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Shades of L’Aquila: Italian Geochemists avoid Huge Miscarriage of Justice

Shades of L’Aquila: Italian Geochemists avoid Huge Miscarriage of Justice

On rare occasions I hear about a story that must be told. This story is one of those and I feel that it deserves attention from the broader geoscience community.

We have all heard of the L’Aquila verdict against the Italian seismologists concerning the devastating earthquake in 2009. If you haven’t, read these articles by Chris Rowan. At the time the guilty verdict was handed down the entire geoscience community felt stunned that such a thing could have happened. The prevailing attitude was that it should not be possible to accuse and convict scientists for practicing responsible science. However, the old adage goes: those who don’t learn from history are doomed to repeat it. This brings me to the topic of this post, which was a very near miss by the Italian justice system against four geochemists from the University of Siena.

I originally heard of the story at Goldschmidt 2013 in Florence during a presentation by Dr. Luigi Marini and I wrote a short note about it in my daily summary of the conference on this blog. After the conference I asked Dr. Marini for more information as I felt the details of this case needed to be heard. I recently heard back from Dr. Marini that the case has now been resolved in favour of the geochemists and I am now free to write about their story on this blog.

The story begins, in December 2002, with several geochemists from the University of Siena being asked by the Italian Ministry of Defense to perform a geochemical-environmental study in the Sardinian Poligono Interforze Salto di Quirra (PISQ), comprising the two firing ranges of Perdasdefogu and Capo San Lorenzo.

Numerous different military activities were carried out at the PISQ since July 1st, 1956, including: (i) launch of rockets (ii) release of bombs from airplanes and helicopters (iii) use of artillery, from land and ships (iv) tests of pressurized pipes.

According to media and some local associations, Depleted-Uranium (DU) ammunitions were used in the PISQ and caused the so-called “Quirra Syndrome”. The “Quirra Syndrome” refers to an apparently greater-than-normal incidence of illnesses in the local population and military personnel that served at the Quirra base. It occurs mainly as cancers and natal genetic malformations. However, the “Quirra Syndrome”  has not been confirmed by the Italian national health authority, the Istituto Superiore di Sanità (ISS).

So one of the goals of the Siena geochemists was to determine if DU had been used in tests.

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Google screen capture of Sardinia. Quirra, which is the subject of the study, is the red pointed location.

On the face of it the task seems simple enough: analyze soil, plants and water for U and its isotopic ratio and other potential contaminants from the munitions range (of which are there many). However, the complicating factor in all of this is that fact that adjacent to the firing range is an abandoned mine site called Baccu Locci. The Baccu Locci mine contains significant quantities of arsenopyrite and galena, which are arsenic and lead bearing minerals. Both arsenic and lead are known to have detrimental effects on the environment and humans. So the real question then becomes which is it? Mine waste or DU or other military contaminants? Furthermore, historical records from PISQ say no DU was used in the region, however, lots of other munitions with their own suite of toxic components may have been. Therefore, isolating a single cause of the possible impacts on the environment and humans becomes very complex indeed.

Taking a quick step back let’s review some of the basic science in question here.

What is DU?

DU stands for depleted uranium and it was the central contaminant discussed in the case. Uranium comes in many isotopes but the two most common are 238U and 235U. Most uranium found in nature is ~99.2% 238U and ~0.7% 235U. However, most nuclear reactors use fuel that is enriched in the isotope 235U to around 20% as it is more easily fissionable than natural uranium. A by-product of the enrichment process is uranium that is missing its 235U and has a larger proportion of 238U than is normally found in nature. This uranium is said to be depleted as it has had the 235U removed. This DU can then be used for other applications outside of the nuclear industry as it has the rare property of being one of the most dense metals known. This property makes it used in a wide variety of industries but particularly in military applications as a tip for missiles, armour penetrating bullets and other types of scary munitions. DU munitions have been used in Desert Storm, Bosnia, Kosovo and recently in Iraq and Afghanistan and at numerous munitions test sites around the world.

Gunner's mates inspect linked belts of Mark 149 Mod 2 20mm ammunition before loading it into the magazine of a Mark 16 Phalanx close-in weapons system aboard the battleship USS MISSOURI

US Navy personnel inspect linked belts of DU tipped ammunition (Wikimedia Commons)

The problem is that when DU munitions are used the uranium is blown into millions of tiny particulates that can spread on the wind and introduce widespread contamination to the environment. DU contamination is a serious issue. The radiological risks of DU are low in comparison to many other radionuclides due the long half life of 238U and the low energy alpha particles that it emits although they cannot be ignored altogether if the concentration of DU is high. The far greater risk from DU, however, is the high toxicity of the uranium metal itself as it attacks the kidneys in people similar to metals such as lead and cadmium. DU exposure has been linked to cancer, birth defects and other diseases for people living in contaminated areas and diseases afflicting veterans of the Gulf War as it acts in concert with other contaminants from these former war zones.

