Environment – IMDG Code Compliance Centre

Monocrotophos (The killer insecticide)

Monocrotophos is an organophospate insecticide mainly used on on citrus, olives, rice, maize, sorghum, sugar cane, sugar beet, peanuts, potatoes, soya beans, vegetables, ornamentals and tobacco and cotton. This highly toxic insecticide is prohibited in many countries.

English: A sign warning about pesticide exposure. (Photo credit: Wikipedia)

Monocrotophos has oral, dermal and inhalation toxicity. This has resulted in death due to accidental exposure and suicides. Symptoms after oral exposure includes but not limited to excessive sweating, headache, weakness, giddiness, nausea, vomiting, hypersalivation, abdominal cramps, diarrhea, blurred vision and slurred speech. Inhalation and dermal routes may not show initial symptoms.

Severe poisoning will affect the central nervous system, producing inco-ordination, slurred speech, loss of reflexes, weakness, fatigue, involuntary muscle contractions, twitching, tremors of the tongue or eyelids and eventually paralysis of the body extremities and the respiratory muscles. In severe cases there may also be involuntary defecation or urination, psychosis, irregular heart beat, unconsciousness, convulsions and coma. Ingestion of 120 mg monocrotophos can be fatal.

Many incidents in developing countries have been linked to monocrotophos. Monocrotophos has been pointed to as a cause, in the following:

Brazil, Parana State Monocrotophos caused 107 of 412 reported incidents analysed in 1990, and the toxicology centre and health clinics also noted 1,650 incidents involving monocrotophos between 1982 and 1991.

Paraguay In a region where monocrotophos is one of the most commonly used active ingredients there have been numerous cases of pesticide poisoning; monocrotophos was identified as the cause of paralysis in children in cotton-growing areas by the Ministry of Public Health and Welfare which found that 2–3 weeks of frequent exposure caused paralysis in children and acute poisoning in adults.

Egypt In a cotton growing region of Egypt the health of 14 farmers who spray was compared with a control group from the same region. Monocrotophos is widely used and 61% of those surveyed showed symptoms of chronic pesticide poisoning.

Philippines, Cordillera region Monocrotophos was one of the pesticides widely used by farmers in a survey that found all farmers suffered some adverse health effects.

Indonesia In observations of 906 spray operations of 214 farmers commonly using monocrotophos and other OPs, over a three-month period, researcher found a significant increase-from two to fiftyfold-in the symptoms of pesticide toxicity during the spraying period. Of these spray operations, 21% brought on three or more neurobehavioural and intestinal signs of poisoning.

India The 2013 incident where 23 schoolchildren in north-eastern India died from eating a contaminated school lunch is believed to have been caused by cooking oil stored in a container formerly used to store monocrotophos.

(Above quoted from Wikipedia)

English: Monsanto pesticide to be sprayed on f... — English: Monsanto pesticide to be sprayed on food crops. Français : Remplissage d’un épandeur (Photo credit: Wikipedia)

Transport regulation classifies Monocrotophos pesticides under class 6.1, toxic substances, packing group II or III depending on the products’ toxicity level.

Forensic report confirms pesticide in midday meal (thehindu.com)
Pesticides found in deadly school lunch in India (cnn.com)
Poison content in midday meal was five times more than what is found in insecticides: report (pesproppt.wordpress.com)
Pesticides banned,refused registration, and restricted use in India (pesproppt.wordpress.com)
Poison content in midday meal was five times more than what is found in insecticides: report (thehindu.com)
Saving The Bees: How EU’s Pesticide Ban Affects The US (blogpestcontrol.com)
Insecticide found in fatal food samples in India (radionz.co.nz)
India school lunch deaths: pesticide found (guardian.co.uk)
Police: Toxic Levels of Pesticide in Kids’ Lunch (abcnews.go.com)

Minamata Convention – New Legally Binding Mercury Rules –

Mercury is used by mankind since early history. Traces of mercury are found in Mayan tomb and many other historical sites. Mercury is released to the atmosphere through

various ways including industrial process, mining, cement and metal production, combustion of fossil fuel etc.

how mercury can enter our environment Image courtesy – Publication of UNEP “Mercury Time to Act”

Though essential in various industrial processes, mercury is harmful to health. Once released, mercury travels great distances and circulates in the atmosphere between air, water, sediments, soil and living organisms. Through agricultural products and seafood mercury can enter human body. Swordfish and sharks carry more accumulated mercury than other seafood.

