and we found both iron and brass. So, like the mineralogical diversity. I'm actually really curious to know if it's, what we see as an outlier instead of breaking down supplies of tin at the end, or if, like in other words, supply-driven innovation, or if there's just a lot more variants of what they're making and we don't know. I mean, like, that's soon we have a diagram of the video around it. Yeah. Can I tell you a story about that? Of course. I, about 2014, I was with a German scientist who was going to measure that. And we talked about it. He said, I think it's made out of iron. So I told him, here's the cal, I built the calibration form, we measured it, we got the nickel and the cobalt. And then I'm like, we need to, can we publish this? He's like, yeah, I'm going to do a little more work and we're going to do it. So we keep doing it, keep doing it, and that's about a year and a half. I'm like, we need to do this. Yeah. And then he says, just turn on CNN. And the team beat us. Oh, I did. I broke my heart. I'm like, that was the first time I'm like, ooh. Yeah. And what's worse is it was a competitor, the broker. But I think I told, I gave this example of media work, I am too. I'm worried that I gave away the photos. And what happened is that they didn't get the permit to measure it. They had an on-contact instrument. So they just walked by and visited without the permit. So just poor German scientists. I think they're pulling away with that. Yeah. I mean, what are they going to do with that? Well, the Egyptian government is pregnant. They might be, this guy might be sanctioned from working again. He works for a company. He isn't. Yeah. Anyway, that broke my heart. Anyway, but let me see. What was I doing? I need to open up broker instrument tools. Firstly, to do it with Windows. But yeah. Anyway, we're just going to do this by the book. What I'll do is I'm going to backtrack and discuss this principle a little more in terms of review where we're at for the purposes of the video. Yeah. Because I think this point is going to be pretty crucial. So let's go. We're discussing fundamental parameters. We're discussing fundamental parameters. So let's start. Which is actually a fundamental parameter is an equation. Yes. Okay. I mean, it's marketing, right? But anyway, let's look at here. So here's the use that's right. Here's geocentric. Which of these, again, is the best predictor for where the planets are moving? Both. Both. They're equally good, right? Equally good. Which one is an accurate representation of reality? This one. And then which one of these is generalizable? If I go to a new solar system in Andromeda, which one of these models can I use to predict those planets? This one. Right? Exactly. So to the point. The point is that prediction is not the standard for accuracy. In other words, like physical observations. And by the way, as an aside, could I quantitatively determine which of these is the best, most accurate? Or do I need qualitative data? Like observing the planets. I need qualitative data. So here's the key thing, right? We had archaeology worship quantitative a bit too much, I think, and we forget how important qualitative is. Do you know what is the difference in quantitative and qualitative analysis? Like what is the fundamental difference? Well, one you can create predictions on, and one is just the description. That's an excellent one. I'm thinking of it even more. So we're going to go this way. What is the color of this unit? Right here. What color is that? Right here. Very closely. Did you see it turn red or orange? What is the uncertainty of green? Qualitative doesn't have that. Now, if I had a colorometer, you can download it after your phone will do this. Can I measure and then change the light source and see flickers of green? Yes, that would be a quantitative measure. If we break down what Lucas is saying even more simply, it's this. The difference between qualitative and quantitative is the ability to demonstrate uncertainty. The qualitative is an absolute measure. The quantitative has uncertainty. With uncertainty, I can make a prediction. I can even put a confidence band on that prediction. With qualitative, it stays a description because without that uncertainty, I don't have additional information to build a model on. With the universe, you had people arguing this. People arguing this. It was Galileo's ability to observe rotation around Jupiter with those three moves that demonstrated the principles of the heliocentric thing. He didn't have to quantitatively model the movement of those moves to disprove this. He could demonstrate that the principle of large object in the center and everything moving around it was observed. Once it was qualitatively observed, this guy worked. Galileo paid a price for that. But in general, that is the crux of it. So, while we celebrate Galileo, there's a triumph of empiricism over authoritarianism. And I don't mean authoritarianism in the like, you know, Risen Brutawon type style governing the Turkey. I mean authoritarianism in the so and so said this, this is the law. Right? This is how it works. An example of this, I was in West Virginia. We had a geology professor come in, one of those older guys, a previous generation thing. And I'm measuring, he gives me a sample to measure. And I measure it with the tracer. And I get this, like it says this is 9% aluminum. And he goes, that, that can't be. And I said, why? He's like, this is red. Granite doesn't have that much aluminum. Like, and I'm like, well, I mean, here's a spectrum peak right here. Like, you can see that. And he's like, something's wrong with your instrument calibrations. And I said, I'm gonna be giving you a calibration. You can see the peak. And he said, I sent this to the most authoritative lab in geology. And I've sent everything. And they've never been wrong. And they said it's only 2% aluminum. And I was like, I don't know what to tell you again. Like, this is what it is. After he leaves, he's kind of angry. So my friend from Florida says, it's a piece of felt spot. Like, that happens all the time. But anyway, but the core point is, there's always argument from a point of empiricism. I can see, I can measure, whether it's a qualitative or quantitative measure, I can see how much aluminum is here. And his argument was from authority, right? This is this class of material that should not have this. That's the difference, right? What Galileo did is demonstrate empiricism. The reason I bring this up is Galileo demonstrated empiricism, not with quantitative data, but with qualitative data. So in archeology, we conflate empiricism with quantitative research. It is combination of the two. So in any case, the idea behind vibrational parameters is that using precise physics, such as here, I can model what is in that sample. So if I know the entry angle of the sample, if I know the fluorescence efficiency, the relative measurement depth, if I understand the detector chip's thickness and how that can affect its emulation, if I understand every physical variable that influences the spectrum, then I can back-calculate and estimate what percent is in here. Now, there's multiple algorithms, and by the way, just FYI, if you see multiple algorithms, there's some time to queue and things are not working out as they should, and people are trying to improve it. But that's the idea here. Is everyone's trying to cover it? I like how this guy calls it the fundamental fundamental parameter software, but that is the key. They're trying to figure out that aspect. So to see what's happening on the unit itself, let's see if we can't connect here, especially in our videos, really. Up there it is. So I'm going to use what is actually a fundamental parameter calibration of this unit, because again, this is originally an industrial unit. So you said it was a piece of felt starts because you happen to be pointing at it. Well, no, we've got to point it out. Goat spires and granite all the time. So you've got these... Yeah, so you said if you ground it, and you said a small portion of your rock off to the lab to take care of it, and that man didn't have granite, and you pulverized the whole thing, and that had no spark, that would explain it, right? Like, there's a simple reason for why he would have been wrong. Because there's a lot of force. Exactly, exactly. The key is, this reasoning was that, you know, what didn't account for, didn't allow for any empirical data to influence, right? So anyway, what I'm going to use here is I'm going to use precious metals, which is a fundamental parameter's calibration. Now, when Bricker makes one of these, it's typically a mixture of empirical and fundamental. In other words, they use real standards, but the majority, but those are designed to send disciplined fundamental parameters. So I'm going to come over here, and we're going to see what's in this gap. What is that? There we go. So this thing, it is 75% copper, 24% zinc with a little bit of lead. Does that make sense? What would this object be, if that's true? Just a brass. This is a perfectly normal alloy. It doesn't have a match in the library, because it can cross-reference, but how much did these add up to 100? Just about. This is probably an accurate result. And it's using fundamental parameters, right? It's using that geocentric model, right? So, not too bad. Where's that obsidian, by the way? Oh, I'm actually curious. This is going to be disciplined right now. Let's see. By the way, the results are here. It's just the Wi-Fi that's above. So, 25% iron, 8% zirconium, 16% ruthenium, and 15% rhodium. Is that accurate? Could this be some obsidian? So, can anyone tell me what's happening? Why does it have a fundamental parameter's algorithm? And if I was in this gap, what's up? Well, what's most... So let's think about it this way. This guy, do you guys remember what this was made of? Mostly copper. Some zinc. Now, does copper fluoresce in the spectrum? Yeah. Does zinc fluoresce in the spectrum? And does lead? So, everything I have to work with fundamental parameters shows up. What is most of this made of? Silica. Oxygen. Oxygen. Does oxygen show up in the spectrum? Yeah. So, how... It's missing the most common element. So, what does the fundamental parameter do? It tries to add up to 100% with all the stuff it can see. And it blows up. That's dangerous. Oh, yeah! It's terrible! The soils method would also be way off if you have some... I mean, so what is the thing? Broker can take soils. It can tell it to fill in the oxides. Right? You've seen this before. If you do this kind of... The soils method? I'm actually really curious. Do you want to press the... The soil? Let's try it. Let's see. I've never used this before. It still shows precious metals on top. Don't worry. It's still in my mind. It's the Wi-Fi refresh rate. I'm actually curious if this is going to do multiple days. Have you already run that? Holding that thing in there as a plan? I've got my fingers on either side of it. Not directly behind it. This is just trace elements, so... The results actually... That rebellion was probably pretty close, right? 140? Yeah, it's only 148. Yeah, yeah. But yeah, in any case... Although the soils isn't empirical. 147? 147. What's your money? I'm supposed to be 128. What's your money? I'm supposed to be 222. Yeah. Not bad. Not terrible. But the soil isn't empirical, unfortunately. So they have a soil mode and a soil count. The soil count in it is soilless. So it wouldn't surprise me if the empirical soil works. I don't think I've got the fundamental parameter. Geo-care. Oh yeah. There we are. That's good stuff. Alright, let's try that. This one is a mixture of fundamental parameters. And it should switch between light and heavy. With filtering? Yeah. We'll move the filter a little bit through. I think this is a dual phase. Can you hear it? Yeah, we will hear it. And you should see the spectrum change, too. So that's the trace spectrum there. I hope this has it. There it is. Do you hear that? Yeah, it does. It switches to the light element filter to do populate. So is that the green and the yellow? Or another filter? It'll be a no filter. There's only two phases here. There. Alright. So 79.9% silicon dioxide. Aluminum 16%. Potassium 4.1%. Calcium oxide 1.2%. I don't know. Do those match up? Yeah, oxides. Let's give it a fair shake. What's the aluminum in this guy? Do you have the oxides on there? 7.31%. Is that elemental or oxide? It's elemental. Here's the oxide. 14. Alright. What's the calcium oxide? 1.2%. Dead on it? That's pretty good. What's potassium? Potassium. 4.35. 4.35. And our iron? No, that's iron. Iron. And then the silicon? What's the SiO2? 73.4%. 79. So, not terrible. But what's it doing? How's it figuring this out? How's it beating the oxygen problem? It's capturing its overalls. Exactly right. So it knows, alright, the aluminum is probably this. The silicon is probably this. The potassium is probably this. That's what it's doing. Can it measure that oxygen directly? No, but it can guess if this is that oxidization stage and this has to measure up to 100, this is what it should be. What probably happened is our silicon dioxide skewed up because of that 100, forcing it to measure up to 100%. Now, if I have calcium carbonate in my sample, what will happen? What's the formula for calcium carbonate? CaCO3. So if I have CaCO3, will this be accurate? Does it know that that's calcium? Can it tell that everything can calcium carbonate, calcium oxide? No. Can it tell the difference between Fe2O3 and FeO? If I have a kaolinite clay, will it be able to tell the difference in Al2O3 and Al connected to potassium and a whole bunch of other elements? So it has to make a molecular assumption and force it to fit. And that's where things start to go awry. That's the key. So you get kind of close when you've got a pure form. By the way, the reason why I can work for obsidian is what is the chance that there's calcium carbonate in this guy? Zero is inspiring temperature when it outgaps all that CO2 anyway. So because it was high pressure fire, you're okay. So anyway, but that's the key. Okay. Let's take a look here at the results. So today, do you know why there's not light in the room? I have no idea. It should be there. It's a habit of the spectrum too. You just don't find it useful. I disagree. I think it's bad to exclude things because who is the judge that's useful to the scientists, right? Yeah, that frustrates me in no way.  It's like a self-affiliate prophecy. Yes, exactly. It's an excellent point. It's an excellent point. But in any case, but yeah, that's the kicker. It's kind of unsettling how good the phenolomal parameters can do when it makes these oxide assumptions. So let's try a new sample. I just got a Washington post and every time I see that, I'm like, what now? R&C says it was hacked. It's hard to see that as an evidence. Couldn't have. So we're going to try this on the time zone. Not mutating it. Not mutating it. I'm actually curious how this is going to work. A weird sample. But this is still the soil. This is the geocamp. So this was designed for miners. The geocamp is the calibration. Yes. So here, I get something that looks a lot like obsidian. Do you see the potassium? What is the potassium in the obsidian? 3.61% What's in my iPhone? It's somewhat obsidian. Gorilla glass is reinventing obsidian, by the way. I don't know if you do that. But that was the core idea. So this adds up to 26%, 71%. Looks like it's going to be close to 100%. But I can tell you there's a huge problem here. This is also a soda glass. It's got about 6% sodium. Can this guy see sodium without a vacuum? Does it include sodium when it tries to add up to 100%? Nope. So then, I can guarantee you this is terribly off. Because when they scale to 500%, they make these results look great, right? If I don't know what I'm doing, if I don't know anything about the sample, I will get 100%. But here, because I can't measure a key element, NaO, it's gone. It's just being excluded. We just need to stand silicon to fill that gap, because that's a safe bet. That's also what happened with the obsidian, too, by the way, right? Remember how the silicon was at 71%. Does this have NaO? Obsidian. Do they report the sodium oxide content? 