CHEMICAL BALLAST WATER TREATMENT PROBLEMS

Captain Michael Lloyd, MNM, FNI, Mines Rescue Marine.

Michael Haraldsson, JOWA USA
The need to meet the new regulations on Ballast water treatment and the
associated significant expense is a serious concern to modern ship owners.
When evaluating ballast water treatment options a number of general factors
must be considered but without doubt, the monetary cost is the deciding factor
for the majority of ship owners, especially on ships already built that may have
to be retro-fitted with equipment.

Many methods now exist to choose from and more are likely to emerge in the
coming years. The common thread in most of these systems is their requirement
of expensive equipment and fitting as well as the space for the equipment.
Moreover questions remains regarding their effectiveness and impact on
operations.

The attractiveness of chemical treatments, especially on ships already built can

easily be understood.
Chemical Biocides.
These chemicals act by destroying cell membranes, which leads to cell death.
They come in two general types, oxidising and non- oxidising.
With the problems and expense of these various systems, there is evidence that
a considerable number of owners are turning to chemical treatment. These
biocides are supplied in either liquid or solid form and can easily be stored on
board a ship and as they have been widely used ashore, the chemical data sheets
for the biocides are easily available and well understood. The machinery
required for applying these chemical biocides is reliable and needs little
maintenance with the only problem being the size of some of the plants.
It is important to note however that the reactions between biocides and
sea water that could produce harmful by products have not been extensively
studied. More importantly, there is definite concern now being expressed
regarding the release of gases in enclosed and confined spaces, by these agents,
especially the oxidising agents of ozone and chlorine.

Ozone
Ozone is an oxidizing biocide that has been used to disinfect water supplies
ashore for over one hundred years. It is the major component of smog and is a
harmful pollutant. It is also often used as a biocide in water. Ozone is inherently
unstable and dangerous to produce, but it is a very powerful oxidizing agent.

The system works by passing water through machinery that releases ozone
bubbles into the water. The gas then dissolves in the water and reacts with other
chemicals in the water to kill the organisms. As not all the gas dissolves in the
water this must be destroyed before it enters the atmosphere, as it is toxic to
humans. Further, reaction between the ozone and the components of sea water
may also result in toxic chemicals.

Due to the strongly oxidizing properties of ozone, ozone is a primary irritant,

affecting especially the eyes and respiratory systems and can be hazardous at
even low concentrations. The Canadian Centre for Occupation Safety and
Health reports that:

"Even very low concentrations of ozone can be harmful to the upper respiratory
tract and the lungs. The severity of injury depends on both by the concentration
of ozone and the duration of exposure. Severe and permanent lung injury or
death could result from even a very short-term exposure to relatively low
concentrations."

To protect workers potentially exposed to ozone, U.S. Occupational Safety and

Health Administration has established a permissible exposure limit (PEL) of 0.1
µmol/mol (29 CFR 1910.1000 table Z-1), calculated as an 8 hour time weighted
average. Higher concentrations are especially hazardous.

Work environments where ozone is used or where it is likely to be produced

should have adequate ventilation and it is prudent to have a monitor for ozone
that will alarm if the concentration exceeds the OSHA PEL.

It must also be mentioned that when Ozone is used, if the treated ballast water is
pumped out in fresh water, the ozone will remain active for up to 30 minutes,
thus having the potential to harm sealife in the area.

Chlorine

Chlorine for ballast water treatment is generated on the ship, from seawater. |It
is commonly used to treat drinking water and has been used for such treatment
for many years at sea, but recent studies suggest that it may not be as safe to
humans as once thought. There is also a possibility that Chlorine may react with
sea water to form toxic chemicals.
Chlorine is a greenish-yellow gas, which combines with nearly all elements. It
is a respiratory irritant to the mucous membranes and lungs and causes cancer.
Chlorinated liquids burn the skin and many fabrics. As little as 3.5 ppm can be
detected as an odour. 1000 ppm is likely to be fatal after a few breaths.
Most harmful chlorine exposures are the result of inhalation. Health effects
typically begin within seconds to minutes. Following chlorine exposure, the
most common symptoms are:
Airway irritation
Wheezing
Difficulty breathing
Sore throat
Cough
Chest tightness
Eye irritation
Skin irritation
The severity of health effects depends upon the route of exposure, the dose and
the duration of exposure to chlorine. Breathing high levels of chlorine causes
fluid build-up in the lungs, a condition known as pulmonary edema. The
development of pulmonary edema may be delayed for several hours after
exposure to chlorine. Contact with compressed liquid chlorine may cause
frostbite of the skin and eyes. There is no antidote for chlorine poisoning, but
chlorine's effects are treatable, and most people recover. People who experience
serious health effects (such as severe eye or airway irritation, severe coughing,
difficulty breathing, pulmonary edema) may need hospital care.
Chlorine can be detected by its odour below the permissible limit; however,
because of olfactory fatigue odour may not always provide adequate warning of
the harmful concentrations of this substance.

