Chemical poisoning – general principles of diagnosis and treatment

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The diagnosis of chemical poisoning is suspected from a history of exposures resulting in typical clinical syndromes and confirmed by the appropriated medical tests.

There are a series of criteria to be fulfilled to make a confident clinical diagnosis of poisoning by chemicals. The following criteria have to be fulfilled:

  1. The subject was fit and well prior to chemical exposures.
  2. There is evidence of exposure to the putative chemicals and toxins.
  3. The subject initially developed local symptoms which became worse with repeated exposures.
  4. With repeated exposures a typical clinical picture emerges characterised by chronic fatigue syndrome, immune disruption (allergies, autoimmunity, susceptibility to infections), accelerated ageing (so the sufferer gets diseases before their time), neuro-degeneration, diabetes and cancer.
  5. Similar patterns of disease are seen in other people working under similar conditions.
  6. Similar fact evidence from other subjects who have been poisoned such as the Gulf War veterans, sheep dip poisoned farmers, aerotoxic pilots.
  7. There is laboratory evidence of poisoning and effects of that poisoning.
  8. There are no other possible explanations for this pattern of symptoms.
  9. There is a response to treatment with clinical improvements as a result of detoxification, nutritional and immune support.

The Clinical Picture of Chemical Poisoning

It is important to realise that the diagnosis of chemical poisoning relies on recognition of a clinical picture. Let me draw an analogy. If I saw a photograph of the Queen, standing on the balcony at Buckingham palace, surrounded by members of the Royal Family, with the flag flying above, the band playing below and thousands of people cheering, I would be happy to diagnose that it was indeed the Queen I was looking at. To be certain I would have to ask for DNA testing, but this has never been requested and never been done because the clinical picture is so obvious.

We have a similar situation with people who have been chemically poisoned. The clinical picture to those trained and used to seeing it is obvious. The problem arises because these people who are poisoned have only presented in the last few years. This is not a long standing recognisable syndrome, it is a new illness. Doctors are traditionally very slow to recognised new diseases and most not only fail to even look at the clinical picture, many do not accept it exists at all because it does not fit into their paradigm of disease! It really does create a new picture! So for example it has taken the Americans 17 years to recognise the clinical picture of Gulf War Syndrome and ascribe this to pesticide poisoning. Fortunately the 9/11 firemen who were poisoned by the fumes inhaled as they fought the flames and picked over the debris of the destroyed twin towers had their illness quickly recognised and a detoxification centre set up in New York allowed effective and immediate treatment.

So for a diagnosis of chemical poisoning to be made, not only do the above criteria have to be followed, but a doctor experienced in seeing and treating these new diseases must be able to see the picture. Just like in the early days of infectious diseases, Koch’s Postulates had to be fulfilled to make a diagnosis of infection, a series of criteria for diagnosis chemical exposures is now emerging.

Symptoms of chronic chemical poisoning

  • Symptoms of chronic fatigue syndrome. Severe, debilitating fatigue which is physical and mental
    • Physical – no stamina, loss of muscular strength (episodic blurred vision), sudden “hitting a wall”, has to rest regularly and pace all activity.
    • Mental – poor short term memory, unable to learn new things, poor concentration, speech difficulty with poor word finding. Long term memory usually fine. See Brain fog – poor memory, difficulty thinking clearly etc
    • Malaise – sufferers feel ill, “hung over”, “poisoned”.
    • Muscle aching – often widespread, flitting from one group of muscles or joints to another, often requiring painkillers; degeneration of handwriting.
    • Drug intolerance (such as alcohol, antidepressants). This is sympotmsatic of poor ability to detox. See Detoxification – an overview
    • Sleep disturbance
  • Symptoms of multiple chemical sensitivity. Sufferers
    1. become more sensitive to the chemical to which they are exposed, which means that they get bigger reactions with smaller doses.
    2. become sensitive to other chemicals. This is called a “spreading phenomenon” and classically these people start to react to any other chemicals such as diesel fumes, perfumes, cigarette smoke, alcohol and so on.
    3. develop an exquisite sense of smell – they can smell chemicals long before anybody else – they are true “canaries”
  • Personality change with destabilisation of mood (mood swings), increased tearfulness, irritability and aggression, impulsive suicidal thoughts, rage. An extreme version of these symptoms results in psychiatric disorders including depression and psychosis.
  • Other symptoms which may arise as a combined effect of the above problems include:
    • Chest pain,
    • Shortness of breath
    • Muscle twitching or cramp
    • Irritable bowel syndrome (abdominal pain, bloating, diarrhoea/constipation etc)
    • Sweating
    • Poor balance and dizzy spells
    • Numb patches, clumsiness
    • Tendency to pick up infections
    • Many other symptoms.

Toxic chemicals also accelerate the normal ageing process

This means that diseases which one might expect in patients in their eighties one sees in patients in their fifties and sixties. These diseases include:

  • Degenerative conditions such as Parkinson’s disease, osteoporosis, heart disease and dementia.
  • Genetic and DNA damage causing cancer (and of course birth defects).
  • Immune disruption – this can cause allergies (to foods, inhalants and chemicals), tendency to acquire infections and difficulty getting rid of infections, autoimmunity.

Making a diagnosis of chemical poisoning

(which includes organophosphates, volatile organic compounds, heavy metals, silicones and noxious gases)

Making the diagnosis is all about recognising the clinical picture as above. At the moment there is no single test which will diagnose acute chemical poisoning. This is because the chemicals get into the body, do damage, and are then distributed throughout the body into fatty departments or are excreted. The problem here is that many tests are done on blood levels. This does not reflect the total toxicity outside the blood. This means that by the time a sufferer gets to see a doctor the chemicals are in such low levels in the blood they are not detectable by conventional tests and only the damage remains.

These chemicals are often highly toxic. Every bodily system can be adversely affected by toxic chemicals, therefore sufferers present with a multiplicity of symptoms. These symptoms singly may be ignored or coped with. It is when they come together and are so persistent, that sufferers present to their doctors.

When sufferers come, they may not arrive with a list of all their symptoms, just those symptoms which they believe might be serious. Many sufferers present with chest pain or headaches suspecting heart problems or a brain tumour. They have to be asked specifically for details of other symptoms, or the diagnosis will be missed. Toxic chemical poisoning is a clinical diagnosis made on the basis of past medical history, symptoms, signs and investigations.

Past Medical History

Often there is no serious illness in the past. However when asked, many sufferers will give a history of reactions to other chemicals such as air fresheners, cigarette smoke, perfumes or whatever. Some people may give a similar history of symptoms following previous flights such as headaches, muscle aches, chest pains and nausea.

These symptoms of acute chemical poisoning also occur in sick building syndrome, sheep dip ‘flu, 9/11 syndrome (firemen being poisoned by toxic fumes), Gulf War syndrome, chronic carbon monoxide/hydrocarbon fume poisoning, Aerotoxic pilots, fumes from toxic waste sites and industrial pollution, photographic and printing industry, painting and carpet industry as well as mercury from dental amalgam and so on.

Clinical signs

Standard medical examinations often reveal no clinical signs of disease and the sufferer looks well. Indeed, his looks belie his feelings. These patients feel terrible but look reasonable. One has to rely on the above clinical picture and tests to support the diagnosis. It is a combination of the clinical history plus positive tests which make the diagnosis.

Laboratory Investigations

Also see CFS – Tests to investigate CFS

Chemicals get into the body, cause damage and are then excreted. Conventional medical tests are not sufficiently sensitive to identify these chemicals and pick up the widespread and subtle damage which results from them. Sensitive tests have to be done most of which are not routinely available and certainly not on the NHS. So many sufferers get the standard “work up” of medical tests which are either inappropriate, or overlook minor abnormalities. For example:

  • Full blood count – usually normal – (there may be a low white cell count)
  • Urea and electrolytes – usually normal
  • Liver function tests – usually normal. There may be slightly raised liver enzymes (often ignored) or a slightly raised bilirubin, suggesting Gilbert’s syndrome.
  • Muscle enzymes – sometimes these are slightly raised
  • Hormone tests – usually interpreted as normal, but actually often show low normal levels
  • X-rays – all normal
  • ECGs – usually normal
  • Nerve conduction studies of the motor and sensory nerves – usually normal. Abnormalities may be found if tests are done within 2 years of the most recent exposure to organophosphates.
  • MRI scan of the brain – often said to be normal

Most chemical sufferers get this standard battery of tests and are told there is nothing wrong with them. However, there are abnormalities which would be picked up by the following tests:

  • Finding the toxic chemical – this can be done with fat biopsies to identify pesticides and volatile organic substances.
  • Mitochondrial Function Profile
  • DNA adducts – seeing chemicals stuck on to DNA.
  • Heavy metals can be detected by measuring blood toxic metals or analysing the metal content of sweat
  • Mercury – Kelmer test for mercury toxicity
  • More in depth tests of mitochondrial function such as Translocator protein studies, Microrespirometry studies, Cardiolipin studies or Antioxidant status profile often pick up these toxins which get stuck onto membranes and proteins.
  • Immune function tests – most of these are research only tests, but, if available, look for low levels of natural killer cells, low levels of B cells, abnormal T suppressor/helper lymphocyte ratios, raised C reactive protein and hypogammaglobulinaemia. ANCA, TNF and interleukin 6 may also be abnormal.
  • Sensitive tests of liver function (glutathione S transferase, red cell glutathione), and tests of the liver’s ability to detoxify (caffeine, paracetamol loading) – often abnormal. See Full GST profile and Standard Detoxification Profile.
  • Hormonal studies suggest a suppression of the pituitary gland with borderline underactivity of the thyroid (hypothyroidism), mild Addison’s disease. Tested for by doing Adrenal Stress Profile (salivary), inappropriate ADH secretion, poor melatonin levels resulting in sleep problems, low levels of testosterone etc. The thyroid abnormality is interesting classically with low TSH and low T4 (in the lowest 20% of the “normal” range). Thyroxine can be very helpful.
  • Osteoporosis – bone density scan at the wrist, hip and spine is mandatory. All people with significant exposure to chemicals should have this investigations. Urine tests may show abnormal levels of metabolites of bone namely deoxypyridinoline (Dpd) and N-telopeptides (NTx) indicating faulty bone metabolism.
  • Psychometric testing – this often shows severe impairment of memory, information processing, learning, concentration etc. This is not easy to get on the NHS but should be demanded – available via consultant neurologists. It should be possible for your GP to refer you to a neurologist because you are suspected to be suffering from a “sub-cortical dementia”. The neurologist has to be asked to refer you on for psychometric testing. This may take several hours to do (if it doesn’t you are not getting the right test!). These tests are an objective assessment of brain function and can be very helpful for getting street credibility (with your GP – there is often a dramatic change of attitude when it is discovered there is something really the matter!) and for getting benefits (as you are suffering from a pre-senile dementia). Indeed Doctor Sarah McKenzie Ross is the most experienced neuro-psychologist in this field and she has identified a pattern of brain damage that is particular to chemical poisoning and different from say dementures or depressions.
  • Nerve conduction studies of the autonomic nervous system – presently only done by Drs Jamal and Julu. The autonomic nervous system controls automatic functions such as temperature, sweating, blood pressure, heart and respiratory rate, gut function etc. Abnormalities are commonly found in OP poisoned sufferers and are persistent.
  • Brain scans to demonstrate function (such as SPECT scanning) may show poor perfusion of particular areas of the brain. Most of this work has been done on Gulf War veterans who were similarly poisoned.
  • Trace elements levels – often deficiencies of magnesium and selenium found.
  • Vitamin deficiencies – particularly of the B vitamins – in fact, this is so common that I do not bother to do tests, but use multivitamins routinely.
  • Antibodies to brain proteins (cytoskeletal antibodies) sometimes raised (test not available in UK).
  • Conduction abnormalities in the heart – arrange 24 hour ECG monitoring for symptoms such as chest pain or palpitations (needs referral to cardiologist).
  • Allergy testing – Lymphocyte sensitivity to metals and chemicals and Lymphocyte sensitivity to silicone

Treatment – the environmental approach

The priority is to recognise the illness and stop further exposure to toxic chemicals. Not all people are equally susceptible to the toxic effects of chemicals – those that get symptoms are more susceptible and need to be doubly careful to avoid further exposure. See Chemical poisons and toxins for a list of common toxins – it is not a case of avoiding the chemical which initially poisoned you, but all the others as well!

