, I would probably suggest 23300.1 instead (photo below) Sky® 4.0mm ID Straight Inlet Liner w/ Wool

 

If you are not using a syringe for sample introduction, but instead the sample is from a purge & trap unit or gas sampling valve, then the liner I usually recommend is 23333.1 (photo below).  Sky® 1.0mm ID Straight Inlet Liner

 

There is one more liner that I think every lab should own, a Uniliner®. Although I usually don’t recommend this liner for any specific analysis, I think it’s a great troubleshooting tool because, when properly installed, it can help isolate & even eliminate injection port issues like activity. Just remember, these liners are designed for splitless injections only (if you experience carryover, try turning on the split flow at 5mL/min after the last compound elutes).

A Drilled Uniliner® with the “hole near top”, like Restek 23311.1, is typically the one I suggest (photo below).  Sky® 4.0mm ID Drilled Uniliner® Inlet Liner with Hole near Top .

 

In summary, I believe every lab should have several, or all, of the liners I’ve listed above in their inventory. Will other liner styles provide even better analytical results than any of these liners? I think it would be safe to say “yes”, but only through trial and error would you know for sure. My suggestion, start with one of the liners listed above, and if the desired analytical results are not achieved, only then would I look for a different liner style. Thanks for reading.

Contamination and Troubleshooting: “Jack, did that really happen?”

I had to blog on this because this just happened again to my colleague Jack last week! Occasionally, a loose spring will make it into a limited volume insert. If overlooked, sample is loaded into this insert. As the spring soaks in the sample, a significant background signal can result. The green chromatogram trace shows background signal resulting from the spring and methylene chloride inside of an insert. The 2 ppm PAH standard chromatogram is shown for intensity reference and indicates the contamination is significant.

 

Although I haven’t experienced this myself, it is a great example of “checking the obvious” troubleshooting rule. Often we immediately think something much more serious and sophisticated is occurring when we run into trouble…like the GC inlet liner is dirty or the column has degraded. Based on symptoms, it is best to start with the simplest causes first…Is there sample in the vial?, Are we injecting the correct sample?, Is the syringe plugged?, Is the rinse solvent contaminated?…Is my sample soaking with a plastic spring?…

 

I learned this lesson the hard way, one time I spent two weeks trying to determine why I wasn’t getting any signal on my GCMS….the problem…the syringe was plugged! You better believe I watch my syringe make an injection when I start a sample queue.

 



 

Handling Your Analytical Reference Standards

Readers of the blog have been presented with a wealth of information on for their GC columns, LC columns, detectors, syringes, carrier gases, TO-Canisters, and the list go on. What’s missing? Analytical Reference Standards.

Although not all reference standards have special handling instructions, the following general guidelines should assist you with the proper handling of these critical resources.

Storage temperatures can have a big impact upon your reference standard solutions. Volatile compounds (ex: vinyl chloride through naphthalene) are normally recommended to be stored frozen, since they can readily evaporate at room temperature. Make sure you store these solutions with minimal headspace in a well-sealed vial. On the other hand, solutions containing less volatile compounds (ex: PAHs and Cannabinoids), are typically recommended to be stored refrigerated. Others, such as Aroclor PCBs, are to be stored at room temperature. Since some of our certificates of analysis (CoA) list “less than 10°C” as the storage condition, I do have some advice for anyone that stores these less volatile compounds in their freezer. Once the solution warms to room temperature, place the solution in a sonicator for 10-15 minutes to allow these compounds to dissolve back into solution. By doing so, you will not be “missing” these compounds from your assay.

Some compounds are sensitive to light and can easily degrade when exposed to it. These photosensitive compounds, such as organophosphorus pesticides, can be protected by storing them in amber vials. For this purpose, Restek supplies a deactivated amber secondary vial with all of its solutions. A good practice is to always store your reference standards, including those at room temperature, away from light. Some additional precautions to avoid light exposure are to work under yellow light and to use red-tinted glassware when preparing dilutions. If you are working with known photosensitive compounds, use amber autosampler vials for your solutions. Minimize exposure to light and to return all standards to their storage area as soon as possible after use.

Finally, some compounds are incompatible with acids, bases, other compound classes or specific compounds. Because of the number and variety of potential reactions, I’m not going to go into specific details. I will note that Restek’s standard solutions are evaluated for solution feasibility to ensure compatibility between compounds. Since there are numerous multi-component methods, analysts do end up mixing solutions to create calibration standards. If you experience the loss of analytes or see new analytes in these cocktails, try analyzing your purchased solutions individually. There’s likely an interaction occurring between compound(s).

