James: Hi, everyone. Welcome to today’s webinar on Peroxide Former Management. My name is James and I’ll be your moderator for today’s event.
Before I turn things over to our speaker, I just want to run through some housekeeping items and give you a brief overview on what this webinar is going to entail for those of you that might not have attended one in the past.
We’ll start with the slide show presentation providing insight into how to manage peroxide formers in a streamlined and cost-effective way. You’ll also learn how to create and implement a peroxide former management plan and see how other institutions have rectified their peroxide former problems during our case study portion.
Following the presentation, there will be an open Q & A period. You can ask questions anytime throughout the webinar by typing them into the questions pane on the right hand side of your screen. Please note that everyone’s microphones will be turned off for the entirety of the webinar. But if you do have a question or a technical comes up, you can use that questions pane to communicate as well.
Anyway, please keep in mind any and all unanswered questions will be addressed and followed-up on via email after the presentation. But we’ll do our best to get to as many questions as we can with the time that we have. You’ll also receive a copy of the slide deck and the recording tomorrow so you would get a copy of the all materials that are presented today.
Today’s speaker, Ted Dubiel, is the New England Quality Manager at Triumvirate Environmental. This is where he heads the Technical Lab Services Division and company reactives program. Ted has over 16 years of peroxide former and high haz management experience. And with that, I’ll turn things over to Ted. Hey, Ted.
Ted: Thank you, James. Good morning, everyone. Thank you for attending today. Today, we’re going to be discussing peroxide formers. We’ll discuss hazards; the most common peroxide former chemicals; different resources and chemical hazard recognition; we’ve guidance around recognizing the material; some of the dos and don’ts for handling these materials; where the regulations come into play for management of these materials; any regulation requirements for these materials.
Then get into how to implement and maintain a management program; some of the components for that; training; setting up a program for discarding; giving a brief outline to implementing a successful program and then getting to some success stories as we get into the case studies.
As the peroxide formers, some peroxide formers and there’s a handful of common peroxide formers, ether, tetrahydrofuran, that we commonly come across that will over time become a hazard to health and safety. There are a lot of documented cases out there where ether, primarily ether and tetrahydrofuran are the two most common that we see that’s having incidence. Either they threw aged containers, just storage, improper storage, in the back of a flammable storage cabinet, in a lab, in the back of a shelf or also when they’ve been run through distillation units and then stored and also when they’ve been run through a rotovap as well. Those are the three most common incidences where we run into solvents- forming peroxides and they just have not been managed properly.
Some of the peroxide formers potential energetic materials, potential peroxide formers, over time will really form peroxides through the oxidation process, slow oxidation process, as air is introduced to the system. You get different hydroperoxide change that can become explosive if not properly handled. Some of the potential peroxide formers will come with inhibitors. [0:04:47] hydroxytoluene and BHT and hydroquinone are two of the more common ones that we see.
But also over the last few years, we’ve seen a trend within research where they’ve moved away from the different solvents with inhibitors and they’ve gone to inhibitor-free formulations which push up the timeline if the material is not managed properly because there’s nothing inhibiting any peroxide formation.
The big part of this as we get into the presentation is really about how the material is stored and a frequency in which it’s checked in. If there is a timeline for the peroxides, a check-in or some sort of structured management program, you can really reduce other potential for peroxides to be forming any of these chemicals. Either they’ll get used up or discarded before any peroxide formation.
From a recognition side of things, as the materials age, there will be, there can be a physical change. A lot of the – primarily solvents are all, they’re all clear solvents, sometimes they’ll get, over time, they’ll start to get cloudy, they’ll see crystal formations floating inside the solvents in some cases or sitting at the bottom of the solution. Over time, you’ve seen it all, three of those ways.
Then there are also some solids that can form peroxides, sodium amide being the most common. And as that forms peroxides over time, it will start to change color. And that’s an excellent indicator prior to handling the material if something’s going on with the chemical so any physical change is the first trigger to something going on.
