L&I Maritime Services FZC

Wall Wash Sampling & Analysis Procedures.

Contents.

1. Introduction.

2. Visual Inspection of Tanks.

3. Wall Wash Equipment List.

4. Wall Wash Sampling.

5. Analysis, Sample Appearance.

6. Analysis, Sample Odour.

7. Analysis for Hydrocarbon.

8. Analysis for Colour.

9. Analysis for Permanganate Fade Time.

10. Analysis for Chloride.

11. Analysis for Acid Wash Colour.

12. Laboratory Organization and Maintenance.

13. L&I Lightwave 11 UV/Vis Spectrophotometer.

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1. Introduction.

Whilst the chemical analysis on a wall wash sample, performed correctly (in
accordance with ASTM test methods) will accurately define a result which can be
both repeated and/or reproduced, the same can not be said for the process of
wall wash sampling.

Wall wash samples can and will differ between two separate samples taken
independently, from the same tank. Therefore, results can be different. One
sample may pass, the other fail.

The reason for this is more clearly understood when a surveyor/crew member,
takes samples from areas blind to the full effect of the tank cleaning machines
or perhaps from sloping bulkheads, as opposed to samples taken from areas
where the cleaning machines have direct action to the bulkheads.

At best, the process of wall wash sampling is random and only reflects the areas
where the samples are drawn from, normally the bottom 2.5meters of the tank
bulkheads. It is not representative of the condition of the whole tank.

When cleaning to Methanol (High Purity) Standard, we need to be as careful as

is possible, to ensure the results we obtain after cleaning, give the best account
of the condition of the tank, so we are not passing tanks that the loadport
inspector will fail on arrival. There are no guarantees on this, so care needs to be
taken when selecting the ‘spots’ we will sample from, to give us as good an
‘average’ of the condition of the bulkheads.

This document is aimed at giving some considerations and background, to help

you achieve the best possible ‘representative’ results on your wall wash sampling
and accurate analysis results.

It is also aimed at assisting the reporting process, so when you communicate

your results to the Ship Operator or Supercargoes, we can more accurately
understand the condition of the tanks and any problems you may be dealing
with.

For this reason, it is also important to follow the suggested ‘Wall Wash Sampling
Procedure (4) below, as this at least, standardizes the technique for all tanks.

2. Visual Inspection.

When preparing for ‘Methanol Standard’, there should be no visible evidence of

previous cargo, lose residue from cleaning materials or IG systems.

If previous cargo(es) were viscous, check machine blind areas, blind side of angle
brackets and under heating coils.

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Take a clean white rag and wipe surfaces, nothing should come off onto the rag.
No grease or any lose dust, rust spotting must be removed.

Tank surfaces and suction area to be completely dry.

The following pictures are perhaps an overstatement of visual surface matter,

but make the point. Tanks need further appropriate washing.

Rust stains on Zinc.

Washing with a Buffer
cleaner can be considered if
extensive. Rusting should
not be lose so it rubs off as

For Epoxy tanks, coatings should be sound. Lose or flaking surfaces should
also be made sound. In general, coating breakdown should not be greater than
2% of the total tank surface area.

Rust spots on
Epoxy coatings
should be sound
with no lose matter
or staining coming
off when wiped with
a clean rag.

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Odour, during the visual inspection can also be a problem. Tanks should not
retain the smell of previous cargo(es) or from washing chemicals.

And don’t forget the

lines!

3. Wall Wash Equipment List.

1.Clear Glass Sample Bottles. 500ml. Best to use new, chemically clean
bottles.
(If you are re-using bottles, make sure they have been carefully washed
with a final D.I. rinse followed by two flushes with Laboratory grade
Methanol).
2.Plastic Cut or Stainless Steel Funnel, Approx 10 - 14 cm Diameter.
3.Plastic Squeeze wash bottle with tube. 500ml.
4.Laboratory Grade Methanol. 500ml per tank.
5.Eye Protection glasses.
6.Latex / Nylex gloves.
7.Shoe covers.
8.Marker pen. (Preferably ‘paint marker’. Methanol will wash away labelling
from most permanent markers).
9.Portable Gas Detector. (Leave this at the bottom of the stairwell or in your
back pocket. It will give an alarm from the methanol vapours if you have it
on your top pocket).

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Keep all
items as
clean as

4. Wall Wash Sampling Procedure.

It is very important to ensure all equipment used is visually and chemically

clean. All items should be washed in the laboratory prior use and again rinsed
with Lab grade methanol before use in each tank to ensure contamination from
one tank does not carry over to the next. Also be careful not to spoil the sample
by picking up contamination from your hands, clothes or sweat from your
brow!

Don’t touch or lean against bulkheads – loadport surveyor may take a

sample from that area!
Do not wall wash tanks that are wet. Water or moisture will affect the ability of
the methanol solvent to absorb contaminants from the coating and may also
give misleading chloride values. It is also best not to wall wash tanks when too
hot, as the methanol will evaporate quickly.

The basic procedure is to pass 500ml of pure Laboratory Grade

Methanol from the plastic squeeze wash bottle over 1 square meter of
the tank bulkhead. The sample is collected via the cut-off funnel to the
sample bottle. Aim to get 50 to 60% recovery of the 500ml, so you will have
around 250ml to 300ml sample quantity for the various tests.

The aim is to finish with a sample that represents the chemical condition of
the whole tank. However, in practice it is only (normally) taken from random
spots on the lower 2.5 meters of the bulkheads. This ‘random choice’ means
that no two samples will be exactly the same and it is quite possible for one
sample to pass the tests, whilst another can fail. And of course, upper tank
levels are not represented.

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Suggested Standard Practice.

Take a total of 8 spots
(samplings) from each tank. Two
spots (samples) from each
bulkhead. Spray the wall wash
medium - usually Methanol - to
allow it to stream approximately
1 meter down the bulkhead, and
collect using the cut wall wash
funnel, to the sample bottle.

Added together, these will give

you an area of approximately 1
square meter sampled. Chose
areas that will help represent
some good and some of the worst
(blind spots) of the bulkheads. It
is better we know the worst,
rather than the inspectors.

If you know of any specific

areas where you expect
problems, take a separate
sample of just that spot,
(machine blind area or upper
tank level) to test separately.
At the top of the tank, put on

the shoe covers.