  • Chronic fatigue syndrome – see section on fatigue. In the short, medium and sometimes long term the commonest problem is a chronic fatigue syndrome. This is just a symptom and the name of the game is to identify and treat the underlying causes. You could download my entire book free of charge. See my CFS Book. It is vital to go through this step by step and address all the issues. Do not be tempted to cherry pick the easy things or you will slow your recovery. In particular the diet – dietary changes are the most difficult to make and people often leave these till last whereas actually they should be done first.
  • Acceleration of the normal aging process See Anti-ageing – Slow the Ageing Process. The mechanism by which chemicals cause damage is to interfere at a fundamental level with biochemical processes and in effect accelerate the normal ageing process. This is what makes these victims of chemical poisoning difficult to detect by a discrete syndrome – sufferers get normal diseases suffered by normal people but before their time. So for example the Gulf War veterans have a greatly increased risk of cancer heart disease and degenerative conditions like osteoporosis, arthritis, prion disorders such as Alzheimer’s disease, Parkinson’s disease and motor neurone disease and so on, none of which constitutes a recognisable and different syndrome but is all symptomatic of an accelerated ageing process.

What can you expect from your GP?

The problem with GPs is that they are not trained to look for toxicological (poisoning) as a cause of illness. You may be referred to the Poison’s Units (now called Medical Toxicology Units). The Poison’s units have not made a single diagnosis of chronic organophosphate poisoning in the last ten years, I suspect because funding for the Poison’s Units comes from the chemical companies. This is an issue I have written about in the Journal of Nutritional and Environmental Medicine which the Poison’s Units have failed to refute.

You can expect your GP to do a series of blood tests and tell you there is nothing abnormal and therefore nothing wrong. The next step might be referral to a neurologist who again will trot out the party line – chronic chemical poisoning does not exist. The next port of call is usually the psychiatrists who do not have a “toxicological” diagnostic pigeon hole and will squeeze you into the next nearest fit, ie chronic depression. The treatment of this, namely anti-depressants, will make the poor sufferer worse, he will refuse to take them and be discharged as an unco-operative patient. The chemically poisoned person is left to sort out his life as best as he can and usually ends up with declining health.

Fortunately most chemically poisoned people are intelligent and realise the above state of affairs. But the lack of street credibility and help from Government Agencies make this illness a social and financial disaster area.

Extrenal link

Dr Claudia Miller’s website from which you can download free of charge a PDF version of her widely acclaimed book written with Nicholas A. Ashford “Chemical Exposures: Low Levels and High Stakes”

Quoted from the back cover:

“Chemical Exposures: Low Levels and High Stakes” explains how day-to-day variations in chemical exposure may cause unusual and seemingly unpredictable symptoms, including many that have been termed psychosomatic in the past. It describes how everyday, low-level chemical exposures may cause fatigue, memory impairment, headaches, mood changes, breathing difficulties, digestive problems, and a host of chronic unexplained illnesses including chronic fatigue syndrome, Gulf War syndrome, and sick building syndrome. The authors are the first writers to clearly describe and document the process of adaptation, a concept that provides a rational and scientific basis for understanding these symptoms. In the Second Edition of this professionally acclaimed work, the authors offer evidence for an emerging new theory of disease-toxicant-induced loss of tolerance-which may have far-reaching implications for medicine, public health, and environmental policy. Based on a report commissioned by the New Jersey Department of Health that won the World Health Organizations Macedo Award, Chemical Exposures is the most comprehensive book ever written on sensitivity to low level chemical exposure and the many health effects associated with it. This work clarifies the nature of chemical sensitivity, shows how it differs from traditional allergies and toxicity, and suggests how federal and state governments can help those who are affected. The book identifies four major groups of people with hypersensitivity to low levels of chemicals: occupants of tight buildings, industrial workers who handle chemicals, residents of communities exposed to toxic chemicals, and individuals with random and unique exposures to various chemicals. The fact that similar symptoms are being reported by members of these demographically diverse groups not only points to a serious problem, it may also contribute to a better understanding of chemical sensitivity.

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The NeilMed Sinugator® (sinus irigator) cordless pulsating nasal wash

NeilMed Sinugator_56.5

walgreens-logoI was in Walgreens the other day and remembered that I wanted another ear wash bulb in case I wore the one I already had, out. I had been thinking about constructing some sort of nasal washer thing out of a submersible pump or syringe with surgical tubing orNeilMed NasaBulb for babies something like that. What a pain to have to do. I made my way over to the pharmacy section and found some baby nasal bulbs that looked OK, so I bought them. They weren’t really like my other bulb, the nozzles were short and didn’t extend past the nostril. I will be returning them, unopened.

Anyway, that’s when the thought came to me that I might find some sort of better solution for flushing my nostrils of the poison toxic gasses. I looked behind me opposite the bulbs and saw all sorts of nasal stuff. At the very bottom of the shelf, I see this nozzle looking thing in a rather large box. I then look at the price tag and it is reduced to $28. More interested now, I take a closer look and see that there is some sort of machine attached to a nozzle, the box top proclaiming it a “Nasal Wash”. I pick it up and try to open the box but it is taped shut. I then take all of the boxes off the shelf and grab the last one, I figure I may as well give it a try since squeezing the bulb is becoming really tiresome.

IMG_20150216_005658In the car I open the box and am pleasantly surprised that it is in multiple parts and requires assembly. I quickly put the pieces together and am again surprised that it seems well made, it even came with three Duracell AA batteries. I re-box it and drive home.

I didn’t put the batteries in until I had water in it, I know that running pumps while dry does damage. I was even more surprised that the battery cover has a little rubber seal that goes all the way around it and a “slide to lock” mechanism too. Even the start button is sealed with a rubber cover, you don’t have to worry about getting it wet. The sound it makes is reminiscent of a “Water Pick”, remember those? I always thought a “Water Pick” was much better suited to blasting ear wax out of your ears, far less messier than shooting your teeth anyway.  It does deliver a rather large stream of pulsed water. I put it up to my nose and press the rubber covered button. Two seconds later, a steady stream of water is flowing out of the opposite nostril, I can smell the familiar chemical smell begin to emanate and fill my mouth. Now that I have a steady stream coming out of the other nostril, collecting samples in the morning will be a snap (for later GC/MS analysis). It works so much better than the blue thing above! I no longer have to fumble with the bulb, just quickly unscrew the blue solution reservoir, hold under running water till full, screw back on and flush.

The instructional video tells you to use either filtered or distilled water, probably because the minerals in regular tap water will shorten it’s pump life. I use way too much water for my flushing, so I just keep the tap running and fill as needed. The detached reservoir works great as a “drinking” cup to swish your mouth out with and to rinse the sink clean of the boogers blasted into it as well. I love this thing!

NeilMed Sinugator_05The Sinugator goes through it’s little blue solution reservoir of water very fast, I use one whole cupful for each nostril. After a particularly heavy toxic gas exposure, I use anywhere from four to six cupfuls, alternating between each nostril per filling. It is easy to use and seems well built, I have yet to use the saline however. If your nasal passages are already swollen, be prepared for your ears to pop from the pressure. The Sinugator really is low pressure as advertised but it also has some force and will keep right on pumping even though it’s nozzle is blocked. Should it encounter blockage due to your swollen nasal canal, it can cause some unpleasant pressure and make your ears “pop”. You can also blow your nose with the free nostril while the Sinugator is helping, but only if you don’t have too much blockage. Your ears will REALLY pop if you blow while blocked (swollen canal). Blowing while irrigating will stop the flow and may cause some backwash into the device, but you are the only one who is going to be using it, right?

One last suggestion I would add is to wear a bath towel like a bib or apron, your nose will be dripping for a little while even after blowing out the excess water. Don’t make the mistake that I did and leave your shirt or blouse uncovered, people will crinkle their noses when they see the long snot trails that have dripped down your front! 🙂

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It breaks down and is able to fit into the small little net bag complete with saline packets, just add your own water. I have yet to take it with me outside of the house but I do get dosed outside too, so it will come in handy when that happens. It is rather loud so you won’t be able to hide while using it, people will look and stare. I don’t care, just another opportunity to hand them a blog card explaining why I am doing what I am doing. If in a touristy area and they want to film it, so much the better.

front of Poisoned By Giftgas biz card design #4

 


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Little teapots with long spouts have become a fixture in many homes for reasons that have nothing to do with tea.

Called neti pots, they are used to rinse the nasal passages with a saline (salt-based) solution, and have become popular as a treatment for congested sinuses, colds and allergies, and for moistening nasal passages exposed to dry indoor air.

However, the Food and Drug Administration (FDA) has concerns about the risk of infection tied to the improper use of neti pots and other nasal rinsing devices. The agency is informing consumers, manufacturers and health care professionals about safe practices for using all nasal rinsing devices, which include bulb syringes, squeeze bottles, and battery-operated pulsed water devices.

These devices are generally safe and useful products, says Steven Osborne, M.D., a medical officer in FDA’s Center for Devices and Radiological Health (CDRH). But they must be used and cleaned properly.

Most important is the source of water that is used with nasal rinsing devices. Tap water that is not filtered, treated, or processed in specific ways is not safe for use as a nasal rinse.

Some tap water contains low levels of organisms, such as bacteria and protozoa, including amoebas, which may be safe to swallow because stomach acid kills them.  But these “bugs” can stay alive in nasal passages and cause potentially serious infections, according to the Centers for Disease Control and Prevention (CDC).