4%. So let's go back actually. So let's pop back one measurement to the obsidian. So this was the obsidian measurement, right? Do we see NaO on this list? But silicon is how much above? 100%. So what's the real value of silicon? Dioxide. 73.4. So all it's doing is it's using silicon to fill the gap. Because silicon will always be close enough. That's the trick. That's how you commit to someone that it's working. That's fundamental parameters in the nutshell. It has to add up to 100%. Otherwise, the entire premise is gone. And that's why, with geologic samples, it can cause all these problems. Because you can actually delete the possibility that that element is present. This is what happened to mining companies. Broker would be able to do good enough. Or Knighton, everyone who's been on one of the parameters would do good enough to make a couple segments. And people would be happy. And then the mining company would find out, oh, how much do we really have in that? Would it be over-invested in this mine? Because we didn't know we had this element. Wait, there's sodium in there. And the sodium makes it more expensive to digest to get the gold out. All those factors start to factor in. And that's where things start to go out by. And the problem is, is because we have an idea that everything should add up to 100%. Yeah. So this is maybe a very basic question so I can all on that. What's the difference between a filter, a computer, what's the difference between a filter, a calibration, and the fundamental parameters? Like what do each of them do, how do each of them work?  Show me some elements.  Exactly. So I can optimize for this or that element. Fundamental parameters is a type of calibration. A calibration is an algorithm that converts spectral intensities to something else. Most typically, that is something else. It's weight percent, PPM, something along those lines. The goal of a calibration for a company is to sell units. So if I make my geochem mode and I can sell it to minors, that's money in the bank. Done and done, plenty of sale. If I can sell to an archeologist, that's money in the bank. That's the goal of a calibration for a company. What is the goal of a calibration for a researcher? That's key. Reproducible, right? What does reproducible mean in science? I can do analysis that replicates what he did. Exactly. If you guys are two separate people not working together at all and he comes up with findings, you can replicate those findings, right? That's the crux of it. Can I replicate this algorithm? You can replicate the algorithm. Sure. So you can go this way. Who made the algorithm? Did I make the algorithm? Brooker did. Does Brooker have a proprietary interest in publishing how its algorithm works? Why wouldn't it? What would be the reason Brooker wouldn't want to publish how its algorithms work? Because it will show the follow-up system. And more importantly, competitors will know what they're doing and up against. The competitor can figure out what sample will trick their algorithm and send it over. Some people try to reproduce results from this algorithm, can they? No, it's not important. So this actually gets to the heart. Even if you decide fundamental parameters is good enough for what I'm doing, the core problem you still run into is your work as a reproducible. So let's talk about the fram shaft of the day. It seems like it has its utility when you know nothing about the first pass. Yeah. It can certainly be useful for that. If you don't know what you're looking at, you can make it a first pass to see what is here, roughly. But the problem is the spectrum can do the exact same thing. If you don't know how to read the spectrum, that can be a nice entry point for a lot of people. No debating that. Don't worry about how you might miss things. That could be important. If you don't know my germanium chart, my germanium might not show up because the algorithm might not know what to look for. But that's just as true with calibration for obsidian. If I try my obsidian calibration on chart and just publish those results, will my germanium ever show up? No, the problem is is any model made by a human being has a chance, not a guarantee, but a chance of missing what could be the most important thing in that object, right? So David, when I was talking about those sediments earlier this morning when I looked at those rather than defaulting to running things through a weight percent calibration or a partial alien calibration I used that R-Tact program that they had yesterday and it was operating through and just through all the spectrum in together and see how well things overlap or see where spikes were or not. So you weren't using any calibration just looking at the spectrum to see how each sample behaves before any kind of computing went into it. In that instance, when you used the filter you're essentially highlighting parts of the spectrum and getting more specific information. Right, so there were three different analyses done on that same sample. So there were three different groups of spectrum. And then you can see where things maybe overlap and go, okay, there's that, this and that and you can figure out how those elements actually go into a standard values unit and then you can compare the standard values units together of weight percent, this and that. But always defaulting to looking at that line first. Rather than just what's being spit out of the calibration. Because it's being selective on what it's doing, because it's made by us. Right, exactly. So when you start, like, you work for a mining company what is the... what is the input in your algorithm? Are you looking? You start with, like, a sort of family of rock or things that you would expect to find or what? So first, I've got to say, full disclosure I'm in need of a particular mining company and the video is rolling, so I can't give you all the stuff I know. What I can tell you is, from the perspective of a company they make the calibration so that it can kind of cover the most general use cases. And they try their darkness to sell on point and walk away. Because that's their responsibility to get the results they need. That's typically how all companies do it. And that's a lot of times how a lot of people start running into problems too, because they can't trust those results. Big mining companies might use it as a first pass, for if something looks weird, what could be here. But that's about it. They still have to send their stuff off for lab analysis. In theory, if I have a specific mining site, I could hyper-focus on that using Lucas2 equations or whatever. But most mining companies don't do that because that would be too much work for mine. And they don't have the sort of human resources to do that. So a lot of times they have not been able to take full advantage of the handheld XRF Revolution because this problem where I can get results that kind of look good initially. But what I'm starting to produce is let's say, well let's go back to this algorithm. Let's say I've got an previously bad algorithm. This is the one, right? So I measured the city with a bad calibration. I knew it was bad going in and I got 16% ruthenium. If I'm a mining company, is that good news? It's a great news, right? So I can plow in money, focus on this, pull out a couple tons of this magical ruthenium rock. Ruthenium costs maybe $700 per pound and I can sell it for profit, right? But what happens to the calibration problem? Not only do I lose a lot of money in all the investment I've gained. My reputation is for it too when I try to pass it off to something, right? Like, that's pretty much it. By the way, can anyone tell me the technical reason why ruthenium and rooting are coming up here in this calibration? If I look at the spectrum, what's this? That's Rodeo. So the calibration is saying Rodeo in an estimating response, right? Even more to the point. What's most of this rock made of? Oxygen. Oxygen. What's the oxygen doing to the Rodeo? Blowing it up. It's causing it to reflect more and more. So if the calibration doesn't account for that, I just read as Rodeo. The content is where ruthenium would be. It thinks the content is ruthenium. That's what's happening. So what the calibration is doing is its assumption of 100% belongs up in its face whether it's a variable to not include which is oxygen. How could it not know that it's in Rodeo 2? It's not a variable. But I mean, Bruecker... Bruecker programmed the Rodeum correction. They might have programmed the Rodeum correction for things that don't have oxygen. Because Rodeo is a precious metals calibration on something with oxygen, right? So it didn't include that as an assumption. The problem is, we could go back to the drawing board to correct this for Rodeo, but I would still have problems out here, too. There's a lot of other elements it's picking up that aren't there and that's causing the problem. But I want to focus on a really, really important thing. What I've just given you is not hypothetical. What I've given you is the basis of a massive scandal in the x-ray industry with wet toys back in 2013. What happened is someone did this with a toy that came from China. A company that will go unnamed. How do you get it that they gave to a customer and they made the basic fundamental parameters calibration. They measured the toy from China and it came up as 30% lead. And so they published an indictment of the company saying they have lead in their toys that they're selling to children. Company name and bold letters. Company scrambles to handle the scandal. Actually, it was bankrupt because stockholders moved out. And then they found out there was no lead in it at all. It was just this background radiation from carbon. Carbon does the same thing oxygen does. Company went out of business because someone did these and they got calibration appropriately. People lost their jobs, lost their savings because of the bad calibration. So this rhodium example I just gave you substitute rhodium with lead. Same physical mechanism. Light elements that weren't incorporated in calibration drove a company out of business unfairly. But if you looked at the spectrum, you'd see the lead. You'd be fine. You'd know there wasn't lead exactly right. So what's the lead? I did that. I had some Mexican maracas. Very nice, colorful peanut. And I used our XRF on it. Did you look at the spectrum and then have the spectrum? At least. Well, that was our Nikon. I didn't even mean it. I didn't give away the choice. Always check the spectrum. So this is the answer to why I'm a little hesitant. So if you say geocad, could we just use it as a first pass to take a quick look, you can. But if there's anything in there that's going to break the algorithm, I mean that's the problem, right? The only guarantee you have is the spectrum. I brought up Plato's allegory of the cave early because we're all chained to this cave. I don't know, you weren't here for this. The allegory of the cave is we're all chained together and our backs are facing the center of the cave and we're looking at a cave wall and there's a fire burning behind us and there's something moving in the back of it. We can always see the shadow on the cave wall and so we try to introduce the true forms of and that's Plato's allegory of the cave. The calibrations are methods of turning those shadows into something we understand. If we look in detail at the fundamental parameters algorithms that are here, these are the fundamental parameters algorithms each of them try to relate the weight percent so the concentration of the analyte into something we understand. Right? C i is the universal and external material science for concentration of that analyte. This can be, so for example in the calibration that backfired where the extra f thinks there's what, 16% rhodium in this obsidian, rhodium is here and the intensity i where rhodium is and it sees that it's super high and it says, oh yeah, we've definitely got a signal for rhodium. Now why would a precious metals calibration have to include rhodium at all? Because rhodium can show up in precious metals, right? So that's what's happening here and then all these physical parameters if I didn't have oxygen present would have worked probably just fine. They worked great for this right here but what's the difference between this and this for the fundamental parameters algorithm? Oxygen, right? Can it measure oxygen? No, but it could measure every element in this. If this had, for whatever reason, rhodium in it in these concentrations, this precious metals algorithm probably would have gotten close to what's actually there because it would have recognized it's outside the balance for what normal performance is on a level. It's the oxygen that throws it up. It's the under variant. So that's the reason why I would recommend learning read to spectral and learning read to spectrum if you're going to be working to that level because a quick pass you might miss something especially if you're working in a research context that's something, typically speaking when you have something important that's unusual. It's not going to show up in the actual fundamental parameters, right? Because it's the algorithm it won't even show up in your empirical calibration that's not showing up. So my best recommendation is learning read to spectrum above all. Going back to Plato's allegory of decay is this algorithm finding a true form? Is CI, concentration of the analyte something that actually exists in this? Yeah. No. What's your case that it exists? That it's a true form? Uh, I mean that has concentrations of... What's your case that it's not? I thought we were talking about rhodium We can say it's... Yeah, the algorithm is basically telling you to play a ton of ideal for that form what your ideal should look like and doesn't account for the fact that it's not always going to hit on the ideal form so like it's not... I'm just guessing. What it is is let's elaborate a little further the concentration of the analyte is weight percent an absolute or a relative measure? Relative. Can a relative be a true form? Sure. In what context? How would relative be if you know what you have is a hundred percent? If there is... If I'm at a hundred percent then I've converged on the absolute but here's the thing it's a preconception of what a hundred percent is In the object let's say humans were back in the age of genosaurus and a piece of obsidian is produced what intellectual ideas we have about terminology, percent science don't exist What is in the obsidian in raw natural state? Is percent something that exists in the obsidian as a product of nature? What is the product of nature? What is it made of? It's made of all these it's atoms. It's just bunches of atoms, right? So atoms in this case would be the true form atoms are what exist in nature percent is a human construction for understanding that reality PPMs. They're great understandings of it but my core point here is that the goal of the fundamental parameters is to take information about the atoms to create what we call a synthetic unit so Aaron Ragnowski and Anna Steffen wrote this article a while back and one of those like tubes that no one reads but it had this really important distinction You need machines in archaeology Yeah, so in that volume it's fantastic to read I'm actually thrilled that someone read it to me it's like I always hate those edited volumes because I feel like they just