The infamous Minamata disease claimed many lives and maimed many. According to Japanese Official government figure as of March 2001 total of 1,784 had died and over 10,000 effected people were compensated. The disease was caused by the release of methylmercury in the industrial wastewater from the Chisso Corporation’s chemical factory.

Crippled hand of Minamata disease victim (Photo credit: Wikipedia)

459 people are known to have died in Iraq during early 70s due to mercury poisoning caused by consuming contaminated bread of which the grains were treated with fungicide containing mercury.

Mercury and Human Health Image courtesy :Publication of UNEP “Mercury Time to Act” — Mercury and Human Health Image courtesy – Publication of UNEP “Mercury Time to Act”

On 19^th January 2013 United Nations Environment Program (UNEP) agreed by a treaty to regulate mercury to protect the world of health hazard.

The new binding rules signed by more than 140 countries at Geneva will primarily focus on

the supply of and trade in mercury;
the use of mercury in products and industrial processes;
the measures to be taken to reduce emissions from artisanal and small-scale gold mining;
the measures to be taken to reduce emissions from power plants and metals production facilities.

By 2020 many mercury containing products will be banned from production, import or export which includes

Batteries, except for button cell batteries used in implantable medical devices
Switches and relays
Certain type of compact fluorescent lamps (CFLs)
Mercury in cold cathode fluorescent lamps and external electrode fluorescent lamps
Soaps and Cosmetics
Non electric medical devices such as thermometers and blood pressure devices

Dental amalgam also will be phased out.

Exceptions are there for some vaccines where mercury is used as a preservative and have been excluded from the treaty as have products used in religious or traditional activities.

For more information visit http://unep.org/

Suggested readings : Mercury Time to Act

Global Mercury Assessment 2013: Sources, emissions, releases, and environmental transport

Khaidarkan Mercury – Addressing primary mercury mining in Kyrgyzstan

Groundbreaking Mercury Treaty Adopted By 140 Countries (businessinsider.com)
U.N. clinches global deal on cutting mercury emissions (reuters.com)

Rio+20 & IMO

The United Nations Conference on Sustainable Development (UNCSD) took place at Rio from 20-22^nd June 2012. Two themes focused at Rio+20 were a green economy in the context of sustainable development poverty eradication; and the institutional framework for sustainable development. Sustainable development means to meet the needs of the present without compromising the ability of the future generations to meet their own needs.

Maersk Line’s Tripple-E class vessels was recognized as an innovative solution to drive sustainable development by Sustainia100, 100 solutions identified includes solar power in Sudan, sustainable fashion in Switzerland; water-cooling in Canada, solar-cooling in Singapore, buses in Brazil, smart buildings in Sydney.

Quote from Sustania

Commercial shipping is a large contributor of air pollution accounting for 3-4% of man-made CO2 emissions worldwide. Larger ships, optimised for lower speeds and able to carry more cargo, can slash fuel.

THE SOLUTION

!In 2011, Maersk Line secured an order to build 20 container ships bigger than anything currently at sea. The company’s solution, the Triple-E (the “E” is for economy of scale, energy efficiency, and environmentally improved), established a new class of container ship. The capacity of each ship is to be 16% greater than the largest ship built thus far.

The ships are to be outfitted with currently available energy- saving and pollution-control technologies. For instance, the ships’ hulls are optimised for lower speeds. An energy-efficient engine will be supplemented by a waste-heat recovery system that contributes to the ship’s propulsion. The Triple E class will also be equipped with an energy efficient ballast water treatment system, and made ready for eventual installation of a SOx scrubber. A “Cradle to Cradle Passport” ensures that when a Triple E ship reaches retirement its components can be safely disassembled and recycled.