Improper use of neti pots may have caused two deaths in 2011 in Louisiana from a rare brain infection that the state health department linked to tap water contaminated with an amoeba called Naegleria fowleri.

Misleading, Missing Information

Information included with the device might give more specific instructions about its use and care. However, FDA staff has found that some manufacturers’ instructions provide misleading or contradictory information, or lack any guidelines.

For example, some manufacturers have recommended using plain tap water; others warn against using it in printed directions, but show its use in pictures or videos.

The device might also come without instructions. If you order a custom neti pot made by an artist, for example, that person might assume you know how to use it.

The procedure for nasal rinsing may vary slightly by device, but generally involves these steps:

  • Leaning over a sink, tilt your head sideways with your forehead and chin roughly level to avoid liquid flowing into your mouth.
  • Breathing through your open mouth, insert the spout of the saline-filled container into your upper nostril so that the liquid drains through the lower nostril.
  • Clear your nostrils, then repeat the procedure, tilting your head sideways, on the other side.

Nasal rinsing can remove dirt, dust, pollen and other debris, as well as help to loosen thick mucus. It can also help relieve nasal symptoms of allergies, colds and flu.

“The nose is like a car filter or home air filter that traps debris. Rinsing the nose with saline solution is similar to using saline eye drops to rinse out pollen,” Osborne says. The saline, he adds, enables the water to pass through delicate nasal membranes with little or no burning or irritation.

FDA staff recommends that you consult a health care provider or pharmacist if the instructions do not clearly state how to use the device or the types of water to use, if instructions are missing, or if you have any questions.

Questions and Answers

What types of water are safe to use in nasal rinsing devices?

  • Distilled or sterile water, which you can buy in stores.  The label will state “distilled” or “sterile.”
  • Boiled and cooled tap water—boiled for 3-5 minutes, then cooled until it is lukewarm. Previously boiled water can be stored in a clean, closed container for use within 24 hours.
  • Water passed through a filter with an absolute pore size of 1 micron or smaller, which traps potentially infectious organisms. CDC has information on selecting these filters, which you can buy from some hardware and discount stores, or online.

How do I use and care for my device?

  • Wash and dry hands.
  • Check that the device is clean and completely dry.
  • Use the appropriate water as recommended above to prepare the saline rinse, either with the prepared mixture supplied with the device, or one you make yourself.
  • Follow the manufacturer’s directions for use.
  • Wash the device with distilled, sterile, or boiled and cooled tap water, and then dry the inside with a paper towel or let it air dry between uses.

Are nasal rinsing devices safe for children?

Some children are diagnosed with nasal allergies as early as age 2, Osborne says, and could use nasal rinsing devices at that time, if a pediatrician recommends it. However, he adds that very young children might not tolerate the procedure as easily as would older children or adults.

What are some negative effects to watch out for when using nasal rinsing devices?

Talk to your health care provider to determine if nasal rinsing will be safe or effective for your condition. If symptoms are not relieved or worsen after nasal rinsing, then return to your health care provider, especially if you had any of these symptoms while using the nasal rinse:

  • fever
  • nosebleed
  • headaches

FDA asks health care professionals and patients to report complaints about nasal rinsing devices to the FDA’s MedWatch Safety Information and Adverse Event Reporting Program.

This article appears on FDA’s Consumer Updates page, which features the latest on all FDA-regulated products.

Posted Aug. 23, 2012; Reviewed Sept. 4, 2013


 

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Defeat Gang Stalker poisoning through sample collection & GC/MS analysis

Gang Stalker Georgie poisoning me

I have a theory. I postulate that a government sanctioned criminal organization which depends upon secrecy for the moment, would best be destroyed through exposure. It is with this in mind that I do all that I can to both spread the word and document. Sure, many people will call you crazy when presented with this “inconvenient truth” but so what? After reading this, you can just give them a business card and say… “I have medical proof on my blog, go see for yourself!” Well, maybe it won’t be that easy, but at least some very hard scientific evidence will have your six whenever somebody claims that you are the exalted king of delusional paranoids (or Queen).

So, if the Gang Stalkers fail to break your will using “no touch” methods of control, they will eventually poison you. It’s a Jesuit thing. Poisoning still affords them plausible deniability since it can be accomplished remotely. It is employed as a last resort due to the observable symptoms it can produce. Although this physical evidence of criminal assault can be mitigated through records forgery and official’s corruption, it is usually a long road traveled to that final destination, leaving bread crumbs all along the way. I am going to teach you how to pick up some of those crumbs which will hopefully lead right back to those responsible. We won’t be able to catch everything they do, but with a little thought and diligence we can pin the tail on certain Donkeys (Jackasses). At the very least the Gang Stalkers will say…

“This is one TI we should have never messed with!”

I should offer not a warning but a reality check. They are very capable of killing you, and in rather unpleasant fashion at that. They have murdered many TI’s before and seem to be doing so more fervently than ever lately. I don’t want anyone reading this to have any delusions about their circumstances, what I am offering is simply my own anecdotal experiences in the hopes that it may help others. Make no mistake about it though, this is a program whose ultimate goal is your physical death. Whatever counter measures that you choose to employ, bear in mind that the Gang Stalkers may still attain their goal (albeit at high cost). Gang Stalking is and always has been a “death program”.


Blood Panels

Becton Dickinson Safety-Lok Vacutainer Blood CollectI consider blood tests to be the least useful of any of the diagnostic tests you can do. First of all, unless you specifically tell your lab or doctor the toxin to screen for, it will most likely be missed. The only way that a standard blood panel might detect that something is wrong is if whatever poison that the Gang Stalkers have poisoned you with causes secondary symptoms. Your liver isn’t functioning right, your kidneys aren’t filtering, something like that. If the blood tests do show something, the deviation from normal will have to be significant and or remarkable. This becomes problematic if you are seeing a new doctor who doesn’t have any of your previous blood panel records to know either what is normal nor abnormal for you.

Another bad thing about blood tests is this; county run clinics usually send all blood work to the lab contained within the county hospital. My personal experience is that county hospital labs are riddled with Gang Stalkers. As I’ve said before, poisoned TI’s calling ambulances and going to Emergency Rooms will encounter Gang Stalking EMT’s, Nurses, Doctors and Security Guards from start to finish. I have. They will turn you away, forge your records and give you medical mistreatment if not outright torture. I’ve even heard of them trying to kill you. You have to be prepared ahead of time for that and reading this is a good start. Have a plan in advance.

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If you must get your blood work done at a county clinic or a place you aren’t sure of, make sure the Phlebotomist uses brand new needles etc. Next, you should have a private blood lab that you have hired yourself. Prices vary for different tests done so it is probably a good idea to just go with a package deal of tests at first, they should repeat the same ones your doctor ordered. Give your lab a photocopy of the panel tests your doctor ordered and any other tests that you would like in addition. In this way you can compare the different lab results and formally complain about any glaring discrepancies (lab results all vary between different labs). At the very least this will put the county lab on notice that you are watching and are willing to complain if mistreated. Even if you can’t isolate the particular poison that is being used, they won’t be so eager to mess with you next time. They hate being exposed.

DirectLabs Price list

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Diagnostic Imaging (X-Rays, CT Scans, Sonagrams and MRI)

When your doctor tells you that he or she is going to order any one of the above, insist that they specify on the orders that you are to be personally given the exposures afterwards. To make sure that the technician knows that they are to give the films, printouts, video’s etc. to you personally, TELL THEM BEFOREHAND. Some techs aren’t used to this and may have to be reminded. Most imaging today is fairly quick and leaving with your images in hand should not be a problem, unless your doctor neglected to specify such in the orders.

IMG_4071IMG_4077

Once you have your images you can photograph them in the window like I did, or have them copied for you. You may even convince your doctor to have the tech make two sets of exposures, one for you and one for the office. Medical records are valuable pieces of paper for the Gang Stalkers, they like to steal them so that you can’t prove their crimes.

The biggest problem with imaging is that the Gang Stalkers will tailor their poisoning of you to minimize presentable symptoms. For example; if they know that you will be going in for a Sinus CT Scan on a certain day and time, they will stop poisoning you the day before so that the scan will come out clear. My idea of how to combat this is to first of all, try to keep these appointments as clandestine as possible. Second, if you have a good relationship with your doctor, ask him or her to just give you standing orders for diagnostic imaging. Next, find all of the local hospitals, clinics etc. that can do the imaging and accept your insurance. Call these places and ask if it would be possible to ever come in without an appointment, spur of the moment. If the imaging is not too complex they will probably say yes. If not, ask them what is a good time to call in the morning to check for other patient’s cancellations that you can assume. Most places will be more than happy to accommodate you since they don’t get paid if the patient is a no show.

Of course, it won’t take too long before your enemies figure out what you’re up to and limit their exposures to hours that are inconvenient to seek medical treatment. Your advantage is that you will have doctors orders in hand which any Emergency Room will more than likely honor, especially if the reason you are there is related. Be sure to tell them that your symptoms affect one or more of your vital functions (mine do) like breathing or heart function, ER triage nurses can turn you away otherwise. They are only required to preserve life, not treat non-life threatening injuries. Give them your doctors orders for whatever imaging or other tests you previously agreed upon (COPIES, YOU KEEP THE ORIGINALS). Also make sure you ask the ER doctor and techs for their names and titles for a medical records release request that you will make later on. You can get these from the nurse’s station as well, if it isn’t too busy. Be firm but friendly, ER personnel see horrors that would drive most of us insane.

If the Gang Stalker’s poison you in a way that shows now, you will be able to immediately go in for testing and obtain medical proof/evidence of it. In this way, the Gang Stalkers will never know when it is safe for them to make you sick since you could just drop everything and go somewhere they haven’t prepared for. This will back them off a lot.


Toxicology and Chemical Analysis

Ah, where the rubber meets the road…

I don’t have any experience with toxicology, to me it seems to be putting the carriage before the horse. I don’t mean to say that seeking out the services of an honest toxicologist is a bad idea, quite the contrary. If, and I do mean if, you can find one that is affordable and most importantly, has integrity, then by all means do so. You see that guy up there narating the video above? Let me tell you a little story about professors who sideline as expert witnesses and give testimony in court, most usually for the “prestigious” State where the steady income is favorable. Toxicology is a field whose only practical employer is the government, where do you think their loyalties lie?

Back in Junior College, I had a psych professor who just didn’t seem to like me at all, for no reason that I could fathom. I was nice, polite, somewhat lackadaisical but did nothing to engender the animus directed at me. I will say that I was young and handsome while he on the other hand, was old and crusty, but it still didn’t add up. Years later I realized that he was a Gang Stalker, as had been many of my male college professors who treated me with the same unjustified hostility. Anyway, this psychology professor had a regular job working for the State Of California and Alameda County as a therapist in the penal system (prisons/jails). He also gave “expert” testimony in criminal cases for the prosecution when called upon, and was compensated for that as well. I can only imagine that his compensation for testimony was dependent upon successfully getting someone locked up and put away. Stop giving useful testimony for the prosecution and suddenly your opportunities for advancement as a public servant mysteriously dry up. Know what I mean?

