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Goldschmidt2013

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.

quirra

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.

Rio_tinto_river_CarolStoker_NASA_Ames_Research_Center

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

 

 

Day 3 and 4 – Craters, Very Old Rocks, Fukushima and Extinctions

Here is my Goldschmidt summary part 3 comprising both day 3 and day 4. I had to prepare my own talk, that I gave on Thursday (day 4) so I had to put the blog on hold to practice.

Here are a few of the most interesting talks that I went to:

Fred Jourdan hailing all the way from Curtin University in South Australia gave a talk called  – Volcanoes, asteroid impacts and mass extinctions (abstract). In his funny and very interesting talk Dr. Jourdan asked the question what is responsible for mass extinctions in geologic history? There has always been considerable debate in the scientific community about what caused all of the mass extinctions that have taken place over geologic time. Was it the volcanoes or the meteorite impacts? Dr. Jourdan compared the dates mass extinctions and tied these to the dates of volcanic eruptions and meteorite impacts to see if any two or three occurred at the same time. He found that volcanic eruptions coincided with mass extinctions better than meteorite impacts and concluded that volcanoes have played a dominant role in mass extinctions throughout Earth history. However, meteorite impact dating needs to improve since they also play some role.

Dr. Phillippe Van Cappellen  from the University of Waterloo gave a fantastic keynote address (abstract) on the mysterious part of the groundwater world called the hyporheic zone. The hyporheic zone is the magical place in a stream bed where groundwater flows into the stream. Sounds pretty simple right? According to Dr. Van Cappellen, wrong! Very wrong. It turns out that the hyporheic zone is extremely complicated and can have major impacts on the flow of chemicals from groundwater into surface water. Imagine this scenario: a local aquifer is contaminated with PCB’s. This is bad, but they have not made it into the nearby stream yet, so we only have to remediate groundwater. However, these chemicals will get stored or released by the hyporheic zone and could potentially contaminate a larger area than we thought. Dr. Van Cappellen’s work aims to understand how the h-zone functions under different chemical conditions and what sort of environmental factors such as water level, organic content or freeze-thaw cycles can affect it.

John O’Neill a new professor from uOttawa gave a terrific talk called Earth’s Hadean Crust: Insights from the Nuvvuagittuq Greenstone Belt about some really, really, really old rocks (abstract). In fact he has dated some rocks located in Northern Quebec at 4.4 billion years old!!!! The Earth is only 4.6 billion years old so these rocks have been around right since the beginning. John’s talk was very well attended and he presented some very interesting results to prove that these rocks are so old. This is still a very controversial topic and I am sure that discussions will continue for quite a while.

The next talk was very interesting to me. Dr. Yasuyuki Muramatsu, one of the leaders in the field of radio-iodine research, presented his talk right before mine. His talk was called: Reconstruction of the Accident-Derived I-131 Deposition in Fukushima Through the Analysis of I-129 in Soil (abstract). A lot of iodine-131 was released from Fukushima, which as a short half life of 8 days. This meant that it was very difficult for researchers to map its fallout over Japan, which is essential. However, using iodine-129 as a proxy for iodine-131 is possible and Muramatu’s group set out to do just that and they produced some really nice maps showing the fallout pattern of iodine in Japan.

So that is it for Day 3 and 4. Instead of doing a Day 5 summary I am going to try and do an interview with someone and cover their research in a bit more detail. So stay tuned for that!

Cheers,

Matt

Goldschmidt2013

Goldschmidt 2013 – Day 2 – Carbon, Uranium, Litigation and London

Day 2 of Goldschmidt 2013 is done and what a great day it was. Hectic, but conferences always are. There is just so much to see and do, so many people to talk to and so many people to meet for the first time that it can be a bit overwhelming. The best thing to do is grab a coffee, and dive right in.

