Sciencemadness Discussion Board

Heavy metals and the non chemist- What could go wrong here...

Bert - 19-3-2018 at 17:08

(Please post any thoughts you have about the degree and mechanisms of heavy metal pollution the below scenario may entail, I am trying to decide IF and how to approach the matter with the people doing this thing)

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I shoot, reload cartridges and cast some of my own bullets from Lead alloys.

A guy who casts bullets recently gave a description on how the Lead bullets he uses are captured and recycled from his home shooting range. I read this in a post to The Fouling Shot, a publication of the cast bullet association and had a few environmental concerns.

This guy uses big wood logs to hold up targets on his home shooting range. The thick wood functions as a safe backstop and captures the many bullets he and his friends shoot there.

When the pieces of wood are sufficiently chewed up and full of Lead that they no longer reliably stop bullets, he splits them and burns the pieces in a heating wood stove (I certainly hope he has an EXTERIOR wood heating setup, with a tall chimney. And no close neighbors downwind).

After burning this "Lead mine" wood, he dumps the furnace ashes which contain many Lead blobs into a large bucket of water, squishes the lot around, and pours off the water with any suspended ashes. Then he dries out the retained solids and smells it, casting ingots for reuse as bullet metal.

So many ways for Lead (plus the alloyed Antimony, Tin, Copper and Arsenic) to be dispersed here. For a start, wood fires may well be hot enough to vaporize Lead, especially if there are Lead bits among charcoal burning on the grate right in front of an air inlet. Charcoal burned in a forced air stream will smelt IRON, this can easily get hot enough to vaporize Lead.

Large quantities of Lead (and possibly Lead oxide(s)) in (hot?) water containing a saturated solution of Potassium and Sodium carbonates from the wood ashes? One may hope whatever stray Lead ions there might be in the bucket of water will all precipitate as the carbonate, there should be a large excess of soluble carbonate compared to any dissolved Lead. But that Lead carbonate precipitate is going to be very fine, and likely would be decanted with the agitated water and wood ash slurry.

So, how does he dispose of that wood ash slurry? In his garden, perhaps?! Since he knows that wood ashes have valuable nutrients. He is smart and frugal, so I would expect such a use.

Even if he is just dumping the ash/Lead carbonate slurry out onto the ground in an area not used to produce human or animal food, there has to be some non trivial ammount of Lead and Lead compounds in this waste. Which, depending on the environment and soil chemistry, may or may not become soluble. And go downstream.

I am trying to decide how bad this whole ongoing scenario may be. And if it is possible to release dangerous quantities of Lead, most particularly, soluble Lead or Lead that may contaminate plant life.

Personally, I would be drying out the contaminated waste, mixing it with cement and disposing of the buckets full of this extra heavy cement chunk somewhere a very slow bleed off of Lead will not matter much.

DavidJR - 19-3-2018 at 18:08

That sounds like a terrible idea.......

I would think that shredding the wood with one of those industrial wood chipper things, then adding to a bucket of water to separate by density, would work pretty well and avoid the hazards of burning lead-laden wood.

Ozone - 19-3-2018 at 19:30

Hmm. Having seen lots of bullet-riddled wood, myself, I'd think that maybe he should get a kudo for at least trying to recover the bulk of the lead. Many places don't even think about it, and it becomes someone else's problem later on... That said, finely divided and dispersed lead can be a real problem (kind of like lead-on-everything back in the days of tetraethyl lead in gasoline).

I suppose you could make lead sulfide of it all and bury it--from lead sulfide it came, to lead sulfide it goes--more lead for the next person who goes digging for it.

I do, however, think the "wood-chipper-and-flotation" approach might be both safer, and higher yielding. I've found that bullets will fall out if you kick this stuff.

As for plants, some plants concentrate lead, some don't. Guess you'd have to sample the plants and see.

I suppose, that as a Marksman, myself, I'd also be concerned with the alterations in density and ductility of the alloy that might result--these can lead to unpredictable behavior, in-barrel, in-flight, and on-target (and lot-to-lot--a total no-no for any kind of precision work). The latter is why I usually buy jacketed match bullets and separate them by mass prior to loading.

Cheers,

O3

Sidmadra - 19-3-2018 at 20:31

The biggest issue I would conceive would be lead salts getting leached into the soil and possibly the water table... however soil frequently already contains 50-200ppm Lead, sometimes up to 500 in some areas. Safe levels for lead in water are 15 ppb According to Google, 1 cubic yard of "average soil" weighs about 1 ton. This is about 37 cubic feet. In 1 ton of soil, at 50ppm, there is 50g of Lead. In a 10ftx10ftx10ft chunk of dirt, 1000 cubic feet, there is over 1kg of lead.