If you’re ever in doubt, don’t forget the CoA. The CoA contains storage recommendations and any warnings be it photosensitivity or chemical incompatibility. The manufacturer should have data to support their recommendations. The ability to search Restek’s CoA documentation is one click at:

Documentation Search

Now, reference standards can have their 15 minutes of fame in ChromaBLOGraphy.

Make a fashion statement and break down air pollutants with Catalytic Clothing

I’ve been delayed in Frankfurt, Germany for several days now while trying to get back to the USA due to Hurricane Sandy.  Any frequent US traveler to Europe knows that your standard English-speaking television stations are CNN, BBC, Sky News International, and Bloomberg.  You really get a different perspective on these stations, including the introduction of new technology that hasn’t hit the US yet.  Specifically, I’m talking about Catalytic Clothing, a partnership between The University of Sheffield and the University of the Arts London / London College of Fashion.  Sounds cool, right?  Well, it is indeed interesting.  Catalytic Clothing is proposed for air pollution reduction by introducing a photocatalyst such as titanium dioxide (TiO2) to clothing via a fabric softener when you do your laundry.  The TiO2 is nanotechnology based.  Theoretically, you then don your favorite jeans and walk around on the street breaking down pollutants, especially those emitted from automobiles, such as nitrogen oxides and volatile organic chemicals.

Now we just need to get Roy Lautamo’s hang glider wing fabric loaded with TiO2 and get him soaring over Sacramento…

50th Anniversary of Rachel Carson’s Silent Spring: DDT, Birds, Mosquitoes, Malaria, and Man

As I flew to Frankfurt yesterday, an intermediate stop on my way to South Africa, I opened my September 2012 National Geographic and read the blurb, “Spring Awakening”, which noted that 50 years ago Rachel Carson published Silent Spring, the classic book that documented the harmful effects of pesticide overuse on the environment.  The words “silent spring” referred to the lack of bird song, but it was “non singing” birds like the Bald Eagle, Peregrine Falcon, Brown Pelican, and Osprey that seemed particularly hard hit by synthetic pesticides like DDT, whose metabolite, DDE, caused thin-shell eggs that were easily crushed during incubation.   The book not only inspired a growing environmental movement, but also led to the eventual banning of DDT in the USA by EPA in 1972.  Since then, the raptors and the pelican have rebounded nicely.

Today, DDT is one of the “dirty dozen”, the Stockholm Convention’s list of persistent organic pollutants (POPs).  Chemicals on this list can be outlawed, but DDT has an exemption specific to “disease vector control”, which mainly means spraying for mosquitoes that carry malaria, a disease that has a staggering human impact with over 200 million cases documented in 2010.  Due to its efficacy against the mosquito, DDT is sometimes used in “indoor residual spraying” (IRS) approaches, where the walls of dwellings are coated with insecticides, which obviously increases the potential for human exposure to DDT.  Malaria versus DDT exposure then is a difficult question.

As I head to South Africa, I keep DDT and malaria in mind, not necessarily because I’ll be in a malarial region, but I will be working with researchers who study DDT, specifically as regards human exposure.  At the University of Pretoria where I will be working on Oct 4 and 5, my friends and colleagues Yvette Naude and Egmont Rohwer, use their multi-channel open tubular silicone rubber traps for determining DDT in indoor air of IRS-treated traditional dwellings in South Africa.  From North-West University in Potchefstroom, where I will be on Mon and Tue, Professor Henk Bouman writes in DDT and Malaria Prevention: Addressing the Paradox:   “Overall, community health is significantly improved through all available malaria control measures, which includes IRS with DDT. Is DDT ‘good’?  Yes, as it has saved many lives.  Is DDT safe as used in IRS?  Recent publications have added to concern – an unqualified statement that DDT used in IRS is safe is therefore untenable.  Are inhabitants and applicators exposed?  Yes, and to high levels.  Should DDT be used?  The fact that DDT is ‘good’ because it saves lives, and ‘not safe’ because it has health and environmental consequences, raises ethical issues.  The evidence of adverse human health effects due to DDT is mounting.  However, under certain circumstances malaria control using DDT cannot yet be halted.  Therefore, the continued use of DDT poses a paradox recognized by a centrist-DDT position.  It is time now, at the very least, to invoke precaution.  Precautionary actions could include use and exposure reduction.”  When I read Henk’s thought-provoking words, it reminds me of the importance of producing accurate data with good sampling, sample preparation, and gas chromatography.  Analytical chemistry is truly the foundation science for DDT studies.

I need a fitting, but which one?

We (tech service) get calls all the time about fittings, especially the ones we sell which are manufactured by Swagelok®, Parker®, and Valco®. It seems like customers are either very familiar with fittings, or they know virtually nothing about them. I will try and provide some information that will hopefully take some of the confusion out of these different fittings.