Next to do, we have a small poll question. I wanted to run by everyone, just take a few moments, just give your input and we’ll answer or build part of the presentation around some of the answers that you give for what your greatest need in terms of peroxide former management is. It takes 30 seconds to do that.
James: Yes. I just launched that poll. Everyone should see the options there for training or identifying peroxide formers to developing an SOP, checking and labelling, and material removal and disposal. So we give you just a few more seconds. It looks like almost everyone has voted.
Okay. So it looks like number one, 38% chose training and identifying peroxide formers. Two is tracking and labelling at 26%. And three was material removal and disposal at 21%. So there you go. And then, 16% was developing SOP. Ted.
Ted: Okay. Excellent. Thank you, everyone. I’m touching on all of those throughout the rest of the presentation. I previously mentioned some of the common peroxide formers, ethyl ether, tetrahydrofuran. Two others that we commonly, the most common ones that we run into in forming peroxides and it is a long list but ethyl propyl ether and 1, 4-dioxane. So those four are really the most common solvents that we see, that I’ve seen out in the fields as forming peroxides and we come across at client sites.
From the solid standpoint and I mentioned this a little earlier but sodium amide is the most common solid, one of the few solids, that will be able to form peroxides. Potassium amide is another one but sodium amide is the most common. We could see that on a fairly regular basis. It will either be a white or a gray powder or as it starts to form peroxides, it’ll turn yellow then it’ll get darker yellow then it’ll get a brown. Then when it’s very concentrated peroxides, it’ll almost get, it’ll get extremely dark, a dark, dark brown for that.
That has... Only seen a handful of the sodium amide is getting that dark. Commonly, we’ll come across and able to dispose of them as it’s starting to turn from the white to the light yellow. As the peroxide formers oxidize, get the hydroperoxide chains, the material can become shock-sensitive.
And there are few different ways that the material can potentially be set off. It be heating it up, running it through rotovap or it could be putting it down in a bottle, putting it down on top of a lab bench with some force if there are crystals, peroxide crystals underneath, a cap potentially opening the material, there are crystals going up the side of the bottle, any shaking, like that could potentially set the material off.
Before taking these stimuli into account, the handling of it is extremely important and that first recognition piece which say, is the age of the material, and if you can see into the container, how the material looks, those are your first two parts to go through from a recognition standpoint. ID-ing was one of the things that was mentioned in the poll; the age and how it appears part of it, then also the way the material’s been stored, taking into account whether or not the material has a peroxide inhibitor in it.
Over time, the inhibitors will break down upon exposure to light, heat and air. If the material is not inhibited and it is exposed to those conditions, it’s going to be more likely to form peroxides. From an ID standpoint, those are your first three steps you want to go through before handling the material because there’s the potential that the material could be set off if it does have concentrated peroxides.
This is a picture of a tetrahydrofuran bottle that we came across in a lab clean-out. It was in the back of a flammable storage cabinet. It’s an older bottle. You can only see part of the label but it is an older bottle. It did test for 150 parts per million of peroxides in there. That was one that when we came across it, didn’t move it, had to come in and handle that separately.
As you can see, there’s crystallization at the bottom of the container. And the first part in the evaluation on our end was that visual inspection. As soon we saw something in the tetrahydrofuran bottle, noticed that the bottle was older, didn’t touch it, worked around and planned for the next step.
This is another picture of tetrahydrofuran. We came across this one, tested for 50 parts per million of peroxides. Over the last two years, tetrahydrofuran has really been counted for 85% to 90% of the jobs that we’ve done for peroxides stabilization.
Everyone has a lot of and we found as everyone is very aware of the hazards around ether, ethyl ether, while they document it, widely known. It seems like the research, as we come across, everyone’s very aware of that one. Tetrahydrofuran is lesser known, widely used, used much more than ether. And the one that we’re seeing is slipping through, that people aren’t really catching. That’s the most common one that we’ve come across.
Next, this one was an unknown solvent that we came across in a lab clean out that we didn’t move, we didn’t touch. Immediately, as soon as we saw this one, we just left it alone and put together a plan on how we were going to handle the material. We ultimately ended up coming out and taking the material out of the laboratory, taking it out of the building and testing and stabilizing the material.