So basically whether or not it has a significant environmental impact is a numbers game. Ethically speaking that person should do whatever they can to not contribute to environmental pollution. I would tell that person to not put that lead into the environment if they can at all prevent it, but if it came down to it, after rain dilution and such, it would probably be negligible difference, especially if they are recovering the majority of their Lead slag.

Bert - 19-3-2018 at 22:01

There are a number of solutions to reclaiming Lead from an outdoor firing range.

The good old fashioned sand or dirt berm behind the targets, and just let it lay there. Lead tends to get covered with carbonate, bullet sized chunks will mostly be there for centuries if not disturbed. You can find the white crusted Lead blobs on revolutionary or civil war battlefields in North America, in Europe, easily found on fields going back to Agincourt (Richard brought some multibarrel crew served weapons and casks of powder, not just longbows and the duplicity to conceal an anti cavalry trench in the center of a muddy field), Lead slugs can certainly be found on battle sites several centuries older in Asia.

Then there is the plan to face the berm with screened for particle size sand, such as septic system "wash sand", and every few years, dig it out and run it over separatory screens. The majority of the Lead and Copper jacket materials can be recovered, but plenty of dust and smaller bits will be left in the berm material, various fine dusts of metal and oxides may be distributed down wind too... Certainly useful for those wanting to recycle the metal, better than nothing for the local environment?

There are some pretty good commercially available systems where the shots are bounced back and forth between converging plates at a shallow angle to the incoming fire, then fed into a "snail" where they dump residual energy and finally drop into a catch tray for collection and recycling. Some use water pools or sprays to lower any chance of Lead dust dispersion around the backstop. Best outdoor range Lead remediation technology I know of, but quite expensive for the installation and somewhat expensive for upkeep.

The firewood guys neighborhood may well be cleaner than those of the "let it lay where Jesus flung it" school of Lead management. But I'd need to see comprehensive heavy metals testing of the locale, especially downwind and downstream to swear to that.

Melgar - 24-3-2018 at 21:20

If he burns it indoors, it's probably no worse than burning it outdoors. When wood fires get hot, they produce a really strong draft up the chimney that carries all that shit with it. Anything hot enough to vaporize lead would basically produce a strong wind up the flue. So the inside of the flue and anything downwind is what would get the vapors.

I think lead is a bit less bad than mercury, from what I've read on heavy metal poisoning. Though, I think the main difference is that methylmercury is just absolutely horrible for you and lead doesn't have an equivalent for that. But you'd probably know more about that than I would.

LearnedAmateur - 25-3-2018 at 01:16

The main reason lead and mercury are bad is because they have water soluble forms. Methylmercury is a cation, where both the chloride and nitrate are both slightly soluble in water, hence are dangerous because they can easily be introduced into the body. Albeit, inhaling both lead and mercury vapours is still a route of absorption since you can’t just breathe it back out and it will be absorbed into the blood that way.

AJKOER - 25-3-2018 at 07:56

I would not worry so much about getting your daily dose of Pb by poor disposal as many localities are converting from Cl2 to NH2Cl to disinfect your drinking/bathing water. Just say thank you!

Here is a typical reference: https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1817707/ suggesting that Lead pipes and Chloramine enjoy complementing each other leading to increased Pb presence.

More problems, lesser known is that chlorinated water and copper pipes (with a CuO presence) can assist aqueous bromides to convert into cancerous bromate, and also, at near neutral pH of 7.6, also increase HOCl disproportionation to chlorate (see https://pdfs.semanticscholar.org/e2f1/b367d46aa6c4376c2ea9c6... ). See possible health related impacts of chlorate on fetuses, infants and young children at https://www.watertechonline.com/contaminant-of-the-month-chl... .

Interestingly, an iron pipe in the presence of a soluble copper salt , leading to an active coating of Cu2O (and not so such elemental Cu itself on the iron pipe surface) seems to actually reduce bromate exposure (see https://www.sciencedirect.com/science/article/pii/S004565350... ).

[Edited on 25-3-2018 by AJKOER]

zed - 2-4-2018 at 16:39

Bah! All of the children in my neighborhood being mentally retarded, is simply due to a random grouping of genetic anomalies.

How dare you, suggest my home-fireplace lead refinery is responsible?

Commie bastards.

Fluorite - 5-11-2020 at 10:59

It's funny because I always believe there's heavy metals like cadmium and mercury in my homemade copper sulfate from copper wires and sulfuric acid :D
And in my potassium nitrate fertilizer that's why before I make nitric acid I'll react my fertilizer with hydrogen sulfide! I know very poisonous and filter the solution through celite or cotton that's how I'm confident 1000% no heavy metals when I distill Nitric acid! Yup metals can distill with water watch nurdrage copper nitrate to hno3 vid

Fyndium - 5-11-2020 at 15:10

There's no politically correct way to state an insignificant environmental impact factor. The chemical scare as to some degree spread to the chemists themselves, fearing for their lives for stuff that was handled by the liter half a century ago. These people literally rinsed their hands with benzene after painting with heavy metal loaded paint and did it for 30 years, and only some of them developed cancers and stuff.