Click here to see Sustainia members, Sustainia concept papers and download A Guide to 100 sustainable solutions

Watch below video about IMO @ Rio+20

Brazil: IMO Reaffirms Its Commitment to Sustainable Maritime Development (worldmaritimenews.com)
7 things you can do to be a part of Rio+20 (one.org)
VIDEO: Rio +20 outcome ‘disappointing’ (bbc.co.uk)

World Oceans Day & MARPOL ANNEX III

June 08^th is observed as World Oceans Day. 2011 & 2012 theme is Youth: the Next Wave for Change.

On this occasion let us look at Annex III of International Convention for the Prevention of Pollution from Ships, 1973/78.

Annex III of the International Convention for the Prevention of Pollution from Ships, 1973, as modified by the Protocol of 1978 relating thereto (MARPOL 73/78), deals with the prevention of pollution by harmful substances carried by sea in packaged form.

Annex III of MARPOL has 8 regulations, below are the explanation of each.

For full details refer MARPOL or part 1.1.2.2. of IMDG Code 35-10

1. Application

This regulation identifies harmful substances as those identified as marine pollutant by IMDG Code or any substance which meets the criteria laid down in appendix to annex III.

Packaged form means the forms of containment specified for harmful substances in the IMDG Code.

It further states carriage of substances is prohibited except in accordance with the provisions of this annex. And ask to treat the empty packages used for carriage of harmful substances themselves as harmful substances unless adequate precautions have been taken to ensure that they contain no residue that is harmful to the marine environment. Further states that the provisions of this annex do not apply to ship’s stores.

2. Packing

Regulation 2 requires the packages to be adequate to minimize the hazard to the marine environment.

3. Marking and labelling

Regulation 3 requires the packages to be marked with correct technical names and marked or labelled to identify the substance is a marine pollutant. Trade names alone shall not be used. The regulation requires the durability of marking to be such that it survives minimum three months immersion in sea.

4. Documentation

Documentation of harmful substances shall contain correct technical names and the words “MARINE POLLUTANT”. Each ship carrying harmful substances shall carry a special list of manifest identifying the goods and its stowage locations thereof. This list must be revised at any port where loading and or discharging of harmful substances takes place.

5. Stowage

Harmful substances are to be stowed on board vessels in such a way to minimize the hazard to the marine environment without jeopardizing safety of the persons on board or ship.

6. Quantity limitations

Certain harmful substances may need to be prohibited for carriage or limited by quantity which may be carried aboard any one ship. In limiting the quantity consideration shall be given to size, construction and equipment of the ship, as well as the packaging and the inherent nature of the substances.

7. Exceptions

Jettisoning of harmful substances are prohibited except when it is needed to secure the safety of life on board vessels or for securing the safety of the vessel.

8. Port State control on operational requirements

Toxicity – Transport Classification

Paracelsus, knows as father of toxicology wrote, “All things are poison, and nothing is without poison; only the dose permits something not to be poisonous.”

Paracelsus (born Philippus Aureolus Theophrastus Bombastus von Hohenheim, 11 November or 17 December 1493 – 24 September 1541)

Poisoning can be caused by Chemical toxicants, Biological toxicants and Physical toxicants. Poisoning can effect the entire organism, specific organs or cells. The routes through which poison enter the body are oral, dermal or by inhalation.

As said by Paracelsus a specific dosage or above is required to cause poisoning. This dosage is measured in LD⁵⁰ value for dermal and oral toxicity and LC⁵⁰ value for inhalation toxicity.

Let’s understand the basic concepts of LD⁵⁰ and LC⁵⁰ values.

LD⁵⁰ = Lethal Dosage. Dosage required to kill 50 percent of the test animals, dosage, measured in mg/kg body weight.