Acid Mine Drainage

Acid mine drainage is a phenomenon that many geochemists work with every day. In brief it occurs when sulphide minerals like galena (PbS), pyrite (FeS2) or arsenopyrite (FeAsS) are left exposed to open atmosphere and precipitation. What happens is a chemical oxidation reaction in which the sulphide minerals such as galena (PbS), pyrite (FeS) or arsenopyrite (FeAsS) react with air and water to release sulphuric acid and free metal ions. In the case of galena you get lead or arsenic from arsenopyrite.

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An extreme example of acid mine drainage from a mine in Spain. (Wikimedia Commons)

Indeed, Frau et. al. (2009), found significant evidence of contamination from Baccu Locci Mine wastes in streams leading from the region, which is a tributary of the larger Quirra River that flows through the village into the Tyrrhenian Sea. The paper found elevated concentrations of lead, cadmium, zinc and arsenic near mine wastes, however, concentrations decreased downstream due to dilution and precipitation of insoluble lead-arsenic minerals. These heavy metals could have detrimental effect on the health of local residents.

OK, so back to the case.

The researchers from the University of Siena did what was asked of them and analyzed over 1500 samples for a variety of contaminants, including the 235U/238U ratio (on selected samples), totalling 25,000 results. Their findings were that there was no contamination from DU in the region and that the 235U/238U was on par with the natural 235U/238U ratio. However, they did find elevated levels of arsenic and lead around the former mine site and in catchments draining it.

Distribution map of uranium concentrations in top-soils of the two firing ranges of Perdasdefogu and Capo San Lorenzo and nearby areas (from the Siena University report, 2004).

Distribution map of uranium concentrations in top-soils of the two firing ranges of Perdasdefogu and Capo San Lorenzo and nearby areas (from the Siena University report, 2004).

Histogram (left) and statistical parameters of uranium concentrations in the top-soils of the two firing ranges of Perdasdefogu and Capo San Lorenzo and nearby areas (from the Siena University report, 2004).

Histogram (left) and statistical parameters of uranium concentrations in the top-soils of the two firing ranges of Perdasdefogu and Capo San Lorenzo and nearby areas (from the Siena University report, 2004).

Furthermore, one of the supporters of the Quirra syndrome conducted health related modelling using a code called HOTSPOT and found that in order to cause the anomalous number of cancers observed in Quirra between 80-140 tons of DU had to have been used, which is an absolutely huge amount (Zucchetti 2005).

These results met with extreme opposition from the local prosecutor who acted on the advice of a nuclear physicist from the University of Brescia who felt that geochemistry was not the proper way to investigate this problem and that the University of Siena scientists were hiding something. Indeed, the physicist felt that thorium was the true culprit and that geochemists were not qualified to analyze for radioactive contamination. (I obviously take great exception to this notion as a radioisotope geochemist and user of an accelerator mass spectrometer). Anyway, the geochemists were charged with two crimes in connection with their results:

  1. Not stating the danger of anomalous concentrations of thorium present at the firing ranges.
  2. Using knowledge the geochemists had gained from their previous work on DU in Kosovo to select methods that prevented them from detecting depleted uranium at PISQ.

In answer to the first charge the geochemists provided results of Th analyses for soils in the Quirra region. These show that there are no Th anomalies present in the soil. Therefore, the notion that Th is somehow the hidden, skulking culprit in all of this is simply not the case.

In answer to the second charge that the geochemists knowingly sampled in such a way as to conceal the detection of DU one simply has to look at the aims of the two investigations. In Kosovo the Siena scientists were sampling a small area with known DU contamination and a documented history of DU use. This makes it much simpler to find DU and sample for it. On the other hand, in Quirra, the use of DU has not been confirmed and the study area was far larger. This means that instead of a small scale, targeted sampling campaign the appropriate investigation tactic was a broad, large scale sampling effort that attempted to give an overview of contamination in the region. If DU was found a more detailed look could then be performed in that specific site. However, since no DU was found no more sampling was necessary.