As you can see, there’s a lot of crystallization in this material. This one was at storage for years just within the lab. I supposed it was in a warm area of the lab. It was out in the light. I’m not sure if it ever had an inhibitor in it. But this is crystallization that I came across in the container.
I mentioned sodium amide earlier. This is a picture of sodium amide we came across and again in another lab clean out we did. There’s some crust on the outside of the material. That had been spilled in the outside and started to react on the outside of the container. This was a lab clean out for a professor that was leaving the institution and this has been stored for 30 years, was the estimate.
This was one that again, I came across at in the fume hood, left it over, left it off to the side, didn’t move it, put together a plan and ultimately came in and stabilized this material.
And again, to the handling of it a little bit, there are different steps for the organic solvents versus a sodium amide. We’ll get into it in a little bit. When this container was opened, when we opened it, it was a dark brown on the inside so there are heavy peroxide concentrations on the inside of that bottle. Again, which makes sense, it’s been stored there for 30 years, wasn’t a surprise when that, when we saw that coloring.
So those are some of the initial steps or some examples that I’ve seen on the field and when we’ve had materials that have peroxides in them. The next part and the common question that I received is what regulations govern this to help get people to follow a management program? And there’s really no clear regulations that say you have to manage peroxide formers in a certain way.
It really falls under the OSHA General Duty Clause, an employer is required to safeguard its employees. There are some guidelines out there. The NFPA has some guidelines. And then if the material is old and turns out to have peroxides, it needs to be handled as a potential explosive.
Certain states are going to get involved or need to be brought into the picture to allow for treatment permits. Up in New England, five out of the six New England states require state approval for treatment. They go above the standard RCRA treatment in tanks and containers.
Again, Connecticut and a lot of the mid-Atlantic allow for a treatment in tanks and containers and start to move from South Maryland those who passed the permit working with the state. As you move down the east coast, most of the states allow for tanks and containers, a treatment in tanks and containers. Speaking of North Carolina, they passed the permit. And as you move west, most of the states allow for a treatment in tanks and containers, don’t require a permit.
One thing that we have encountered, that I have encountered even though there’s no requirement for notification, it’s been requested by fire departments, local fire departments, to be made aware of these situations when they come up. And that ties partially to the relationship the institution has with the fire department. But we’ve had cases where it wasn’t required. The contact was unaware. The client was unaware of any notification requirements and the fire department afterwards requested notification just so in the event of an emergency, they would be able to respond and know what they were responding to.
Along with the NFPA guidelines, there are safety council guidelines. There are different lab safety manuals that outline management. But again, no clear regulations for it. In the event of or whenever we need to do these treatments regardless of state or permit requirements, we always are doing them off hours, in a secure location within the institution, just to minimize the foot traffic. And then we’ll isolate all the areas that are going to be affected by or we have to, as we move the material through the building. So it can be blocking of hallways, elevators, parts of buildings just to get the material out the door and then having a secure location. We don’t have to worry about delivery trucks or foot traffic or any cars coming in. So it can be as a guideline, rule of thumb, that’s the best way that we manage the material.
And identification and stabilization process as we go through it, we’re really asking a lot of questions on the frontend and again tying to the ID comment before. Before you do that visual inspection initially, you determine the material that needs to be handled in a safer way or it could be a potential explosive. We’re looking for a lot of information, what the material was being used, how it’s being used within the institution, how it’s being stored, approximate time, different information, any information at all.
Sometimes, we run into cases where researchers are trying to create a new chemical or a new long chained chemical and this is a by-product of it. So those are all the things that we need to know on the frontend so that we can determine the most appropriate way to handle the material. In some cases, we’ve had to use three journals or recipes with general chemistry knowledge to determine how to properly handle the material.
Diluting the material is a common misconception. If you have a peroxide former, just diluting it down does not remove the peroxides. All you’re doing is separating the solvent and the peroxides and actually you can concentrate the peroxides and make it actually more of a hazard because you’re concentrating those peroxides. So dilution is not the answer.
