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Pickle turning dark green


#1

Hi, I’m a newbie and I’m using Otto Frei citri pickle in a ceramic
crock pot. Our jewelry teacher at the JC says you never have to
change your pickle. Mine is turning dark green and I can’t see
through it. Copper comes out looking yellow colored. Any advice?

Thanks. Best, Susan


#2

Whoever said that pickle is forever is way off! It becomes depleted
as the acidic part removes oxides, becoming a solution of copper
salts and water in the process. Pickle is a consumable. By all means
dump it and put in new pickle when it becomes heavily discolored.

Dick Davies


#3

Susan,

Our jewelry teacher at the JC says you never have to change your
pickle. Mine is turning dark green and I can't see through it.
Copper comes out looking yellow colored. 

Your teacher is dead wrong, or does no work. Even when not using it
enough bugs drown in mine while using it as a spa that it gets pretty
disgusting. Pickle dissolves metal oxides consuming the acid, that is
the source of the colour. There comes a day when no acid is left.

jeffD
Demand Designs
Analog/Digital Modelling & Goldsmithing
http://www.gmavt.net/~jdemand


#4

Susan; Wrong, your pickle is oversaturated with copper. Dispose of
properly and make some new.

Dave Owen


#5

REMEMBER, before dumping old pickle, neutralize the solution with
Baking Soda. Its also really important to be sure to add a little
Baking Soda at a time and to do this in a WELL ventilated room,
directly under the exhaust, or outside.

Steven Brownlee


#6
REMEMBER, before dumping old pickle, neutralize the solution with
Baking Soda. Its also really important to be sure to add a little
Baking Soda at a time and to do this in a WELL ventilated room,
directly under the exhaust, or outside. 

Nonsense. Sodium bisulphate pickle is sufficiently neutralized
simply by dilution. Nothing in the basic acid compound is toxic or
difficult for waste water treatment streams to deal with once
diluted. Adding baking soda is simply a waste of good baking soda.
The part of the old pickle you might really want to be neutralizing,
the metal content, isn’t affected by the baking soda, and remains in
the waste, so you’re wasting effort to neutralize it. by the time a
small pickle pot’s contents are diluted by the water in a single
toilet flush, it’s diluted pretty much enough already, and it gets
quickly added to additional water in the waste stream.

And as well, adding baking soda to sodium bisulphate pickle
generates nothing in vapor beyond a bit of carbon dioxide gas. Why do
you think you need a high level of ventillation for this? Ok, if
you’re doing it quickly, all the fizzing might get some aerosol
droplets of acid into the air before it’s neutralized. But if you
dissolve the baking soda in water before adding it to the pickle,
then you won’t get so much bubbling and mess, and no more
ventillation is needed than for normal pickle use.

Concentrated sodium bisulphate pickle is a pretty corrosive mix, a
salt of sulphuric acid. it needs to be treated with care, just like
the acid. But as I said, once you dilute it a lot, there’s not much
there that you wouldn’t find in an ordinary swimming pool, where it’s
used to adjust ph values and is considered benign.

You don’t need to neutralize. You DO need to dilute. Much easier.

Neutralizing the acid does not remove the ions in the material. The
sodium, well, baking soda adds more. The sulphate ions? Still there.
If there were something toxic in the pickle, baking soda wouldn’t do
anything about it. It only raises the ph, which is the main concern
here. Dilution does the same quite adequately. If there is a concern,
it’s the metal content, which you can’t simply neutralize. Some metal
containing solutions, depending in part on your location and how
local waste water is processed, may actually need to be disposed of
as hazardous waste rather than being treated in any form by you.

Note that the above this is not true of every sort of stuff you
might need to get rid of. Plating solutions, for example, are a very
different sort of beast…

Peter Rowe


#7

your teacher is very wrong in fact I would demand a refund of the
course fee as that will lead to your ruining precious metals - at a
great monetary loss to you -and that person is probably continually
telling students that ( unless you misunderstood!) …the school at
least should be alerted that that teacher is giving out dead wrong
… seriously, be a good consumer and demand your money
back. So many “teachers” haven’t the knowledge to be standing in
front of a class teaching anything but how to string beads…

Pickle becomes depleted rapidly if you use a great amount of
sterling. you are seeing the copper salts being leached out- first
pickle will turn deep blue ( that’s when you change it !) and can be
saved for a copper plating solution or neutralised with baking soda/
bicarbonate of soda crystals and then disposed of in any water
system. When it turns green it is way beyond the point of usefulness
ecven as a plating solution, and will not pickle anything properly -
so neutralise and toss. Then wash out your ceramic liner with
detergent and baking soda rinse and re-fill with fresh pickling
solution. Remember to never boil it and it is best used at about 114
degrees, (the low setting on most crock pots).