Ultimately, the court appointed an independent expert to examine the results of the University of Siena geochemists in the light of these two charges before proceeding to trial. The expert found that the methods used by the University of Siena researchers were completely reasonable and that there was no evidence of a Th or DU anomaly. Thus on July 11, 2014 the case against the geochemists was dismissed and they were completely exonerated as the victims of unjustified persecution.

This entire episode was certainly very hard for the scientists from the University of Siena. In addition, it should also serve as a cautionary tale for the larger scientific community. This story can only breed hesitation and reticence on the part of scientists to participate in such efforts to help the public. Such aggression on the part of the local prosecutor is a warning to other scientists to stay away from the Quirra region and avoid the potential liability that comes with it. On a larger scale, this trial warns scientists outside of Italy that participating in issues involving human health, or ones that are emotionally charged, can be a bad thing. This lesson is not one that helps people. By telling scientists that if we don’t like your results we’ll attack you personally only turns us away and ultimately enhances ignorance and short sighted decision making. It will be a sad day indeed when I or others turn down a project because of the liability risk involved when we could actually be helping the public interest by practicing responsible science. I hope that this is not what Italy or other nations are coming to.

Thanks for reading! I would also like to acknowledge Dr. Luigi Marini for keeping me updated over the past several months as the trial progressed and his permission to blog about such an important issue.

References

Cristaldi M, Foschi C, Szpunar G, Brini C, Marinelli F, Triolo L. Toxic emissions from a military test site in the territory of Sardinia, Italy. Int J Environ Res Public Health. 2013;10(4):1631–46.

Frau F, Ardau C, Fanfani L. Environmental geochemistry and mineralogy of lead at the old mine area of Baccu Locci (south-east Sardinia, Italy). J Geochemical Explor. 2009;100(2-3):105–15.

Marini L. – Goldschmidt Abstracts 2013. Mineral Mag. 2013;77(5):1661–817. Available from: http://goldschmidt.info/2013/abstracts/finalPDFs/1685.pdf

Zucchetti M. Environmental Pollution and Health Effects in the Quirra Area, Sardinia Island (Italy) and the Depleted Uranium Case. J Environ Prot Ecol. 2006; 7(1): 82-92

 

 

Modelling the Vadose Zone…What fun!

Modelling the Vadose Zone…What fun!

Sometimes our projects take stage and unexpected turns down pathways that we have no experience in whatsoever. My project on the input of Fukushima iodine-129 into groundwater has taken one of those turns. This is not a bad thing, but it is a time consuming one, as these deviations often are. However, instead of bemoaning my new lot in life as modeller of the unsaturated (vadose) zone, I thought I’d share a bit of what I’m doing. By the way, if any of you reading this have any experience modelling the vadose zone I’d love to talk in greater detail with you.

Modelling is an interesting field. The basic idea behind modelling is to try and make a computer program predict what is happening in reality by putting in a bunch of experimental or estimated parameters in and letting the model work through calculations that predict what would happen in nature. This is terrific since it is impossible for me to actually observe what is happening in the vadose zone of my field site. Sure I can do a bunch of experiments to try and empirically measure what is happening over time in the field. However, the cost and time is simply too prohibitive and there is no guarantee that I could even sample in such a way as to get good data back. This is the sort of circumstance where the model really comes into its own.

Models are great, but it is important to remember they do not provide the final answer. It doesn’t matter what is being modelled, the real world is orders of magnitude more complex than the model. Therefore, drawing conclusions based solely on the results of modelling is risky and certainly provides and incomplete picture of reality. Furthermore, models provide such pretty pictures and simple explanations for complex phenomena that it is easy/tempting to fall into the trap of over concluding from the model results. Therefore, when using a model to try to simulate reality is it very important to take the conclusions and results with a grain of salt whether you are the modeller, reviewer or reader.

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A picture from my model showing 129I transport in grams. The height of the column is proportional to depth.

The beautiful column of blue and green above shows a very preliminary attempt by me to model the transport of iodine-129 through the vadose (unsaturated) zone of an aquifer over a period of time in 2011. The way the model works is I input a bunch of data (educated or even not so educated guesses) on the soil conditions such as porosity, hydraulic conductivity, moisture content and much more. Then I add in the amount of rain that fell on my study area that has a known concentration of iodine. I then let the model run and watch the 129I infiltrate into the ground. When it gets to the bottom that means it has reached the water table. I can then look through the dataset that the model produces and see the number of grams of 129I that have travelled through the vadose zone and how long it took for them to do so.

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A graph of the model output showing concentration with depth. Each line represents a different snapshot in time. e.g. 7 represents 7 days.