To get all that information, you make that determination on the frontend. It’s extremely important prior to the handling of the material. These are all steps that we go through before we handle anything when working with our clients.
So it can be very labor-instense. It’s off hours. It can be very inconvenient to do any of these stabilizations of the material. So a way in which to avoid all of this is through a management program. 95% of all the remote openings that we do, that I do, can be avoided if the material was managed under a system and was properly checked-in upon every few months and was disposed of when the time came as opposed to it sitting around for years on end.
Three things that we commonly see mentioned the long term sitting around. Also, improper storage mentioned that no preventive maintenance. But also big one that we see in, I think a lot of places have and researchers have gone better with this, but the bulk purchasing which we still do see a fair amount, not just buying it just because it may be cheaper and then it’s not used then it sits around with the intent of it being used at some point and then next thing you know, three or four years go by or longer and the material still has never been touched and it may not be properly stored, moving around a bunch of times. Who knows? Those are the things that if monitored can all prevent any remote openings.
The biggest challenge in every institution is different. It’s really what’s going to work for you. So to develop a standard SOP that will capture everything, capture a proper management system so that you can remove the material before it becomes a stabilization and a remote opening event, so again developing that can be difficult and every institution’s going to have different ways of doing it. Hopefully, what we’ll go through now is a guideline that can be adopted for your program.
The biggest challenge is collecting the information and tracking it. In working with some of the clients, we had success with getting the researchers involved by getting their input and making them part of the solution, making them aware of the issue and part of the solution. In some cases, we’ve had other cases where we worked with our clients and researchers to get inventories of the laboratories we tie to, to reporting requirements to adhere to, fire department notifications, flammable storage, inventories which were all required.
We’ve been able to tie in through that with the researchers’ help or we’ve been able to just help the client just go in to the laboratories, inventory, and set up a tracking system by a laboratory or our clients if they know what material they have on site. The regulatory requirement and fire department notification has been one that’s been very helpful.
Once you get through that tracking piece and determine what’s going to work is that as an Environmental Health and Safety group can, you do that inventory, set up that tracking system, working with the researchers. In some cases, we’ve come in and helped our clients with the inventory piece to keep that off and help manage it. Once we set up that, you’ve determined that system. The next part would be and to set up a timeline on how often the materials are going to be checked upon.
Some institutions have every three months, some are monthly, some are every four to six months, some are annually. Again it’s going to depend upon the materials, how feasible it is, besides your institution’s going to impact that and how often you can dedicate resources to doing those testing. And the other part is the volume that you’re seeing or the amount of solvents, potential peroxide-forming solvents that you see.
Another way that we found that’s been successful is central purchasing which we don’t see very often but that can be controlled. You’re able to minimize the amount of the material that’s bought at the time. You’re able to track when the material was received. And you can track how long it’s been on site from that information. That’s been successful.
But again, it is something that is on a lesser side. We often see that too often. There are only a handful of places that we’re trying to see that central purchasing system set up. But if you have that, it could be something that would work for you.
Once the program started, it could be maintained with depending upon the size of your group. It could be maintained within the existing staff once you get that program up and running which is usually the most difficult part. But once you determined the best way to do it, the best system for tracking that’s going to work and kick that off, after that, the program will keep education of researchers’ up and the Environmental Health and Safety group can help manage the program. And the program will essentially run itself once you keep up with the training.
We talked about the central purchasing already but the training piece, if it’s written into the chemical hygiene plan as researchers culled and go through, if chemical hygiene plan applies to you, a lot of safety protocols, training people to those when they first come in, refresher trainings, keeping people up to speed, of from that side of things can help minimize any potential materials lingering for too long, able to manage it that way.
Another part is you have that set program but then there’s that maintenance piece. In a lot of cases, the training program will run itself but there doesn’t need to be a check and balance. So having the labs inspected periodically, making sure that they’re maintaining their materials in timely fashion, it’s not lingering along for too long.