My point is absolutely not to neglect safety protocols and dump dioxin downstream, but to keep a sense of reality and scale of actions.

I would not personally burn lead loaded wood, but I wouldn't definitely be worried about metallic lead traces in dumps, because like said, it is already on the environment, and while it's persistent, it's also very stable. Leaching from lead ammunition from range and hunting activities is basically nil.

B(a)P - 5-11-2020 at 17:39

Quote: Originally posted by Fyndium  
Leaching from lead ammunition from range and hunting activities is basically nil.


I have performed contamination assessments at numerous range facilities and I can tell you it is not nil. A well managed and maintained facility with good sediment and erosion control and appropriate material in stop butts has minimal impact, but otherwise the environmental impact can be quite significant.

Fyndium - 6-11-2020 at 09:28

How much lead leaches from the landmass, in numbers, and what are the normal and tolerable limits? Does the pH of the soil or other factors affect the leaching rate? Just out of interest.

City Gardens

MadHatter - 6-11-2020 at 17:07

Some horticulturists here in the U.S.
advise city dwellers that before planting
the 1st garden to grow plants that take
up heavy metal contamination out of
the soil. This is particularly true in cities
when a lot of lead was released by the
tetraethyllead in gasoline. Some plants
can even absorb toxins in the atmosphere
without harming the plant. Sunflowers,
ornamental cabbage and mustard greens
are good at this along with a few others.
Some of these plants can be used for
reclaiming lead by smelting later on.

Texium - 6-11-2020 at 19:13

Interesting point, MadHatter! I guess before I plant food crops in my new garden plot next year it wouldn't be a bad idea to give it a cycle of sunflowers or mustard greens first. I have good soil in my back yard, so I'd like to plant directly in the ground, but I hadn't thought about heavy metal contamination being an issue.

karlos³ - 6-11-2020 at 19:31

Mushrooms are said to be even more effective for that purpose, although it is probably not nearly as easy to grow them on a wide area as are plants.
Maybe I've fallen for the advertised claim though, but I've seen certain saprophytic species advertised as a bio-remedy for contaminated soil... and now laugh, the species being sold as such are Psilocybe cyanescens and P. azurescens(from serious and reputable mushroom suppliers, who sell only edible species, or those having health benefits).
We know that mushrooms are exceptionally well at enriching certain substances from the soil they are growing in though, and the mentioned species can grow quite aggressive.
Maybe that isn't just a trick claim to sell those species but is somewhat factually supported?
I remember the book of Paul Stamets claiming that these "shady" species are growing exceptionally well compared to any other, so I'd like to believe I just didn't fell for that advertisement.

Phytoremediation

MadHatter - 6-11-2020 at 20:54

The process by which plants absorb contaminants.

Wikipedia link: https://en.wikipedia.org/wiki/Phytoremediation

karlos3, I don't see any mention of mushrooms in the wiki
article. On a side note, in Tuesday's election the voters of
Oregon by double digit margins passed a law to allow the
medical use of psilocybin mushrooms and decriminalize
hard drugs. Oregon, like Maine and 10 other states already
allow recreational weed growing by its citizens. :D:D:D

andy1988 - 6-11-2020 at 21:21

This was published on BBC earlier this year. A quote:
Quote:

Nickel hyper-accumulators could do it better, he says, by improving soil health by removing the nickel and bringing back the major nutrients needed by normal plants. “Eventually, normal crop plants can be cultivated on these soils after phytomining has finished,” he says. It could also give an economic benefit for the mining company because the nickel residue that has been accumulated in their shoots could be harvested. Currently, only soil that consists of at least 1% nickel can be mined in the traditional way. “But a hyper-accumulator can achieve high levels of nickel accumulation in a soil that consists of just 0.1% [nickel],” he says.


Really interesting read. Thought provoking considering articles about dwindling reserves worldwide of high grade ores.

Near me in the U.S. around a lot of Uranium mines, a man early in the 1900s became quite wealthy because he learned of a plant which tended to grow near uranium deposits, so he bought that land. That's what I was told by word of mouth anyway, as they pointed at a mansion up above a town.

On this thread's topic of lead shot and environmental contamination, in the past I'd read an article detailing how a group found a food with elevated levels of lead, and they traced it to a farmer who was shooting clay pigeons over his crops. I wish I'd bookmarked it, I've not been able to find it again.

karlos³ - 6-11-2020 at 21:35

Quote: Originally posted by MadHatter  
The process by which plants absorb contaminants.