You should have heard this guy in class. He had the nastiest, most derisive and vulgar of attitudes towards anyone incarcerated, guilty or not. He would ridicule the suspects of cases that he had evaluated, would try to goad them into admitting their guilt, illicit false confessions, try to persuade them with misleading legal advice just to get them to say they did it. He was not an impartial medical professional to these people under criminal charges, he was a prosecutorial primer by proxy. He was devoid of any professional ethics, flaunted his contempt of standards, prioritized making his accused “clients” look as guilty as possible and was arrogant as all get out. Whenever I would score a high mark on my tests, he would look absolutely dejected instead of congratulatory. Absolute garbage.

Since my JC days I have seen this same type of person in public service over and over again. It is for this reason that I would caution any Targeted Individual to stay well away from any Toxicologists or medical personnel that have any connection to the State or government, whatsoever. When trying to find someone honest to help you, question them to find out if they have ever worked in or for government, have any family working for government or express any pro government attitudes. You may have stumbled upon a Gang Stalking fascist hiding behind a professional title. Listen carefully to the guy in this video, Dr. Alan Wu, and try to discern whether he would be impartial and fair or not. In my opinion, he is too closely allied with the UC System recently headed by New World Order General Ms. Janet Napolitano, works at SF General Hospital where I was turned away from after having been poisoned (they have asshole Sheriffs and kill patients by staircase exposure too) and just seems to express to many negative attitudes towards people that the state is prosecuting. I almost fell out of my chair when he said that he actively sought out The Church Of Scientology to be a forensic expert witness when they murdered that woman. What an ambulance chaser! These are the type of people you need to look out for as they are most likely government sanctioned stalkers. They would not have been allowed to their positions without becoming complicit, it’s just that simple.

As for me, it would be hard to pay the fees that would come from what is sure to initially be, a “wild goose chase.” Maybe not, as I said, I have absolutely zero experience with this medical field, it just might be the answer. My reservation is that it seems plausible a majority of Toxicologists would have long ago been recruited as Stalkers, it just seems an obvious conclusion. If the Gang Stalkers are going to make you sick, they need to have people (toxicologists) to intercept you. I am especially leery since I’ve had more than one Gang Stalking Troll try to persuade me to employ their own “approved” toxicologists. Yeah, right.

To my reasoning, a better idea would be to identify as accurately as possible just exactly what poison or poisons you are being exposed to. The most scientifically expedient way to accomplish this is not through the blood, but through your exhaled breath. You see, every toxin in your body can be found in your breath, the breath contains everything. Exhaled air is better than blood since it is coming straight from the blood in your lungs and is much easier to work with. Enter Gas Chromatography and Mass Spectrometry, bastions of chemical analysis. Between these two types of analytic procedures, almost any chemical compound can be separated individual parts and identified. It can be expensive but not excessively so, you should seek out “non-specific” GC if you have no clue what could be poisoning you. This type should be requested anyway because it scans for everything, it should tell you just what all is in your system, chemically speaking. GC/MS uses database references to compare to the graph produced. When your graph matches the database, there is a very high probability that your compound is what the reference database says that it is. Without getting too complex, let me just say that this technique used first may be the only one you end up needing. It has been around for so long that it’s results are universally accepted as sound.

Figure 3: Sampling end-exhaled air with a gas sampling tube; mouthpiece screwed on; left hand: one of two sealing caps with septum; plastic net sleeve to protect glass.

Figure 3: Sampling end-exhaled air with a gas sampling tube; mouthpiece screwed on; left hand: one of two sealing caps with septum; plastic net sleeve to protect glass.

When being poisoned by gas or otherwise, collect an exhaled breath sample immediately in a special glass sampling tube. The beauty of this method is that wherever you are, no matter what time of day or night, you can collect a sample of your breath and preserve what was used on you. Then, you can send off your breath sample to the lab of your choice (certified) for analysis, at your convenience. Once you have the results back you should then have a very good idea what is in your body that should not be there. If you want to know how much of it is in you, you would ask for “quantitative” as well as “qualitative’ non-specific analysis. Because human breath has been studied for so long, they know exactly what should and shouldn’t be in it as well as how much. Bingo! Now you not only have proof that you are sick, you now know what is making you sick. The what will probably lead to the “who”, since it will most likely be a chemical that only a state has access to. Now when you go to the doctor for a blood panel, you can tell him exactly what to test for. The nitty gritty sciencey stuff can be found here;

Trace Analysis in End-Exhaled Air Using Direct Solvent Extraction in Gas Sampling Tubes

Biological pathogens are easier since any med lab can culture for those. I saw the below video while researching this the other day, showing a little girl with asthma using a virus collection tube for exhaled breath.

 


Forensic Examination (Autopsy)

Not much to say about this one, other than you would do best to make private forensic exam arrangements beforehand, should the worst happen

If there is even the slightest hint that your death was the result of foul play, the police will at the very least order an autopsy by the county medical examiner and he or she will find absolutely no evidence of poisoning. If your survivors start making wild claims about you being killed by poison, forget about the truth ever surfacing.

As was the case with the late murdered actress, Mrs. Brittany Murphy, county coroners are corrupt and complicit with the Gang Stalkers. Instruct whomever may find your body that you have made pre-arrangements and that those people should be called first. If there are any police or county examiner personnel involved after your demise, you can be sure that absolutely no evidence of poisoning will ever see the light of day.

If at all possible, instruct someone to take samples of your hair and nails at least (at the roots and quick), before your remains are removed. I know that may be a hard thing to do but if you are a TI in the poisoning stage, those around you should have seen enough by now to understand. Also have them a prepared suitcase or box full of any other evidence of your harassment you have managed to collect and preserve. If you death is a suspected homicide, all of these precious bits of evidence will be stolen by the police or others.


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Our Commitment

Providing effective, efficient and accurate private pathology services and tissue recovery services is critical to its impact on families, public health and safety. National Autopsy & Tissue Recovery Services is committed to this end, and standing by this claim we pride ourselves on hiring only the best specialized experts in the field, who consistently meet the highest industry standards, and deliver on our commitment.

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On private autopsy services our basic fee for a full autopsy examination is $3000.00. This includes transportation costs and toxicology testing, if so desired or needed. Limited autopsy examinations cost less, depending on your needs. A unique service about our company is we have private morgue locations throughout the Midwest. We will take your loved ones remains to the closest location to you or make arrangements to use a private morgue or funeral home for the procedures. This allows us to make the process smoother for you and your family so that we can help provide the answers you are seeking. Please contact us to learn more.

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Our pathologists are board certified by the American Board of Pathology in anatomic, clinical, forensic, and/or neuropathology. All have performed thousands of autopsy examinations and are experienced in civil and criminal court testimony.

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Neurosciences is a field that has made leaps and bounds in terms of advancements over the years. We specialize in assisting families and institutions in the recovery of nervous system tissue and recovery of the brain to help document neurological disease, help families under the complexities of what their loved ones suffered from during life, and to further neurological research.

We are also active in teaching the neurosciences to help healthcare professionals understand the “pathological-clinical” correlation. That is, teaching them the pathology of neurological diseases so they can better asses patients clinically. Often times, clinically it is very difficult to discern what pathological processes are going on. With a brain autopsy, not only can the family benefit from understanding the pathology of the disease, but the clinician can also advance their clinical skills to help future neurological patients

That’s about it for now, but this post will be a work in progress and be amended as I learn more. Stay tuned for revisions and new info.

Take care and God bless.

Business card designs for my new blog “Poisoned By Gang Stalkers”

Poisoned By Gang Stalkers front me in resperator

front of Poisoned By Gang Stalkers biz card design #3.1

 


The Mask bust unsharp masked 2allstaractivist note:

Well, it’s about that time to order a new set of marketing tools for my latest blog, Poisoned By Giftgas. I’m playing around with several designs and haven’t quite decided which one to go with yet.

With the graphic design of the first set of cards I made for allstaractivist.com, I discovered that what I considered ugly was actually a boon. I found that the frenetic collage of images had a hypnotic effect on those I gave it to. The person stares intently at the card trying to figure out what they are looking at. The glossy finish of clay coated card stock seems to lend an undue formality to printed material, gravitas of the content notwithstanding.I liken this to much the same way the finish of a concrete sidewalk can set the tone for an urban foray, be it a Rodeo Drive pamper or an Inner City excursion.

All of my training told me that a clean and spartan layout was the most effective design for a card however, my experience has proven that false. While the person is trying to figure out just what the heck they are looking at, I have ample time to talk to them enthralled in a mildly suggestive state.

Ha! Take that Gang Stalkers!

PoisonedByGiftgas biz card back draft 1

back of Poisoned By Gang Stalkers biz card design #1

front of Poisoned By Giftgas biz card design #4

front of Poisoned By Gang Stalkers biz card design #4

PoisonedByGiftgas biz card front draft #3

back of Poisoned By Gang Stalkers biz card design #3

back of Poisoned By Giftgas biz card design #2

back of Poisoned By Gang Stalkers biz card design #2

back of Poisoned By Giftgas biz card design #5

back of Poisoned By Gang Stalkers biz card design #5

Trace Analysis in End-Exhaled Air Using Direct Solvent Extraction in Gas Sampling Tubes

International Journal of Analytical Chemistry logo

International Journal of Analytical Chemistry
Volume 2014 (2014), Article ID 904512, 10 pages
http://dx.doi.org/10.1155/2014/904512

flask & med signallstaractivist note: I kind of have a unique mind (some say genius, others say crazy…). It does have it’s advantages sometimes however, and the below article is one of those times.

The poisoning I am enduring is accomplished by forcing me to breath noxious and toxic stuff. That stuff comes back out in the form of my spit, feces, urine and most obviously, exhaled breath. In the morning I can blow my nose and an extremely strong chemical oder comes out. I have to be careful not to take breaths through my mouth because the chemical will burn and blister my tongue if I do.

The thought occured to me that I should capture samples of what is flushed out. I then wondered if there was some way that I could capture my exhaled breath too. I have found such a method and it was created only last year. Basically, it is a vacuum tube with one way valves on each end. I had thought that any glass vacuum tube with a sealed end would do but if they already make one, so much the better. There may be a better suited device (absorbant in tube) for catching breath for analysis, consultation with your lab of choice is probably a good idea. The below article is a good place to start, it concerns detecting exposure levels to a known hazardous chemical in an occupational setting. Good enough for me, I used to be a HAZWOPER ironically enough.

Because the Gang Stalkers use an unkown poison (unknown at least to me), a wide variety of samples from all bodily secretions would be a good idea, the lab will likely appreciate it. Also, if the chemical is not already known, testing can get expensive. Bio pathagens are a little easier because they can be cultured.