disappear especially when they hit like the 20-30 year mark Richard Hughes as a chapter He does he's got the creative city in chapter where he distinguishes from geochemical and geospatial sources but the argument of Anna Steffen and Anna Ragnowski in this is I feel bad because I just dissed their work and said don't read it but I guess I did but my apologies but the key behind their idea in that volume was that there was an analytical and synthetic unit synthetic units are the product analytical units are the raw output from any instrument it could be XRF, it could be FTNR, it could be GPR and it's this raw and filtered data the synthetic unit incorporates assumptions about reality right so like in this case what would the raw unit for let's say Zirconian in the subsidy and B from the analytical interpretation Photons? Photons, suspecting what is the synthetic unit that incorporates some of my assumptions that's the key so my core point here is where fundamental parameters most often fail is in the assumption that CI they don't recognize that CI is a synthetic they don't recognize that assumption so the reason the there's nothing wrong with using physics to predict properties of the atoms of the spectrum there's something wrong with trying to predict the concentrations in the spectrum because the atoms are something that exists it's a real true form that exists in the object always has, always will our idea of percent and PPM incorporates assumptions about its composition in the case of this object everything adds up to 100% is correct everything in that spectrum the copper, the zinc, the lead adds up to 100% for your key does not factor in for here because we can't measure the oxygen so we're missing that variable so the assumption goes awry and thus the synthetic unit does not properly reflect the analytical product of this does that make sense? so I'm missing the oxygen just because we can't measure it so in fundamental parameters fundamental parameters, algorithm just for obsidian could it be good enough to do most of my work? yes, but there will always be the chance I get surprised by something and that throws things up and that's the key thing to understand about fundamental parameters so for me having worked in the industry and having been a published scientist so I've been on both sides of this the problem we run into is that in science, when I put my name on that paper I'm accountable for those results the company once it sells the unit is no longer accountable for those results because you bought it their incentive is not the same as yours and it doesn't mean that they're evil or bad it just means that they don't have the same incentive structure as you do which is why empirical calibrations work better because that way the interests align and you end up with something that works out very well now let's put that in mind let's have over here to the Lucas-Toothed Algorithm the Lucas-Toothed Algorithm this is what is going on this is the opposite this is the empirical so the difference in empirical and fundamental parameters isn't in what they're trying to do they're trying to predict CI the difference is fundamental parameters the difference is in physics within the instrument and its parameters to hard calculate what the CI should be empirical gives up on that and says we're just going to use some standards and figure out what it works best so empirical is just it's been criticized for being just brute force statistics I'm going to use the slope the intercept I'm going to basically model it out statistically and figure out what it is and my answer is only as good as the standards empirical so this would be y equals mx plus b right here and then I add in the influence of other elements and that's basically the idea behind empirical so in empirical my assumption is that my standards are good and final parameters my assumption is that all these physical parameters can correctly estimate any unknown sample that comes up to it and in the case of the Eucidian standards they're analyzed using ICPMS activation and then XRF was calibrated to match other results whereas when I'm on a parameter you don't know you don't have the same basis of knowledge but one thing I often like to comment on is this quote from Winston Churchill that I've always loved it was when I started working for Brooker I got really into World War II because everywhere I went in the world I remember when I was on the small island in Taroa in the Gilbert Islands in the Pacific seeing Japanese soldiers being on Earth after the like it was so crazy we were there trying to recover American skeletons and I remember they found this one bunker and there were three Japanese soldiers still fully dressed bullets on their chest lying as they had died from the initial bombardment and it was crazy to see that finding but this was on a small island where of course you can see lots of effects of World War II I went to China where I saw other effects of World War II like it was such a major it's sort of like World War II was Lord of the Rings and we're just kind of after that not realizing how profound the world was transformed after that and so I really got into Winston Churchill because he strikes me such a heroic leader during that though he made mistakes but he had this quote about the rise of fascism that's always resonated with me that democracy is the worst form of government except for all the others and that was his defense of it and his point was is that it has all these failings it's terrible but when you get married to all the alternatives it works out pretty good like it tends to get the better result every time the same can be said empirical calibrations empirical calibrations are the worst kind of calibrations I've only as good as my standards can I find a piece of the city that represents that it's absolutely possible I'm very aware of those standards is it a pain to measure and build the calibration for every instrument every time absolutely it's the worst way to calibrate XRM instruments except for all the other ways because they have all these crazy problems that can really come back to bite you the lead example is only one of them let's take a look at and I don't know if you're going to use XRM in your work but it is very important to understand because this debate comes to the epistemology of these scientific instrumentation and archaeology and that is Nico and Lucas have probably heard this to death but that is the debate between Ellery Fram Ellery Fram and that's Robert Speakman Robert Speakman and Steve Shepp I forgot Steve's first name so it's about these guys and the background of this is he had a niton unit and the niton unit is basically designed to do fundamental parameters and figure out what's quick and easy and Ellery Fram is really attracted by it because it's cheap so in other words it removes an economic hurdle for people to do research because in nitons I collect half the cost of one of the worker systems typically so it's half the cost because they're not going to have time to calibrate individually and they don't have all these basic fundamental parameters algorithms and by the way fundamental parameters algorithms are just written and they're just pasted on each unit separately they'll usually do a little bit of standardization to customize and paste the tubes a little off but by and large the algorithm exists independent of how hard bear it's on kind of like how the macOS operating system is on all these different computers where your phone system is so anyway what Ellery liked about it was that I can just get a result quickly and this is great for developing countries where they don't have an unlimited amount of money to spend on these things and it also means I can do everything out in the field as quickly as possible so I can start to get a giant set of data like his viewpoint is very understandable but what he wanted to do was assess its validity if we go back to that same obscure volume that was published by the 1980s or something but that, oh no, 1980 1990 because that's when Third Eye Blind's album came out anyway I remember on Twitter someone asked like what's the thing from your childhood that you weren't looking forward to but don't look forward to anymore and I was like Third Eye Blind's next album but in any case in that volume which accused article was that there's validity and reliability in understanding these systems reliability kind of comes down to precision but validity is does it correspond to what's actually there at the heart of it and we're actually valid for understanding what I'm looking at and Fram wanted to say do these off the shelf calibrations work and so he tested the fundamental parameters algorithm and he tested the versus of MERS results for the same week's standard so as you can see he measured a ton of samples here it is, it is he did a lot of work he compared Serena with a team in here he used a laboratory system of Mer and then compared it to what he called the HHPXRF for the handheld portable XRF so is it a miton 3, 4 it's a gold or whatever by the way you can tell with Mer that they were going for that name right but anyway, so this is the lab result and then this is the result from his handheld factory calibration what do you think, is that good or bad it's not great not great what would we use which of these numbers would we use to assess the performance of his handheld versus the lab R squared R squared miton it's a residual between yes, so the idea here is so this is the known on the X axis here it should be flip definite but this would be our authoritative states so to speak from the lab and by the way they destructively overestimate so one of the ways labs give accurate results is they take this, grind it to a fine powder press it to a pallet, put it in the machine and the machine is precisely calibrated for exactly that matrix so it gives a much more reliable result as handheld we just kind of measure it as it is it works and all so anyway if we flip it around and the other parameters change the R squared would mean 83% of what the lab saw was predicted by the handheld so that's pretty good I would actually argue the R squared is not the best measure for this instrument the best measure is the slope how do we interpret the slope so slope to me if I'm going to compare two different instruments the slope is more important and like the R squared value it should be as close to 1 as possible a slope of 1 means for every ppm to the lab saw the x or x on that ppm yeah what's the slope here so how do I interpret that slope that means for every 1 ppm to the lab saw how many ppm to the the unit C half the ppm 50% off is true value so in other words the R squared measures precision reliability the slope measures accuracy it's kind of hard to wrap your head around it but when you're working with a known and you do know what it is the R squared is only telling us how close the line the points are to a given line the line itself this is the core problem the line itself the data is not a product of the know that's by the way a shameless plot of laying cloud cowl whatever it is cloud cowl you see this dotted line that dotted line is the slope of 1 so that way I can see does my regression line have the same slope as the dotted line in the case here it does if I use the bad cowl let's do total counts trying to shake it off that line so what are the problems when I coded my calibration algorithm I actually forced it to come with the closest answer to the line so it's really hard for me to break it let's see I don't think I can break it here but in any case the idea here is in this algorithm even though this calibration is terrible it's going to ask for a point 2 the slope is still 1 in other words it's still according to those basic predictions let's do rainforest again when I do my rainforest algorithm I should take a second here I might break so in your red cloud cowl in every case you have the counts on the lock in the estimate percent people like to like to do it the opposite way but I far, far, far prefer to see the known on the Y XORF material scientist calibration terminology exactly backwards how the rest of the statistics does it they typically want to see the counts as they know exactly that's exactly the right drives me nuts every time I like to be as strict as possible but everyone's got the preferences I might get too much blowback I might switch cloud calisthenics and technically Ellery Fram is doing it right in the material science sense but in any case I designed this so that you can compare the actual line from a regression to what it should be with the slope of 1 if on Ellery Fram's paper I plot the 1 to 1 it's going to course up here right so that would tell me immediately visually what I know from reading the slope which is he's systematically off every one of those predictions from the handheld is going to be 50% off because it's not getting oxygen or I don't know why on the instrument it's not I think for titanium it could be the oxidization state it could be it's not factoring the influence of iron on titanium there's all kinds of reasons why it could be so far off the point is is that it's always going to be off now what Fram argues is that he can post-process this he says look I can add in and correct that but then what he's basically doing is he's making it here for calibration anyway instead of using the photons he's using a derived method from someone else and then fixing it it's what we call type standardization in the x-ray field which is I'm matrix correcting but like if you have to do that anyway why don't you just do it here from the beginning isn't even going to result so that's titanium and it's not a black box exactly so let's look here this is a neutron activation analysis versus the handheld x-ray how does this calibration look? better, why is it better? it looks like it's supposed to 45 at least what's the slope of value? so it's still 38% off it's actually going to overestimate the manganese, right? so if my manganese is here it's going to systematically overestimate my 40% these units are different it tricks you into thinking it's a 45 degree angle that this drives me nuts I'm curious I don't know like I like to say journal archeological science is like the Daily Mail of Archeology like you get some really good articles in there and some you get are just terrible but yeah, no that right there he forces it there basically with the axis I don't think he intentionally did this I know the software he's using, it's Mach numbers he just plopped it and Mach numbers does that but I think it fooled him as well as the reviewers but in any case, yeah, it's still 38% so let me put it this way just to highlight why finding out parameters causes a problem in mining if I'm a mining company, let's say I've got manganese money and I need to have 1 weight percent of manganese in the rock to make a profit extracting it because it costs money to pulverize it to adjust an asset and extract the manganese to this calibration to make money because the problem is it's 38% over if the calibration tells me I have 1 weight percent manganese I might actually have 0.6 weight percent and I'm in the rep you can see my mining companies got bitten pretty hard by these fundamental parameters algorithms right, because systematically if they measure the misstanders the misstander comes up great, that's wonderful they probably use the misstander to guide the model but when it actually comes time to make money I'll bet a million dollars on this and I've got that kind of an error I'm out so I won't last long so anyway, that's the key there how about this one, zinc good or bad? 78 so it's closer it's only 22% off now it's going to underestimate 22% of the time you can kind of see here where I think the core problem is anyway which is you're systematically gone now I'm doing