At the bottom of the tank, put

on the protective gloves.

Transfer the pure methanol to

 the wash bottle.
Rinse the wall wash funnel

with pure methanol.

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With the flat side of the wall wash

funnel against the bulkhead, spray
the methanol up in straight line, to
collect in the sample bottle, via the
w/wash funnel.

Observe the methanol as it flows

down the bulkhead surface. If oil is
present or perhaps a film of Veg Oil
remains, you may observe small
ripples. Watch the area washed as
the methanol evaporates. If you
observe brown ‘burn marks’ to the
edges, it can indicate the presence
of Non volatile matter (NVM), which
can lead to failure on Hydrocarbon
and/or PFT.

Visible
signs that
the wall
wash
methanol
has
extracted
surface
contaminan
ts. Edge of
wall wash
area ‘burn
marks’.
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Rinse the sample bottle cap with clean methanol and close securely. Mark the
bottle with the relevant tank number. Good sample identification is important.
Be aware that most marker inks will dissolve in methanol.

Analysis Procedures.

It is very important to have a designated laboratory area, preferably a dedicated

laboratory space, to perform your analysis. The location should have a good
supply of fresh water (sink), good ventilation and air conditioning. Safety
equipment such as latex gloves and eye glasses should be worn. A fire
extinguisher should be near-by.

As with the wall wash sampling procedures, cleanliness is vital. If a sample is

contaminated for reasons other than bulkhead condition, a test may fail and
the tank will be un-necessarily re-washed. Ensure all test tubes and equipment
are clean. Don’t assume because they look clean, they will not contaminate
your sample. Before using any glassware, give them one or two flushes with Lab
Grade Methanol. A well organized and maintained laboratory space greatly
assists to ensure results are correctly determined and reported.

Newly delivered supplies of Laboratory solvents should be in sealed containers

and checked for purity before use. Laboratory Grade Methanol should be in
sealed 2.5 litre amber glass bottles. Laboratory Grade D.I. water should also be
in sealed bottles, plastic containers for DI are okay.
Laboratory reagents should be clearly labelled and indicate an expiry date (or at
least delivery date).
Results from each test should be recorded immediately. Work in an organized
and logical manner.

5. Analysis – Sample Appearance.

Equipment Required
1.Sample bottle of pure methanol – for comparison as blank.
2.Tank wall wash samples.

Procedure.

Compare each tank wall wash sample with a blank sample of pure methanol.

Reporting – Sample Appearance.

The individual wall wash samples should have the same clear and bright
appearance as the pure methanol.
Note any sediment in the bottom of the bottle and report.
Note any matter still suspended in the sample (fibres etc) and report.

For a sample to pass on appearance it should be ‘clear and bright’ and be

substantially free from ‘sediments’ and/or ‘suspended matter’.

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1 2 3 4
Sample 1. Blank Laboratory Grade
Methanol. Will be ‘Clear & Bright’
and without any ‘Suspended
Matter’ or ‘Particles/Sediments’.
Sample equivalent is ‘Pass’
Sample 2. ‘Clear & Bright’ with
some very slight ‘Suspended
Matter’ and Particles that settle out
to the bottom of the bottle. This
sample should be acceptable.
Sample is ‘Borderline’.
Sample 3. ‘Clear & Bright’ with
more obvious ‘Sediment’ which
settles out to the bottom of the
bottle. This sample would fail the
appearance test. Sample is ‘Fail’.
(Tank may need spot sweeping or
flushing with D.I water to remove).
Sample 4. ‘Clear & Bright’ with
heavy ‘Sediment’ settling out to the
bottom of the bottle. This sample
fails the appearance test. Sample is
‘Fail’. (Tank will likely need flushing
with D.I. water to remove).
Sample 5. ‘Hazy’ appearance, with
(or without) ‘Sediment’ and
‘Suspended Matter’. Sample fails
the appearance test. Sample is
‘Fail’. (Tank will likely need re-
washing).
Sample 6. Sample is coloured and
will therefore fail the test. This
comes into appearance of sample
based on the colour, which could
be the effect of a dye used in
previous cargo(es). (APHA colour is
based on a ‘yellow’ scale).

6. Analysis – Sample Odour.

In section 2. Visual Inspection, it
was noted that on entering the
tank, any noticeable odour should
be reported. This can be
particularly relevant where a cargo
like Styrene Monomer was the last
cargo. Such odour should be
removed.

For the wall wash samples, there is

a test for ‘Odour of Volatile
Solvents and Diluents’ ASTM D
1296.

This test looks for ‘Characteristic or

Non-characteristic’ odour. ‘Non
Residual or Residual’ odour.

Any solvent used for wall wash

sampling, normally methanol, is a
hazardous, toxic substance so it is
inadvisable to inhale. The test
method is based on immersing
strips of absorbent paper into the
Laboratory Grade methanol and

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wall wash samples; and in a well ventilated space, making a comparison to

detect any difference in odour.

Most ships will have a box of ‘filter paper’ (circles) on board, which can be used.
(Make sure they are clean and odour free before use. These can be cut into
strips of around 25mm x 75mm.

For Characteristic or Non-characteristic test.

Immerse a strip of absorbent paper into the blank Lab Grade Methanol to
around 50mm. Whilst the paper is still wet, compare the odour with a strip that
has been immersed into your wall wash sample.

If the odour is the same, Report the Odour result as ‘Characteristic’. (MCO –
Methanol Characteristic Odour). If you detect a difference in the odour, report
the result as Non-characteristic. (NC – Non-Characteristic).
For Non Residual or Residual’ odour, allow the absorbent paper to dry. The
Laboratory Grade Methanol should not have any residual odour, and would be
reported as Non-Residual. Compare this with the wall wash sample. If you detect
a lingering odour, this would be reported as ‘Residual’.

7. Analysis – Water Miscibility / Hydrocarbon.

This test serves to determine water immiscible contaminants in the wall wash
sample. The level of detection will vary widely dependent on the solvent used for
wall wash and the type of impurity. However, the test is qualitative, not
quantitative. Results are either ‘Pass’ or ‘Fail’.

Methanol is soluble in water. When a wall wash sample is mixed with water, any
contaminant which is soluble in the methanol, but insoluble in water is forced
out of the methanol and shows up as haziness in the methanol-DI water
solution. The turbidity is actually composed of emulsified contaminants
scattered evenly throughout the solution and can be seen as a ‘blue-ish tinge’ or
opaque, milky turbidity.