One final caveat and encouragement for all of you Targeted Individuals out there, troll Gang Stalkers will try to befriend and mislead you. I have had so many trolls try to tell me the poison is a pesticide this, a solvent that… I just ignore them. So much disinfo out there. Follow your own mind and common sense and you will make your way because if you have been targeted, God is probably looking out for you.

The encouragement is this;

  • Time is winding down for the Gang Stalkers, people are waking up to their crimes
  • Criminals will be criminals and will commit crimes against their own. Defectors are sure to result and they will have their revenge by telling on their former partners. It won’t be too much longer until we uncover most if not all of their methods of control.
  • God doesn’t like what they are doing and will put a stop to it soon enough, just stay strong and faithful to Jesus. He will deliver us in due time, in due time.

jesus-on-the-cross-with-sky1


septum

(ˈsɛptəm)

n, pl -ta (-tə)

1. (Biology) biology anatomy a dividing partition between two tissues or cavities
2. (Anatomy) biology anatomy a dividing partition between two tissues or cavities

3. (Mechanical Engineering) a dividing partition or membrane between two cavities in a mechanical device

Plural septa

A thin wall or membrane that separates two parts, structures, or individual organisms. The chambers of the heart are separated by septa.
904512.fig.001

Figure 1: Sketch of the valveless gas sampling tube, sealed with septum caps.

Figure 3: Sampling end-exhaled air with a gas sampling tube; mouthpiece screwed on; left hand: one of two sealing caps with septum; plastic net sleeve to protect glass.

Figure 3: Sampling end-exhaled air with a gas sampling tube; mouthpiece screwed on; left hand: one of two sealing caps with septum; plastic net sleeve to protect glass.

2.1.1. Sampling

(1) Exhaled Air Sampler. Breath samplers of the valveless glass-tube type were not commercially available. An internally developed sampler was therefore used (Figure 1). The valveless exhaled air sampler, similar to the description by Stewart [28], consisted of a glass tube (outer diameter 2 cm, length 20.5 cm) with threads (thread size 13–425) on both ends and two open-top septum screw caps. Unlike in Stewart’s work, however, not only were the tube dimensions changed, but the glass tube openings were also optimized. The tube openings on both ends were formed as cylindrical holes (inner diameter 3 mm, length 10 mm). The glass tubes were custom-manufactured to our specific requirements by Glastechnik Gräfenroda GmbH (Gas Sampling Tube—Type BAuA, Gräfenroda, Germany).

The screw caps were made of glass-filled nylon in a robust design (thread size 13–425, Kimble Chase, Rockwood, USA) and contained PTFE-lined silicone septa (75 mils thick, Supelco, Bellefonte, USA). The volume of a sealed tube was approximately 37.5 mL and was determined gravimetrically for each tube. Open-top screw caps for autosampler vials (thread size 13–425, wide mouth, Infochroma, Zug, Switzerland) without a septum were used as disposable mouthpieces (Figure 2).

OPEN TOP NYLON CAPSPTFE-Lined 13-425 Phenolic Cap KimbleSepta for open top caps - Part # Z106496 ALDRICH


Poor Man’s (or Woman’s) Version – by Eldon J. Brown

VWR logoPrecision-Septa-sm

Suba-Seal® Septum Stoppers 29/26–29/42 Outer Joints and 25.5mm I.D. Tubing CG-3024-09 80062-452 Pack of 50 $103.58
Glass Tubing Cutter BX10 by C & A Scientific $10.95

Glass Tubing Cutter BX10 by C & A ScientificThis C&A Scientific Glass Tubing Cutter is spring loaded and accepts tubing up to 1½ (38mm) in diameter. Individually boxed, 10/box.
$10.95 on amazon.com

Flint glass is also known as soda lime glass. It has a lower melting point, chemical resistance, and expansion rate than does borosilicate glass. American Educational Glass Flint Tubing. This tubing is known as apparatus weight tubing.

Flint glass is also known as soda lime glass. It has a lower melting point, chemical resistance, and expansion rate than does borosilicate glass. American Educational Glass Flint Tubing. This tubing is known as apparatus weight tubing.$20 – $40 on amazon.com

UL100 - Basic Pencil Flame Torch Kit Basic torch kit produces 1/2"-wide pencil flame for light work. Brass burn tube for durability Solid brass regulators for durability Adjustable flame for controlled heat output UL2317 Basic Pencil Flame Torch 14.1 oz. Propane-filled Cylinder

UL100 – Basic Pencil Flame Torch Kit
Basic torch kit produces 1/2″-wide pencil flame for light work.
Brass burn tube for durability
Solid brass regulators for durability
Adjustable flame for controlled heat output
UL2317 Basic Pencil Flame Torch
14.1 oz. Propane-filled Cylinder$14.94 / each – Any hardware store.

How to Cut and Fire Polish Glass Tubing

Updated November 02, 2014.

Glass tubing is sold in a variety of lengths. Typical lengths are 6″ (~150 mm), 12″ (~300 mm) and by the foot. There is a good chance you’ll need to cut the tubing to make it the right size for your project or experiment, so here is what to do.

  1. Use the edge of a steel file to score or notch the glass perpendicular to its length. A single score works best. If you saw back and forth, you’re asking for a messy break. Also, a light score works better than a deep cut. 
  2. Put on eye protection and heavy gloves. If you don’t have gloves, you can minimize a chance of being cut by wrapping the tubing in a towel. 
  3. Place your thumbs on either side of the notch and apply gentle pressure until the tubing snaps in two. 
  4. The ends of the tubing will be extremely sharp, so you’ll need to fire polish them before using the tubing. Fire polish the tubing by holding the sharp ends of the glass in the flame of an alcohol lamp or gas burning. Turn the tubing so that it is heated evenly. Stop when the ends are smooth. Be careful that you don’t leave the glass in the flame too long, which melts the tubing and may block the ends. 
  5. Allow the glass tubing to cool before using it.

How To Bend and Draw Glass Tubing


International Journal of Analytical Chemistry
Volume 2014 (2014), Article ID 904512, 10 pages
http://dx.doi.org/10.1155/2014/904512
Research Article

Trace Analysis in End-Exhaled Air Using Direct Solvent Extraction in Gas Sampling Tubes: Tetrachloroethene in Workers as an Example

Federal Institute for Occupational Safety and Health (BAuA), Group 4.2 “Biomarkers”, Nöldnerstrasse 40-42, 10317 Berlin, Germany

Received 29 November 2013; Accepted 31 January 2014; Published 18 March 2014

Academic Editor: Hian Kee Lee

Copyright © 2014 Chris-Elmo Ziener and Pia-Paulin Braunsdorf. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Simple and cost-effective analytical methods are required to overcome the barriers preventing the use of exhaled air in routine occupational biological monitoring. Against this background, a new method is proposed that simplifies the automation and calibration of the analytical measurements. End-exhaled air is sampled using valveless gas sampling tubes made of glass. Gaseous analytes are transferred to a liquid phase using a microscale solvent extraction performed directly inside the gas sampling tubes. The liquid extracts are analysed using a gas chromatograph equipped, as usual, with a liquid autosampler, and liquid standards are used for calibration. For demonstration purposes, the method’s concept was applied to the determination of tetrachloroethene in end-exhaled air, which is a biomarker for occupational tetrachloroethene exposure. The method’s performance was investigated in the concentration range 2 to 20 μg tetrachloroethene/L, which corresponds to today’s exposure levels. The calibration curve was linear, and the intra-assay repeatability and recovery rate were sufficient. Analysis of real samples from dry-cleaning workers occupationally exposed to tetrachloroethene and from nonexposed subjects demonstrated the method’s utility. In the case of tetrachloroethene, the method can be deployed quickly, requires no previous experiences in gas analysis, provides sufficient analytical reliability, and addresses typical end-exhaled air concentrations from exposed workers.

1. Introduction

If a worker is exposed to a workplace chemical, the chemical can enter the body. Analytical determination of the chemical or its metabolites in the body allows estimation of the absorbed dose and ultimately the health hazard. Biological samples such as blood or urine are routinely used for this kind of analysis, which is known as biological monitoring, or biomonitoring for short.

Absorbed volatile chemicals are partly eliminated from the body via exhalation. Exhaled air, also referred to as exhaled breath, is therefore also suitable for analysis in biological monitoring. Nevertheless, exhaled air is rarely used outside of research applications within this specialist field. Possible reasons for this include a lack of practical, reliable, and commercially available sampling systems, as well as analytical difficulties [1].

Against this background, a new exhaled air analysis method is to be developed that overcomes the previous operating limits and can be used in routine situations. Tetrachloroethene was chosen as a model substance for the development process.

Tetrachloroethene (CAS number: 127-18-4; synonyms: tetrachloroethylene, perchloroethylene, PER, PCE) is a volatile solvent widely used in various technical processes and as an intermediate in the chemical industry [2]. Solvent applications are well known in cleaning procedures such us dry cleaning, metal degreasing, and film restoration [2]. Workers are exposed via inhalation and dermal absorption [3]. The majority of the incorporated neurotoxic substance is eliminated unchanged via exhalation [3]. The American Conference of Governmental Industrial Hygienists (ACGIH) and the Scientific Committee on Occupational Exposure Limits (SCOEL) have suggested assessment values for tetrachloroethene in exhaled air from exposed workers [3, 4].

Several sampling and analytical methods have been reported for the determination of tetrachloroethene in exhaled air: for example, exhaled air sampling has been achieved using glass tubes that can be sealed with septum caps [58] or valves [9, 10], bags made of polyvinyl fluoride [1118] or polyvinylidene chloride [8,19], adsorbent tubes [20, 21], more complex sampling devices [22, 23], or by direct exhalation into an analyser [24, 25]. Sample analyses were performed using a gas chromatograph [513, 1522], surface acoustic wave sensors [14], an atmospheric-pressure ionization mass spectrometer [24], or an infrared spectrometer [8, 25]. The gaseous samples were transferred directly into the measurement device using gas-tight syringes [59, 11, 1519, 22], or the tetrachloroethene was extracted from the breath or breath samples using solid-phase microextraction (SPME) [10] or adsorption tubes and then analysed following thermal desorption [10, 13, 14] or liquid elution [12, 20, 21].

Application of the suggested assessment values for tetrachloroethene requires strict adherence to the specified sampling times “prior to shift” [4] or “prior to the last shift of a work week” [3]. Routine use of exhaled air in biological monitoring therefore requires sampling methods that could be performed by the clients themselves under field conditions if necessary. The requirements for routine use are not currently met by direct-reading instruments, for example, an atmospheric-pressure ionization mass spectrometer [24] or infrared spectrometer [25] coupled with a breath inlet system, or by technically complex sampling systems, for instance, with built-in pumps and a multitude of valves [23].