My first talk of the day was by J. Schmitt and was called CF4 and CO2 – Coupling Weathering and Carbon Cycle. This very interesting talk introduced me to a new gas that can be used as proxy for weathering over time: CF4. CF4, it turns out, comes from fluorite that is contained in very small quantities in granite. When glaciers scrape the top off a granite outcrop they expose this fluorite and it weathers to release CF4. The CF4 then hangs out in the atmosphere for 50-400 thousand years. It eventually gets trapped in ice cores and can then be used to calculate long term weathering rates.

One thing that everyone does a conferences like Goldschmidt is support their colleagues from home. With this in mind the next talk I attended was by Mike Power from uOttawa. Mike gave a great talk on exploration geochemistry and how we can use noble gases and metals in soil to look for deeply buried uranium deposits.  I won’t go into more detail here. If you want to read about Mike’s work check out the guest post he did for me a few months ago.

Once Mike finished his talk I went to support another familiar face. Not that he needs it since his talk was standing room only. I speak of Dr. Kurt Kyser who hails from my beloved alma mater Queens University at Kingston. Kurt was speaking about the importance of geochemistry to our lifestyles (abstract). Amazingly, Kurt stated that in our lifetimes we each use approximately 2 million kilograms!! of metal, mineral and fuel resources. In order to sustain this quality of life we are always searching for new mineral deposits that can provide us with these things. However, most of the easily obtainable ores deposits have already been obtained. This leaves us with the problem of finding new deposits that are not so easy to discover. Kurt gave a great overview of the techniques we can use to do this, such as sampling unusual things like tree sap or leaves to find deposits. He also made the point that a good geochemical characterization of ore deposits makes remediation much easier when it is time to close the mine and reclaim the land. Yeah Queens!!

The next talk was an interesting look at the source of iodine and chromium in the Atacama desert. It was given by A. Perez-Fodich and was called The role of groundwater in the formation of the giant nitrate deposits of Atacama: Iodine-129 and stable chromium isotopic evidence (abstract). The Atacama desert is one of the dryest places on Earth and is home to some very unusual mineral deposits. Indeed, it is one of the only places on Earth where minable quantities of iodine can be found. The iodine is found in huge nitrate deposits and is likely coming from weathering of nearby ocean sediments. It is then transported by groundwater to the desert where the water evaporates leaving the iodine behind.

The next talk I am going to highlight really galvanized me. I intend to write a full post about this once I get a chance to do some more research. The speaker was Luigi Marini and the talk was called How to Protect Geochemists Working on Environmental Issues from Litigation? (abstract). The talk covered an ongoing Italian court case in which several geochemists from the University of Siena have been sued after publishing results stating that they could not find above background levels of depleted uranium and former Italian military firing ranges. These results infuriated the public which felt that some sort of cover-up was occurring and a local prosecutor initiated litigation against the researchers. This incident has strong shades of the L’Aquila earthquake verdict and therefore it is crucial that strong technical advice is provided by the scientific community to ensure the no miscarriage of justice like that of L’Aquila can happen in this case.

John Ludden, Director of the British Geological Survey, gave a great closing talk in the Importance of Geochemistry session entitled the Geochemistry of London (abstract). At first, I wasn’t sure what to expect. I mean, what geochemistry is there in a city. Wow, was I ever wrong. John introduced the projects that the BGS and partners have going on to monitor and understand pollution in London. This is massive undertaking and they have actually mapped the geochemical distribution of many contaminants on a street by street resolution for the entire city as well as numerous analyses of the water and sediment in the Thames. The most interesting points were the numerous indications of pollution from the past still present in soil and sediment. Indeed, the Thames had very high PAH levels that were left over from the coal burning era and leaded gasoline er, petrol left its mark on London soils. Incredibly, there was one place, the site of a former manufacturing plant, that had such high nickel it could be considered valuable ore material by today’s standards.

Stay tuned for Day 3!