Test for Hydrocarbon/Water Miscibility as defined by ASTM D 1722 states that

the sample dilution in D.I.Water is based on 10% sample to 90% D.I.Water
(25ml sample to 225ml D.I.) However, some loadports use differing dilutions.
This can be 25% sample to 75% D.I. Water or even 50% sample to 50%
D.I.Water. These differing dilutions will have an impact on results, so make
sure you know 'which' dilution level is used at the intended load-port.

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Equipment Required.

1. Graduated Glass Cylinders - 100ml (Avoid tubes with blue graduation

markings)
2. Laboratory grade methanol
3. Laboratory grade D.I. Water.

On board Procedure.

1. Using the Laboratory grade methanol, make up a 'blank' sample with 10ml
Laboratory grade methanol and 90ml Laboratory grade D.I. Water. (This
'blank' sample is used for comparison purposes against your individual tank
samples. It also proves your blank methanol is clear and free from
contaminants. If there is any haziness or turbidity in the blank sample –
same source methanol as used for wall wash, you will have to throw all away
and start again, as all samples will be contaminated!)
2. For individual tank samples, mix 10ml of wall wash sample with 90ml of
Laboratory grade D.I. Water.

Samples should be well mixed, invert the glass cylinders, mix with mild
agitation, leave for 20 minutes before reading the result.

Reporting.

Samples must be free of any haziness or turbidity. Compare with the blank
sample. If Hydrocarbon is present, you will see a blue-ish tinge if slight
Hydrocarbons to a milky haziness for heavier Hydrocarbons. The degree of
the haziness indicates the degree of contaminant that has been picked up by
the wall wash sampling. Some surveyors will use a torch beam to ‘highlight’
any turbidity in the sample. Place the tubes against a black surface in a
darkened room and pass a torch beam horizontally through the sample
tube. If the sample shows any cloudiness/turbidity compared to the blank,
the sample fails the test.

Also note if there is any foam on the surface. This can indicate that washing
chemicals have not been completely rinsed away.

Results are given as either 'Pass' or 'Fail'. There is no allowance for the degree of
failure.

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1 2 3 4

Pic 1. (Above)
Sample 1. Blank of 10/90 Lab MeOH & D.I. – Pass Result.
Sample 2. Result is equivalent of 20 FAU on Spectrometer. – Fail Result.
Sample 3. Result is equivalent of 50 FAU. – Fail Result.
Sample 4. Result is equivalent of 200 FAU.- Fail Result.
Sample 5. Result is greater than 200 FAU. – Fail Result.

Pic 2 (Left) Samples observed under

torch beam.
Sample 1. Blank of 10/90 Lab MeOH &
D.I.
Sample 2. 20 FAU on Spectrometer.
Note that even in the blank sample, a
1 beam is highlighted by torch-light.

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8. Analysis – Colour. Platinum Cobalt Scale ( Also referred to as

APHA Colour).

The Platinum Cobalt Scale Test describes the visual determination of

essentially light coloured liquids (yellow scale). For most accurate visual
determinations, you will need ‘long stem’ clear glass tubes and Platinum
Cobalt Colour standards. As you will note from the below Colour examples,
the colour variations between 0, 5, 10 and 20 on the Pt-Co scale is minimal.
For Methanol standard wall wash, it is usually required that the wall wash
sample is ‘less than 10’. In some cases, ‘less than 5’. If you do not have long
stem tubes, use 100ml tubes as substitute.

Equipment Required.

1. Long stem or 100 ml glass tube.

2. Colour standards. Pt-Co 20 / 15 / 10 / 5.
3. Laboratory Grade Methanol

Procedure.

1. Use tubes of the same length. Decant 100ml fixed mark with
Laboratory Grade methanol.
2. Take the appropriate colour standard into a glass tube to 100ml, or
same fixed mark on the tube.
3. Decant the same quantity of each wall wash sample into similar tubes
and fill to same level as the blank and the standard.

Reportin
g.
Looking down the length of each tube against a clean white background,
compare the blank sample against the required colour standard to confirm
your Lab Methanol is clear.

If you are working to a colour standard of max 10 Pt-Co, use the Pt-Co 10
standard and compare this with your wall wash samples. If they are lighter
than the standard, you can report the result as ‘less than Pt-Co 10’. If they
are darker, they do not meet the specification required. (You can also
report ‘greater than’ the particular standard – if you do not have the next
required colour standard).

Note. In event no colour standard or Spectrometer is available, compare the

tank sample with the blank, pure methanol. For Pt-Co 5 or 10, you should
not see any visible discolouration. If you do, the colour will probably be
higher than Pt-Co 10. The Pt-Co scale is based on a yellow colouring, so if
you can

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see a yellow tinge in your wall wash sample, this will likely not meet Pt-Co
10. Of course, any other noticeable colour will also fail the test.

Blank Pt-Co ‘0’ Pt-Co ‘5’ Pt-Co ‘10’ Pt-Co ‘15’ Pt-Co ‘20

9. Analysis – Permanganate Fade Time.

This test is a non quantitative, non specific analysis for oxidizable

contaminants found in the wall wash sample. These can be from previous
cargoes or even traces of detergents used in the tank washing process.

The chemical principle behind this test is the colour change permanganate
undergoes as it oxidizes contaminants. Permanganate is purple in solution and
as it is consumed in the oxidation process, it is transformed into brown
Manganese dioxide. Where the contaminant is acid, the purple permanganate is
converted to colourless Manganese ions. The rate of the reaction is dependent
on the amount of contaminants: the more contaminants in the sample, the
faster the colour change.

It is also important to keep the required temperature of 15˚C constant

throughout the analysis as the rate of reaction is also dependent on
temperature: the higher the temperature, the faster the colour change. Light
also speeds up the reaction, hence it is important to do PFT in dark conditions.

Equipment Required for onboard testing.

1. Laboratory grade Methanol

2. Nessler Tubes or Glass Cylinders with glass stopper.
3. Cool box with lid. (Igloo Box).
4. Potassium Permanganate KMNO4 solution. (Supplied in 0.1gram
ampoules.)
5. Thermometer to read 15 deg C
6. Cylinder rack for glass cylinders (as required)

Prepare the Cool box with Ice to maintain a 15 deg C temperature. Water
level to equal level of liquid in the test tubes.