First, the Swagelok and Parker fittings that Restek sells are designed for similar applications. Although each of these companies offer a huge variety of products, we only sell the items usually requested by our customers in the field of chromatography. These fittings are commonly used to plumb gases to a gas chromatograph, install packed columns, install gas filters (traps), etc…

 

A few things to keep in mind:

1. We sell both brass and stainless steel fittings. Brass is for use with copper tubing, and stainless steel is for use with stainless steel tubing. If you try and use a brass fitting with stainless steel tubing, brass isn’t hard enough for the ferrule to “bite” into the stainless steel tubing; therefore, you will not be able to obtain a proper seal. In addition, connecting two dissimilar metals may lead to galvanic corrosion

2. The fittings we sell may have compression or National Pipe Thread tapered ends (NPT). Compression ends are made for a tube which has a specific outside diameter (OD). For example, a ¼” compression fitting is designed to connect a section of tubing which has an OD of ¼”. When the nut (which contains the ferrules) is tightened, it compresses the ferrules onto the tubing to make the seal. Keep in mind that most metal tubing is designated by its OD while most plastic tubing is designated by its ID (and usually needs a plastic fitting to obtain a proper connection).

3. NPT (ends) look very different than compression (ends). NPT has no nuts or ferrules, but instead relies entirely on a thread connection. Like plastic tubing, the product designation for NPT (and pipe in general) is the internal diameter (ID), not tubing OD like compression. To help clarify the difference between compression and NPT, the photo below shows a fitting with male NPT end on the left, and compression end on the right.

4. The metal ferrules that are included in the compression end(s) can be replaced with ferrules of different materials. For example, if trying to connect a fitting to a ¼” OD glass tube, you would want to replace the metal ferrules with a softer material like graphite. Similarly, you would want to replace the metal ferrules with PTFE ferrules if using the fitting with PTFE tubing.

5. Finally, unlike compression, NPT fittings can be either male or female. Just remember that the threads on a male fitting are on the outside, and threads on a female fitting are on the inside.

 

We also sell Valco® fittings. These are considered low (or zero) dead volume fittings, meaning they are designed to eliminate any dead space (volume) within the fitting. Common uses for these fittings are to connect capillary columns and other small ID tubing where dead space may cause chromatography (or other) problems such as tailing peaks. These fittings usually include stainless steel ferrules. Just like with other compression fittings, the metal ferrules can be replaced with Valcon Polyimide ferrules when connecting tubing other than stainless steel. Note that these fittings, while containing nuts and ferrules like other compression fittings, have a very different style (see photo below), and are not compatible/interchangeable with the Swagelok® / Parker® fittings described above.

A few final thoughts on the topic of fittings:

For gas flow rates less than 5mL/min, consider Valco® connectors to minimize dead volume. For the most inert fittings, consider Siltek®/Sulfinert ® Treated products. When in doubt as to which fitting to use, always ask someone first, as using the incorrect fitting can be dangerous if a proper seal is not made. Remember, we are just a phone call or e-mail away.

 

George Fong Interview – Florida Pesticide Residue Workshop

Restek just published an interview with the founder of the Florida Pesticide Residue Workshop.  Read it. To quote Stan Lee: “Nuff said”. 

Sitting Down With a Chromatography Icon: W. George Fong

First e-Posters Presented at Dioxin 2011

At Dioxin 2011 in Belgium recently, the first e-Posters that I’ve ever seen at a scientific conference were presented.  The e-Posters were arranged by NEXT, a European technology provider for conferences and meetings, and consisted of touch-screen monitors (screens approximately 1m wide x 0.5m high) on stands placed strategically throughout the poster venue.  Dioxin posters were prepared in PowerPoint as 6 slides maximum, and loaded on all e-Poster monitors where they could be accessed at any time during the conference by searching authors, keywords, poster number, etc.

According to conference attendees I spoke to, the e-Posters got mixed reviews.  Most of the graphics were very good, but some presentations showed reduced resolution, making tables and text illegible.  And while there was a convenience to seeing any poster you wanted in one place, that meant you had to actually call the poster up, rather than just walk up and see it.  However, a MAJOR benefit was being able to accommodate more posters in less space, which means that more scientists could present their work at the meeting.

I remember when we used to present our posters tacked up as multiple 8.5 x 11 inch panels years ago before PowerPoint (or Lotus Freelance Graphics; anyone remember that one?) and large format printers revolutionized that industry.  I suspect that is what we’ll see with e-Posters also, a revolution, and I congratulate the Dioxin 2011 organizers for being at the forefront.  Given that younger people are always early adopters of e-technology these days, it’s only fitting I leave you with a photo of my colleague, Michelle Misselwitz, standing in front of her e-poster on large volume injection for PBDEs and pesticides.