Consider writing that teacher and the school - this information
should not be given out to anyone learning to become a jeweler or
metalsmith. teachers that have wrong should not be in
front of any class, whether as volunteers or paid staff. Aat William
Hooland School, many teachers “volunteer” their time- most are
adequate and some of the lapidary teachers are masters, but among the
rest there is much incorrect disseminated and the school
does nothing to stop them, nor does the director ask them to refrain
from giving out mis-.Always check on an instructors
background before taking any class - contact them before you put down
a deposit and ask them where they learned the craft, where they
taught in the past and a bit about what will be covered in the class-
Even if you are totally new to jewelry making, you still have the
right to be taught by an experienced professional with some
credibility… many schools operate on a “good friends” policy; the
instructors are friends of the school’s owner or the directo
/resident jewelry srtist and are pinch hitting, or filling in a last
minute cancellation, or otherwise getting paid to hang out with the
schools administration…I have seen it happen in 4 schools on the
east coast and the instructors give out dead wrong, or very vague
instruction- unfortunately you had this experience. Research is
always a good thing before paying for anyone to teach you what you
can learn yourself from a good manual like "The Complete Metalsmith"
by Tim McCreight…in many cases that single book is far more valuable
and info packed thatn any course you pay hundreds of dollars for.
Seek out local rock clubs too. Often the membership maintains a
studio and the members are highly experienced jewelrs and metalsmiths
or lapidary that also make jewelry.

It really infuriates me to hear of yet another bogus teacher out
there- as they seem to be proliferating at an exponential rate as
jewelry making becomes more faddish, as opposed to people that are
passionate about it and want to make a living at it but need to be
shown " how-to "… I can’t stress enough that there are credible
teachers out there and perhaps more that are not as the number of
small scale “schools” open around the USA in poarticular. Always do
some homework before you send in a deposit and ask for some past
students reviews from the school too (most credible schools collect
reviews of their experiences at the end of a given class and make
them available for potential students). You may learn more in reading
the reviews than travelling to a school, spending money on class fees
and materials and misc. expenses and being disappointed in the end.
The bottom line is : any school you atend that you don’t come away
from knowing how to use and make pickle is not a school I would ever
re-attend. … rer


#8
your teacher is very wrong in fact I would demand a refund of the
course fee... and that person is probably continually telling
students that... ... teachers that have wrong should
not be in front of any class, whether as volunteers or paid staff. 

Um, RER, don’t you think you’re jumping a little overboard here in
criticing this teacher whom you know nothing about?

You do not know anything of the context in which the question was
asked, nor the conditions the teacher was referring to. It’s quite
possible that the the teacher was relating was correct
for the conditions within that class.

For example, I can recall studios where a good deal of work was done
with copper and bronze holloware raising. Students were often
annealing and pickling work in large tanks, which quickly became dark
blue. Standard practice, and correct in my view, for those pickle
tanks was to not change them until the acid content was pretty much
used up and it didn’t work any more. That would often take over a
year with full day to day frequent use. With only copper and bronze
going into that tank, no harm would come to the work with even highly
depleted pickle.

On the other hand, any decent commercial jeweler knows the pickle
pot needs to be changed when it starts to present a danger of
contamination or excessive plating, etc. Such pickle pots, smaller,
and used with many different metals, are a different case. Many
school or other teaching studios are much closer in nature to that
first example in terms of the risks posed by older pickle.

You don’t know just what the exact question asked was, nor the
qualifiers if any, in the answer. You don’t know whether the student
(as you did mention) might have misunderstood. Lord knows that’s
commen enough, especially with beginners, who sometimes can give even
a very good teacher the impression that they are deliberatly
misunderstanding almost everything…

I’d suggest, before getting on too high a horse over your impression
of this teacher and suggestions of drastic steps to be taken with
refunds, letters, or the like, that you take a moment to reflect that
you really don’t have enough not by a long shot, to make
such a suggestion. You don’t know what really was said, what really
was asked, or the context of either, nor do you know whether that
teacher does in fact actually know what they are doing. I’ve
benefited from the selfless efforts of many wonderful teachers, yet
every one of them occasionally was misunderstood, or made a mistake
in a class, or otherwise proved to be human. And I certainly have
made enough of my own too, as have you, and pretty much everyone else
on this list as well, I’m sure.