Prepare the Potassium Permanganate KMNO4 solution by adding 0.1 gram

of KMNO4 crystals to 500ml of distilled water in an amber bottle. (Cover a
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clear glass bottle with silver foil), Keep in cool dark place when not in use -
fridge if possible.

Procedure.

1. Using the Laboratory grade methanol, add 50 ml to one cylinder as 'blank'

for comparison purposes.
2. From each wall wash sample, pour 50 ml of sample to a glass cylinder.
3. Place the samples in the cool box and leave for 10 minutes to achieve
temperature of 15C. (If using a Fridge, check the internal temperature is
stable for 15C. You may need to leave the samples a bit longer to bring
the temperature down to 15C).
4. To each sample, using a clean pipette, add 2ml of the Potassium
permanganate solution, invert to mix and place back in the cool bath/fridge.
5. Place the lid on the cool box to maintain darkness and note the time.

Reporting.

Check the samples every 10 minutes. For most Methanol loadings, the
samples should maintain their 'Purple/Pink' colour for 60 minutes. (Some
loadports allow 50 minutes and for MEG, 30 minutes is the normal
specification. You should know the 'test time' specification for the applicable
cargo and load port).

Pure Laboratory Grade Methanol should maintain its Pink colour for well
over 60 minutes.

Having noted the time the Potassium Permanganate was added and placed
the samples in the cooler/darkness, after 10 minutes, check the colour of
each tank sample. Check the ‘blank’ sample (which should not have lost any
of its Purple/Pink colour). When checking the samples, also make a
temperature check to see the 15C (+/- 1C), is maintained.

Compare the tank samples with the blank sample. Colour should maintain
its 'pink' hue. If this colour degrades to an orange/brown/yellow, no pink
hue remains to the colour, the time should be taken.

Reporting will be based on the ten minute intervals. So if a sample has lost
its pink colour when you check the results after say 30 minutes, then the
time is reported as 'less than 30 minutes' (< 30). If the colour is still similar
to the blank, with a pink/purple colour then continue the test to the next 10
minute check time.

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Blank Sample is Sample Sampl

sample acceptabl is e fails
should e, some borderlin
maintain oxidizatio e/
Bright n has fail,
Purple/Pin occurred.
k
colour for
60-120

Samples Pass Borderline Samples Fail

In cases where the samples fade to a clear colourless solution before the
specification time, this is still a failure and can indicate that the contamination
is acid based, as below image.

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10. Testing for Inorganic

Chloride.

This test determines the level of

Chloride in the wall wash
sample, which will normally be
present from earlier seawater
washing. This can also come
from fresh water. Typically
seawater may have a chloride
content around 15,000 to
20,000 ppm. Normal
freshwater, around 300 to 500
ppm. Technical grade D.I water,
used for tank spraying, should
be below 0.5 ppm.

The chemical principle behind

this test is the formation of
insoluble silver chloride, when
any chloride from the wall wash
sample reacts with the silver
from the silver nitrate reagent.
This reaction can be seen as
turbidity after adding the
reagent. The level of turbidity
 indicates the level of chloride in
the sample.

The reaction is a 1:1 ratio. So, 1

part of chloride will react with
one part of silver. Silver nitrate
is sometimes supplied as 2% or
5% or in some cases 10%
concentration. A 2%
concentration is equivalent to
20,000 ppm of silver. If we use
5 drops of 2% concentration, we
have the ability to react with up
to approximately 200 ppm of
chloride. If we used a 5%
concentration, we would have
sufficient concentration from 5
drops, to react with up to 500
ppm chloride.

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As we are looking for chloride levels of less than 10 ppm, typically 2 ppm or
less, we do not need to use more than a 2% concentration. (We could even
use 1% and it would be quite sufficient to precipitate the expected chlorides
in a methanol wall wash sample).

Equipment.
Laboratory grade Methanol.
Graduated 50ml glass cylinders, with 25ml graduation.
Silver Nitrate 2% or 5%.
Nitric Acid 20%
*Or, (Acidified Silver Nitrate 2% or 5%)
Dropper Bottle or pipette.
Standard Chloride Solution. 10ppm

‘* Laboratory prepared reagent based on Nitric Acid 20% and Silver Nitrate
2%

Procedure.

Decant 25ml of Standard Chloride Solution, 10ppm to one graduated

cylinder.

Decant to one graduated cylinder, 25ml of Laboratory Grade Methanol, as

your blank comparison.

From tank wall wash samples, decant 25ml of sample to test tube.

Add 5 drops Nitric Acid 20% and 5 drops Silver Nitrate 2% (or 5%) to each of
the above samples. (If you have Acidified Silver Nitrate, you can just add 5
drops of this reagent.

Leave samples to develop for 15 minutes in a dark space.

Reporting Results.

In much the same way as you read the Hydrocarbon results, darken the
room and compare the blank sample against your Chloride Standard. The
blank should have no turbidity. Then compare your wall wash sample
against the Chloride standard.

Using a 10ppm standard, if your wall wash sample is less turbid, you will
report ‘less than 10ppm’. If more turbid, ‘greater than 10ppm’.

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0 0. 1 2 5 10
pp 2 pp pp pp pp

0 0. 1 2 5 10
pp 2 pp pp pp

Samples under torchlight show the turbidity intensified.

ppm

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0 0.
pp 2

11. Analysis for Acid Wash Colour of Aromatic Hydrocarbons.

Scope:
This method covers the determination of the acid wash color of benzene,
toluene, xylene, refined solvent naphtha and similar hydrocarbons. The
test is also used for detecting impurities in Methanol.

Definition:
Acid wash color: The color developed in the separated acid when a sample is
agitated with sulphuric acid under the conditions described in this method.

Apparatus:
Acid wash color standards, numbered 0 to 14.
Stoppered cylinders, 30 ml.
Sulphuric Acid 96%. (For High Flash solvent or Heavy Solvent Naphtha, use
Sulphuric Acid 78%. See below chart.)
Toluene (or Xylene) to be used as wall wash medium.

Procedure:

Fill a dry and clean 30 ml glass stoppered cylinder up to the 7 ml mark

with acid of the strength specified in Table 1 for the type of sample to be
tested.

