@casperwyomingxer
I don't know much about REEs, so take this with the appropriate grain of salt; I'll include links to all the papers and we'll see where this goes at the end, lol.
"Ion adsorption-type" REE deposits are when granites with high quantities of REEs (hosted in fluorocarbonates, allanite, and titanite) weather. The REE-minerals are dissolved by acidic groundwater and the REE 3+ ions travel along the weathering profile until there's a pH increase. They typically adsorb to the surface of kaolinite and halloysite or other Mn oxides/cerianite. [1]
Leaching occurs with "concentrated inorganic salt solutions". This paper says they started with tank-leaching HCl and the most common, older process is ammonium-sulfate which moved to heap leaching in the 1990s. Dissolved REEs are selectively precipitated with oxalic acid to form oxalates that are converted to REO via an oxidizing roast. The REOs are separated with HCl and fractional solvent extraction.
Oh wow, 90% REE extraction. That's extremely good. And oh my god, they want to move it to in-situ and switch to MgSO34 to improve Mg deficiency in the soil. Based, based, based, based, based. Dude, China is so ahead of these things it's not even funny. That's the exact tactic we should be taking for this sort of thing. 5-7% loss REE is nothing if you're improving the quality of the soil/material while you're at it. [2] We'll just overlook the years of soil degradation while using ammonium-sulfate, lol.
Huh, in 2021, the German Bundestag passed a law on corporate due diligence in supply chains to protect human rights and the environment. Based.
Okay, it looks like the environmental impact of the clay leaching, from this paper, relies heavily on whether they clean up the ammonium-sulfate used in the process. In copper in-situ leaching, it's part of the remediation process to pump water into the area so that the whole area is "rinsed" and no pollution occurs. There are also legal standards on monitoring and recovery wells that ensure no acid is escaping the pump zone itself while mining is ongoing. It looks like a lot of REE-ISL operations are mined illegally though, so there are both no quantities on the amount of pollution and no oversight to ensure it isn't happening. [3] Damn, there are even bioleaching agents for this. [5]
Looking at the properties of ammonium sulfate, it's extremely stable up to 280C, unlike cyanide, which is extremely unstable. It has a pH of about 5.5. It is used as a fertilizer though, because of the high nitrate wt%; so it kind of depends how much is going where. [4] The primary risks of ammonium sulfate pollution are soil acidification and groundwater contamination. It seems you can wash the ammonium sulfate with magnesium sulfate (or magnesium chloride) and that also does the trick. However, when you wash clay shit multiple times, lo and behold, it destabilizes the ground. So they're now concerned about landslides. This paper looks at the viability of a papermaking sulfo-organic byproduct to wash residual ammonium sulfate instead. [6]
(This paper was more hidden than the others: Qiuhua et al 2016: 10.11785/S1000-4343.20160602)
Cyanides are typically detoxified after leaching by oxidizing the cyanide, adding sulfite, H2SO5, or hydrogen peroxide, or bacteria. Primary pollution stems from cyanide going where it isn't wanted in the leach heap and drainage from legacy mining sites where the waste wasn't detoxed. The most dangerous forms of cyanide are HCN (gas) and CN- (liquid). When it forms strong complexes like FeCN, CoCN, or AuCN, or oxidized, it's fairly benign and decomposes under sunlight. [7] As I'm looking at the techniques for monitoring (a note more for myself than anything else) it's really hard to determine how much cyanide is in a sample. There are a dozen methods and only half of them seem to work in specific situations, and they can still be miscalibrated by the presence of volatile metals like Hg, Bi, and Ge. Very unpleasant scientifically. I hate metals that think they have a right to be gases.
The summation of all of this, is that you either want extremely stable cyanide metal compounds (unpleasant but if you're going to put them into the ground, they better be stable); or you want any ions released with accessibility to air, plants, and people in general to be as volatile as possible, so that aeration and sunlight exposure are maximized and both C and N break down into harmless gases. (Typically a variation of CO / NCO or NH. [8] [9])
-=-
In my mind, (and this is personal opinion, so YMMV) the least damaging method is the method that doesn't stick around.
Cyanide definitely has more acute toxicity, and after reading, I don't like the variations of soluble compounds it can form in groundwater. If cyanide isn't exposed to sunlight, it also takes some time for plants to break down the compounds into gaseous form. BUT the fact that when oxidized it breaks down quickly is a huge win for me.
Ammonium sulfate is less harmful than I anticipated it being, tbqh; I really like the next-best-option being MgSO4 too. But both solutions make the soil extremely acidic by having sulfur. Sulfur is also not as volatile as C or N, (or HCN), so instead of leaving the soil, even after the ammonium is scrubbed, it will make the soil and groundwater more acidic. Both compounds are clearly hard to control when used in-situ too and stick in the clays since the ions are being swapped.
My position on this could change though. Ammonium sulfate is clearly what artisanal mercury mining was/is for gold at the moment. NH4(SO4) used responsibly by large operations that clean up after themselves isn't as big an issue. Sulfur can be oxidized into solution (quite easily) so the soil can be detoxified just like cyanide; it's just a little more effort to do.
But if cleaning isn't addressed, ammonium sulfate has more long-term ramifications on soil quality, groundwater quality, algae blooms, and metallic toxicity that are just as bad if not worse than cyanide when it doesn't break down.



