The next step once the model produces a scarily large table of numbers is to try and make some sense of what happened. The blue-green thing is nice, but it doesn’t give a whole lot of information about what is happening over time at different depths. With this table I can then make graphs showing the movement of my iodine over time into the vadose zone. As you can see the “peak” migrates downwards pretty rapidly and within just over a month has moved 7 metres! Of course, this result makes us all think that iodine infiltrates into groundwater really rapidly. The actual truth is not nearly so black and white however. In fact, if I tweak the parameter that controls how iodine sticks to soil I can prevent it from ever getting past the ground surface. This is why all models should be taken with several grains of salt. The input control the outputs, however, a small change in the input can result in a radically different output. Which is the truth??? Only observation and more modelling can tell us!

 

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#AESRC2014 Highlights

Well, AESRC is done for another year and with it my role as co-chair of the organizing committee! Thank goodness for that! Hopefully, I can finally get some actual thesis related work done in the coming months…and maybe get back to blogging a bit as well. However, as grateful as I am that AESRC is done, I have to say that it was a fantastic conference this year with a host of terrific talks from keynotes and grad students alike.

As I mentioned in my conference opening post AESRC is the only conference in Ontario, maybe Canada for all I know, that is organized by and for graduate students. The entire organizing committee is composed of graduate students and all of the talks, with the exception of keynotes, are given by graduate students. AESRC is meant to be a place where new and experienced grads alike can talk about their work in a less nerve-racking environment. We encourage in progress research or research that does not even have results yet. The idea is that every graduate student can feel comfortable, practice presenting to an educated audience and hopefully enjoy themselves and meet their colleagues from across the province.

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This AESRC was by far the most well attended in the past 10 years, with over 100 delegates attending from 8 different universities. The conference kicked off with the Icebreaker at a campus pub, where we all got meet each other or reconnect in many cases, while watching hockey and drinking beer. A nice relaxing end to the week and prelude to the science of the weekend. On a personal note, it is always worth attending the Icebreaker at every conference I have been to. More often than not there is free food and drink, but it is a great opportunity to meet new people, spot that keynote you want to talk with and introduce yourself. I try to make of point of meeting at least one new person at every Icebreaker I go to.

Saturday started with some great talk on Environmental Geoscience (my session) and Sedimentology and Petroleum Geology. We had two keynote speakers on Saturday: Paul Mackay from the Canadian Society of Petroleum Geologists and Dr. Jack Cornett from uOttawa. The video of Jack’s talk is below.

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To summarize, in case you didn’t watch the entire video, Jack discusses the incredible range of radionuclides that are found naturally occurring on Earth and the vast range of geologic problems these nuclides can be applied to. He also talks about how we can use accelerator mass spectrometry to measure these radionuclides at incredibly low levels, which is how we are able to apply them to geologic questions. To illustrate this point Jack discussed the case study of chlorine-36 in the Cigar Lake uranium mine in Saskatchewan, Canada.

Saturday concluded with a fantastic dinner at the nearby National Arts Centre and another terrific keynote by Dr. Becky Rogala on the challenges of extracting bitumen from the oil sands and the importance of having an accurate understanding of the sedimentology to ensure maximum efficiency of SAGD recovery. There was also quite a bit of beer.

Sunday started nice and early with the Geophysics session as well as the Paleontology and Tectonics sessions as well. Our keynote for the geophysics session was Dr. Glenn Milne from uOttawa, who was an author on the most recent IPCC report and is an expert on sea level change.

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We also had another great keynote from uOttawa in the tectonics session in Dr. Jon O’Neil. The video of his talk on the oldest rocks on Earth (4.4 billion years old) is coming soon! That pretty much wraps up AESRC2014! It was a great weekend, there was lots of great science and I am really glad its over. I likely won’t be around for next year’s AESRC at Queens University (fingers crossed), however, I am sure it will be great.

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Yours truly giving his talk on iodine-129 fallout from Fukushima. (Photo: Viktor Terlaky)

 

 

 

The Most Epic Unboxing Ever

The Most Epic Unboxing Ever

There is a strange phenomenon on the internet called unboxing. Unboxing is when a person receives a new package of something and takes a video or pictures of the process of opening it for the first time and posts it online.  Mostly, from what I can see, people “unbox” electronics or hockey cards or things of that nature. However, what I have today could be called the granddaddy of all unboxings; I have a series of photos of the unboxing and, initial stages of set-up of the University of Ottawa’s new, 3 million volt, accelerator mass spectrometer (AMS), which cost 5 million dollars. This takes opening your new laptop or that Sidney Crosby rookie card to a whole new level!!! The AMS will be housed in uOttawa’s new Advanced Research Complex.