Add sufficient sample to bring the total volume to the 28 ml mark.

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Insert the stopper, hold a finger over the stopper and give vigorous shakes
with a stroke of 10 to 25 cm, shaking for a total of 150 cycles over a period of
40 to 50 seconds, that is at a rate of 3 to 3,75 cycles per second.

Allow the cylinder to stand, protected from direct sunlight, for the period of
time shown in Table 1.

Without further delay invert the cylinder gently once or twice to obtain a
uniform color in the acid layer and compare the color of the acid layer with
those of the standards. Make the comparison against a white background or
at daylight.

Designate the color of the acid layer by the number of the nearest matching
standard and add to the number a plus or minus sign if the sample is
respectively darker or lighter than the standard color.
Note: Concentrated sulphuric acid will cause severe burns on contact with
the skin. When spilled, remove with plenty of water.

When performing the test, use clean plastic disposable gloves. Ensure the
test tube and top make an effective seal.

Table 1
Acid strengths and standing times
Sample Acid strengths Standing time
Group 1 Benzene, all ASTM grades 96% l5min
Toluene, all ASTM grades
Xylene, nitration grades
Xylene 5°
Xylne l0°

Group 2 Xylene industrial grade 96% 5min

Refined solvent naphta

Group 3 Hi-flash solvent 78% 5 min

Heavy solvent naphtha

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Acid Layer Colour Scale 0 to 4.

Acid Layer Colour Scale 5 to

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Acid Layer Colour Scale 10 to 14.

12. Laboratory Organization and Maintenance.

A dedicated laboratory space is

essential to ensure;

· Good
organization.
· Safety.
· Cleanliness.

The area should be cool, well

ventilated and provisioned.

Poor organization WILL lead to

unreliable analysis results and
incorrect reporting.

At best, you may only have to re-take

the wall wash. At worst, you can be
recleaning a tank that does not need

This WILL cost time &

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Good organization is very important when working in any laboratory. Clear

operational practices help ensure equipment is in good condition and properly
clean for use. Correct recording of results is absolutely essential. (You don’t
want to be re-cleaning the wrong tank!)

When you have finished your analysis, it is a golden rule to clean all your
equipment before putting it away; and just as important to ensure it is cleaned
before using on the next occasion.

Clean glassware frequently. You can use a solution of Peroxide 3% and

Hydrochloric Acid 2% Follow with freshwater rinsing, Deionised water rinse and
then Methanol flushing.

Glassware does stain over usage. You will see this particularly after tubes used
for PFT (Potassium Permanganate Fade Time) analysis. The tubes will show a
brown staining, which needs to be removed, as noted above.

Safe working practices come from good organization. Ensure the space is well
ventilated and cool.

Use latex gloves when handling chemicals and chemical resistant gloves when
handling acids. (Avoid the powdered type latex gloves).

Eye glasses should be worn and an eye wash bottle should be on hand.

A good supply of freshwater should be available.

A fire extinguisher should be within easy reach.

MSDS sheets should be available/posted, for any chemicals used.

Solvents and Reagents should be clearly labelled and securely stored in a cool,
dark and dry space. Ensure they are well sealed after use. Labels should
indicate an expiry date.

Make random tests on newly delivered stocks of Lab Grade Methanol and
D.I.Water, to ensure their integrity.

Record Results immediately and after each step. Keep a formatted results log so
you can compare results as the cleaning progresses.
Basic Equipment Requirements.

Glassware.

100 ml tubes will be required for the Hydrocarbon analysis. Best to avoid blue
graduation markings as these can lead to mis-interpretation when reading
results visually. Detachable plastic bases are good as they can be removed and
the tubes used in a rack.
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50 ml tubes are best for use in both Chloride and PFT analysis. Glass or plastic
stoppers are best as they are easier to keep clean.

100 ml ‘Long stem’ Glass cylinders are used for Colour determinations.

Sufficient quantity should be available for testing all tanks, per test. Saves
considerable time, especially when checking PFT. The test needs to run for one
hour, so best to check all necessary tanks in one batch.

· 100 ml Graduated Glass cylinders. (Avoid blue markings)

· 50 ml Graduated Glass cylinders with glass/plastic tops.
· 100 ml ‘Long Stem’ Glass cylinders.

General Equipment.

· Plastic 500 ml Squeeze bottles, with spray tube tops. (2 for wall washing,
2 for Lab use).
· Plastic or Stainless Steel wall wash funnels
· Dropper bottles – 30ml.
· Glass Pipettes, 2ml & 10 ml.
· Plastic Pipettes, 2ml disposable.
· Plastic disposable shoe covers.
· Latex disposable (unpowdered) gloves.
· Cool (Igloo) Box. (sufficient size to take rack of 50 ml tubes).
· Glass Cylinder racks. (Correct size for Glass 100 ml & 50 ml tubes).
· 500 ml clear glass sample bottles. (Sufficient stock for wall wash samples
from tanks.
· 500 ml amber glass sample bottles. (For mixing of Potassium
Permanganate solution.
· Mag-light type torch.

Solvents and Reagents.

· Laboratory Grade Methanol. (Avoid supplies in plastic bottles, always test

on receipt of new order).
· Laboratory Grade D.I. water. (Test on receipt of new order).
· Acidified Silver Nitrate 2% OR
Silver Nitrate 2% or 5%
Nitric Acid 20%
· Potassium Permanganate Crystals 0.1 gram. (Mix with 500 ml D.I. water).
· Hydrochloric Acid.

Standard Solutions.
Standard Chloride Solutions. Usually 10 ppm and 2 ppm.

Standard Colour Solutions. APHA 20, APHA 10 and APHA 5

Standard PFT Solution.

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New deliveries of Methanol and D.I. Water supplies should be randomly checked
for purity.
Supplies of reagents should be properly labelled and show an expiry date.

The above list is not exhaustive, but will allow you to perform all basic and
usual testing for Methanol Standard analysis.
L&I Wave 11 UV/Vis Spectrophotometer.

Testing within the Visible Range.

Using the L&I Wave 11 Spectrometer, has distinct advantages for reporting of
your wall wash analysis results. For the normal wall wash analysis tests, the
scaled results given by the Spectrometer are definitive and allow you to see the
improvement (or lack of improvement), as your tank washing progresses.

