On June 1, 2016, Transport Canada issued an amendment to the “Transportation of Dangerous Goods Regulations” (TDG) under the Transportation of Dangerous Goods Act. This amendment substantially revises the requirements for reporting spills of dangerous goods during transportation. It also addresses changes to air shipment of lithium ion batteries and makes various minor corrections and changes. The “Reporting Requirements and International Restrictions on Lithium Batteries Amendment” reflects concerns that the previous requirements for reporting spills, called “accidental releases,” was inefficient and didn’t allow the reporting parties to evaluate the risk to the public when deciding if a release had to be reported.
Chlorine gas is a scary material. This yellowish gas can kill people at very low concentrations in air. Travelling wherever the wind takes it, leaking chlorine gas is an emergency situation. A mere 10 parts per million in air is classified as Immediately Dangerous to Life and Health (IDLH). The whole city of Mississauga, Ontario, was evacuated for a week in 1979 due to the threatened release of chlorine from one damaged railway tankcar.
And yet, people clean their swimming pools on a regular basis using products called “pool chlorine”. How is this possible?
It turns out that the chlorine we use in swimming pools isn’t actually chlorine gas. Instead, pool chlorine is composed of chemicals that react with water to give off chlorine gas, slowly and safely. Typical chemicals used for pool disinfectants may be inorganic (such as calcium hypochlorite or lithium hypochlorite), or organic (such as trichloroisocyanuric acid and sodium dichloroisocyanurate).
When these chemicals are mixed with water, they break down to generate chlorine gas in small amounts. However, chlorine is a highly reactive material. It reacts with water molecules themselves to form a substance known as hypochlorous acid. This acidic compound will destroy the cell membranes of harmful organisms such as bacteria and algae, killing them and disinfecting the pool.
Hypochlorous acid, however, is quite reactive itself. Therefore, stabilizers may be added to the chlorinating product, or may be added to the pool separately. Ironically, if you can smell a strong odour from a chlorinated pool, this may mean that the pool is not properly chlorinated – the strong smell is usually from reaction of the acid with organic materials to form chemicals called chloramines, which are highly irritating to the respiratory system. Proper monitoring of water quality, including chlorine level and pH is essential to keeping your pool healthy for swimming.
Still A Hazard . . .
Although pool chemicals aren’t as dangerous as pure chlorine gas, they still pose hazards for transportation, use and storage. Many pool chemicals are classified as oxidizers (that is, chemicals that will react with combustibles to cause ignition) as well as corrosives (chemicals that will attack metal or burn human skin tissue).
Due to their oxidizing properties, chlorinated pool chemicals should be kept away from any flammable material (such as gasoline) or combustible items such as cardboard boxes. Never allow pool chemicals to become contaminated with organic material, such as sawdust or oil. The Canadian Centre for Occupational Health and Safety (CCOHS) advises:
- Do not store pool chemicals near gasoline, fertilizers, herbicides, grease, paints, tile cleaners, turpentine, or flammable materials. This tip is especially important when pool chemicals are stored in sheds or small storage rooms.
- If a fire breaks out, do not use a “dry chemical” fire extinguisher. Only use large amounts of water. If you cannot extinguish the flame immediately, leave the area and call the fire department.
Since the chemicals may also be corrosive or at least highly irritating, always wear proper protective equipment when handling. Work gloves and eye protection, such as goggles, will protect against accidental splashes or contamination. If concentrated product lands on your skin or eyes, immediately flush with large quantities of water, and get medical attention when necessary. Of course, make sure to keep these chemicals away from children and pets, and never store leftovers in containers labelled as food or drink.
Since chlorinated chemicals are highly reactive, do not allow them to become contaminated by other chemicals. Especially important is keeping them away from acids – contamination with acid will result in rapid generation of chlorine. In 2012, a maintenance worker in St Catharines, Ontario, accidentally mixed about 90 litres of chlorine with 900 litres of muriatic acid (another common pool chemical). The resultant release of chlorine gas sent a dozen people to hospital with difficulty breathing and other respiratory symptoms.
Even mixing these chemicals with water can generate heat, which can cause the corrosive mixture to boil and splash back at you. Follow the rule from your high school chemistry teacher to always add your chemical to the water, not the water to the chemical, so that the heat can be dissipated by a larger amount of water.
CCOHS has a webpage dedicated to safe handling of pool chemicals at
http://www.ccohs.ca/oshanswers/chemicals/swimming.html. Users should also see if Safety Data Sheets (SDSs) are available from the supplier. SDSs are not mandatory for consumer products, but are usually provided upon request as a customer service. And, of course, always read the label before using or storing chemicals.