LC⁵⁰ = Lethal concentration. Dosage required to kill 50 percent of test animals, dosage measured in mg/per liter of volume of air.

Some examples

Placard for Toxic Substances (Photo credit: Wikipedia)

IMDG Code

The word “toxic” has the same meaning as “poisonous” in IMDG Code. Toxic substances, liquids and solids, are classified under Class 6.1 and toxic gases under Class 2.3.

Definitions and properties according to IMDG Code

LD50 (median lethal dose) for acute oral toxicity is the statistically derived single dose of a substance that can be expected to cause death within 14 days in 50 per cent of young adult albino rats when administered by the oral route. The LD50 value is expressed in terms of mass of test substance per mass of test animal (mg/kg).

LD50 for acute dermal toxicity is that dose of the substance which, administered by continuous contact for 24 hours with the bare skin of the albino rabbit, is most likely to cause death within 14 days in one half of the animals tested. The number of animals tested shall be sufficient to give a statistically significant result and be in conformity with good pharmacological practices. The result is expressed in milligrams per kilogram body mass.

LC50 for acute toxicity on inhalation is that concentration of vapour, mist or dust which, administered by continuous inhalation to both male and female young adult albino rats for one hour, is most likely to cause death within 14 days in one half of the animals tested. A solid substance shall be tested if at least 10% (by mass) of its total mass is likely to be dust in the respirable range, such as the aerodynamic diameter of that particle fraction is 10 microns or less. A liquid substance shall be tested if a mist is likely to be generated in a leakage of the transport containment. For both solid and liquid substances, more than 90% (by mass) of a specimen prepared for inhalation toxicity testing shall be in the respirable range as defined above. The result is expressed in milligrams per litre of air for dusts and mists or in millilitres per cubic metre of air (parts per million) for vapours.

Class 6.1, Toxic substances for packing purposes been assigned with packing groups according to the degree of their toxic hazards in transport.

Packing group I: substances and preparations presenting a high toxicity risk;

Packing group II: substances and preparations presenting a medium toxicity risk;

Packing group III: substances and preparations presenting a low toxicity risk.

BETSY, LAURA & PESTICIDES

Laura’s garden is infested with insects and she kept wondering why her next door neighbor Betsy’s garden is not having this problem.

One day morning while going out Laura meets Betsy hurrying to catch her regular bus.

Laura: Good Morning!

Betsy: Good Morning Laura!

Laura: Betsy! My garden is full of insects, dear; tell me which insecticide I should use. I can see your garden blooming.

Betsy: “Just go to any shop which sells gardening stuff and ask for 2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolyl methyl carbonate”

And off goes Betsy her way. What did she say? Two times ethyl and six times dimethyl?

Chemical names of pesticides are not short and are very complex to remember. In order to simplify ISO has issued common names for pesticides. These names can be used in scientific publications as well throughout the industry.

Now let’s hear what Betsy said again

Betsy: “Just go to any shop which sells gardening stuff and ask for flometoquin”

Easier to remember what she said? This is the reason for ISO common names.

ISO common name for for 2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolyl methyl carbonate is flometoquin.

IMDG Code –

For package marking and documentation purpose which ever Dangerous Goods entry in IMDG Code assigned with special provision 274 must have a technical or chemical group name.

The technical name shall be a recognized chemical or biological name, (for those assigned with special provision 318), or other name currently used in scientific and technical handbooks, journals and texts.

In the case of pesticides, only ISO common name(s), other name(s) in the WHO Recommended Classification of Pesticides by Hazard and Guidelines to Classification, or the name(s) of the active substance(s) may be used.

Trade names must not be used for this purpose.

If interested you may download WHO publication here

One of the best internet site which lists out pesticide common names is http://www.alanwood.net/pesticides/

Valentines, Roses and Pesticides

TRANSPORT OF WASTES

For sea transport wastes which are dangerous goods must be transported in accordance with the provisions of IMDG Code

Transboundary movement of waste is governed by “Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their Disposal (1989)”.