Tank wall wash sampling and analysis is performed in the same way as
described above. However, the Spectrometer very accurately reads the sample
giving you a scaled result.

For wall wash analysis, this is extremely important. Load port surveyors will
normally take their samples to a shore lab where results are determined using
specialized equipment. The analysis is performed by a chemist in laboratory
conditions. They are ethically bound to report the result they find. Where you
have a Chloride maximum specification of 2 ppm, if they find 2.1 ppm, you
technically fail the test. Where a colour specification is maximum APHA 5 and
they find APHA 6, again you fail.

Visually you really can not tell the difference in either case. Most Masters, Chief
Officers, will clean to well below these standards to be sure of passing. This is
expensive and possibly un-necessary.

Using the Spectrometer also puts you in a better position to ‘know exactly’ the
condition of your tanks not only before tendering your NOR, but during the
washing process.

This knowledge allows you to better amend your cleaning plan so it is

appropriate for the required load-port specifications and not leading to over-
clean tanks.

Ultra Violet (UV) Testing.

Perhaps even more important is the UV capability of the Spectrometer. Wall

wash samples can now be tested for trace contaminants that are not detected in
the normal wall wash analysis, but may still contaminate a sensitive cargo.

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Tank Coatings.

· Stainless Steel. In good condition, generally accepted as being the

easiest to clean.
· Inorganic Zinc paint. Absorbs oil based cargoes, waxes, heavier CPP
grades, and as these cargoes are viscous, will be retained in the matrix of
the coating. They also absorb ‘smaller molecule’ solvent cargoes, but due
to the open matrix of the coating, these are not retained.
· Organic coatings. Unlike Inorganic coatings, do not absorb oil based,
waxy heavier CPP grades, but are more likely to absorb and retain the
‘smaller molecule’ solvent cargoes that can penetrate the coatings and
actually retain them in the structure of the coating.

· Organic coatings are made from extenders, pigments, fillers all held
together in organic solvents (hence the name), typically higher alcohols
and aromatics.
· As such, there is an inherent attraction between the coatings and all
organic cargoes ... a massive amount of cargoes.

· Experience tell us which cargoes are most absorbed (and retained) and
these are what create the greatest tank cleaning challenges, because
there are really only two ways of removing cargo residues once they have
been absorbed.
i.) Heat.
ii.)Transmission into another cargo.
· However - If the retained residues are transmitted into a cargo that is
sensitive, it may become contaminated.

Looking at Organic coatings, it is their ability to retain these lighter grades that
makes cleaning for later high grade or sensitive cargoes a significant problem.

The most common “nasties” that are absorbed into organic coatings are:

· Styrene Monomer
· Methanol / Ethanol
· EDC / MEC
· VAM
· Acrylates in general

Residues of these cargoes can be retained in the coating for months until they
are completely desorbed.

We also, can not rely on the pre-loading wall wash tests, to confirm the coatings
are free from trace contaminants that will cause a sensitive cargo to be found
‘off-Spec’ at the next disport.

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Remember the contact time of the methanol during wall wash is minimal. The
contact time for the cargo will be days or weeks.

UV Graph Display.

Different chemical cargoes produce different UV traces, just like a finger-print.

These finger prints always occur in the same place on the UV graph, with the
variation in peak size being directly related to the concentration of the chemical
cargo. Some examples are as follows:

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By accurately monitoring the

presence of the previous cargo in a
wall wash sample allows far greater
control of cleaning processes,
which allows for optimisation of all
tank cleaning procedures.

During Tank Washing.

The below graph, illustrates the

‘read-out’ on a series of Wall wash
samples taken during tank
washing from last cargo ‘Styrene
Monomer’

The smooth ‘blue’ curve is the UV

read-out for Pure, Lab Grade
Methanol. The remaining read-outs
illustrate ‘peaks’, consistent with
levels of contamination of the
sample from Styrene Monomer.

The tanks had received initial pre-

washes with the 1st wall wash taken
(18/09/11), prior to making a hot
wash.

You will note that on the 2nd wall

wash (20/09/11), the graph shows
the sample has picked up an
increased level of contamination.
This is likely due to the hot wash
opening the coatings, allowing the
methanol to more easily penetrate
and absorb a higher level of the
Styrene.
Further solvent washing proceeded
to assist desorption of the Styrene
over a 2 week period, with some
impact. However, significant
content of Styrene was still being
picked up by the wall wash
methanol after this time. Probably
sufficient to render a sensitive
following cargo to be found ‘off-
Spec’ on UV Transmittance.

It is also important to note, that all

parameters of the wall wash tests,
including PFT, passed on normal
Ethylene Glycol load port
requirements.

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The UV Spectrometer, in addition to being able to detect trace elements which

may contaminate a following cargo, gives a clear indication on progress over the
tank washing period.

We can see whether our tank cleaning plan is working and amend as necessary
to optimize efficiency.

You might have noted in the above graph, the line display is not the same as the
earlier graph examples given for Styrene Monomer, Phenol and Acrylonitrile.

The example graphs for Styrene Monomer, Phenol and Acrylonitrile are based on
a flat line graph.

The above graph showing the improvement over the cleaning time, is based on a
curve graph.

The curve graph is useful to us because we can use this procedure to show what
the pure methanol looks like. A smooth curve (Pure Methanol/Dark blue line).
This is our blank sample to compare with the wall wash samples. We actually
want our wall wash samples to look the same, just as we make a blank sample
for Chloride, Hydrocarbon and PFT testing. We use the bank as a reference ‘for
the perfect result’. If it doesn’t appear the same, we know there is some
contamination in the wall wash sample, just as in the Chloride sample being
more turbid than the blank, we know there is contamination. The UV helps us to
find out what this can be.

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L&I LIGHTWAVE 11 – Spectrophotometer.

The spectrophotometer is a simple-to-use UV/Visible

instrument with a CDD array detector (1024 pixels). It

has no moving parts, which is the basis of the rapid

scanning operating system.

The user interface is built around folders which are

displayed on the home page when the instrument is

switched on. After switch on and calibration, the

default home page is ‘Lightwave 11’ offering a choice of

menus.

The L&I menu offers the choice of programs for determination of results for;

Chloride in Methanol (0.2 to 20.0 ppm by weight).