the obsidian sourcing so this is a rubidium rubidium is a core, how accurate do I need to be with rubidium to be able to accurately source what would you say your acceptable error is in obsidian rubidium to source you want like 95% well let's say what about absolute terms, right each source has an absolute definition of how much rubidium is in it or is acceptable in ppm so 5 or 10 ppm 5 or 10, does that sound reasonable it depends on the region but what region would rubidium be essential it's important in the Andes in the Andes how many ppm off from a value do you have to be to say this isn't from that source to do a negative test what would you guess for alka I mean it's the ratio that's fair, that's fair from North-East California where there's a lot of variability we wouldn't want it more than 15 ppm 15 ppm off if it was like if everything was off the same way that would be workable you wouldn't want just rubidium off so if I've got let's say I've got this calibration which is 0.66 so not great but this wouldn't work that wouldn't work but let's say it was 0.9 let's say if I have 250 ppm from the handheld what's the actual concentration of rubidium in that rock if my estimate is under well 85 that'd be 30 ppm off in addition to the inaccuracy that's the crux of it so that to me this has a failing instrumentally right then but here's the thing Frant makes an argument where he says look these still cluster I still know, even though these results are inaccurate that this is a cluster and this is a separate source I can still make my source assignments this way so what he uses and this drives me now he quotes what I told Adam Nazaroff back in 2007 he quotes us and he says even though the calibration is off the instrument itself is still internally consistent and I remember the bar that I said that to Adam that we put it in our paper internally consistent so I can still make the source attribution as long as the instrument is internally consistent so his argument from his data we published it we did publish it in Jats in 2010 actually so he's using our research in this case which still drives me nuts but I remember talking to Adam taking through the results because what we did back in 2010 is we used Steve Schatt's machine here as the control for the broker tracer, we did the test I remember it because I had worked on the Obama campaign and it got done and I was like I really need to do something like a launch floor so I jumped on that project which is so funny this is a case where something like Bronze Age never got me a job but this like a third author position on this project launched my career but anyway, it's funny how the world works but I remember when I looked at that data let me see if I can bring up our paper it's just funny because I'm like where that lab is oh by the way my favorite part of this is we document I shouldn't have used the shadow of the figure again, Jester viewers but this is the diagram of HughesNet's 98 paper so that way you can see what he means by validity so in any case if we use this if we use this precision would be the replicability of the measurement accuracy would be comparison of the nine sources validity is the ability to distinguish the two components of the source and then validity is the ability to address archeological inquiry that's HughesNet to 98 so in this case let's judge the Necton unit making replicable measurements with Fran's data on the blood of Necton right, let's give it a no comparisons of known sources, does it work? no, does it accurately distinguish two chemical sources? it distinguishes the two that's a yes, we're going to do that but accurately it is the problem we'll put it aside we're going to take these in isolation I'm going to give this as a yes to Fran and then does it address archeological inquiry? yes so that's by the way why Fran called it validity because it meets Hughes's definition he is totally side stepping reliability and precision and accuracy he's saying is it valid and so in that case that's what he's thinking so yeah but anyway what we did is we used cluster analysis to compare Berkeley's unit with our tracer so that's why I'm really proud of this, I came up with the bullseye idea because I didn't know how to visualize how two instruments performed so I used K-Means cluster analysis which means I tell it how many clusters there are in the data and it automatically draws the bullseye the bullseye had to calculate the core of it is is a trance to find the center of the data and admit that for the tracer you can see the offset it's a miss it's systematically off here I can see the I can see the systematic drift one unit to the other by about 10 ppm so the bullseye is the initial equation now? the bullseye right here that is drawn that is Steve Scheffer's history so these are the letters there along the tracer we had that we just got and then we measured the same same obsidian pieces here at Berkeley as Steve Scheffer used to do so the dots are from the tracer the bullseye here is from the lab unit here because again visualizing the two is really hard so the bullseye is designed if you eyeball it you can see the drift between the two and I am coming in about 20 ppm, 2 lb zirconium and 10 ppm, 2 lb zirconium I can quantify the difference between the two it's not like a standard deviation or something, the outer and inner circle exactly right, this is standard deviation number one standard deviation number two on a single on all these measurements these are 1, 2, 3, 4, 5, 6, 7, 8 samples of Mr. Pecquet this is the deviation of the k-meat cluster so the deviation here by the way is not based on the data it's based on the k-meat clustering algorithm it's a little complicated that's why it's not in the list that's exactly right, not in the list because the idea of k-meat cluster is I've measured a center point of the data and then I have the variation in that center point as varying standard deviations so that's why it isn't in the list although I would argue that if I did draw it once in this lecture it was already right here anyway but the idea here is is that theorist is meant to be off but when I told Adam in the bar he was like well what do we do I don't want to publish this paper until Bruce is wrong and I might be absolutely do that what's more but we will point out we'll give this bomb to everyone that the device itself is internally consistent once I understand my offset then I can directly calibrate it so our point in this paper was it's a solvable problem Brooker just isn't there yet I got so many angry emails from Brooker when we published this and then they hired me on a PhD but this was the crux of what that was so anyway but that's the key right so we argued this and the point of the paper that we wrote was that this is solvable so I argued this is my mistake I argued that the Berkeley instrument here by Steve Shackley was accurate the authority of Steve Shackley meant this is a known value and the instrument is off I went wrong that was right so the calibrations this is from a conversation with Bruce I've been videotaped if I misrepresent you with Bruce or Steve Shackley I apologize what was explained to me was that there were many centers of obsidian who wanted to do obsidian work that was Mer and Steve Shackley I don't want to name any names one group put obsidian on epoxy that we were talking about yesterday so their backscatter was influenced by epoxy another group normalized to all the background so instead of normalizing the component they normalized everything from 20 to 40 keb so either of those two things either having the obsidian on the epoxy or that would cause this type of error that type of systematic error so what we're seeing here is not that the Berkeley instrument is correct and that the tracer is off that same goes about 5 ppm around each I would say we're seeing a difference in how the data of the spectrum is processed because if we mount the obsidian on that epoxy we're violating the assumption that it's 5 ppm that's the crux of it so this is actually what the student yard was back then this was as good as any archaeologist was going to get with any study so are these calibrated there at this point and what kind of calibration was it it was the Mer version 1 obsidian calibration but like I said I'm not going to name any names because I don't want to name but there are two problems with the existing calibrations back then one was that they were mounted to epoxy so this backscatter was inaccurate and two they were using that normalization protocols and so it was a consequence but those two in place by the way if you normalize from 20 to 40 kev can you tell me what the biggest thing that's going to predict the value of rubidium how thick the obsidian is because I'm normalizing all that backscatter I'm exposed to how thick the obsidian blade is so blades will show up over here and this happened to some like well back not in the night I think it was in the 80s or 90s something like that and they ended up completely supplying all the obsidian sources they made an argument that all the blades were from here but all the cores were from here so obviously they were importing obsidian from one place and then exporting to another that was the economic relationship the backscatter was causing the underestimated rubidium and the straw team and the misassociated to another source you can totally see how that could happen though right yeah anyway so here I was being unfairly critical I think that's just a critical out of that Steve but either way, if you measure and later I think Kurt Ruddmaker did something similar in Olga and he actually found the differences between neutronation analysis wavelength dispersive and hemilextrorept actually come out to about 10 ppm they did ICP in the mass as well and then they saw that time level of variation right and then there was that report that from my class colleague who was Kaiser where they did all three methods exactly and then they came up with this is sort of the 2012 exactly what frustrates me is that they never published that officially that should have been a jazz article I think even looking through for citations too I was surprised no one did that but anyway this is the case with Graham's article he used our argument what I thought we were arguing for good calibrations he took it as as long as the instrument is internally consistent it is valid in Richard Hughes sense and we don't have to worry about reliability we don't have to worry about accuracy or precision so in other words this right here is beside the point we don't need to worry about that enter speakman and shackley who take a very different case they come coin this turn that's going to be hard to read they coin this turn it's silo science and what they mean is that as promulgated by Graham and others I think I'm the others that it is perfectly fine to provide results that are only internally consistent and do not conform to established international standards and data then we are entering a time of silo science where each researcher's data is self-contained independent and cannot be verified we find this is not only unacceptable but another aspect of the social science that is definitely the science aspect plays scientists with portable XRF technology burn mic drop right so the core point they have here is that Fran arguing that internal consistency is the only metric for the performance of these XRFs means that each XRF is its own self-contained world this XRF could I get it could I get it to tell me what's another South American G. Viad, etc yeah I can do all that that's good in archaeology these guys are like who can test you who can come in and test your results and find a problem with them if it's fundamental parameters and it's a locked box that it's not reproducible and then every individual worker is working independently we just have to take their arguments on authority we can empirically test them that is the argument of speakman and chaplain so to point out the reason we use weight percent in standards and empirical calibrations is to make everything reproducible so that way the work you guys can do can be picked up by someone else and it's reproducible, it's invalid and it's reliable in the full sense which are used back in 98 that's the idea behind this world about that and that's really what the fundamental parameters on empirical calibration is about it's not about whether physics is a standard in terms of estimated concentration it's about whether or not you're doing science or not because if you can't reproduce it it's not science, it's just authority we haven't moved that much far past the allureo if that's the case that's the crux of the argument so in the report this is the report from I think I've got a copy I can bring that up too so in conclusion he says do you guys feel like using this method for the best results with so any best elements for NAA analysis are sodium, aluminum, chloride, potassium S, C B, E, S, C V, N, S, B C, S sodium, sodium wait the double is sodium yeah yeah and then that's what is that the microwave so I I don't know what the M.A. is ICP, M.S. is a couple plasma mass spectrometry so anyway the ones we care about are strontium, petroleum, aluminum better from exactly exactly and then what they do with their calibration is they use the values we use for strontium the values we use for rubidium come from NAA exactly so to understand the difference between these two techniques neutron activation this is really important for you to understand because you're going to have to cite a lot of this out neutron activation analysis is I take my sample I put it in the nuclear reactor I close the door I close another lid door I go over to the next building and I put turn it on and the nuclear reactor activates everything in this guy like in other words we're irradiating every single element here and those elements start decaying we're just filling them up with neutrons and now they start breaking down and they produce a spectrum spectrum that shows the decay of those elements and elements like rubidium decay into other elements and produce a spectral signal so they can measure by the atom what is being produced and they can use that to infer how much rubidium was there based on how much rubidium was activated and decayed when they're done they have a machine that takes the sample puts it in a nuclear containment thing because that sample is now radioactive for the next 400 years and now it's radioactive waste but we now know a lot about what was in that sample what makes neutron activation analysis good and we can do partpabilia and we can do a lot of elements so there's an argument by Patty Crono from 1983 she's the wife of my disfacer advisor and she's our nuclear surrounding source and this is the best method XRF can't compete even though XRF is attractive it doesn't give you the range of elements you need to know you'll need to know that because you'll have to cite that if you find good results with this or if you find bad results with this that's good you didn't say what is the difference between long and short irradiation you know I don't think that long irradiation, long something I think it calls smart is he talking about the wavelength in that context or is he talking about the duration do you know I think it's duration if it's duration it should be the same basic energy the longer you run it for the more expensive it's going to be because it's a nuclear factor but the chance of getting smaller quantities of exotic elements I think is what's key there so that will change the detection limit I think that's probably what he's referring to but I don't know for sure but if I had to guess that is what it would be but that's for your navigation analysis now the thing is not all elements break down in the same way so that's why we see that some elements are great for M.A. and ICP M.S. that's what we're using in the next couple of hours of time what we do there is we fire a laser by the way the ICP, this determines I'm going to be digested in the acid into the solution or you do it on the physical sample in this case they put it in a four fold acid dilution which is crazy dangerous they're using stuff like hydrochloric acid that is just fantastic stuff but it dissolves everything and decouples from every other element and they take that solution and they fire lasers at it and the lasers break down the outer electron shells and that creates characteristic spectra and that can be used to quantify things I think M.A. is a typo down there it's called M.D. it's microwave digestion that makes sense so one thing I want to highlight here FE is better started by new generation of analysis FE is not better studied by ICP M.S. brooker has made a handheld ICP system it's using a laser and physically works a laser evaluation it actually works great with ceramics by the way let me show you that it is it's not exactly on a ceramic you usually don't notice it but it is absolutely destructive this is what it looks like here and I wrote a fingerprinting out it's similar to what you get from ICP M.S. so here it's better it kind of looks like XORF with two different lines this is what it would look like so here I've got oxygen, calcium, silicon, phosphorus but there's multiple sodium is actually super easy to measure with this technique it shoots a laser on the sample it basically creates a ball of plasma and the ball of plasma spits out photons from the outer electron shell of what was just in it elementally it's still the same thing you're basically creating this cloud of electrons and then you're able to measure from that light what you're seeing in any case when you produce that the fluorescence is changed so how many peaks does iron have in XORF? two two, right? can you guess how many peaks iron has in ICP M.S. or laser induced inflation? 