“When Comparing GC Columns make sure comparisons being presented are “apple to apple” comparisons and NOT “apple to pear” comparisons”

You know, what I really do not like in today’s business, is to see comparative tests being presented at scientific meetings, where quality statements are made, based on incorrect product-comparison. The problem is,  that companies make the wrong comparisons and make claims which  are biased.  So to say: they are comparing apples with pears.

 

This one comes from the recent meeting in Singapore on Separation Science where a technical poster was presented about a new high temperature column. This column was shown to elute components that were not able to elute from an other commercial column.

Figure 1 shows the chromatogram that was displayed.

Fig. 1 Comparing elution profiles of a THIN and a THICK film column is like comparing apples with pears. 1.00um film has 4x More retention which is not a recommended choice if you want to elute high boilers.

 

Issue is that the comparison shows a THIN film (0.25um)  compared with a THICK film (1.00um).  Retention increases linear with film thickness, meaning that the thick film will ALWAYS have at least 4x higher retention then the thin film. This is not a matter that peaks do not elute, but a matter of choosing the wrong column dimension for comparison. Retention of a thick-film column cannot be compared with thin-film column as components will always elute faster from a thin-film column.

 

For high temperature analysis one always should consider a thin-film column because it allows quantification of higher boilers because they elute faster. High temperature phases like Rxi-1HT and Rxi-5HT that can take 400C without loosing inertness, are therefore only commercialized as 0.1 and 0.25 micron film.

So when reviewing column comparison it is always best to look at the details to make sure the data presented is chromatographically logical, comparing “apples to apples”..

The Bard Hits the Bong?

I was listening to “Wait Wait… Don’t Tell Me!”  (WWDTM) today on the local NPR station and heard an interesting story.  WWDTM is a humorous quiz show on topical news items, and features celebrities and comedians bantering with each other and the host, Peter Sagal, while chosen listeners are called and asked questions.  The prize for answering correctly is a Carl Kassell (WWDTM’s Official Judge and Scorekeeper) greeting on the contestant’s voicemail.  OK, that may be interesting, but that wasn’t the story…

 During the carrying-on in the show, it was mentioned that William Shakespeare had possibly used marijuana, since pipes were found in his garden that contained traces of cannabis and (even more incredibly) cocaine!  Just recently, an anthropologist from the University of the Witwatersrand in Johannesburg, South Africa, Francis Thackeray, made a request to the Church of England to uncover Shakespeare’s remains in hopes of proving this theory, as well as determining cause of death.  Given that an epitaph on the stone slab covering Shakespeare in part reads, “Blessed be the man that spares these stones, And cursed be he who moves my bones”, it seems doubtful that his request will be honored.

 The story is interesting on its face, but even more so to me since it involves the forensic chemistry of marijuana, something  my colleagues Frank Dorman at The Pennsylvania State University (PSU) and Amanda Rigdon at Restek, and I, were practicing just last week.  Thanks again to Randy Hoffman, a Police Officer Specialist/Evidence Technician at PSU, we were able to use QuEChERS and other extraction techniques on seized cannabis to (1) develop methods for possibly fingerprinting marijuana types, (2) characterize marijuana potency, and (3) analyze for pesticides in marijuana with GCxGC-TOFMS and LC-MS/MS.

Amanda will be reporting soon on the potency extraction techniques she’s using, checking out different solvents for efficiency, and she’s also developed GC and LC methods for potency characterization, using new Restek standards that contain cannabidiol, cannabinol, and THC as a mix (catalog# 34014), and THCA as a single component (catalog# 34093).  Michelle Misselwitz, Sharon Lupo, Julie Kowalski, and I are working on the pesticide determinations and we should have those done in time to report the results at the 48th Annual Florida Pesticide Residue Workshop.   

To wrap this blog up, first I go back to WWDTM, where Peter Sagal theorized that if Hamlet’s hobby was the same as the one suggested by Shakespeare’s garden pipes, the famous line might have been:

“To be or not to be, what is the question?”

And finally, Sonnet 76 (William Shakespeare):

Why is my verse so barren of new pride,
So far from variation or quick change?
Why with the time do I not glance aside
To new-found methods, and to compounds strange?
Why write I still all one, ever the same,
And keep invention in a noted weed,
That every word doth almost tell my name,
Showing their birth, and where they did proceed?
O! know sweet love I always write of you,
And you and love are still my argument;
So all my best is dressing old words new,
Spending again what is already spent:
For as the sun is daily new and old,
So is my love still telling what is told.