Cheers,

Matt

Goldschmidt2013

Goldschmidt2013 – Day 1 (Monday)

Wow! I have finally arrived at Goldschmidt 2013 and it is so, so great to be here! Day 1 was already a whirlwind. Unfortunately, I missed the icebreaker last night and arrived a bit late this morning due to scheduling conflicts so I missed a few talks, but I am here now and ready to listen, learn, discuss and blog!

Talks I went to today:

Sadly, I missed the first talk I wanted to see. My friend, Erin, from uOttawa presented her research at 9:30, while I was still in the Florence airport so I missed out on that one. Her work is titled Fluid Evolution Recorded by Alteration Minerals along the P2 Reverse Fault and Associated with the McArthur River U-Deposit and the abstract can be viewed here. Basically, water running along a fault making all sorts of strange minerals and carrying lots of radioactive goodness.

So the first talk that I actually watched was by Mitch Kerr from Saint Mary’s University and was entitled Preliminary Evaluation of Trace Hydrocarbon Speciation and Abundance as an Exploration Tool for Footwall-Style Sulfide Ore, Sudbury Igneous Complex, Ontario, Canada (abstract). The talk raised some fascinating points about using the occurrence of light, thermogenic hydrocarbons as a possible took for exploration of platinum group elements in the Sudbury Impact Crater. Indeed, the results showing the different types of light hydrocarbons and their relationship to ore bearing zones was very promising.

Next was a talk by Wooyong Um from Pacific Northwest National Lab about Limited releases of U and Tc from Hanford tank residual wastes (abstract). The talk explored how to safely close radioactive waste storage tanks located at the Hanford site. The waste will be moved to a long term repository, but some sludge will remain on the bottom that contains high concentrations of uranium and technetium. This talk compared the efficacy of three methods for immobilizing the U and Tc that remains in the tanks by creating minerals that will bind the U and Tc and make it unavailable to groundwater leaching. The authors found that all three techniqies they attempted were successful and preventing leaching of U and Tc. So a good news story all around!

I then speed walked over to another session where keynote speaker M.O. Andreae from the Max Plank Institute was asking if any answers were blowing in the wind. Seriously though he was Can Saharan dust explain extensive clay deposits in the Amazon Basin? Radiogenic isotopes as tracers of transatlantic transport (abstract). He attempted to answer this question using a number of isotopic and geochemical methods. He used total geochemistry, lead, strontium and neodymium isotopes to show that unambiguously the Amazon clay does not come from Saharan dust despite visual evidence showing it across the Atlantic. Indeed, the source of the Amazon clay deposits turned out to be the high rate of weathering of the bedrock due to the humid conditions. However, Dr. Andreae also found that the despite the fact the clay is not from the Sahara a substantial amount of the nutrient potassium is transported to the Amazon from the Sahara. Very cool!

The last talk for me but not least was by fellow Canadian Chris Weisener from the Unversity of Windsor. His talk: Bacterial Mineral-Metaloid Redox Transformations in Anaerobic Environments (abstract) covered how bacteria can influence the uptake of heavy metals into the mineral jarosite, which is found in many low pH, iron/suplhur rich environments. Indeed, almost all mine drainage sites have jarosite. Chris showed that metals such as selenium can actually be incorporated into the jarosite mineral structure by bacteria which reduce them for food and in doing so make these metals available for incorporation.

I followed this up with a quick visit to the Goldschmidt press conference to hear about the work of Victor Sharygin of the Institute of Geology and Mineralogy in Novosibirsk, Russia. Dr. Sharygin talked about how the Chelyabinsk meteorite may have had a brush with the Sun before falling to Earth because it shows signs of having been melted prior to colliding with Earth. Furthermore, the meteorite also contained some very interesting and unusual mineralogy and mineral morphology such as sceptors made of platinum, osmium and iridium in the fusion crust of the meteorite. This press release has already picked up some international coverage and more complete articles can be found here.

Thanks for reading. I am excited for what great discoveries Day 2 will hold.

Cheers,

Matt

Goldschmidt2013