Exhaled air consists of ambient air retained in the respiratory dead space and alveolar air [26]. The latter has been involved in gas exchange in the lung and can be sampled after the dead space air has been exhaled [26]. For this reason, alveolar air is also called end-exhaled air. The quoted assessment values for tetrachloroethene are defined explicitly for end-exhaled air. The breath-sampling method must therefore ensure that only this exhaled air fraction is sampled.

For routine uses, the most appropriate sampler seems to be a valveless glass tube that can be sealed with septum caps. Due to their design, such tubes sample end-exhaled air if the tube volume is less than the alveolar air volume. For sampling, a subject needs only to exhale once completely through the open tube. Tubes of this kind allow self-sampling [27], are inexpensive to manufacture, and do not allow gas to permeate through their glass wall. Glass tubes equipped with valves can be sealed very quickly after sampling, but valves make the sampling device bulky and expensive for the purposes of routine sampling.

In contrast to glass tubes, bags do not collect end-exhaled air automatically [26]. The subject therefore has to exhale the dead-space air into the environment and then the alveolar air into the bag [18]. The sampling procedure therefore seems error-prone, and the results are more strongly influenced by the subject’s cooperation.

Direct exhalation into adsorption tubes is well suited to analyte enrichment and stabilization of gaseous samples for transport and storage. However, the sampling procedure requires that the sampled volume be measured using an additional device, which reduces the routine practicality of the method.

To overcome the current barriers to routine exhaled air analysis, a proposed method must take into account the technical realities of typical biomonitoring laboratories. The basic equipment of such laboratories often includes a gas chromatograph coupled with a liquid autosampler. In contrast, the handling of adsorbent tubes and thermal desorption techniques is more common in air-monitoring than biomonitoring laboratories. The latter are familiar with solid-phase microextraction techniques, but the use of such techniques for routine breath analysis requires sophisticated automation solutions. The same applies to direct injection of breath samples into the analyser. Furthermore, calibration is carried out using gaseous standards in both cases. Unfortunately, biomonitoring laboratories are not usually familiar with gas calibrations.

Liquid sample analyses are one strength of biomonitoring laboratories, which commonly analyse blood and urine samples. Solvent extraction of analytes from exhaled air samples allows direct transformation of the gaseous samples into “liquid samples” and, consequently, the use of existing skills and technologies. The process calibration can therefore be performed with liquid standards, and a typical liquid autosampler can be used for the automation of the measurement step. In conclusion, the method presented in this work was conceived based on sampling end-exhaled air using valveless glass tubes, solvent extraction of the analyte, and automated liquid-sample analysis using gas chromatography. To the authors’ knowledge, no end-exhaled air analysis methods have yet been published that use direct solvent extraction.

2. Experimental

2.1. Exhaled Air Analysis
2.1.1. Sampling

(1) Exhaled Air Sampler. Breath samplers of the valveless glass-tube type were not commercially available. An internally developed sampler was therefore used (Figure 1). The valveless exhaled air sampler, similar to the description by Stewart [28], consisted of a glass tube (outer diameter 2 cm, length 20.5 cm) with threads (thread size 13–425) on both ends and two open-top septum screw caps. Unlike in Stewart’s work, however, not only were the tube dimensions changed, but the glass tube openings were also optimized. The tube openings on both ends were formed as cylindrical holes (inner diameter 3 mm, length 10 mm). The glass tubes were custom-manufactured to our specific requirements by Glastechnik Gräfenroda GmbH (Gas Sampling Tube—Type BAuA, Gräfenroda, Germany).

904512.fig.001
Figure 1: Sketch of the valveless gas sampling tube, sealed with septum caps.

The screw caps were made of glass-filled nylon in a robust design (thread size 13–425, Kimble Chase, Rockwood, USA) and contained PTFE-lined silicone septa (75 mils thick, Supelco, Bellefonte, USA). The volume of a sealed tube was approximately 37.5 mL and was determined gravimetrically for each tube. Open-top screw caps for autosampler vials (thread size 13–425, wide mouth, Infochroma, Zug, Switzerland) without a septum were used as disposable mouthpieces (Figure 2).

904512.fig.002
Figure 2: Sketch of the valveless gas sampling tube, ready for sampling; open-top cap screwed on as a mouthpiece.

(2) End-Exhaled Air Sampling Procedure. For sampling, the subjects breathed normally and then exhaled completely through the glass tubes (Figure 3) after inhaling and holding their breath for 5 seconds. The subjects then removed the mouthpieces and screwed the sealing caps onto the tubes. Samples collected in the field were transported to the laboratory at ambient temperature and in the dark. The glass tubes were protected using plastic net sleeves to ensure safe handling and transport (Figure 3).

904512.fig.003
Figure 3: Sampling end-exhaled air with a gas sampling tube; mouthpiece screwed on; left hand: one of two sealing caps with septum; plastic net sleeve to protect glass.
2.1.2. Sample Analysis

(1) Sample Preparation. The analyte tetrachloroethene was extracted from the exhaled air samples using a microscale solvent extraction procedure: 200 μL isooctane (Suprasolv, Merck, Darmstadt, Germany) was injected into the breath samples in the sealed gas sampling tubes using a 250 μL syringe (Series G, ILS, Stützerbach, Germany). The tubes were then placed horizontally on an RM10-V 30 tube roller mixer (Labortechnik Fröbel, Lindau, Germany) for 20 minutes at a speed of 1 revolution per minute. After mixing, the tubes were placed in a vertical position with the intact septa at the bottom for 15 minutes to allow phase separation. Figure 4 shows the separated isooctane phase of the exhaled air extract; it is located within the cylindrical hole of the gas sampling tube.

904512.fig.004
Figure 4: Sketch of the lower side of a gas sampling tube in the vertical position: the exhaled breath extract (the isooctane phase) is located within the cylindrical hole.

The extract was withdrawn from the sealed tubes using a 250 μL syringe (Series G, ILS, Stützerbach, Germany) as shown in Figure 5 and then injected directly into 250 μL glass microvials (iV2 μ-Vial, Glastechnik Gräfenroda, Gräfenroda, Germany). The vials were sealed immediately with PTFE-silicone septum screw caps (MS Pure, Glastechnik Gräfenroda, Gräfenroda, Germany) and placed in the autosampler tray of the gas chromatograph for analysis.

904512.fig.005
Figure 5: Withdrawing the extract.

(2) GC/MS Analysis

GC-MS System. GC-MS analysis was performed on a 6890 N gas chromatograph coupled to a 5973 N mass selective detector (Agilent Technologies, Palo Alto, USA), equipped with an MPS2 autosampler (Gerstel, Mühlheim, Germany), and controlled with a ChemStation (Agilent Technologies) and the embedded Maestro software (Gerstel). The gas chromatograph was fitted with a split/splitless injector (split liner: cup design, unpacked, Supelco, Bellefonte, USA) and an HP-1 ms capillary column (30 m × 0.25 mm × 0.25 μm, coated with cross-linked and bonded 100% dimethyl polysiloxane; Agilent Technologies, Palo Alto, USA). Sampling and injection were performed using the autosampler in the syringe-based liquid sampling mode with a 10 μL syringe (Gerstel, Mühlheim, Germany).

2D GC Agilent inovations for complex mixture analysis_2015-02-22_185726

2D GC as quality control tool_2015-02-22_1858582D GC test sample verification_2015-02-22_185423

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GC-MS Method. The autosampler injected 2 μL of a sample with a split ratio of 1 : 20. After the injection, the syringe was washed using n-hexane (puriss., absolute, Sigma Aldrich, Munich, Germany) to avoid carryover effects. The gas chromatograph temperature settings were as follows: injection temperature was 250°C; column oven temperature programme was 40°C for 2 min, followed by an increase to 60°C at 5°C/min and then to 90°C at 30°C/min; the transfer line was set to 250°C. Helium 6.0 was used as a carrier gas at a constant flow rate of 1 mL/min. The mass selective detector was operated with electron impact ionization (70 eV) in selected ion monitoring (SIM) mode. Tetrachloroethene was monitored using the target ion 166 m/z and the qualifier ion 131 m/z. The target ion was used for quantitation. The analyte was identified using the retention time and the abundance ratio of qualifier ion to target ion. Peak integration was performed using the ChemStation software. The position of the isooctane peak was explored using the ion 99 m/z; the solvent delay was then set to 4 minutes.

(3) Calibration. For calibration, 200 μL of calibration solution (isooctane spiked with tetrachloroethene) was injected into gas sampling tubes containing end-exhaled air from subjects not exposed to tetrachloroethene. The resulting calibration samples were treated the same as real samples after the addition of isooctane according to Section 2.1.2(1) and analysed as described in Section 2.1.2(2). The exhaled air from the subjects who gave the matrix samples was checked for blank values. Calibration curves were obtained by plotting the peak areas of tetrachloroethene as a function of the concentrations or masses used. The latter allowed the actual sample volumes to be taken into account. The determined tetrachloroethene masses were therefore divided by the sample volumes, which corresponded to the volumes of the sampling tubes used.

Preparation of Calibration Solutions

Stock Solution I. 30 μL of tetrachloroethene (analytical standard, Sigma-Aldrich, Steinheim, Germany) was drawn into a 50 μL syringe. The standard was injected into a 10 mL volumetric flask partly filled with isooctane (Suprasolv, Merck, Darmstadt, Germany). The syringe was weighed before and after injection to determine the mass of standard injected. The flask was made up to the mark with isooctane.

Stock Solution II. A 200 μL aliquot of stock solution I was pipetted (200 μL, variable, Eppendorf Research plus, Eppendorf, Hamburg, Germany) into a 10 mL volumetric flask and diluted to the mark with isooctane.

Calibration Solutions. Microlitre volumes of stock solution II were aliquoted into 10 mL volumetric flasks using adjustable pipettes (Eppendorf Research, Eppendorf) and diluted to the mark with isooctane. The aliquots of stock solution II were calculated such that 200 μL of each calibration solution corresponded to the required tetrachloroethene concentration in the gas sampling tube.

All solutions were stored at 4°C in 10 mL capillary bottles (Certan, Sigma Aldrich, Steinheim, Germany), where they remained stable for at least one week.

2.2. Method Performance Evaluation
2.2.1. Calibration

For the purpose of method evaluation, a 10-point calibration was established in the concentration range 2 to 20 μg tetrachloroethene/L exhaled air. The calibration samples were prepared and analysed as described in Section 2.1.2(3). Table 1 shows an example pipetting scheme.

Table 1: Example pipetting scheme for the preparation of the calibration samples
Table 1: Example pipetting scheme for the preparation of the calibration samples; concentration range 2 to 20 μg tetrachloroethene/L exhaled air.
2.2.2. Method Precision

To determine the precision of the method, spiked end-exhaled air samples ( in each case) were analysed intraday at the concentrations levels 4 and 15 μg tetrachloroethene per litre according to Section2.1.2. The spiked samples were prepared as follows: end-exhaled air was obtained according to Section2.1.1 from a subject not exposed to tetrachloroethene and spiked with tetrachloroethene standard gas (10 μL or 37 μL) using gas-tight syringes (1701N/1705N series, Hamilton, Bonaduz, Switzerland). To keep the septa of the gas sampling tubes intact, the screw caps were unscrewed at one end for gas injections and then screwed back on quickly.