May I suggest a slightly gentler assumption as to the qualifications
of that teacher until you really have much more detailed

Peter Rowe


#9
Nonsense. Sodium bisulphate pickle is sufficiently neutralized

simply by dilution. Nothing in the basic acid compound is toxic or
difficult for waste water treatment streams to deal with once
diluted. Adding baking soda is simply a waste of good baking soda.

Peter, Not to beat a dead horse, but after the pickle absorbs as
much copper salts as the poster said - wherein it has turned green,
it is a solution of vitriol, and indeed toxic to fish and other
aquatic life., If one has gravity fed spring water and that is also
the source for disposal it will in fact kill every salamander, spring
lizard, and fish in the area of disposal at the source (the pipe
end). It is far better diluted into a couple of gallons of water,and
sprayed on roses or other plants to kill black spot if you do have
spring water as your source. In a city water system it is less a
concern- nonetheless, it should be neutralised as it can react with
chlorine (much like adding pool chlorine to a cleaner/degreaser like
’’ pine-sol" which after a few minutes you get a violent and
propelling explosion- try combining the two in a coke bottle if you
do not believe me…but wear safety glasses and stand back after
mixing even a tablespoon of each ingredient in the small bottle
because you will be sprayed with broken glass!).

I do not agree with you on this one at all, and hope the readers will
continue to responsibly dispose of jewelers chemicals particularly if
they are responsible for their own water resources, flora and fauna
and land stewardship in rural areas.

rer


#10
after the pickle absorbs as much copper salts as the poster said -
wherein it has turned green, it is a solution of vitriol, and
indeed toxic to fish and other aquatic life. 

But adding baking soda doesn’t change that. The toxic copper is
still there. In fact copper carbonate is used as an anti-bacterial
and a fungicide.

Al Balmer
Sun City, AZ


#11
Peter, Not to beat a dead horse, but after the pickle absorbs as
much copper salts as the poster said - wherein it has turned
green, it is a solution of vitriol, and indeed toxic to fish and
other aquatic life., 

Yes, absolutely. I couldn’t agree more. The thing is, adding baking
soda doesn’t change this. It’s not the fact that it’s copper sulphate
in particular, any copper salt will be equally toxic, including
copper carbonate, or whatever else you might get by adding baking
soda. So that issue remains, as I DID mention in my prior post. You
are correct that if your waste water stream is sensative to copper or
other metals contaminations, then used pickle should not go in there.
Most municipal water treatment plants do not fit this description, as
treatment generally will remove the worst of metals, IF IN SMALL
CONCENTRATIONS, such as a small amount of pickle. This is not true
if you’ve got more than a little, when it needs to be treated as
toxic waste according to local requirements.

If one has gravity fed spring water and that is also the source for
disposal it will in fact kill every salamander, spring lizard, and
fish in the area of disposal at the source (the pipe end). 

Obviously, if you’re not dealing with municipal sewer systems, but
instead have a septic tank or similar waste water stream, you’ll need
to carefully consider how to dispose of ANYTHING. And again, I’d
stress that adding baking soda does not change this, either for your
type of water / sewer system, or typical larger municipal systems.
For the latter, and probably the first too, in most situations,
dilution with lots of water is sufficient for the acid content. But
as I mentioned, and you again bring up, the copper content can be a
considerably different issue, more difficult to deal with.

It is far better diluted into a couple of gallons of water, and
sprayed on roses or other plants to kill black spot if you do have
spring water as your source. 