Currently, we partnered with some of our clients to do those periodic inspections. In some cases, our clients do their own periodic inspections and if they have anything in question, they’ll ask us to come in to review the material and to check-in on it, or to get our input on it or they may ask us to just come and take it away. There are a couple different ways to do it but that maintenance really has been a very successful for all the clients that we’re working with on this.
The other part of collecting the information, once you get the researchers to do it, a format that’s going to work is in their Excel spreadsheet. There’s a home grown database that you can collect all the information, whatever will work best for you. In some cases, some institutions have a web-based form along with the chemical inventory.
Whenever they receive a peroxide former, they have to notify Environmental Health and Safety that they receive the material and there’s a form that they fill out with the notification; what the material is, when it was received, catalogue number, cast number, all of that so you can tie exactly what’s in there, the size of the container, all that’s tied into it.
An email sent off to Environmental Health and Safety. They’re aware of the material now. They know how to keep an eye on it. So, forms, inventories, there are a couple of different ways that we’ve seen programs work, that we’ve helped implement programs for our clients. It’s really whatever is going to work best for your institution. It’s something you have to determine.
So the biggest thing is the lab can never have too much information. I mentioned before that everyone has a very good understanding of the hazards of ether. But they may know that ether’s bad but not necessarily know why or what contributes to the peroxide formation. They may just know that ether can explode but not really know why. They may not really know and this is one where tetrahydrofuran’s one that’s often overlooked from what we’re seeing and that’s been reflected in the amount of remote openings we’ve been doing for tetrahydrofuran to treat contaminated THF.
Getting involved in the lab meetings is something we found a lot of success with going through to help educate lab people, work with the lab personnel and get them involved, talk it through, see what will work for them, see how we can help. Along with that, it helps with getting any potential safety issues out on the floor so that people are aware. There’s no mystery. We’re handling the chemicals.
A couple of the case studies now that I’d like to get into are within our company while from Boston down to the mid-Atlantic area. Some examples of clients that we’ve worked with to streamline and develop a program management system and they’ve been very successful. One up here in the Boston area is a large university.
We started up doing annual walk-throughs. We moved it to semi-annual, every six months, and now we’re doing quarterly walk-throughs of other laboratories, inventorying any potential, evaluating and inventorying any potential high hazard materials, bringing it back, presenting that, putting up a report together, presenting it to Environmental Health and Safety into the researchers, talking with the researchers and working with them if it’s something that is okay now but they’ve stopped doing an experiment and they no longer need the material.
In a lot of cases, they’ve just said, “I don’t need it anymore. Can you take it away?” We’ve been able to eliminate any remote openings as a result of the walk-throughs. It’s been very successful.
As the program’s grown, we’ve been able to get any potential materials off site, really stay on top of it, and working with the Environmental Health and Safety. We’re able to actually eliminate any remote openings. It’s been a huge cost savings which is an added benefit.
Next is our, this is one example of the central receiving where everything gets centered into chemical inventory database upon receipt, know exactly what the material is, where it’s going, when it was received. We do walk-throughs through the laboratories, periodic walk-throughs through the labs.
And then also, once a year, we’re running a report, the inventory report and flagging any materials that appear to be still on site and that are in the inventory and we’ll go to those labs, check on the material, evaluate it and remove it for disposal. Again, this has been a very successful program where we’ve been able to eliminate any potential remote openings as a result of the management program that we put on quest.
This was a large hospital in the Boston area as well where we go in and there’s a chemical inventory program. We go in periodically and evaluate the inventory, QC going through the laboratories and re-inventorying, making sure that the inventories are up to date. We started identifying potential peroxide formers.
As we came across them, we flagged them in the inventory. They were all tested, worked with the lab staff. If it was something that they didn’t need, we took it. We’re able to test the material, flag it before it became an issue and again, ship it off site and dispose of it before there were any issues. And this has been another very successful program where we’ve had no remote openings within this institution since we started doing this program.
This program’s been very successful. With that maintenance piece, once the program has been set up, that will work best for our client and working with our clients and able to have excellent success rate with really eliminating any potential remote openings.