Wikipedia link: https://en.wikipedia.org/wiki/Phytoremediation

You might have forgotten that plants and fungi aren't in the same kingdom :P
Wikipedia has their own article about the process when mushrooms are used: https://en.wikipedia.org/wiki/Mycoremediation :)
Although they don't mention the specific genus, hmm.

Fyndium - 7-11-2020 at 01:21

Quote: Originally posted by andy1988  
food with elevated levels of lead, and they traced it to a farmer who was shooting clay pigeons over his crops


These are the exact words I used to google-fu it, and found this as a first result. :P

https://www.researchgate.net/publication/229593901_The_Effec...

unionised - 7-11-2020 at 05:06

It's important to remember that the lead naturally present in the environment is typically trapped as very insoluble sulphides.
But after it's been smelted and shot it's present as carbonate which has a solubility of about 1 mg/ litre compared to a safe limit of about 15 micrograms per litre.
So, rain water running through sand coated with lead carbonate will dissolve about 70 times the safe limit for lead in drinking water.
(More really, because of dissolved CO2.)

Fyndium - 7-11-2020 at 05:53

But that water will usually dilute into huge bodies of water, and where there are lots of ions, including sulfates that it reacts with and eventually settles. Hence the bottoms of the oceans are enriched with certain stuff.

Morgan - 7-11-2020 at 06:49

Tidbit
https://www.researchgate.net/publication/229593901_The_Effec...

B(a)P - 7-11-2020 at 12:40

Quote: Originally posted by Fyndium  
How much lead leaches from the landmass, in numbers, and what are the normal and tolerable limits? Does the pH of the soil or other factors affect the leaching rate? Just out of interest.


The pH of the soil and underlying lithology have a significant impact on the solubility of lead, as does the presence of organic material and the annual precipitation. Lead is most soluble in acidic soils. The greatest mass of lead leaving a range site will usually be in overland flow (assuming poor sediment and erosion control). Fine particles of lead formed by the impact with the stop butts (up to 5% of a bullet will be transformed into particles small enough in size to be washed away in overland flow upon impact) able to be are washed into drainage lines and eventually waterways. It then accumulates in sediment, sometimes to concentrations toxic to aquatic life. It also contributes to high concentrations of dissolved lead in the waterbody. The mass of lead migrating off-site is obviously highly variable and in a worst case could be in the order of 1 kg per year.
In groundwater it is not just the lead that is the issue, high levels of copper, arsenic and antimony are also often observed. It is much harder to estimate a mass of lead leaving a site through groundwater and it is much more variable from site to site. Groundwater monitoring wells located near to a stop butt will usually have unacceptably high concentrations of heavy metals. Depending on a huge number of factors, including the size and age of the facility, proximity to the boundary as well as the the geology and hydrogeology at the site the heavy metal concentrations can persist in groundwater migrating off-site.

unionised - 8-11-2020 at 05:37

Quote: Originally posted by Fyndium  
But that water will usually dilute into huge bodies of water, and where there are lots of ions, including sulfates that it reacts with and eventually settles. Hence the bottoms of the oceans are enriched with certain stuff.


The sea floor gets enriched because the river water evaporates but the minerals don't.
Lead sulphate is a lot more soluble than the carbonate.

Before the river water reaches the sea, it will probably be used to supply drinking water.
In the meantime, it will have transferred lead to places like fields and gardens.


outer_limits - 8-11-2020 at 13:35

Quote: Originally posted by Bert  

I shoot, reload cartridges and cast some of my own bullets from Lead alloys.


I know one person who did this at least two times a week few years ago. After 2 or three months he developed lead poisoning but didn't stopped until he was placed in a hospital in very serious condition.
It was performed without any PPE using propane burner. No fumes extractor, just the wind from time to time.

Fyndium - 8-11-2020 at 14:15

They had a discussion about this on a reloaders forum:

http://castboolits.gunloads.com/showthread.php?121103-Lead-F...

They investigated that if lead is heated too much (over 500C), it will start to release significant amount of fumes. Lead dust has also been confirmed as a cause for elevated lead blood.

I'd be curious to measure my lead blood after I handled some lead acetate multiple weeks ago. I did everything by the safety standards, so I don't expect there to be any noticeable increase.

B(a)P - 8-11-2020 at 15:31

I have my blood analysed every 6 months (work requirement) for a range of heavy metals, other contaminants and health indicators.
Despite doing a lot of work on lead contaminated sites over the years and regularly working with lead at home in my lab, I have never returned a detectable concentration of lead or any other contaminant. If you know the element/compound/reaction you are working with, are careful, and use PPE appropriately, you are quite safe.