Pool chemicals that are oxidizers or corrosives will also be regulated for transportation. While both U.S. and Canadian regulations usually exempt transport by a retail purchaser of consumer products, these exemptions will not apply to third party carriers.
Do you have any further questions about the regulations involving pool maintenance chemicals? Contact ICC Compliance Center here at 888-442-9628 (U.S.) or 888-977-4834 (Canada), and ask for one of our regulatory specialists.
On April 28, 2016, Transport Canada issued its latest Protective Direction. This Direction, number 36, will replace a previous one, Protective Direction 32, with more detailed instructions for rail carriers.
Protective Directions are rules that are not included in Canada’s Transportation of Dangerous Goods Regulations (TDG). Instead, they are announced by Transport Canada, and are published on their website. Usually, these directives are used when Transport Canada believes it’s important to bring in a new rule quickly in order to protect the public. Since amending the regulations can take months or longer, Part 13 of TDG allows them to use this method to respond to important issues with appropriate speed.
Protective Direction 36 requires Canadian Class I rail carriers to either publish information on the carrier’s website, or provide information to designated Emergency Planning Officials (EPOs) of each jurisdiction through which the carrier transports dangerous goods. This information includes:
- Aggregate information on the nature and volume of dangerous goods that the rail carrier transported by railway car through the last calendar year (broken down by quarter);
- The number of unit trains loaded with dangerous goods operated in the jurisdiction in the last year (again, broken down by quarter); and
- The percentage of railway cars carrying dangerous goods that were operated by the rail carrier through the jurisdiction in the last calendar year.
Rail carriers transporting dangerous goods by railway car in a province must, by March 15 of the following year, publish on its website a report in both official languages detailing the dangerous goods shipments, including the percentage of cars that were loaded with dangerous goods, the top ten dangerous goods carried, the percentage of these top ten goods as part of the dangerous goods transported in this province, and the percentage of all residual dangerous goods on the total dangerous goods transported in that province.
Further details are given in the Protective Direction about how the rail carrier must communicate with the designated Emergency Planning Official in each jurisdiction, and how they must provide information to the agency CANUTEC to improve communication during accidents.
Protective Direction 36 replaces the earlier Protective Direction 32, and takes effect on April 28, 2016, the day it was issued. The full text of the Direction can be found at http://www.tc.gc.ca/eng/tdg/safety-menu-1281.html.
Do you have any further questions about Protective Directions? Contact ICC Compliance Center here at 888-442-9628 (U.S.) or 888-977-4834 (Canada), and ask for one of our regulatory specialists.
Zika virus – the name itself sounds exotic and dangerous. It is believed to be a serious risk for pregnant women. And it’s due to arrive in North America. Just how great a danger is this virus, and how should research and medical facilities prepare for the regulatory burden?
First of all, Zika is not a new virus. It has been known since the 1950s in equatorial Africa and Asia, but only recently has it appeared to migrate to new territories, including South and Central America, the Caribbean and Mexico. It is primarily a mosquito-borne illness, transmitted by the Aedes genus of mosquitos. Possibly climate change has increased the populations of these mosquitos in the areas where Zika is spreading. Aedes mosquitos are found in some parts of the U.S., and although they are not currently believed to be in Canada, they may spread as the climate warms. Person-to-person transmission by body fluids is possible, but this would be relatively rare compared to the mosquito vector.
Zika is classed in the Flaviviridae family of viruses, along with dengue fever, West Nile virus and the notoriously dangerous yellow fever. However, compared to these, Zika is usually a mild affliction. According to the Centers for Disease Control (CDC), only one in five persons infected with the virus shows any symptoms at all. For those who do fall ill, the symptoms are described as flu-like: fever, joint and muscle pain, inflammation of the eyes (conjunctivitis) and a rash. Although there is no cure, and the virus does not respond to antibiotics, the infection normally resolves without treatment within a week. Fatalities are extremely rare. In other words, Zika is, for most people, a mildly unpleasant illness that they recover from quickly. Even better, exposure to Zika usually results in lasting immunity.
So, why has Zika become such a big issue in public health? While most people only become mildly ill when infected with Zika, the infection appears to be correlated to increases in two much more serious conditions: the neurological condition called Guillain-Barré syndrome (which can be triggered by a number of infections), and most tragically, the birth defect called microcephaly.