I have moved out of the New England area, in New York or research manufacturing institution we do work with that we did a walk-through of the facility. We identified any potential peroxide forming materials, any of the materials that they were no longer using. We tested some of the materials we did have to initially remote open.
We tested the materials after, removed any of the materials that were an issue or any materials that they didn’t need any more, the materials that they wanted to keep once they were deemed safe. We put them on a management program. We’re checking in every three months. Material’s being tested. And once it expires, the material will be disposed of.
Since that initial walk-through, I mean, we’ve been able to, in that initial remote opening, been able to again eliminate any potential remote openings with the management of the program. Then another, down the coast, the Baltimore area, we came in, started doing work with the client, chemical inventory, reviewed their chemical inventory, identifying potential peroxide formers, spoke with the researchers and worked with Environmental Health and Safety as to the need for the materials.
Any material that was no longer needed, we tested and removed for disposal. Now we’re doing any more walk-throughs while maintaining the chemical inventories so that the material is tracked. Also, we have that as a review and that’s been a very successful program as well.
Once we have the program set up, had a lot of success in working with our clients to really eliminate any of the remote openings which can be completely eliminate them, some materials may get missed or you found somewhere but overall the program, we’ve had great success in working with clients developing and maintaining these systems and there’s a lot of benefit to it.
Again, each one of those institutions has their own internal systems and we had to work with them to develop the appropriate program. But in all cases, the programs have been very successful to minimize, if not eliminate, any of the remote openings of any high haz material. So there are multiple benefits from safety standpoint, from financial standpoint so there are a lot of benefits with that.
If there are any questions, please let me know. Thank you very much, everyone.
James: Thanks, Ted. You’re in high demand. That was a great presentation. Look, we’ve got questions already waiting in the queue that I want to get to. And also encourage those of you that have a question about this information. So again, feel free to type it in. We’ll get to as many as we can with the 15 minutes or so that we have left. So let’s start with the few that came in early. There were some questions around testing. And Thomas asks, when we get back to that sodium amide container you showed earlier in the presentation, how would one test that container for peroxides?
Ted: We wouldn’t test it, we just base it on color. If there’s any discoloration in the material, it’s starting to form peroxides. So you wouldn’t need to test the sodium amide. That one, you could base it on color.
James: Okay. So it’s clear based on that. Got it. And this I think is about the same bottle. Paula asks, are the exterior crystals of the bottle peroxides or is that another chemical or it’s a mix of both?
Ted: That is, the sodium amide had reacted off. That’s sodium hydroxide crusted on to the side; one of the by-products of the sodium amide. That’s just sodium hydroxide crusted on to the bottle.
James: Okay. Got it. Thanks. And another follow-up here. This one also from Paula. Are aqueous solutions of peroxides still reactive with solvents?
Ted: Is it reactive with solvents? I’m not sure I’m clear on the question, Paula. If you have an aqueous solution that contains peroxides then it’s mixed with other organic solvents? Is there potential for it to form more peroxides?
James: That’s what it sounds like to me. We can dive into that further and not ask some follow up. No worries. Let’s move on. This one’s from Joanne. What are the materials used to stabilize peroxide formers?
Ted: There are a few different ways out there, different ways to do it. There is a sodium hydroxide solution that can be used to deactivate peroxides. There’s a sulfuric acid, ferrous ammonium sulphate and water mixture that’s used to stabilize peroxides. There is a product that is sold that is designed to dissolve, to deactivate peroxides and the name of the product is escaping me right now but there’s a commercial product out there that you can purchase to deactivate peroxides.
James: Do have any favorites? How do you determine which one you use?
Ted: Either the sulfuric acid solution or sodium hydroxide are the two that I use. I haven’t used the commercial product yet but sulfuric acid is the main one that I will go with. But either has worked for me in the past.
James: Great. Well, there are a few options that she can look into. Excellent. Another question asks, what is your recommendation for companies that do not have centralized purchasing?