Chloride in Water (0.2 to 10.0 ppm by weight).
Permanganate Time Test. (Pass of fail in line with
ASTM D 1363).
APHA Colour. (APHA 5 to 500 in line with ASTM D
1209 on the Platinum – Cobalt Scale).
Hydrocarbons. (Pass or Fail in line with ASTM D
1722).

The instrument is supplied with a program PVC (Print via Computer) on the
accompanying CD. When used with a USB cable to connect to a PC onto which the
software has been installed, it enables the user to ‘print through’ the PC directly to the
connected printer. Files may also be saved to PC for storage or email transmission.

The unit is supplied with full user manual and L&I instructions for test procedures. On
request, L&I can also provide accessories to the base unit. Hard carry case. Additional
crystal 40 mm cells and 10 mm UV quartz cell.

L&I also provide full training programs for ASTM wall wash analysis testing and use of
the Lightwave 11 Spectrometer.
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950 Chloride in Methanol

Range 0.2 – 20.0 ppm by weight.

Acidified Silver Nitrate Reagent – 2% Silver Nitrate in 20% Nitric Acid

Dissolve 10 g of silver nitrate in 500 ml of 20% nitric acid. Store this solution in a dark bottle.

Alternatively, separate solutions of 2% silver nitrate and 20% nitric acid can also be used just as
successfully.

Procedure

1. Switch the L&I Wave II instrument on. After a few seconds and if all self checks are accepted,
the instrument is calibrated and ready for use. A screen showing four files is shown.
2. Press the button relating to the LI Maritime Programs, file number 2.
3. Press the button relating to 950 Chloride in MeOH. The tests can now be performed.
4. Transfer 25 ml of test sample into an appropriate sample tube.
5. Add 5 drops of the acidified silver nitrate reagent, or 5 drops each of 2% silver nitrate and 20%
nitric acid.
6. Prepare a zero sample (reference sample) to run concurrently, by following steps 4 and 5 using
reagent grade (pure) methanol. Leave to stand for 15 minutes.
7. After 15 minutes, follow these instructions.
8. Fill one Hach 25ml glass cell to the mark with the prepared reference sample and insert into
the square cell holder with the mark facing left, ensure the cell is seated fully in the cell
holder.
9. Press the 0A/100%T button to set the instrument to zero. Once the instrument is zeroed, it
does not display any result, 0.000 can be seen in the Absorbance box.
10.Remove the reference sample from the instrument and pour it back into the reference sample
tube.
11.Rinse the same glass cell with the test sample and then fill to the line before inserting into the
instrument, with the mark also facing left. Press the GREEN button and read the ppm of the
CHLORIDE directly from the Concentration box.
12.It is recommended to regularly check that the reference sample still reads zero. If the reading
shows any significant drift, reset the reference by repeating steps 8 and 9.

Interpretation of Results

The chloride content of the test sample in ppm, is read directly from the instrument.

Interferences

1. Hazy and / or coloured test samples

2. The presence of excessive detergents
3. The presence of excessive phosphates
4. The presence of excessive water immiscible contaminants (hydrocarbons)

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951 Permanganate Time Test

Range Pass or Fail in line with ASTM D

1363. Potassium Permanganate Reagent

Prepare a 0.02% solution of potassium permanganate in water by dissolving 0.1 g of crystalline

potassium permanganate in 500 ml of de-ionised water.

Procedure

1. Switch the L&I Wave II instrument on. After a few seconds, and if all self checks are accepted,
the instrument is calibrated and ready for use. A screen showing four files is shown.
2. Press the button relating to the L I Maritime programs, file number 2.
3. Press the button relating to 951 Permanganate Test, the test can now be performed.
4. Prepare a water bath at 15 oC  1oC
5. Fill a sample tube with 25 ml of the test sample and place it in the bath for at least 10 minutes to
allow it to cool down to 15 oC
6. Now add 1 ml of the potassium permanganate reagent to the sample tube, mix the contents well
and replace in the bath. Note the time
7. Leave the sample tube in the bath for 50 minutes, or whatever length of time the potassium
permanganate time test specification is set at
8. Fill one Hach 25ml glass cell to the mark with pure methanol, with no potassium permanganate
solution added (reference sample) and insert into the square cell holder with the mark facing
left
9. Press the 0A/100%T button to set the instrument to zero. Once the instrument is zeroed, it does
not display any result, 0.000 can be seen in the Absorbance box.
10. Remove the reference sample from the instrument
11. Rinse the same glass cell with the test sample and then fill to the line inserting into the
instrument, with the mark also facing left. Press the GREEN button and read the % TRANS
PTT directly from the Concentration box.
12. It is recommended to regularly check that the reference sample still reads zero. If the reading
shows any significant drift, reset the reference by following steps 8 and 9.

Interpretation of Results

Samples having a reading greater than 35.0 % by this procedure, will still show a pink
colour, and pass the test

Samples having a reading less than 35.0 % by this procedure will appear to be brown in
colour, and fail the test

Interferences

1. Hazy test samples

2. The presence of extremes of pH
3. The presence of excessive colour

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952 APHA Colour

Range APHA 5 – 500 in line with ASTM D 1209 on the Platinum - Cobalt scale.

Procedure

1. Switch the L&I Wave II instrument on. After a few seconds, and if all self checks are accepted,
the instrument is calibrated and ready for use. A screen showing four files is shown.

2. Press the button relating to the L I Maritime programs, file number 2.

3. Press the button relating to 952 APHA Colour, the test can now be performed.

4. Fill one Hach 25ml glass cell to the mark with pure methanol (reference sample) and insert into
the square cell holder with the mark facing left

5. Press the 0A/100%T button to set the instrument to zero. Once the instrument is zeroed, it does
not display any result, 0.000 can be seen in the Absorbance box.

6. Remove the reference sample from the instrument

7. Rinse the same glass cell with the test sample and then fill to the line before inserting into the
instrument, with the mark also facing left. Press the GREEN button and read the COLOUR
reading directly from the Concentration box.

8. It is recommended to regularly check that the reference sample still reads zero. If the reading
shows any significant drift, reset the reference by following steps 4 and 5.

Interpretation of Results

The colour of the test sample is read directly from the instrument

According to the ASTM reference the colour should be reported either as an exact multiple
of 5 or “lighter than” the next highest multiple of 5 whichever is the most appropriate

Interferences

1. Hazy test samples

2. Off hue test samples

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953 Hydrocarbons
Range Pass or Fail in line with ASTM D 1722.