Microcephaly is a condition where a baby’s head is smaller than normal, and often includes abnormal brain development. The CDC indicates “problems can range from mild to severe and are often lifelong. In some cases, these problems can be life-threatening.”
It should be noted that we don’t yet have a conclusive linking of Zika to microcephaly, but some relatively strong evidence has been gathered. There appears to be a statistical increase in microcephaly in the children of mothers infected by Zika, as well as evidence that the virus can pass the placental barrier. The virus has been found in the brains of affected infants. So, it seems at least plausible that there is connection between the condition and exposure to the virus during fetal development. We don’t yet know just how likely the condition will be if the mother is infected with the virus, and we don’t know if it can occur at any stage in fetal development, or if there is only a short window of time for the defect to arise.
It would appear, therefore, that the main public health issue is the risk to developing fetuses. This is not a new problem; pathogens such as those responsible for rubella (German measles) and toxoplasmosis are also known to cause serious birth defects. But Zika has gathered headlines due to its fast spread, its previously unknown status to the public, and the difficulty in avoiding exposure to mosquitos if you live in an area where the disease is prevalent.
Based on mosquito distribution, it’s likely that Zika will obtain at least a foothold into the United States. Canada may be at less risk due to its colder climate, but there is a possibility of spread as global temperatures warm. The CDC and Health Canada have put out advisories to help people protect themselves from exposure to the virus. But medical facilities and laboratories must also take steps to prepare for Zika’s arrival, from preparing the infrastructure to send samples for analysis and diagnosis, to disposing of contaminated linens.
The first step in transporting infectious substances is to classify it according to either the U.S. “Hazardous Materials Regulations” of 49 CFR, or Canada’s “Transportation of Dangerous Goods Regulations”. Although many disease organisms have accepted classifications established for them (such as those found in the IATA Dangerous Goods Regulations), Zika virus is so new to North America that there has not yet been an official classification assigned.
Pathogens fall under two categories. Category A is used for organisms that are “transported in a form that, when exposure to it occurs, is capable of causing permanent disability, life-threatening or fatal disease in otherwise healthy humans or animals.” Pathogens that do not meet that criteria will be classed as Category B, less hazardous.
Although it is not immediately dangerous to the person affected, Zika is capable of causing permanent disability (birth defects) or life-threatening conditions (Guillain-Barré syndrome). However, it is not likely to cause these effects simply from a spill in transportation – it appears that direct blood contact is necessary to contract the disease. Unless the Department of Transportation or Transport Canada make an official determination of the appropriate category, as they did in the SARS outbreak, the decision will be the shipper’s, and should be guided by medical or scientific personnel. It may be noted that many other viruses in the Flaviviridae family have a split classification; they are placed in Category A when transported as a culture (artificially propagated to increase the virus concentration), but Category B when transported in samples in their natural state, such as blood or other body fluids.
Once the classification has been determined, packaging must be selected for Category A or B as appropriate. Obviously, the highly dangerous Category A organisms will require a much more secure packaging, one which must be approved to a standard created by the United Nations. Category B packages do not have to meet UN specification, but they must follow the regulations for construction and use. Note that ICC Compliance Center can provide packagings for various needs, from shipping small samples to disposing of contaminated linens as hazardous waste.
Once assembled, you must identify the package as containing Category A or B substances with the appropriate safety marks and labels. Note that Category B substances do not have to show the Class 6.2 label, but must show a diamond with the applicable UN number, UN3373, in the center. Category A pathogens will require full dangerous goods shipping papers. Most regulations exempt Category B from some or all of the shipping paper requirements. While placards are not required for Class 6.2 materials under the “Hazardous Materials Regulations” in the U.S., Canada does require placards if the shipment exceeds 500 kilograms or is subject to an Emergency Response Assistance Plan (ERAP). And, of course, personnel performing dangerous goods functions must be trained and certified in the appropriate regulations.
If you intend to ship pathogens outside your own country (for example, for international research efforts), remember that exporting and importing of infectious substances will involve additional regulations, such as the CDC’s Import Permit Program.
Do you have questions about how to transport infectious substances? Need labels, packaging or other supplies for such shipments? Contact ICC Compliance Center here at 888-442-9628 (U.S.) or 888-977-4834 (Canada), and ask for one of our regulatory specialists.