Ted: That’s the majority of the clients that we work with and we found the inventory piece has been extremely helpful or even if not a complete chemical inventory, if that’s something that your institution has, we’ve had cases where we’ve gone through the laboratories with the client and looked for just the peroxide-forming materials or any potential energetic materials. And that’s the sole purpose of the walk-through. And we document where we find the material, what the material is.
And that’s the one thing that we do with the university in Boston. We don’t base it of the chemical inventory. We do a walk-through specially targeted for these materials, identify them, their locations, put a report together, present it to the Environmental Health and Safety and then the work of the researchers.
It’s the most appropriate way to handle the material. Either they just take it because it’s really old and is disposed of or it’s no longer being used or it’s tested and it’s maintained from that point. So there are a couple of different ways to do it. It could be a chemical inventory or it could be just a walk-through specifically targeting those materials.
James: Okay. Great. And sticking with processes, what kind of processes can produce by-products or waste that could form peroxides? How do you identify it?
Ted: It’s based on what the material of the solvent, the solvent that’s being used, if it’s a potential peroxide former and there’s a long list out there. And from a process standpoint, if the material’s been purified, really in anyway, that’s where you get the high likelihood of peroxide formation.
Ted: Again, there are no inhibitors in there. The material’s being run through under a system and purified, once you get a little, you get a little bit of air onto that system, you can start to get the peroxides and then it’ll just expand from there.
James: Okay. Here’s a good question. I don’t know if there’s an exact timetable you can put on this but maybe a benchmark. For the five common peroxide formers you mentioned earlier, how long can they be safely used before needing to be disposed both with inhibitor and without?
Ted: There are a lot of things that tie to it. Part of it. There are a couple of things. One, there are guidelines, NFPS guidelines and limits for the materials. Also, the manufacturers have their shelf life. But the biggest thing is it comes to how the material is ultimately stored be it with inhibitor or without inhibitor.
If it’s stored in a cold, dry place, that’s less likely to have any peroxides versus some place that is hot, it’s being opened and closed repeatedly, you’re getting that air in there, you’re storing it in a warm place, that’s going to help with the formation of peroxides. So it really depends upon storage for the material and ultimately how it’s handled.
James: Okay. Right. So there are a lot of factors at play.
James: Ted, Thomas wants to know what triggered Triumvirate to do this or depends upon to identify those peroxide formers that need removal. Is there a certain trigger? Ted: It depends. We’ll identify materials that are potential peroxide formers. We will do an evaluation of the material, test the material and then make that determination. If the material has peroxides in it, it’s most likely not going to be something that the researcher is going to use. It may not be something that Environmental Health and Safety would like to stay on on the campus.
It depends upon what the results of our testing, what the use of the materials is, all those factors. But from an evaluation standpoint, we have to test them in order to make that determination. But also any of the facilities that the material will be disposed of, peroxide forming chemicals are one of the things that they’re looking out for and they want to know that the material’s been tested.
We’ll test any potential peroxide formers after that initial evaluation just so we can say whether or not it has any peroxides for ultimate disposal or the client to make a determination if they want to keep it or not.
James: Okay. And here’s a good follow-up from Emily, I think. So when identifying potential peroxide forming compounds, how can you safely discern if the chemical is safe to open and test on site or when is it necessary to remove and do off site?
Ted: Any of the testing we’re going to do on site, it’s just be a difference of if it’s done within a lab or if it’s done outside in like a parking lot. That testing is going to occur prior to any of the material being removed from site. So part of it is storage, age, if it’s inhibited or not, how the material looks, like any of the ones in the presentation that all the pictures of the solvents that had visible solids in tem . Those were all the ones that we remotely opened.
Again, if you have, if I have one that was received in December of 2015, it’s an ether. It’s been stored in a cool, dry place. It’s only a month old, inhibitor free. A lot of the ethers, they’re coming in the liter amber bottles. You can see right in it.
It’s a clear liquid. It has the sure seal. They have that sure cap there on there. There’s no air getting in. All those factors, the potential for peroxide formation has been taken out based on the factors that go into the formation.