18,000 so so that's why they use the neutralization analysis for iron because it's just impossible to do with ICP M.S. it's a hot mess they typically take one of those peaks and hope it works so anyway, your spectral interpretation issues you can do qualitative XORF spectrum work it's really almost impossible to do qualitative ICP Lids work because there's just too much but anyway, that's the key there so that's just one example of why one envelope could be better than another because they have different properties on a rich method but they combine both leaves and they produce that and the point here is using this approach with this set of obsidian if Niko does work and if Lucas and Kapter do work it's equivalent they can compare each other's results if Niko goes, Lucas is crazy, this is wrong jumps in with this unit, he can test Lucas directly and get the same result and that's reproducible and now it's science, right? the arguments you make are substantiated by that data set in any case, but that's the core of what they could hear Fran, unhelpfully comes in with a new argument wrote in his papers here so this is where Fran responds to Steve Shackley or Robert speaks to Steve Shackley and I'm just going to read you the title is it a city in sourcing about geochemistry or archaeology what would your answer be? both, both, yeah why would it be both? because you can't do both without the other so Fran is trying to divorce the idea that archaeological questions require good geochemical data whereas I think the argument from Steve Shackley and Robert Speakman would probably be thinking Jeff he does prefer Jeff, I know it's just the published words it's sort of like when I was a kid I pronounced items items because I would say a freak inside in a box of cereal there was also 19 oz so in any case the argument that's the fundamental debate can be divorced, archaeological inquiry from the base of geochemistry the group who uses empirical data standards of data says no, you can't the group who likes to buy cheap instruments and point and shoots says it's good enough for government work so I wanted to make sure that we're staying on the point of ceramics because the obsidian has kind of been monopolizing some of this conversation so it's really easy to source obsidian and have enough ceramics when you have a site that somebody worked out 10 years ago and they end the tracer and they created chemical groups based on their analysis have you been have you seen people going back to those same ceramic assemblages and analyzing them again the same way we would do with obsidian are people doing that are there issues let's hold that thought the answer is yes there are people looking at it but there's a lot of mixers because you're not necessarily sourcing the ceramics you're just creating geochemical groups that is even more complex than doing much more obsidian you don't have sources you just have chemical groups powder comes with clay clay sources ceramics are complicated I think a lot of the work is obsidian sourcing is fundamentally predictive ceramic analysis is mostly descriptive we're describing the different groups we have as best as we can I think in most cases true sourcing is geochemically impossible whether or not this is extra for NAN because the reality is in spite of a volcano there's a dot on a landscape that produces rhyolite every once in a while boom, right there, that's my source there's this defined region in space and time that produces that a geologic formation can extend across half the continent and have outcrops in different areas and geochemically I might be able to find a Scandinavian ratio pinpoints this formation that formation is huge the nature of this variation is fundamentally different than it is with by the way, I cut myself with the obsidian good job making it I'm good for now we were talking about earlier you can't really necessarily source ceramics because you have different ingredients and different residences we're talking about how cookware in the mycelium world gets tempered with salt and other various things obviously you can't source each of those to one location in argument, some people use micro probe so they'll use an SEM and what the SEM does is it fires electrons which gives you a nice surface topology but I can target a clay species and ceramic I can shoot electrons at it and I can get a spectrum just like XRF it's a little different because I'm using electrons I'm also doing it in pure vacuum so I can see things like carbon too but it's also all going to be the same thickness you guys have one? I'm just going to leave the question to you guys you will want to use that if some of you are working, absolutely the negative by the way of that is it's spectrum is typically confined by about 25-30 kV so electrons like the medium strontium don't show up well at all XRF is way better for those but for light elements compositionally it can be very very useful for your work too but it isn't necessarily helping us to change it it's like 7 7 cm we've got an older model the composition per size is larger they've got the same amount because they're miniaturizing the same way everyone's miniaturizing people are using it as a circuit board oh yeah you can see the carbon but anyway, yeah, so that's the deal so in any case if you are sure it's small enough you will get the EDS spectrum and by the way the rules of EDS are a lot different than XRF so in XRF we're talking about the resonance where titanium fluoresces and activates another thing, not quite as true in energy disperses in electrons because the electrons don't do that now in the product light they still do that but it's not working with the same depth of penetration so those effects are much reduced so you can use that for some of your work if the struts are smaller you just have to bring it back to the US you seem to bring the EDS with you put it back to the US maybe there's no but anyway, that's the key thing but it works with some of the properties so on the note of ceramics I want to segue, actually I need to use the rest of it first when I come back I'd like to segue but I'd like to do, since we've got a very qualified crowd here, I'm going to do a really deep dive into ceramics and not just ceramics but the environments that form them so when you see elements you don't have to interpret them it doesn't have to be relevant because if you keep the stratigraphy and archaeology these same rules apply they're just not on a different scale of time but all of the chemical interactions can be very simple so I'm going to hold that thought and I can like 10 seconds and we'll continue so have you started doing any kind of analysis with this? no, no, no for me this is very yeah it's just like it's this, you know the things I do about x-ray control coming in are that it's non-destructive and it's purple so for someone who works in Greece where you're not really allowed to do any part yeah, it's portable it's incredibly portable wow, so this is like straightening this is like out of the front you painted it in the fire exactly that's why you have to go portable so tell me what a filter it is cause I don't quite get that even for me I'm like if I go to the bathroom to go back I'm going to be lost I have to go and I have to make it as fast as I can really possible this is all really good because I'm starting to understand yeah, right well you can make a lot of different deals just keep going back for a lot of what I would this is not something you can do for my dissertation but the research I want to do after that basically having something like this and I can go to Greece and I can point to XRF at the Connery another artifact and be able to say it's just not Greek is yeah, it's helpful because there's debates on that I mean you maybe are you a fan of the video that I'll approach at the third plaques at my CD? no, I've not been to my CD yet but yeah that's one of the things I look at at my CD you have sort of a series of these finance plaques they're still in some debate about whether they're even made in Greece or Egypt I do think they're probably made in Egypt but they're still yellow do you want to source that another plaques to see what it might be? yeah, potentially that's one of the things my exhibition that I worked on requested the XRF to bring to other stuff and shoot the one that you have because there's only one that's been found outside the palace that's in the first site shoot that potentially compare to that with other finance and sort of be able to prove I would just like give this a tip what is finance exactly? I can go over that later but I heard the term come around I haven't really looked into it but it's helped more than all that it's solid it's a silicate essentially I don't know a lot of the science that I'm used to looking at let's just google it but I think it's essentially it's ceramic adjacent the glaze on it it's a style so what I would say it's not ideal as you can remember what I would say is this we're going to go into this a little bit this is like the finest watch you're ever giving to I love paleoformatic reconstruction a lot of deep time I really shouldn't have done archaeology I should have been a geologist but the thing is you want to know how Egypt Egypt's geologic history and Greece's geologic history and I'll make it simple Greece is the product of the uplift of coastal sediments from the movement of Africa north so in other words the Europe and Africa are squeezing together that's confined to Mediterranean it used to be bigger than the Pacific it's the Tethys Sea and it's shrunk down to nothing both Egypt and Greece are the product of that uplift so they're covering the geology of the Tethys Sea which is good because different marine basins have different complex geochemistries that happen because that salt and water makes things possible and aren't possible in fresh water in terrestrial areas so you end up with so what you end up with is these geochemistries and that can be how you answer questions related to this there's that kind of that kind of deep time so in any case that's the idea so I would argue that the most important thing you need to look at is the geology which is not a welcome news I think because you're much more interested but the more you understand about the geology you will understand how to interpret what lived it up in a clay and what that means about the environment it formed in and then the probability that it formed in the Greeks or the Egyptians or something along those lines no one in archaeology looks at it to that depth typically speaking it's almost always geologists who ask themselves those questions but to me understanding that formation process is going to be the absolute clue to what's going on there which means there's a calibration if you get the five up and that is the mud rock calibration because it is calibrated for exactly that I get a lot of flak from this from archaeologists because archaeologists and I'm going to talk about that when Kathy comes back here too but like Brooker didn't like it either Brooker's like this is not just calibration it's built for but you have to understand where these things come from and we'll kind of go into that in a little bit so mud rock we can't create it ourselves you need these standards and the reason we have 169 yeah that's fine you can certainly add that to the calibration if you'd like to too after the fact the calibration that Brooker has now is an updated version of mud rock that's based on 40 42 standards I think not the original 26 but I'll talk about why I think it's crucial to these kind of ceramic sources it's not because ceramics and clays from the earth are two different things because they're not really like obviously we have tempered salts and it starts to change the amount but remember the XRF is measuring everything, two of the XRF a compressed clay from a geologic formation and a ceramic are the same thing clouds of oxygen with other things mixed in like silicon, aluminum and all that so quantitatively you get close to the same weight percent what's important about the mud rock side is it's trained on the elements that can key you into paleo environments and it's the paleo environments that can help you source within a geologic formation let alone an entire way and that's why I think it's essential to add a lot of clays from different areas it also helps you understand the verbs not just the nouns because like obsidian we don't need to consider the fact that obsidian forms from different environments because by definition it's always from the same thing a rhyolite producing volcanic eruption almost like a tech type let's say a tech type or about the salt or let's say it's compressed ash or something like that once they start to develop those different kinds the elements aren't just paths of descriptors of source, they're active descriptors of what happened to producing that rock and that's the key, the more you understand about those formation processes the better around you're going to be in conferring from the water so with that let's take a look at the mud rock calibration they did what I think my last lecture which is publish the cow in journals so this is in chemical geology now what they did there, I can send you this paper too if you'd like I think this is my favorite empirical calibration paper because they've published, by the way which element which line there's slow corrections, there's background corrections and the standard cabinet so it's the most open calibration I've ever seen and let me tell you something even more the people who funded this this to me is the most open science approach to abstract analysis, they published everything about their calibration everything exactly, and they did it at the behest of the evil oil companies so the background of this is this calibration was not built for archaeologists it