Now that’s a brilliant idea, one that hadn’t occured to me. Copper
sulphate is sold in the hardware or garden stores for exactly this
sort of use, so why not make use of the spent pickle to do the same.
You do then need to neutralize excess acid, either by dilution or
adding something, including baking soda, or (I think…) urea powder,
or other such. My guess is that sufficent dilution would suffice. Mix
perhaps with a properly prepared compost tea, and fertilize at the
same time…

In a city water system it is less a concern- nonetheless, it should
be neutralised as it can react with chlorine (much like adding pool
chlorine to a cleaner/degreaser like '' pine-sol" which after a few
minutes you get a violent and propelling explosion- 

Yes, with concentrated chlorine and concentrated chemical. However,
again I say that well diluted, the low levels of sodium bisulphate
added to the very low levels of potential chlorine remaining in
municipal waste water, is completely harmless. Saying that the
concentrated chemicals will react violently, as they may, has
absolutely no bearing on what a highly diluted mix of one, added to
waste water with an even more extremely diluted level of the other,
would do. Which, by the way, is that nothing happens.

But by all means. If it makes you feel better, go ahead and dump a
bunch of baking soda into your used pickle before disposing of it
down the drain in a municipal waste water sewer system. Try not to
let it make too much of a mess…

I do like your idea of using it to spray the roses, though. Thanks.
I might try that…

Peter


#12

It is the copper in spent pickle which is nasty and not easily cured.
When dead and really blue I dilute it enough so that it doesn’t eat
my sprayer and use it to kill weeds in my gravel drive way. It works
better than commercial herbicides for free; Roundup is not cheap and
reminds me too much of Agent Orange. And no, I do not depend on well
water, no fish in the drive, but no way is the stuff is not going
into the septic tank. Even stuff with silver (vibe tumbler waste
water) are diverted from the septic.

jeffD
Demand Designs
Analog/Digital Modelling & Goldsmithing
http://www.gmavt.net/~jdemand


#13

I also work in clay and have thought about using the saturated
pickle solution in or as part of a glaze. You might offer it to a
potter, continuing the life of the copper salts.

Bobbie Horn


#14
Now that's a brilliant idea, one that hadn't occured to me. Copper
sulphate is sold in the hardware or garden stores for exactly this
sort of use, so why not make use of the spent pickle to do the
same. You do then need to neutralize excess acid, either by
dilution or adding something, including baking soda, or (I
think...) urea powder, or other such. My guess is that sufficent
dilution would suffice. Mix perhaps with a properly prepared compost
tea, and fertilize at the same time... 

I would not try this unless you know what the other major components
in used pickle would do to your roses. Copper is not the major
contaminate in used pickle it is only one of them. There are likely
far more boron compounds than copper compounds in the spent pickle.
Also if you work on nickel alloys like white golds and nickel silver
there is going to be nickel in solution along with zinc and iron etc.

Used pickle is a toxic soup and should be treated as such. I agree
the occasional pickle pot in the municipal waste water stream is
negligible in its effect but hey all that stuff adds up. Normal muni
waste treatment is definitely not designed to remove metals from the
effluent. In fact if you were to ask one of their engineers about
this they would not like the idea of adding metals in solution to
their system. The problem is that there is typically no good system
in place for small amounts of this kind of waste to be disposed of.
Some communities have home owner toxics disposal but small business
will typically not be able to use these and commercial toxics waste
disposal is prohibitive in cost.

James Binnion
James Binnion Metal Arts


#15

I have botany degrees well as many, many years of practical and
applied gardening experience as well as rsearch in the field to back
this up:

I have used spent BLUE (not green- at that point it is toxic vitriol
salt harmful to birds, and amphibians as well as the edible or
usable plant by-products (resins, root barks, gums, distillations,
tinctures and esential oils and terpenes, etc.) pickle not destined
for Cu plating or to be mixed with hide glue for use in granulation
adhesives can be used safely and in fact, highly effectively on
roses, gardenias, tomatoes, and other nightshade (solanacea Sp.)
plants as I have for many many years.

I also add it to light oil sprays (sunspray is a good brand, as is
any non-petrochemical based/derrived light oil applied to fruit trees
(spray a fine mist to saturation in the early morning before the sun
is at it’s apex in the growing season, or later in the afternoon but
allowing plenty of time to dry thoroughly before dark as this
encourages powdery mildews and black spot will proliferate. It also
curbs, if not kills tobacco mosaic virus (if one does not reintroduce
it by smoking or not washing hands before touching leafy plants, etc.
susceptible to the disease and can arrest leaf miners if sprayed
directly onto the soil around affected plants, and diluted to
container grown plant’s solis as long as ther is no evidence of salt
build up in the container (this can be fluushed for about seven days
then the spent Cu pickle applied in a fine mister - columbines are
noted hosts; leaf miners leave whitish irregular trails that are
actually used tunnels that the vermin have burrowed through on their
way to the stem to wreak havoc and eventually kill the plant as it
deposits it’s “babies” for gestation and insured destruction with
subsequent generations. In other words-Once you have leaf miners
they are hard to erradicate if not chequed at the first sign of
infestation, at which time one should apply the BLUE pickle in a 1:1
dilution (Cu sulphate / blue to deep blue pickle: H2O) and if they
are not halted as is noticed and over a period of 3-5 days and again
10 days later with no further signs, you should consider destroying
the plants affected or the vermin will spread to nearby plants and
weaken or kill them while providing a literal breeding ground for
further generations of leaf miners… nasty beasts they are!!!).