The standard gas was prepared using a static method: using a 25 μL syringe, 20 μL of tetrachloroethene (analytical standard, Sigma Aldrich, Steinheim, Germany) was injected into a 2.2 L static dilution bottle with a valve (Sigma Aldrich, Bellefonte, USA). The syringe was weighed before and after injection to determine the mass of standard injected. The exact bottle volume was determined gravimetrically. The bottle was stored overnight at room temperature to evaporate the substance fully and to equilibrate the gas concentration.

2.2.3. Accuracy

Spiked end-exhaled air samples, prepared as described in Section 2.2.2, were used for recovery experiments. These samples—10 at each of the concentration levels 4 and 15 μg/L tetrachloroethene—were analysed according to Section 2.1.2.

2.2.4. Storage Stability of Breath Samples

The storage stability of end-exhaled air samples was determined using spiked samples at the concentration levels 4 and 15 μg/L. Twenty samples at each concentration were prepared as described in Section 2.2.2. In each case, 10 samples were analysed according to Section 2.1.2 on the day of their creation and 10 samples were analysed after one week of storage in the dark at room temperature.

2.2.5. Limits of Detection and Quantification

The limits of detection and quantification were determined using the calibration curve procedure, following the description by Bader et al. [29]. Calibration standards were prepared in end-exhaled air according to Section 2.2.2. However, the standard gas was diluted beforehand as follows: 5 mL of the standard gas was injected in a second static dilution bottle and the resulting gas was used as the spiking gas. Ten equidistant calibration points in the concentration range 0.005 to 0.05 μg tetrachloroethene/L were analysed according to Sections 2.1.2(1) and 2.1.2(2); the lowest concentration point was close to the expected detection limit.

2.2.6. Field Study

End-exhaled air analyses were performed on four dry cleaners (two men, two women) with known exposure to tetrachloroethene while working in a dry-cleaning shop and a control group of 10 subjects (five men, five women) without such exposure. The dry-cleaning shop used tetrachloroethene as the cleaning solvent and worked primarily with leather garments. The employees’ work tasks were as follows: operating machines, pressing, dyeing, and tagging/inspection. The ethics committee of the Berlin Chamber of Physicians approved the study protocol. All subjects signed informed consent forms.

End-exhaled air sampling was carried out as described in Section 2.1.1 and, in the case of the exposed workers, on a Friday prior to the last shift of the working week. All subjects filled two gas sampling tubes for tetrachloroethene analysis using the proposed method. Samples were collected outdoors to avoid contamination. The ambient temperature and atmospheric pressure were recorded at the sampling site at the moment of sampling. The samples were transported to the laboratory, stored in the dark and at room temperature over the weekend, and analysed on Monday as described in Section 2.1.2. A calibration was performed on the day of measurement for the purposes of quantification. In addition, the mass of water in each of the tubes was determined gravimetrically by weighing the tubes before and after sampling.

3. Results and Discussion

3.1. Method Development—Basics
3.1.1. End-Exhaled Air Sampler

The end-exhaled air sampler used in sampling was self-developed in the form of a valveless gas sampling tube made of glass and sealable with septum caps (Figure 1). The tube openings were designed as cylindrical holes with a diameter of 3 mm. The small openings were intended to reduce the chance of losses during sampling, and the special design of the holes allows withdrawal of the solvent phase after extraction (Figure 5). The tube volume was set at about 37 mL so that the sampling device was easy to handle. To sample pure alveolar air, the tube volume must be less than the volume of the alveolar air fraction in a single exhaled breath. Since the latter volume is approximately 350 mL [30], this requirement has been met. Due to the small tube volume, the tube is flushed with alveolar air approximately nine times until the sample is accommodated. The manufacturing process of the designed glass tubes is comparable to the manufacturing of disposable, screw-cap, laboratory glass vials. The manufacturing cost should therefore be comparatively low. The choice of the 13–425 screw thread (Glass Packaging Institute/USA) at the tube ends allows the use of common mass-produced screw-vial caps and septa, as well as Mininert valves (Supelco, Bellefonte, USA). The latter could be useful for the preparation of gaseous standards in special cases.

The volumes of the gas sampling tubes varied slightly due to manufacturing. Volume determinations in part of the production batch () had the following results: mean 37.5 mL, range 37.2–37.8 mL, and RSD 0.29%. All calculations in this paper took account of the tubes’ individual volumes. For the purposes of future routine analysis, however, it may often be sufficient to use the mean value and to ignore the volume variations.

3.1.2. End-Exhaled Air Sampling Procedure

Since the blood/air partition coefficient for tetrachloroethene is above a figure of about 10, for example, Koizumi determined a value of 11 at 37°C [31], alveolar air sampling without a breath holding time provides a valid index of the solvent’s mixed venous concentration [32]. This assumes, however, that the subject is exhaling after a period of normal ventilation at a constant rate [32]. Unintentionally, however, some subjects spontaneously tend to inhale more deeply to blow into the tube. In these cases, gas equilibration in the lung is slowed [32]. A breath holding time of 5 seconds was therefore chosen for the sampling procedure.

3.1.3. Solvent Extraction

Before development of the solvent extraction method could commence, a suitable solvent had to be selected. The solvent had to meet the following criteria:(i)miscibility with the analyte,(ii)immiscibility with water,(iii)lowest possible vapour pressure,(iv)significantly lower retention time than the analyte in gas chromatography,(v)no interfering impurities.

Isooctane satisfies these criteria and was therefore chosen as the extraction solvent. It is miscible with tetrachloroethene but immiscible with water. The latter is important because breath samples in the gas sampling tubes always contain condensed water. For example, the results of the field study in Section 3.3showed a median value of 33 mg of water per tube. The relatively low vapour pressure of isooctane reduces solvent losses during analysis and increases the robustness of the method. Blank isooctane samples showed no interfering signals in chromatographs. Under the selected chromatographic conditions, isooctane has a significantly lower retention time than tetrachloroethene: 3.1 min versus 5.2 min. Isooctane therefore does not interfere with the analyte signal or extend the analysis time.

The isooctane volume used for the extraction process should be as small as possible in order to achieve a high level of analyte enrichment yet also large enough to achieve good extract recovery. Against this background, the solvent volume was set at 200 μL. The use of the roller mixer in the extraction step leads to the formation of a film of isooctane on the glass wall with a large surface area for gas absorption. Partition equilibrium is therefore reached quickly. Isooctane has a lower density (0.69 g/mL) than water, but the isooctane phase collects at the bottom of the gas sampling tubes if the tubes are held up vertically (Figure 4). The condensed water adheres to the glass wall, mainly in a thin dispersion. It is therefore possible to separate the extract using a syringe (Figure 5). About 50 μL of the extract can usually be transferred into the gas chromatography vials. Water very rarely entered the syringe; when it did, two phases were visible in the vials. The water phase was then simply removed using a syringe.

3.1.4. Gas Chromatographic Analysis

Gas chromatographic analysis of the solvent extract of an end-exhaled air sample is very simple and is completed in about 7 minutes. Excellent chromatograms were obtained using a standard column (HP-1, 30 m), as shown in Section 3.3. Since only a very small quantity of the solvent extract is used for analysis (only 2 μL in the proposed method), a sample extract can be analysed repeatedly. Moreover, the extracts can be diluted if the analyte concentration value exceeds the upper limit of the working range. In this regard, therefore, the use of liquid extracts has advantages over direct exhaled air analysis.

3.1.5. Working Range of the Method

The working range of the analytical method must cover the suggested limit value of 3 ppm tetrachloroethene in end-exhaled air [3, 4]. Since today’s typical concentrations in workers at dry-cleaning shops are well below that limit value, the method should also cover these levels; for example, McKernan et al. measured a preshift value of 0.51 ppm (arithmetic mean, 18 subjects from four shops) [18]. The working range was therefore defined as 2 to 20 μg/L, corresponding to about 0.3 to 3 ppm.

3.2. Method Performance Evaluation
3.2.1. Calibration

Calibration curves were obtained by plotting the peak areas of tetrachloroethene against the concentrations or masses used. Representative calibration curves are shown in Figures 6 and 7.

904512.fig.006
Figure 6: Calibration curve for the determination of tetrachloroethene in end-exhaled air; peak area against concentration used.
904512.fig.007
Figure 7: Calibration curve for the determination of tetrachloroethene in end-exhaled air; peak area against mass used.

The curves are linear within the investigated working range of the method (between 2 and 20 μg tetrachloroethene per litre of exhaled air). High values were obtained for the coefficient of determination (). In the calibration curve procedure for determining the limit of detection in Section 2.2.5, one calibration was shifted to a lower concentration range (0.005 to 0.05 μg/L). The curve thus obtained was also linear, with a coefficient of determination of 0.99. The method of calibration is therefore acceptable and can easily be adapted to other concentration ranges.

3.2.2. Method Precision

The intraday precision was determined at the concentration levels 4 and 15 μg tetrachloroethene per litre of end-exhaled air. The results are presented in Table 2 and show that the precision expressed as relative standard deviation is less than 7%. It must be noted that the stated precision includes variations arising through sample preparation, especially with regard to the tetrachloroethene spiking procedure.

Table 2: Method precision and accuracy expressed as relative standard deviation and mean recovery
Table 2: Method precision and accuracy expressed as relative standard deviation and mean recovery, respectively; determined using 10 individual samples in each case.
3.2.3. Accuracy

Reference materials were not available and there was no possibility of interlaboratory comparability investigations. Spiked end-exhaled air samples were therefore used for recovery experiments at two concentration levels. The results are presented in Table 2. Slightly less tetrachloroethene was recovered than the calculated additions, but the recovery rates are reproducible and sufficient for routine biomonitoring measurements. In addition, the spiking gas was prepared using a static method. Adsorption effects [33] in the static dilution bottle and the syringes may decrease the actual tetrachloroethene concentration in the spiking gas and subsequently lead to an overestimation of the method’s inaccuracy.

The use of an internal standard, for example, 13C tetrachloroethene, might improve the reliability of the method, including the recovery. The extra effort for the internal standard procedure could be considered particularly in nonroutine applications which are beyond the aim of this work.

3.2.4. Limits of Detection and Quantification

The limits of detection and quantification of tetrachloroethene in end-exhaled air were determined using the calibration curve procedure and spiked end-exhaled breath samples. A realistic extraction step was therefore included in the experiment.

Under the given conditions for sample preparation and gas chromatographic determination, the limit of detection was 0.005 μg/L and the limit of quantification was 0.02 μg/L. The limit of quantification is therefore one-thousandth of the suggested biological assessment values [3, 4] and shows the capability of the developed method.