was not even built for scientific research it was built because oil companies owned lots of money so the background of this is the fracking revolution so in the United States, fracking as a technology has completely transformed our economy, right? America back in Bush years, we talked about energy independence all the time how do we get independence in countries like Saudi Arabia and all that because the things they do now, we don't talk about energy in the heads anymore because we are energy dependent most of the oil used in America is produced by all of America now we outproduced Saudi Arabia now, which is crazy, right? it's all because of fracking now, we say in Saudi Arabia, not because we need the oil but just because we're okay with killing journalists but but anyway, the key thing here is what transformed that well, it has to do with the horizontal movement of pipes so in an oil company, do you guys remember that you guys remember watching the Simpsons episodes who killed Mr. Burns? do you remember how the school found oil underneath and then Mr. Burns built well, it tilted sideways that's what fracking is what fracking does is the oil they drilled pipe here and then it goes here not for a few meters but for a few kilometers and then they can just go through the entire geologic deposit all along its side and yank everything out before, these weren't economically to extract because of geologic formation, if I just drilled down and I've got oil, the oil's kind of captured under the salt dump this big pool and I can suck it out the fracking exists across the entire geologic formation what they do is they drill the pipe in they go this way and then they pump the water and they just break that geologic formation apart and then they gap, shake solution floats to the top and then the longer they can break it apart the more gas they can get this was not possible 20 years ago it's possible 10 years ago and that led to a resurgence of the oil industry in the United States they have to know those geologic formations they have to be able to predict where it is because if you drive your pipe into the wrong formation, you can break it there's an even bigger danger so a while back Harry wrote he was with Bruce Kaiser and they had a grad student measuring a core like this, every 10 centimeters and he's talking to Bruce they're talking about, oh yeah oh yeah, it's in his little chillies there's a heater in here what? yes, there was wine see, by the way I got a good comment I used to be super activist-y when I was in college during these and all that we always do plans for production but we never do nice consumption what we just did there is why we have to drill all that stuff, right? but the key thing is here that's the process behind it all so what drove all this change was that you don't want a frack in it but you open yourself to vulnerability so an example is Harry Rowe had a student he was talking to Bruce and the student is scanning every 10 centimeters like this with the tracer it was the same tracer you guys have right now and then the student takes Harry Rowe aside and says there's a gypsum from about 1 meter to 1.5 meters so Harry Rowe interrupts the conversation gets on the phone, calls him and says, I need to add a cement cap and the guy says, ok, Harry Rowe goes over to Bruce and says I just sent him $100 million what happens is what's gypsum made of? Does anyone know? calcium sulfate the sulfur if you drill a hole the gypsum is crumbling if it falls in to the deposit of oil and natural gas that sulfur will dissolve in and contaminate it and that sulfur is not prohibited by regulation because sulfur is the main pollutant for acid rain in the air so that higher deposit is worth $0 so $100 million worth of oil is now zero because of that contamination that's why they built this calibration one pipe would it go through? if I get a rock of gypsum this big to drop into a pot of oil like that's 38% sulfur all those sulfur atoms percolate out and if that sulfur goes to 0.1 yeah, that's a pollutant hazard that's going to create acid rain in damaged environments so where's the cement chopped in? it just blocks the gypsum you just coat it, right? I put like a little blocker in so that way it cannot fall in it's just like a retaining wall so as they drill they're pulling you down? exactly, then the gypsum can't come in so the oil companies funded open science no oil companies stepped in and said they're the only ones who know how to do this they do know, they pay Harry a lot of money now that they know how important this work is but they made this open for everyone to use because everyone had the same problem no one is invested in someone else burning the natural resource it's like the oil fields in Iraq by the fire all it does is add pollution with no economic effect so that's why they made this an open calibration so what they did was they drilled these cores in the formation iron, almost, right? like the entire set of history of life on earth is captured in one of these cores and what they did in each of these cores, you can guess they're a lot of money, a lot of money goes into Germany they take slices of each core horizon and they turn them into standards because each geologic event tells me something about the history of the earth and if I've got built the calibration for mud rock I've built an earth calibration for all the sediments now the reasons of our archeologists are ceramics made of the same place but what the point is, is they're exposed to more variation than we are so their calibration publishes a bigger elevation and this is a free calibration essentially because it's been published? I mean, you still have to understand it somehow you can talk to Bruce, by the way if you talk to Bruce and you ask and bag and actually what you can do is is you get your tracer, you fly up to Bruce and he will meet you when you calibrate on at his house and that's something he does as a favorite scientist because he likes people who are interested in having this incidentally we have access to a copper standard set that's great excellent wonderful yeah, you guys have this calibration in your units this is used for that way you can use this for ceramics I use it for geochemistry but we have a green, yellow did you do it through Bruce? yeah, good call Bruce will help you out if you ask very nicely I just really put in a good work for you because I love my Palestinian Greeks but yeah, that's the key thing is that calibration gives you the ability to do that so that I can share with you how we scan this so if you have a sample you can treat it the same way and run it through exactly the calibration but to get the calibrations it's not just like you enter the data from here you have to actually because you have to calibrate because you're training your tube to see that much oh, it's a tree okay, that makes sense so these are like cores, then? why does it actually be... so each of these dot points is a standard from a geologic horizon from one core that's what they are so if I have my core and I have a geologic horizon it's this big, it's a light gray something like that have you seen pictures of these cores? I've seen mining cores here, let me see if I can do this right and so do they just take a whole bunch of them from an area? yes and kind of average amount kind of thing let's see if this works guys I can show you an unbelievable map of what these cores from data that Harry's donated before he was bought if I kind of oil it we really have to lose this video, I'm talking too much but it's still recording I haven't talked to Harry in a couple of years because he's gotten a really crazy contract but it's got a very strong confidentiality requirement so I'm going to upload a spreadsheet drop box or no, desktop projects so while you're doing this as a clarification we basically there are different types of calculation we've been talking about the one that is the parameters is essentially it's not an object like elemental calibrations you basically are uploading a formula that you're telling how to interpret the data whereas these calibrations are training your XR, you're shooting at things and teaching it to recognize it in the future you've got it okay, that's it so yeah, you got it so like NAA those are constructed methods and so yeah, I've really dialed in and we can use XRF non-destructively so like if you're for example looking for a source of gold without the calibration you can shoot the gold or a diamond or a city and you can get all of the information out of it but you can't source it because you haven't sort of taught the XRF how to look for that whereas you can then go and be like here is the gold mine in say California, here's one in Mexico and then the difference is you're not training the XRF the XRF is only telling you what's in it you are training yourself in that case this is what this character is the silver gold ratio in this mine matches this object there you go, I can make an argument the problem with gold is that they re-milk it because it's valuable but yeah, in that case you got it this is an example of a core by the way this is a map from a tracer by the way they took a tracer and they measured that force, it's an elemental map of the core so this is what the XRF kind of see so you can imagine pretend for example this is a gypsum layer well you can see why tapping right there can save you all that money maybe this is the clay I don't want maybe this is the formation that has the oil and I can target it that way so that's how they use this for that it's basically that idea that's why this calibration was made it was made to interpret the history of the earth and then I can grab a different element that's iron there and then I can see with iron I've got these flecks of iron maybe the iron pyroite can hurt my equipment so I need to change my process and chop up the core so I don't damage my pyroite there's all kinds of ways to get this information and then I made it so you can flip your map and see what it is you can also add one of my cloud killed up files and it will calibrate this so I can see the weight percent of each pixel this is my favorite app no one uses it so what does it look like is it a raster no this is a vector it's like points well sorry this is a raster I raster the elemental data so it's coming in exactly exactly exactly you've got it anyway and I've written this for the tracer you can upload data to the tracer you can measure the grid in a specific way it can infer from the filename the coordinates of that so for example if you want to do a whole palace a mycenaean palace you could go over to mycenae and measure every quarter meter or whatever increment you want you create a map of that floor we did this in shallow oil for eating hotter we worked really well because we could actually measure we did it there so we could measure contamination that was damaging things you can also do it for living surfaces so we had the opportunity to meet with Bruce for that mudrock calibration but brooker provides one that's apart from that one or it's the same thing so the one you do with brook with Bruce has the 40 standards full the one brooker had at the time you purchased the unit was the one that's in this paper which is 26 standards that said brooker has bought the same one Bruce has it's the we call it mudrock 2 and so it doubles the number and it actually vastly increases the number of operation curves from a brook and then there's another paper 2015 husband speakman where they provided their team of brookers mudrock yes they do yeah they absolutely do I've got strong opinions about that paper and their argument but that's okay people can disagree so this is another one that you will probably want to look at just as background you can just type in speakman mudrock they're these kind of papers aren't really getting a lot of them are available you're going to have to have a lot of their signed in what is mudrock it's not made that's what it sounds like it's like a compressed wet mud that's in a geologic formation they dehydrate it before they make the pop so it's still a drain pop and they're still in those little discs so it's compressed pellet discs but it's compressed mudrock and the mudrock is how geologists refer to it there's sand, there's silt style it refers to some of the water properties of the stones so the ones that first had it were these big pucks that all stick together and these big little things and they're brown, red, yellow they're all different kinds of colors so let me go to desktop projects tracers like silk stone or different like what would geologists call it mud rock that's like the slang term it's not mud rock it's sort of like when you're talking about something it's a mud rock that's what it's named after but they're really funny but here's the calibration curve from that mud rock set so here's iron, cobalt nickel, copper zinc, gallium selenium, arsenic selenium so the reason why I like it for ceramics these are elements you can source with with ceramics, selenium and gallium so it captures those better than the soil because the soil calc doesn't have enough of these to make a calibration curve so because the mud rocks have all this they're selected for error length of variability it makes a good general calibration for silicates in my opinion if I make a soil compressive mud rock I still get very good results and they're reproducible terrible results as long as your sample is a compressed silicate that's made of mostly oxygen mud rock will do a good job of capturing its elementary ability that's the rationale behind it so that's why I like it the best people disagree with me but if you're trying to capture a lot of exotic elements that show up in these that can be sourceable this to me gives you the best platform you can paint worker to do this it'll cost you I think $4,000 for the two phase whereas I think we're planting to sell in the city in a couple days can also work too but that can be a way to say if I have a choice between really begging Bruce to measure his standards and getting the 5G or getting the 5I with the worker supplied mud rock I would probably go with the 5G plus asking Bruce really nicely that said if you ever need to get your machine repaired the worker will recalibrate it for you for the first time whereas you have to ask Bruce especially again I'm turning the excuse I got it two birds with one stone I would be reliable at the same time the mud rock looking at it to help you improve your video it's actually hitting a city level of good that's where we are by the way notice here look how high the Australian goes it goes up to 3% because I've actually seen this in ceramics in the sourcing project I'm working with University of Chicago Accommodated Persian tablets from SUSE have up to 1% straw table then so you actually have to have that much variation in these whereas a normal ceramics model wouldn't miss that but that right there is super sourceable right? like it's geologically weird that's the problem when you do find something sourceable the problem I see people have is that their calibration is too narrowly defined in that case they miss the exceptional ones that are sourceable so that's why you want to make sure you do it this way zirconium can I show you something too by the way I've learned this when I build my calibration curves do you see how these two are weird that's because the standard's got switched this one goes here that one goes there so in my calibration plots you can actually see when someone gets confused who puts one standard on before the other you can create this T shape with the validation slope you can draw a little square around it whenever you can do that between points the most likely explanation is that the standard's got swapped you'll see it on multiple calibration curves so I can see it here too