In fall and/or winter apply spent pickle in an oil spray too (at the
beginning of each season : during the equinox and solstices). Your
fruiting and flowering trees and shrubs will be healthier and the
trace mineral saltsand any dissolved metallic elements are
beneficial. However, do inspect any plants during the growing season
for evidence of ladybug larvae (black and orange odd looking bugs).
You do not want to apply any oil, or even a “natural” chemical if
they are noticed on a particular plant, tree or shrub. If you have
pine tree lizards, anoles or other reptilians that are living in or
on a plant or tree do not apply it until they are dormant (in fall
and winer in temperate zones and in winter in the sub tropics and
tropics). If you have blue tailed skinks, copper coloured skinks or
cross bred skinks avoid their habitats as copper is toxic to their
young and manifests as horrid mutations in adult populations- frogs
cannot tolerate copper sprays nor oil sprays at all, unless there is
a source of exchanged oxygenated water (for example, a filtered
pond, of which you closely monitor the pH, or a natural spring
stream that has active populations of spring lizards, newts and/or
and salamanders as they indicate clean waters).

Additionally, any trace silver or gold is highly beneficial in the
garden environment acting as a natural bactericide and anti-fungal,
anti-viral and excellent sanitizer of chemically treated soils that
you are trying to restore to n organic state. In fact there is no
better sanitizer as an adjunct to slaked lime for sweetening salty
or acidic soils and silver gives a natural inoculation of sorts to
not only the soils but earthworm populations and other sub
terrestrial animals that helps improve their resistance to maladies.
Just as we use silver bandages and eye drops silver clay actually
kills worms in canine species (all dogs, wolves and most fox species)

I’m betting you metal clay enthusiasts didn’t know that little
tidbit! Silver clay works better than icthammol ( black drawing
salve) for bringing foreign matter to the skin’s surface from sub
dermal ulcers, sores and it speeds healing of many skin conditions
too! I thought about marketing Metal Clays as a first aid product
for a while as it’s far more cost effective in that form in my
opinion that as an alternative to fine silver raw materials… but
I’ll avoid positing my opinions of metal clay as a jewelry making
media for now!!!)…

Any way, Depleted blue pickle is safe and beneficial in the garden
if used attentively and respectively with awareness of all
micro-environments within the realm of one’s garden or acreage when
viewed as a whole. Feel free to email me with anything that requires
more explanation I know of what I speak on this topic… rer


#16
Copper is not the major contaminate in used pickle it is only one
of them. 

Many people want to do what is right concerning pickle disposal, but
for the quantity most jewelers generate you probably will cause more
harm messing around with it than you would if you just flushed it
down the drain. By the time it makes it to any place in the
environment where it could do any harm it is so vastly diluted that
any person, plant or animal that comes in contact with it will
encounter levels of infentissimal concentration of no consequence.
The greatest environmental risk is to the jeweler who is using it. So
do be careful of it and use some ventilation. If you are worried
about it, you can cut down on how much you dispose of by using the
same solution longer. If it gets green or flakey, it probably still
is doing its job. Don’t replace it until it stops working. I bet I
only change my pickle 3 times a year. Not much liquid to dispose of,
perhaps 2 gallons a year. As far as dissolved metals go, it probably
does more harm to the environment to toss a couple of flashlight
batteries in the trash.


#17

Hi folks,

Wow this thread certainly warmed up! I just want to mention
"electrowinning" as a possible way to remove metals from pickle, for
further use or disposal, less metals is less of a problem. I think
there are articles in the database here about how exactly, so I’ll
not repeat.

Daniel Ballard
PMWest.us