Before commencement of movement of waste from one country to another, competent authority of the origin country must sent notification to competent authority of country of destination. All parties involved, origin, destination and transit countries, shall approve the movement.

Together with dangerous goods declaration a waste movement document must also accompany the consignment.

Wastes which are not dangerous goods according to IMDG Code but covered under the Basel Convention may be transported under the class 9 entries for ENVIRONMENTALLY

HAZARDOUS SUBSTANCE, LIQUID, N.O.S., UN 3082, or ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S., UN 3077.

BASEL MOVEMENT DOCUMENT

Carbon or Charcoal

A bottle of 50gms activated charcoal with 180g... — Image via Wikipedia

Purest form of carbon is diamond….

Carbon is the 15th most abundant element in the Earth’s crust and the fourth most abundant element in the universe by mass.

All known form of life has carbon.

Charcoal is the dark grey residue consisting of impure carbon obtained by removing water and other volatile constituents from animal and vegetation substances.

Charcoal is usually produced by slow pyrolysis, the heating of wood or other substances in the absence of oxygen. The resulting soft, brittle, lightweight, black, porous material resembles coal.

http://en.wikipedia.org/wiki/Charcoal

Activated carbon is a form of carbon that has been processed to make it extremely porous and thus to have a very large surface area available for adsorption or chemical reactions.

Activation/Oxidation: Raw material or carbonized material is exposed to oxidizing atmospheres (carbon monoxide, oxygen, or steam) at temperatures above 250 °C, usually in the temperature range of 600–1200 °C.

Chemical activation: Prior to carbonization, the raw material is impregnated with certain chemicals. The chemical is typically an acid, strong base, or a salt (phosphoric acid, potassium hydroxide, sodium hydroxide, zinc chloride, respectively).

http://en.wikipedia.org/wiki/Activated_carbon

Transport Regulations – Dangerous Goods

Listed in IMDG Code Index as below

Activated Carbon,	see – 4.2 1362
Activated Charcoal,	see – 4.2 1362
Non-activated Carbon,	see – 4.2 1361
Non-activated Charcoal,	see – 4.2 1361
CARBON, ACTIVATED	– 4.2 1362
CARBON animal origin	– 4.2 1361
CARBON vegetable origin	– 4.2 1361

Highlighted in BOLD are the assigned proper shipping names for Charcoal or Carbon vegetable or animal origin

Assigned to Division 4.2 – Spontaneous Combustion.

Self-heating substances, which are substances, which, in contact with air without energy supply, are liable to self-heating. These substances will ignite only when in large amounts (kilograms) and after long periods of time (hours or days). If the rate of heat production exceeds the rate of heat loss, then the temperature of the substance will rise which, after an induction time, may lead to self-ignition and combustion.

A substance shall be classified as a self-heating substance of class 4.2 as per tests performed in accordance with the test method given in the United Nations Manual of Tests and Criteria, part III, 33.3.1.6

CARBON animal or vegetable origin – 4.2 1361

CARBON, ACTIVATED – 4.2 1362

1361 PG II & III / SP 925 and 223 for PG III

1362 PG III / SP 223 & 925

SP 925 states

The provisions of this Code do not apply to:

– non-activated carbon blacks of mineral origin;

– a consignment of carbon if it passes the tests for self-heating substances as reflected in the UN Manual of Tests and Criteria (see 33.3.1.3.3), and is accompanied by a certificate from a laboratory accredited by the competent authority, stating that the product to be loaded has been correctly sampled by trained staff from that laboratory and that the sample was correctly tested and has passed the test; and

– carbons made by a steam activation process.

When Charcoal/ Carbon is considered as non Hazardous?

a) Either it is non-activated carbon blacks of mineral origin; or

b) Passed the UN test as per SP 925; or

c) carbons made by a steam activation process

MSDS must contain either of the information in ‘a’ or ‘b’

Shipment must be supported/accompanied by test report in ‘b’

Shipping lines may have individual house rules with varying conditions for acceptance of hazardous and non-hazardous carbon.

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