3.2.5. Stability of End-Exhaled Air Samples

Exhaled air from workers exposed to tetrachloroethene is commonly sampled on the last day of a working week [3]. The samples are then sent to the laboratory by standard post. Typically, the laboratory receives the samples after the weekend, so they must remain stable for at least three days at ambient temperature. The stability of breath samples was therefore determined for a storage time of one week at room temperature. Figure 8 shows the results of the stability test. Whereas no tetrachloroethene loss was observed for the concentration level 15 μg/L, a very slight loss of 5% was obtained for the level 4 μg/L. The samples therefore remain sufficiently stable for one week. This conclusion is supported by other authors, who have reported breath sample stability for at least five days in glass tubes [5, 22].

904512.fig.008
Figure 8: Results of the storage test of end-exhaled air samples over seven days; per level per day; mean concentration of the start day (Day 0) defined as 100%.
3.3. Field Study

A field study was conducted to verify the applicability of the proposed method. Table 3 shows the results of the end-exhaled air analyses of subjects exposed to tetrachloroethene () and nonexposed subjects (, control group).

Table 3: Measurement results of the field study: tetrachloroethene in end-exhaled air in exposed
Table 3: Measurement results of the field study: tetrachloroethene in end-exhaled air in exposed (dry-cleaning workers) and nonexposed (control group) subjects.

The sampling procedure was easy to apply and was accepted well by all subjects. Double sampling, in which the subjects filled two gas sampling tubes consecutively, took about 4 minutes. The water content in the tubes ranged from 14 to 60 mg (median 33 mg, ).

Representative chromatograms of solvent extracts from end-exhaled breath samples from the study participants are shown in Figures 9 and 10.

904512.fig.009
Figure 9: Representative chromatogram of an end-exhaled air sample from a dry-cleaning worker (machine operator) exposed to tetrachloroethene; tetrachloroethene peak (retention time 5.2 min, m/z 166).
904512.fig.0010
Figure 10: Representative chromatogram of an end-exhaled air sample from a nonexposed subject (control group).

None of the chromatograms showed any interfering matrix signals. The method therefore exhibits excellent selectivity. The chromatograms obtained for samples from the dry-cleaning workers showed well-shaped tetrachloroethene peaks. In contrast, no significant peaks were observed in the chromatograms for the nonexposed subjects. Table 3 shows excellent agreement between the results for both samples (A and B) from the participants. The level of tetrachloroethene ranged from 3.4 to 16.7 μg/L for the exposed workers. Here, the ion ratios m/z 166 to m/z 131 (target to qualifier ion) for the tetrachloroethene peak agreed between the standards and samples.

When the exhaled air leaves the mouth of a subject during the sampling procedure, the exhaled air will adapt to the ambient pressure and to the temperature of the glass tube, which is commonly equivalent to the ambient temperature. It can be assumed that this adaptation is complete by the time the tube is closed. Measuring the ambient pressure and temperature therefore allows the measured concentrations to be converted to standard conditions (1013 hPa/20°C). This conversion decreases the concentrations stated in Table 3 by 3%. The need to convert the concentrations arises from the respective accuracy requirements. For routine analysis, it may often be acceptable to ignore the real pressure and temperature conditions.

The tested method therefore allows determination of occupational exposure levels and distinction between occupationally exposed and nonexposed subjects.

4. Conclusions

The desirable routine use of noninvasive exhaled air analysis in occupational biological monitoring requires simple sampling procedures that are suitable for field use and analysis methods that can be performed in common biomonitoring laboratories. The method developed here fulfills these requirements: end-exhaled air sampling is performed using the classical glass tube technique. A special tube design, developed and used within this study, enables reproducible sampling and means that the tubes can be used directly as separating funnels. The latter allows a simple transformation of end-exhaled air samples into “liquid samples” using a microscale solvent extraction. The liquid samples can be analysed using a common gas chromatography system. A simple liquid autosampler allows the analytical step to be automated. Since the calibration procedure is based on liquid standards, there is no need to prepare gaseous standards.

The method’s concept was successfully applied to the determination of tetrachloroethene in end-exhaled air, which acts as a biomarker for occupational tetrachloroethene exposure. Validation experiments demonstrated acceptable sensitivity, selectivity, precision, and accuracy in the analytical method. A field study proved the applicability of the method, which addresses typical end-exhaled air concentrations from exposed workers. The method can be deployed rapidly, requires no previous experience in gas analysis, and seems to be easily transferable to other workplace chemicals.

Conflict of Interests

The authors declare that there is no conflict of interests in relation to the publication of this paper.

Authors’ Contribution

Chris-Elmo Ziener developed the analytical concept and the special gas sampling tube construction, designed and executed experiments and the study, and conceived and wrote the paper. Pia-Paulin Braunsdorf participated in the development and validation of experiments, the field study, and the data analysis and the incorporation of the measurement results into the paper. Both authors read and approved the final paper.

Acknowledgment

The authors thank Mr. Christian Baumli, Infochroma AG (Zug, Switzerland), for many helpful discussions regarding the production of laboratory glass vials. Thanks are due to his advice; it was possible to take ease of production into account in the design of the gas sampling tubes.

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  27. P. P. Egeghy, L. Nylander-French, K. K. Gwin, I. Hertz-Picciotto, and S. M. Rappaport, “Self-collected breath sampling for monitoring low-level benzene exposures among automobile mechanics,” Annals of Occupational Hygiene, vol. 46, no. 5, pp. 489–500, 2002. View at Publisher ·View at Google Scholar · View at Scopus
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  29. M. Bader, D. Barr, T. Göen, K. H. Schaller, G. Scherer, and J. Angerer, “Reliability criteria for analytical methods [Biomonitoring Methods, 2010],” in The MAK-Collection For Occupational Health and Safety, Wiley-VCH, 2002.
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  31. A. Koizumi, “Potential of physiologically based pharmacokinetics to amalgamate kinetic data of trichloroethylene and tetrachloroethylene obtained in rats and man,” British Journal of Industrial Medicine, vol. 46, no. 4, pp. 239–249, 1989. View at Scopus
  32. G. R. Kelman, “Theoretical basis of alveolar sampling,” British Journal of Industrial Medicine, vol. 39, no. 3, pp. 259–264, 1982. View at Scopus
  33. R. S. Barratt, “The preparation of standard gas mixtures a review,” The Analyst, vol. 106, no. 1265, pp. 817–849, 1981. View at Scopus

 

The Diagnostic Potential of Breath Analysis – Clinical Chemistry, Vol 29, No. 1, 1983

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Normal vs. abnormal bodily secretions

flask & med sign

 

What Makes Snot Turn Green?

By | Posted February 1, 2010
Posted in: Ever Wondered?
Tags: , , ,

 

We all do it, one time or another. You blow your nose for what must be the hundredth time that day. Before you throw out the tissue, you take a surreptitious glance inside. Rather than the usual clear or slight yellow, you see something different. Something green. Suddenly, your snot resembles the color palette of an overly ambitious landscape architect — lime, olive, even a speck of chartreuse.

Tossing the tissue in the wastebasket, you wonder: Why has your snot turned green?

You’ve been fighting your sickness with decongestants and hot tea. But your immune system has been fighting it with neutrophils, the body’s most common type of immune system cell and your first line of defense against infection and inflammation. In this case, the neutrophils have gathered in your nasal mucus to combat infection there.

“They do their job by essentially surrounding and gobbling up microorganisms, and they hold them inside the cell in little digestive sacs,” says Dr. Harry Malech,a neutrophil expert at the National Institute of Allergy and Infectious Diseases. To digest the microorganism — the virus or bacteria that’s making you sick — the neutrophils rely on enzymes, proteins “that can help to kill or chew up the microorganisms.”

By far, the most plentiful enzyme within a neutrophil is myeloperoxidase. Myeloperoxidase has a lot of iron in it, and in the environment provided by the surrounding snot, the iron turns a green color.

After they’ve been fighting infection for a while, neutrophils fall apart and spill their myeloperoxidase into your mucus, Malech says. “Once the myeloperoxidase is released, the green color for some reason becomes more prominent than when it’s in the cells,” giving your snot that verdant tinge.

This only happens when your nose is running for certain reasons, says Carol Shoshkes Reiss, a New York University microbiologist who studies the immune system. “You don’t see it with an allergy, and you wouldn’t see it with just irritation, like how some people sneeze when they see the sun,” she says. “But people often get that kind of response when they have an infection” in their sinuses or upper nasal passages.

Does this change in coloration mean you should call your doctor for an antibiotic?

“If all you see is leaky clear stuff, you probably don’t need an antibiotic,” Malech says. “But if it turns green, that’s an indication that you might have a bacterial infection and need antibiotics.” When your immune system is already weakened from battling a cold, it’s much easier for disease-causing bacteria to set up camp, leaving you with a secondary infection such as sinusitis.

Green snot alone isn’t enough to warrant antibiotics, Reiss cautions, because it’s sometimes caused by a virus rather than bacteria. Antibiotics don’t work against viruses, and widespread prescription can lead to drug resistance.

“It depends on the quality and quantity of it,” she says, and whether you have other symptoms like swollen lymph nodes, a fever, or a feeling of all-around rottenness — all things that might point to a bacterial infection.

Otherwise, stick with drinking hot tea and — don’t  be embarrassed — inspecting your tissues. If someone catches you at it, just say you’re checking on the myeloperoxidase content.

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What’s in Your Toilet?

 

TESTING – CT Imaging the Sinuses (Sinus CT Scan)

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allstaractivist note: These are Sinus CT scans of my head that were ordered by my ENT. I came into his office presenting novel symptoms after having had him perform Sinus Surgery with Balloon Sinuplasty in October of 2014. My novel symptoms of nasal swelling and green expectorate caused him to laugh and exclaim that in thirty years of practice he had never seen this before. Of course I had explained to him earlier before the surgury that my symptoms were due to Gang Stalker poisoning (government experimentation and torture) however, I’m not sure he believed me. Now, all other explanations have been eliminated. So, he is going through a process of elimination (standard diagnostics) to find the cause, I trust him. Miraculously, as soon as I started to see him again the poisoning dramatically curtailed however, I have enough evidence for proof now.

The day of the CT scan the Gang Stalkers backed off so that my sinus cavities would not be swollen however, they have other poisons and weapons (military grade DEW weapons) that make you just as sick without so many observable symptoms. They have had time to develop these due to covert and nonconsensual experimentation on the public and soldiers, like me.

From this point on I am publishing all of my medical records as they are received. I do this to both establish a baseline (although I’m already sick) as well as show other TI’s methods for exposing government/police sanctioned Gang Stalking criminals. A trail of bread crumbs should I meet an untimely demise. Below are my Sinus CT films and an instructional guide on how to read them. Enjoy!



 

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TESTING – CT Imaging the Sinuses (Sinus CT Scan)