The accelerator portion in its shipping container being transferred into our new building. (Photo: Dr. Liam Kieser)

The accelerator portion in its shipping container being transferred into our new building. (Photo: Dr. Liam Kieser)

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Easy does it. Now pivot!!! (Photo: Dr. Liam Kieser

Since I am showing pictures of this incredible piece of equipment being installed I’ll explain a bit about what it is an how it is used as well. I use the AMS in my own work to analyze iodine-129, chlorine-36 and once or twice carbon-14. In short, tools that can be used for groundwater dating. However, the AMS is capable of analyzing for a huge range of isotopes and this allows its use a wide variety of disciplines from health science to homeland security.

The AMS works on the same principles and a regular mass spectrometer, but it has a few key differences that make it extremely powerful.

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Lots of boxes to open. (Photo: Dr. Liam Kieser)

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Once the boxes have been unloaded the building begins. It is like building an IKEA desk, but somehow more… (Photo: Dr. Liam Kieser)

The process of AMS analysis begins with the preparation of the samples, which involves large amounts of lab time in extremely clean conditions. Contamination of samples with unwanted isotopes is a real problem in AMS so great care has to be taken to prepare good samples. The sample is then mixed with niobium powder and pressed into a steel cartridge. The cartridge then gets loaded into the ion source where cesium ions get fired at the sample like shooting a gun. The Cs ions physically break bits of the sample off the cartridge and these get negatively ionized and accelerated out of the ion source towards the first magnet. 

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Xiao-lei carefully taking the glass rings that are in the accelerator. These are to kill any free electrons that could escape from the stripper canal as well as keep the ions on a stable flight path. X-rays charged to 3 million volts are very bad! (Photo: Dr. Liam Kieser)

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The glass rings all put together with the stripper canal in the centre. The stripper canal is where electron get stripped off the negative ions turning them into positive ions as well as keeping the ions on a straight and even flight path. (Photo: Dr. Liam Kieser)

This is what the ion source looks like. Up to 200 samples sit in the big wheel waiting their turn. The AMS control room is those windows in the background.

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Our fancy new SO-110 ion source. (Photo: Matt Herod)

Once the samples leave the ion source they are accelerated to the first bending magnet which can bend an incredible range of masses. From tritium to plutonium tri-fluoride.

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The first magnet looking towards the accelerator. (Photo: Matt Herod)

The next step is firing the ion into the particle accelerator that carries a charge of 3 million volts! Inside the accelerator is a passage called a stripper canal that pulls electrons off the ions turning them from negative into positive ions. The reason for this is that this allows us to get rid of interferences that normal mass spectrometers face. For example, chlorine-36 has an interference with sulphur-36 making it impossible to analyse using normal mass specs. Actually, our AMS has another modification that makes 36Cl analysis possible on a 3MV machine, which is generally considered too small for this isotope. Usually, 36Cl needs a much larger accelerator however, our isobar separator for anions (ISA) allows this. Once the ion leaves the stripper canal it is accelerated at very great speed into the next magnet.

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Dunh, dunh, dunh. This is the A in AMS! (Photo: Matt Herod)

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This is the biggest magnet I have ever seen!! It is over 3m long and weighs 18 tonnes! This is why the room needs an overhead crane. (Photo: Matt Herod)

Once the ions are redirected and isotopes are further separated by the magnet they are ready to be analyzed in either the Faraday cups for the common isotopes or the gas ionization detector for rare isotopes.

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Me, touching the Faraday cups. (Photo: Laurianne Bouchard)

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The gas ionization detector. This bad boy literally counts atoms as they come around yet another magnet and through a silicon nitride window. Once they enter the detector which is filled with gas they ionize it which leads to pulses of electricity that are counted. This is the end of the AMS!!! (Photo: Matt Herod)

Once the atoms are counted in the gas ionization detector their trip around the AMS is over! It is quite a journey and full of positives and negatives (haha, a little pun there). Seriously, though this gigantic instrument is used to quantify the smallest of small quantities and can very literally count atoms. The AMS has a massive number of possible uses and I’ll likely be posting about these as this new facility starts to ramp up in the next few months. In addition to the AMS we also have an SEM, microprobe, stable isotope equipment, two noble gas mass spectrometers, ICP-MS, LA-ICP-MS, ICP-AES and a host of other MS’s as well. There will be very few types of isotopes that we cannot analyze for and this facility will be one of the best in the world for this type of geological research. Stay tuned for further developments as we start to move in soon!

Cheers,

Matt