The recommended exposure rates for chlorine gas are;

TIME-WEIGHTED AVERAGE (TLV-TWA): 0.5 ppm - Carcinogenicity

Designation A4

SHORT-TERM EXPOSURE LIMIT (TLV-STEL): 1 ppm - Carcinogenicity

Designation A4
Most chlorination systems are applying a dose in the region of 2 mg/l residual
chlorine, which has proven to be effective.

Unfortunately, some Ballast water solutions are using Sodium Hypochlorite

with a concentration of up to 10 ppm, which can leave a potentially dangerous
the gas residue in the tanks after the water is pumped out. Not only that, but the
water pumped out with this level of chemical can be harmful to sea life in the
local area. This contamination can also occur when a ballast tank or ballast hold
is overflowed. Using a ballast pump that can pump 2,000 tons per hour, the
overflow rate will be over 33,000 litres per minute.

According to the International Convention for the Control and Management of

Ships' Ballast Water and Sediments, regulation D2, vessels are prohibited from
pumping out ballast water still containing an active substance and in November
2011, the US environmental protection agency proposed a vessel general permit
for discharges incidental to the normal operation of vessels permit that, for the
first time would include numeric discharge limits of active ingredients for most
vessels.

These limits are as follows;

Table: Maximum Ballast Water Effluent Limits for Residual Biocides

Biocide or Residual Limit

(instantaneous maximum)

Chlorine Dioxide 200 µg/l

Chlorine (expressed as Total Residual Oxidizers (TRO as 100 µg/l

TRC))

Ozone (expressed as Total Residual Oxidizers (TRO as TRC)) 100 µg/l

Peracetic Acid 500 µg/l

Hydrogen Peroxide (for systems using Peracetic Acid) 1,000 µg/l

Mud and Sediment gas bubble morphology in sediments

In 2005, a micro computed tomographic evaluation completed by a US Navy

department showed the feasibility of gas bubble formation in sediment and mud
using examples of bay mud.
Even with a forced ventilation system, gas contained in mud may not be entirely
released and this is dependent upon the gas composition, mud volume, rheology
and ambient temperature.

In other circumstances, a quantity of gas may remain in stable solution in the

mud and not be released until changes in the mud chemistry, temperature or
other conditions.

This could give rise to a situation where a ship with a depth of mud in a tank
could assume that the tank is clear of gas. Then when the tank has been closed
for some time, the gas could be released from the mud and now become a
potential danger to crew entering the tank later.

Conclusions
As ships may at times fill a ballast tank by overflowing the tank or ballast hold,
if the ballast water is treated with these chemicals there will be spillage into the
harbour or sea. As all bulk carriers are required by IMO to have a water ingress
alarm in the holds, if a Level Gauging system was fitted this would show the
water level in the coaming area and thus would prevent the overflow. If the
water ingress alarm system had a continuous level sensor that measured up to
the coaming area, it would be easy to add an additional high level alarm. Ideally
a fixed level gauging system that can be maintained from the tank top should be
selected, as this would eliminate the need to enter the tank.
Both Chlorine and zone are heavier than air gases and this means that any
ballast tank or hold that has been treated with these chemicals should be uprated
in the ship enclosed space management plans to dangerous until they are
completely ventilated and tested. Natural ventilation will be inadequate for
these spaces and forced ventilation that reaches to the bottom of these tanks will
be necessary for complete ventilation.
No one should enter tanks that have contained chlorine or ozone treated ballast
water until the tanks can be verified as being clear of the gases. This could be
problematic for vessels that need to have tanks surveyed or examined in the port
of discharge and without adequate forced ventilation equipment, delays could
be experienced.
All ships that use chlorine or ozone treatments should carry ozone and chlorine
gas detectors.
Where vessels are using ozone or chlorine ballast water treatment, mud or
sediment build up must be avoided and the bottoms of ballast tanks should be
water blasted periodically to clear the mud or sediment from the bottom.