One of the most common tests for determining hazard classification is the flash point. This humble piece of physical information is defined in various ways in various regulations, but generally is the lowest temperature at which the vapours from a flammable liquid will ignite near the surface of the liquid, or in a test vessel. This can be critical for safety, because this temperature will be the lowest possible for the liquid to cause a flash fire if released or spilled. If the material can be handled and transported at temperatures lower than the flash point, the fire risk will be much smaller.
The flash point has become the standard test for classifying flammable liquids. It’s used by the U.S. OSHA (Occupational Health and Safety Act) and HMR (Hazardous Materials Regulations) classification systems, as well as Canada’s WHMIS (Workplace Hazardous Materials Information System) and TDG (Transportation of Dangerous Goods Regulations).
Obtaining a flash point on a new product is usually easy enough. Many laboratories, particularly those that deal with petrochemicals, can perform the test for a reasonable charge. If your company has too many products to make outsourcing practicable, a flash point tester itself is comparatively low cost (as scientific apparatus goes), and a trained person can obtain data quickly and efficiently. However, both of these options do cost money. Wouldn’t it be nice if there were a way to avoid the expense?
For example, toxic materials are usually classified by a test called the LD50 (the lethal dose to 50% of test subjects). This is a more expensive, complicated test, but there’s one beautiful feature for mixtures. You don’t have to do the test if you can calculate it. This calculation basically prorates the LD50s of the ingredients based on their concentrations. While there is debate about how accurate this system is, it’s directly mentioned in the above regulations as an option if testing of the actual product has not been done.
Unfortunately, the same regulations do not directly provide us with a method for calculating a flash point. But OSHA and WHMIS are based on the Globally Harmonized System of Classification and Labelling, and TDG and the HMR are based on the UN Recommendations on the Transport of Dangerous Goods. Both of these documents do include a reference to calculating flash points if directly measured ones are not available.
That’s the good news. The bad news starts when we discover that both the Globally Harmonized System and the UN Recommendations don’t give the specific formula for the calculation. The GHS reference can be found in sub-section 22.214.171.124.2, while the UN Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria places the reference to a calculation in Appendix 6, paragraph 4. At least both of them refer to the same method, one reported by Gmehling and Rasmussen in the journal Industrial & Engineering Chemistry Fundamentals 21, 86, (1982) titled “Flash points of flammable liquid mixtures using UNIFAC”.
When we look up this article, we encounter another road block – like many scientific journals, this one is not free, and the article is behind a paywall. We have a choice; either pay up to read the full article, or see if the formula appears somewhere else.
Oh, and it helps if we know what UNIFAC is. Apparently the acronym stands for “UNIQUAC Functional-group Activity Coefficients” (making it an acronym containing an acronym), and is “a semi-empirical system for the prediction of non-electrolyte activity in non-ideal mixtures.”
A little more digging on the internet comes up with an article summarizing how to calculate various flammability measurements, published by M. Hristova and S. Tchaoushev in the Journal of the University of Chemical Technology and Metallurgy, 41, 3, 2006, 291-296, titled “Calculation of Flash Points and Flammability Limits of Substances and Mixtures.” This can be accessed, with no paywall, at http://dl.uctm.edu/journal/node/j2006-3/04-Hristova-291-296.pdf .
So, we finally have our method to calculate our flash points. Except it’s nothing like the relatively simple method for calculating LD50s. Hristova and Tschaoushev tell us the calculation will take four steps:
- Determine the flash point which satisfies an equation relating “the actual partial pressure of component i in a vapor-air mixture” with “the partial pressure in a gas-air mixture with a composition corresponding to the LFL (lower flammable limit) of pure component i”.
- Determine the flammability limits at the temperature under study using the Zebatekis equation. (This equation is helpfully included.)
- Determine the partial pressure of each component, using the Antoine equation, and
- Determine the activity coefficients using the UNIFAC method.
At this point, it becomes obvious that these calculations are currently of use, perhaps, to physical chemists, but are not yet a workable solution for companies simply trying to determine if their product is in Packing Group II or III. It turns out that the molecular forces in flammable liquids are far too complex to reduce to a simple equation such as can be used for toxic mixtures. Even computer systems that model these mixtures must be taken as provisional, and certainly not nearly as reliable as measured data.
So, the day when we can toss aside our flash point testers and classify flammable liquids based only on the composition is yet to come. To comply with the classification rules for workplace safety or transportation, a measured flash point is still the simplest and most accurate solution.
Do you have any questions about classifying hazardous materials? Contact ICC Compliance Center here at 888-442-9628 (U.S.) or 888-977-4834 (Canada), and ask for one of our regulatory specialists.