that's the calibration curve so I wrote the algorithm to not do a linear regression but to do a loss curve if the loss curve is straight I know I've done very good slope and intercept corrections if it gets wavy I know I need a lot more work that's the reason I need to work on the calibration more although in this case I think it's because ICPMS is not great for niobium which is one of the reasons why they use NEA for that the problem I brought is they didn't do NEA they only did ICPMS so any elements that are bad with ICPMS like niobium aren't going to be as strong so what we're going to work on are going to be solved there's an issue it's the it's on the iterator and we use the yellow filter and this is with the yellow filter so the brimstone is contributing a lot more to it if you use the green filter it looks a lot better the gray and arched is that like a two standard deviation? it's a this is a 95% confidence band based on the e-regression model this is based on lows, this is based on linear regression but yeah it's a 95% confidence band I'm using did you plot step smooth method LN here and then here I just default to lows so yeah but anyway the reason I do that is because what I learned quickly in building cows is when you look at the cow if the calibration curve is straight you've got a really good cow if it's slopey like this that means I need to take my spectrum with a different parameter so that's something nice so I did that as a visual cue for me to know what I'm looking at but in any case the key point here is that when R2 is really good you should use it for these kinds of things and Harry Rowe did a phenomenal job of validating it so what they did to validate it is they took cores and they measured the cores using with a dispersive extract destructively with a black line and the WDXRF is the red look at that agreement with the handheld in the laboratory and so they did this because then they can scan it pretty quickly as they come out so anyway long story short mudrock is very well validated for quick horizons now what I'd like to do is we might do a late lunch today is that okay? I'd like to do a deep dive into what the elements mean because I think this will be useful to any of you who do anything other than do you guys anticipate using Qtracer for more than just obsidian I don't know if it's a what's that in this? let me give you an example of how that can work I think it is do you guys approve of this? I have too many things open so I'm taking that critical mass I lose everything you may use it in Mexico on anti-virgin surface layers as opposed to just geological surface layers on anti-virgin surface layers awesome this is from chocolate candy in New Mexico I'm published I really need to get out of this but here we took a profile of the Arroyo Bank by the way this right here is what we think is the drought during the end of the Civil War period that led to the abandonment of chocolate candy because we find the classic base surroundings right down here and they disappear and then you see the kind of flow lines here so here's the droplet you see all the lines dropped there yeah so what we looked at was calcium ratio this is a proxy for evaporation so in other words what happens is calcium and strontium behave similarly right? they both have two valence electrons because calcium is the right amount of strontium on the periodic table so two outer valence electrons are binding so they behave similarly and they're about the same size chemically which is why we take up so much strontium in our bones you've heard of strontium isotope sourcing in your intellectual work that's because our bones take up strontium because when our body digests something it doesn't say I want calcium it says I want an atom with two outer valence electrons and an ionic radius and what and you grab that strontium as well as calcium typically speaking if I'm doing ocean studies the ratio of calcium and strontium is easy even calcium is a proxy for temperature the warmer the temperature the less costly it is to incorporate strontium so if you've heard of C2 C3 and C4 plants or you know about carbon let's do carbon 14 carbon 14 dating is central in archaeology we all know how it works why does the plant take up carbon 14? well it's just carbon it reacts the same way but does it take up carbon 14 carbon 12? no which one weighs more? 14 14 which one costs more metabolically and moves through the system? 14 14 so there's a kinetic cost to incorporating carbon 14 we can actually mathematically model this for every atom of carbon 12 you take in for every... let me get this right so what it is is if you take up 10 atoms carbon 12 you will take up only 8 of carbon 14 because there's a cost to taking in the carbon 14 the same is true for strontium isotopes are all over the calcium the strontium weighs more so it costs more in a bit it's like you have salmon go up a river up a waterfall skinny salmon do better than fat salmon because they have less mass to move in other words gravity forces kinetic fractionation it's kind of complicated but the reason we have isotope ratios is because not all isotopes behave equally there's a difference in abundance there's also a difference in how we take them up and that's called fractionation when you start losing it well which one weighs more calcium and strontium? so if I have water evaporating is calcium or strontium more likely to go into the air? no, into the air calcium exactly right because calcium is like so atom for atom whatever my starting ratio is it will start to tilt and that's why you see things that happen with the lines as I have a water event there's more evaporation of calcium relative to strontium so strontium increases relative to calcium the more water is exiting the system you can use this to calculate the water that had to be there if you know what the parent calcium strontium ratio is by the way what happens here we call this the strontium bowl is that evaporation stops and that's the drought if there's no water the calcium strontium ratio is what it was originally when water is added you start losing that calcium relative to it so that's an example of geochemistry we can calculate if I can prove that all these sediments have the same background chemistry which fortunately in a place like Choco it's pretty easy because we know the geological formations we can actually model what is being lost from the system with the process of evaporation this is what we call a proxy we can kind of estimate the movement in the system based on the effect it has how about like erosion of stuff into the system you can use rubidium rubidium strontium is what people typically use because the rubidium is highly variable in rocks and the strontium seems to be confined be kind of maintained by benthic systems in other words plankton in a water system you can measure it that way if it's a regular system let's say it's a terrestrial sands are mixing in there's a lot of proxies for that but let's go over these systematically and talk about what it is that happens in this process so let's see I want to open up something city topic this is my favorite presentation that we were given by the way this topic is so fun to talk about alright so we're going to talk about the analysis I call it core analysis but it's really geochemical analysis and it all begins with physics so we want to put on our physics hats on first and then think about what chemistry does with those physics so here's the periodic table right the key to understanding how to interpret data from either sedimentological sequences cores or ceramics is understanding why the periodic table is the way it is so if you look at the periodic table and I ask you why is strontium taken up by bones then why do we incorporate strontium in our bones looking at it can you tell me based on the periodic table why that happens we're strontium so it behaves the same way let me ask you another question why is arsenic poisonous it's simple as AS what's it below does our body need phosphorus what happens when arsenic enters our body what does it try to do so do you know what your energy it's adenium triphosphate what happens is the way your body makes energies you got energy so when you eat food one of the products of all that food is adenium triphosphate that goes into your mitochondria and then your mitochondria split a phosphorus off so it becomes adenium diphosphate that process releases energy and that's the energy that power your muscle movements your thoughts all that if you put arsenic in your body guess what starts to happen guess what system starts to break down it's not a system you want to break down it's sort of the equivalent of pouring water into your gasoline tank it's liquid your car's going to use it like it was gasoline but it's not going to behave like gasoline and your car won't work great and that's the reason why it can kill you why is lead bad for us where is pb of periodic table two what's at the top of that column carbon what does lead do well it can start making several binds your body needs carbon so now it's not like adenium triphosphate it doesn't go into a critical part of your body that specializes with phosphorus does it just kind of ends up in random places the problem is your body can't get rid of it it just stays there it's sort of like I have a well-oiled machine and I put in a gear that's way too heavy so it doesn't move at the same speed so then things start breaking up and that's one of the things you see with lead poisoning Legionnaires disease you typically see people start to have four cognitive functions they tend to commit more crimes there's an argument, have you heard about the argument for why crime dropped in the 1990s unledged gas before in the 19th century what it was in 1976 gasoline had lots of lead in it they unledged it by legislation and so there's a generation of children who weren't sprayed at the face by lead every time a car passed by and when those kids got to be in the 20s they committed far fewer crimes and so the crime rate dropped and plummeted in New York they were like, oh this is the success of stomp and frisk policies but it isn't happening in every city not all cities have the same policies you know, Freakonomics, they talk about this and they attribute it to Roe v. Wade yeah, I disagree with them entirely I disagree with them entirely because you don't actually see that the worst was happening before Roe v. Wade they just weren't happening legally I don't like their argument because it's a correlation argument the lead argument is cosmic we know what lead does to the brand we know that people who eat lead paint are more likely to commit crimes there's an established positive relationship to it so I'm much more persuaded by that data and it's systematic everyone is affected by it we can't go and prove that every person who robbed the store did it because their mother didn't want to have them in 1973 we do know that a kid who was born in 1973 was exposed to magnitudes in the word for lead so that the lead caught that cause causes changes in risk perception you're still using loaded gas in India in 2000 when I was there so you can actually test that yeah, absolutely you can well, yeah, does all of it in America, is that the only reason? in Libya I had it it was for fuel ejection oh yeah there's a reason people didn't want to do it it was not a cost-free change so, yeah, what was it it was like lead-trying and methylene or something I can't remember yeah, you didn't need to do it there was an argument this is, you can look this up there's a scientist who worked for the oil industry at the time at the let he also did something else that was super dangerous he's argued to be the worst scientist in history or the most harmful of scientists in history because everything he worked on led to public health crises in his career and I think he died because this blanket caught fire and he worked alive because of the environmental failure there's something funny about that look it up, I don't want to misrepresent it but it's a funny, it's an apocryphal story is, yeah, one industry scientist has so much damage because like lead is yeah, like lead is bad stuff because it comes to you up basically arsenic takes over a key body process and kills you lead goes up your body processes in terms of endometrial trauma it just, it has these long-term effects on your cognition and your impulsiveness and all that because it doesn't hit a critical body function not just cheeseburg oh like, it depends on whether cheeseburg or made it, yes, but yeah but in any case, but what we're talking about here is the core to understanding the creative table do you remember the story about how Dmitry with Memblev predicted the properties of an element that didn't exist in his time he could predict how much of lead what it's a chemical properties were that was Jamaican, it's between silicon and lead carbon he understood how it could bind and all these properties before bliss discovery because he knew how to organize and the way to organize is one valence electron two valence electrons three valence electrons, four valence electrons these guys get heavy and form a new geometry of those and actually if you see how it drops in here like this by two it's actually the same here the true periodic table if we come over here the true periodic table I forgot the border of all this because that works really hard to do this so you see how this drops in by two exclude these because these are a separate branch put these two and then these guys form one table this forms a sub table and then you only see this broken out this is what happens this is what it really looks like it's another drop that's the same way and if we find a new row it's going to drop again if we keep creating synthetic elements that's the periodicity of it and that's what the table looks like so what you do is is each of these blocks you can compare then with this block there's a set of behaviors and then with this block there's a set of behaviors I hope that makes sense but that's kind of the big picture but anyway let's focus in on each class to understand what's going on class one elements by the way what I want to do is I want to make a horoscope and instead of giving you like Aries or Leo you're super volatile reactive but you're ready to form Carmen Bond but in any case that's what happens these all behave with each other by the way typically speaking when I run my machine learning stuff I'll find that rubidium can be predicted by potassium if I don't have 40k eb I find that sodium can be predicted by potassium plus rubidium if I don't have light elements you can actually predict the relationships here because of long term geologic processes where you find one typically find others so that's class one elements they've got one element from binding that's by the way like sodium do you want to throw a brick of sodium in your water laps to cool it down but it happens because that sodium wants to combine with every oxygen molecule in there and it wants to push up hydrogen so that's class one elements super reactive what number are they trying to get to because they don't remember from chemistry 8 so class two elements these have two valence electrons they also tend to be basic why are they basic? well because they don't have one valence electron by the way what does ph what does ph mean? what does this mean? I only give you a simple mnemonic device ph percent hydrogen that's free and available for binding determines how acidic it is acidic is very reactive hydrogen is very reactive basic has a different number of electrons and so it behaves a little different but yeah that's what we have here these all behave each other when you have one you have all so for example if I have a lot of barium I will often have a lot of strontium if I have a lot of strontium I will