So in that case, that one would be one that would be okay to open and test. And in those cases, but the sure seal cap, you can extract some of the solvent and then actually test it on to the peroxide strip to make that determination. So the bottle doesn’t necessarily have to be completely open.
Again, it ties to a bunch of different factors and how the material is stored and managed and the age. It’s taking all that into consideration when making that determination. If there’s any visible solids, crystals in there, that material’s not moved and it’s a remote opening because there’s obviously some potential peroxide formation in there.
James: As a preventative measure, would you recommend an SOP disposing of anything more than one year old? Robert wants to know if this a best practice you would recommend.
Ted: Yes, and depending upon and there are different guidelines out there and depending upon the solvent. A year’s a good benchmark. A lot of the potential peroxide formers fall in under a year. There are other materials that are three to six months. But a year is a good time frame to manage all those materials.
James: Great. I think you touched on this before. But just to clarify, is there any benefit to storing peroxide formers in our refrigerator and what are those?
Ted: That’s the cool, dry or cool, dark place. The one thing with that would be assuming that the refrigerator is readied for flammable materials but just keep them in cool, dark location. I’ve come across ethers that were stored in a refrigerator that were north of 10 years old and they had some peroxides formed in them.
While maybe stored there, the use is also going to play a part. And if it’s opened and closed, you’re still getting that oxygen in there. Over time, the material potentially could form peroxides. The age is going to play a part. That takes the heat out of it assuming that the refrigerator can handle the material.
James: Okay. Thanks for clarifying that. We’ve got a couple of minutes left and a few more questions. Let’s try and get these done. Again, if there’s anything else, we can follow up later on. This one comes from Brian. I believe you said dilution is not a valid method of treatment for peroxides. Can you explain this again?
Ted: So if I had a one liter bottle of ether that had peroxides, if I try to dilute it down with just water for example, you’re going to get separation of the peroxides. The ether is going to be on top of the water. The peroxides are going to be at the bottom of the bottle. You’re going to potentially concentrate the peroxides with deactivation and it doesn’t change the peroxide concentration. If anything, it’s going to concentrate it further.
So you still have that, from handling and shipping and management hazard, you still have the peroxides there. So it’s a diluted. You really haven’t done anything except potentially made the hazard worse.
James: Okay. Thanks for expanding on that. Thomas has a follow up to his earlier question. What if a one year old ether container tests negative? How long do you think it can stay after that test?
Ted: Again it ties back to, not to always hop on back to this, the management piece. If it’s managed properly, I’ve found and tested bottles of ether that have been a couple of years old that were stored properly and managed to maintain well. They were two years old and had no peroxides. I’ve also tested ethers that are under a year old and heap of peroxides. So that management piece is really the biggest part to it.
James: That’s the key take of the how long after?
Ted: It varies.
James: Okay. Proper management. So Ted, let’s wrap up here. One more question and then we’ll close down. This one asks what materials have a tendency to form peroxides in less than six months? Does anything come to mind?
Ted: Isopropyl ether and ethyl ether can. Those are the two most common.
Ted: That I’ve come across.
James: Great. Good examples. Excellent, Sir. I think we got pretty much the majority of the questions. Ted, nice job there. And I really appreciate the presentation and I hope everyone was able to take away a few points to help with your own peroxide former management plan. Ted, do you have anything else to add before we start to wrap up. I think there’s maybe one more slide at the end here.
Ted: No. Thank you very much, everyone and if you have any questions, please don’t hesitate to reach out.
James: Excellent. And as mentioned earlier, we will be sending a follow up tomorrow. This will include the recording of today’s webinar as well as the slide deck for you to review at your own convenience and also maybe some other links on some upcoming webinars. We have one on OSHA Inspection, Preparation and Preparedness next week so stay tuned for any upcoming webinars.
And feel free to reach out if you want some more advice from Ted or other peroxide former experts. I think that’ll do it for today. Thanks, everyone. I appreciate your attention and your participation. Some great questions. And we’ll see you soon. Take care.
Ted: Thank you.