certainly have calcium calcium I simply have magnesium and they tend to form in groups and you can use the ratios of these with each other to understand kinetic events the same that you can do with the class one elements because if these all start off now what happens is that calcium is the most common all of the magnesium, all of the strontium all of the barium if I know that there are 100 atoms of calcium for every one of the strontium and that's my starting system deviations from that tell me if something happened to take away calcium and that's how I can infer heat or water or some other property of that material so that's what these guys are doing so you can, so it's accurate to say that they occur together just because they behave similarly exactly exactly exactly yeah that's right especially calcium strontium they have similar ionic radiuses barium is a bigger ionic radius or I think it's got a smaller ionic radius don't quote me on that I need to look it up the more protons you have the more the electrons cluster in closer so that ionic radius struts down it behaves a little differently magnesium behaves a little differently too because it's bigger but yeah, that's the idea behind it all so in any case the other one that behaves kind of similarly is beryllium do you remember what your XRF detector windows made of in the tracer 5I in this guy beryllium it's a beryllium window so you have an idea that you notice the properties from that information by the way beryllium is fatally toxic to 15% of humans and fine for the other 85% and no one knows why so if you're beryllium window vaporizes for some reason not an attendee you're probably going to be fine but anyway so that's the class 2 elements where's graphene in here that would be carbon class 4, now 4 so if I have 4 bonds I could put a carbon in each of those bonds and if I can cap it out that forms a perfect crystal that's one atom thick and that's what carbon behaves the way it does alright transition metals these guys as they gain mass they tend to lose reactivity but the properties tend to be shared on the columns so typically speaking even the rules we have about the classes follow the same rules here well I'm going to give you an example what is the most valuable element on this list traditionally if I'm a likening Greek which one of these is the most valuable gold right what's the next most valuable and then after that what do you notice they're all lined up have you ever noticed that before they all look similar to each other the property gold has that is so attractive to people it doesn't do great well but why silver attractive there's some silver it's very readily right what is it that gold and silver have in common to make people value them they're valuable yeah they're valuable other things are valuable what sorry that was my original absolutely you are absolutely right they're shiny remember yesterday with primates when we talked about our cone cells how all of our perception of art ultimately boils down to seeing red fruits and green trees why would shiny be important to human ancestors well we can see a lot of other things too but I mean it stands out but what about it stands out to something else that would be a stressor for our we needed fruit and trees why would we be attracted to shiny water what does water look like on the horizon when you're thirsty that glimmer right this is pure speculation but that's why all those elements in that column that's the property they have with visible light the visible light that we shine down from the sun reflects off them in a very specific glimmer this is invented as of two years ago in a laboratory but can you guess some of the properties before he came he was ready to act by the way do you know who this is named after he's like the already discovered x-rays very good anyway so the name with the type of gold you can only see with x-rays after him so anyway yeah that's the core of that column some of that more copper is at least to an ancient society more economically useful than gold but it's still kind of a precious metal because it still has that glimmer to visible light if we lived on a different planet where infrared substituted for visible light we might find that zinc and cadmium are more valuable because they shine just right these properties are based on our perceptions of nature but they're not unique to them it's just that configuration of atoms has that configured reaction of light by the way the other thing there's one other way that gold differs and copper differs from every other element on here what is it what color are they to visible light so what color is titanium silver what color is rhodium silver it's kind of metallic what color is pure cobalt what the oxides but the metal they're all grates they're all boring grates all of them without exception except because they react to visible light especially so that's the key behind it there's another spectrum, ultraviolet maybe iridium it goes crazy but the point is our eyes revolve for this range of light and that range of light interact with those guys in a special way and that's the basis of our economy for the entirety of written history that is our economy it is this shiny stuff in visible light but the core point that I want you to understand here is not necessarily that but for example this right here is probably more insightful do our bodies need zinc so what becomes poisonous so tell me do our bodies need iron yes is this good for you yes because what would it mimic iron is niobium that for you do you need this new diet do you need a vitamin with benedium in it no because your body can't use it the key point here is toxic elements it's our fault we're the ones who are so sensitive to zinc that we confuse cadmium with zinc and create that so that's the key but the core thing to remember is the columns are essential next column class 3 elements these elements have low reactivity and they're very stable so that's the key thing about these in geochemistry by the way when you do ratios this should guide your ratios these stable elements are good things to ratio to the only two here you will be able to ratio to at least with current XRF technology are these guys aluminum and gallium in paleochromatic studies aluminum is the most frequent denominator for elemental ratios aluminum so if I want to understand so for example let's go back to your head to think a lot of what's coming in well my sediment is going to have aluminum and silicon the ratio of silicon to aluminum could tell me changes in sedimentation source because the chance that the ratio of the aluminum and silicon in two different geologic horizons is not very good so that ratio can tell me that difference but I would do that because I know aluminum is stable it's not going to react with anything locally there is no chemical process in temperature or climate it's going to change the aluminum that I have so it's inert it's like gold basically in terms of metallurgy so aluminum is a good denominator for that can you predict which one of these elements is in all of your pop cans and beer cans if you don't believe me we can try it out what am I saying here let's come over here let's open up Rtax device connect does anyone have an aluminum backed iPhone I guess my computer but I'll just use my computer I know this is a little bit of a cut up so I'm going to do 40 kph I'm going to do 10 microamps I'm going to do the titanium filter rated at this for only 10 seconds it'll automatically turn that extra beam off we can disable that but that's enough to work with gallium right there that big peak what is the purpose of gallium in here do you want to open it no it came with what so the ratio of gallium to aluminum could be a sorcerer and by the way just to highlight this you don't read about gallium at all in the archaeological literature but the mud rock 2 set it's in the obsidian calibration it is but it's not a good curve that's terrible this one is a much better gallium curve it still has some problems they're L lines right K lines it fluoresces right amazing by the way the other thing you need to do a correction for gallium is lead so that can cause problems too but anyway that's gallium so it comes along for the ride with aluminum almost without exception I don't think we had an aluminum production that's capable of aluminum would you want to it depends on what purity you need I'm curing a silicon chip on it to make a computer chip that gallium could be important so if I have more gallium its normal properties might cause a little ripple that causes the crystal crack so it actually can become important to have these things pure especially the level of which we produce things so coming back here let's come to the class 4 elements this is the important stuff so with 4 valence electrons these guys are the most flexible in forming chemical bonds they're sort of happy with any circumstance so like that person who doesn't get stressed out in life everything works out great buying all these other things so by the way notice for example on earth what is the basis what is the element that unites all life on earth what is the most common what is the element here that unites almost all geology what is the element here that unites all bronze age metal do you notice the thing these form the basis for that by the way now you understand my tenders so important in bronze age because it forms such stable connections that it hardens the metal to make it usable and lead is used as a flux to help make things work too so each of these is super important what does that tell you about germanium do you think germanium is valuable so here's the thing it was one of the most valuable elements on the planet you can get right now for two reasons it behaves like silicon it makes a semiconductor but it operates at different temperature threshold so if I'm making a flying robot it will operate more stable if I have germanium in that chip for satellites it can be super important too second it's strategic metal so in other words it's important to natural security and third almost all of it is in china so if you can find it in the US by that land like I said I know one lithic source that has a lot of germanium in it but I also know where it comes from and I won't publish it or buy it because I don't want to hurt the stuff there but yeah it is super valuable it is useful stuff here but Dmitry Mendelev knew that when he made his pair out of table this was the only thing that was missing before it was discovered interesting arsenic is right in the spirit because arsenic is the other bronze ingredient absolutely and Peru too you actually see a lot of it in the old world but I think the new world understood why arsenic was important I don't think the old world understood why it was important because they had 10 and they could get covered to the chase but yeah good insight and Timony can do something similar too in modern metals but yeah, class 5 elements these guys really changed their reactivity based on their weight but same deal they read the reactive minus here do you guys remember the paper from 2010 that people were convinced that arsenic existed for phosphorus in life NASA had a press release everyone thought it was going to be aliens but life had an arsenic and what they found was that life they thought it was replacing phosphorous it turned out to not be the case they could just handle a little bit of arsenic in a system and not die but the reason is because its chemistry changed how it treats phosphorus ours can't do that so we don't do so well with one arsenic in our system by the way, arsenic I have eaten so much arsenic it's not even funny before I did archaeology I used to eat dinosaurs do you know how you find a dinosaur bone? what do you do? 16 times so I found like 40 dinosaurs in my hometown from outless Wyoming I liked a lot of rocks one of the sites is actually called LLT for lead like this after I did all this work and measuring and finding all these dinosaurs I grew up learning how to use x-ray fluorescence and I thought hey what's in all those dinosaur bones I was looking for there's lead, there's arsenic, there's uranium and there's thorium so lots of nasty stuff yeah but anyway arsenic you body can accommodate a little bit if you're exposed to too much of it on mythrodates famously did that um so yeah so in any case these guys have those properties so so yeah alright then the last group of elements class 6 elements these guys again become more and more reactive oxygen as you know is super reactive sulfur is reactive by the way for ceramics we were saying these two are super important in geopemple environments I'll talk about them a little more later but in circuit geochemistry well let's just jump over it right now if I have oxygen so there's lots of oxygen in ocean waters right? one of the big chemical transformations that happens is that oxygen leaves oh by the way sand machine where's my bag? over here zero just to keep track of all this so with these guys I have oxygen in the system and oxygen leaves the system metals that are soluble in water with oxygen volumes become insoluble with sulfur bubbles why would sulfur replace oxygen? same reason everything else right? it has a similar number of valence electrons and binds in a similar way so it happens is have you heard the statistic that there's a ton of uranium in the ocean because uranium is soluble in water if there's oxygen if uranium combines with sulfur it precipitates out and so if I see a sudden spike in uranium in my ocean waters that tells me there's no oxygen so that if you have an anoxic basin that formed in Egypt 200 million years ago when it was in the pan-classic ocean and then you had an anoxic event then you would see a spike in uranium if grease didn't have that anoxic event you would just see leadstone and so that would tell you aha I know what I'm looking at you can open up a geologic map and see where people look for oil because that will tend to follow with the uranium you might know how fracking is radioactive you might have read this in the news it's because of uranium precipitating out when you have these vents so in any case that's all these guys here it's also one of the reasons why we love you Mr. Aganski because our bodies are incorporated in our tissues we ingest it so it's not just radioactive it hurts you but you'll get stuck in your tissues and then you're not in a good way yeah the russian agent 2007 that's how you know that that was meant to send a message they wanted that to be an eclipse because they used that specific voice if you really want to take someone out what you use is you use potassium chloride and you inject it in their bloodstream and that equalizes the verbenium sodium potassium channels and they just die silently without pain and it's very hard to trace anyway, we'll talk about it so point is that Putin wanted that but anything you read in the news Putin killed so-and-so they wanted it yeah, that one can be really nasty too but then the nerve agent they used you notice how they always use something different to get it in the news there's a reason for that yeah, exactly anyway, so class 7 elements the halogens these guys are super, super, super react they're like the bizarre versions of the class what evidence by the way, fluorine can catch anything on fire anything, if you spray liquid hot fluorine on the ice the ice will catch fire because fluorine will outcompete the oxygen for the hydrogen that's not what it can do chlorine by the way, as we moved down reactivity slows a ton because reactivity is relative to the atomic weight of the material as well so chlorine it's still very reactive but not nearly as best as fluorine fluorine, same deal iodine, it actually can be beneficial for our bodies I read somewhere correctly if I'm wrong but the more iodine you have in yo