Procedure
1. Switch the L&I Wave II instrument on. After a few seconds, and if all self checks are accepted,
the instrument is calibrated and ready for use. A screen showing four files is shown.
2. Press the button relating to the L I Maritime programs, file number 2.
3. Press the button relating to 953 Hydrocarbons, the test can now be performed.
4. Add 10ml of the methanol test sample to 90 ml of distilled water, in a suitable sample tube.

NOTE: By adding progressively more methanol to the distilled water (25 : 75 / 33 : 67 / 50 :

50), makes the hydrocarbon test progressively stricter. These dilutions deviate from ASTM,
but may be required at the load port. The test result is appropriate whatever the methanol
to distilled water dilution rate is.

5. Invert the tube once or twice to mix the water and methanol.
6. Prepare a zero sample (reference sample) to run concurrently, by following steps 4 and 5 using
reagent grade (pure) methanol instead of the test sample.
7. After 20 minutes follow these instructions.

NOTE: To avoid the formation of air bubbles in the sample cell, samples should be
transferred very carefully. Similarly, the sample tube should not be re-inverted after the
initial mixing. If air bubbles are present in the sample cell at the time of analysis,
inconsistent results may be observed.

9. Fill one Hach 25ml glass cell to the mark with the prepared reference sample and insert into the
square cell holder with the mark facing left
10. Press the 0A/100%T button to set the instrument to zero. Once the instrument is zeroed, it
does not display any result, 0.000 can be seen in the Absorbance box.
11. Remove the reference sample from the instrument and keep it for future reference (if required)
12. Rinse the same glass cell with the test sample and then fill to the line before inserting into the
instrument, with the mark also facing left. Press the GREEN button and read the Hydrocarbon
value (in FTU) directly from the Concentration box.
13. It is advisable to regularly check that the reference sample still reads zero. If the reading
shows any significant drift, reset the reference by following steps 9 and 10.

Interpretation of Results

All results are relative to the reference sample. The results are quoted in formazine turbidity units
(ftu), they do not directly relate to hydrocarbon concentration (ppm).

Samples having a reading of 0 by this procedure pass the test

Samples having a reading greater than 0 by this procedure fail the test

Known Interferences

1. Hazy test samples.

2. The presence of excessive detergents

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954 Chloride in Water

Range 0.2 – 10.0 ppm by weight.

Acidified Silver Nitrate Reagent – 2% Silver Nitrate in 20% Nitric Acid

Dissolve 10 g of silver nitrate in 500 ml of 20% nitric acid. Store this solution in a dark bottle.

Alternatively, separate solutions of 2% silver nitrate and 20% nitric acid can also be used just as
successfully.

Procedure

1. Switch the L&I Wave II instrument on. After a few seconds, and if all self checks are
accepted, the instrument is calibrated and ready for use. A screen showing four files is
shown.
2. Press the button relating to the L I Maritime programs, file number 2.
3. Press the button relating to 954 Chloride in Water. The tests can now be performed.
4. Transfer 25 ml of sample water into an appropriate sample tube.
5. Add 5 drops of the acidified silver nitrate reagent, or 5 drops each of 2% silver nitrate and
20% nitric acid.
6. Prepare a zero sample (using laboratory DI Water) to run concurrently, by following steps
4 and 5. Leave to stand for 15 minutes.
7. After 15 minutes, follow these instructions.
8. Fill one Hach 25ml glass cell to the mark with the prepared reference sample and insert
into the square cell holder with the mark facing left, ensure the cell is seated fully in the
cell holder.
9. Press the 0A/100%T button to set the instrument to zero. Once the instrument is zeroed, it
does not display any result, 0.000 can be seen in the Absorbance box.
10. Remove the reference sample from the instrument and pour it back into the reference
sample tube.
11. Rinse the same glass cell with the test sample and then fill to the line before inserting into
the instrument, with the mark also facing left. Press the GREEN button and read the ppm
of the CHLORIDE directly from the Concentration box.
12. It is recommended to regularly check that the reference sample still reads zero. If the
reading shows any significant drift, reset the reference by repeating steps 8 and 9.

Interpretation of Results

The chloride content of the test sample in ppm, is read directly from the instrument.

Interferences

1. Hazy and / or coloured test samples

2. The presence of excessive detergents
3. The presence of excessive phosphates
4. The presence of excessive water immiscible contaminants (hydrocarbons)

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Basic Instrument Guidelines

The following guidelines are written to provide the user with a convenient reference document and
to familiarise the user with the sometimes unique responses that this spectrophotometer can
provide. This guide should not be used in place of the manufacturer’s instrument manual or in
place of the method cards provided to determine various Wall Wash Test parameters.

Powering the instrument

This instrument can be run on either 120 or 240V mains supply and is supplied with UK, US or EU
mains cables. The instrument should be sited on a dry, flat surface. Due to its mode of operation,
its readings are stable, even in relatively rough seas.

Instrument start-up

After switching this instrument on, a series of rapid self-calibration tests are performed. During this
switch on, the cell holder area should be free from cells. If there are any problems during the
switch on, the faults will be reported by the instrument and the user advised how to remedy the
problem. After successful switch on, the screen will show 4 optional files.

To allow the optical and electrical components to stabilise it is recommended to allow a minimum
of 15 minutes for the unit to warm up.

Cells and Cell holders

There are two sets of sample cells and sample cell holders supplied with this instrument.

For ‘visible’ spectra work, (e.g. Chloride, Hydrocarbon, Colour or Permanganate), the long (40
mm) crystal glass cells should be used.

For UV work, the Quartz glass cells (10 mm) should be used. Quartz glass cells are invisible to UV
light, but they are very delicate and should be handled with great care. When using these cells the
clear sides should be exposed to the light path, and the cell should be placed at the far right hand
side of the cell holder.

Due to the unique light path and optical arrangements of this instrument, it is not necessary to
have a cell cover on this instrument.

Navigating the display

The operation of this instrument is by simple file driven menus. Navigation through the screens
and methods is performed by pressing appropriate numerical keys and by the GREEN ‘accept’ or
the RED ‘cancel’ key.

Pressing the RED key also takes the user back one step/page or aborts the current operation.

The 0A/100%T key is for zeroing the instrument.

The GREEN key takes a measurement or accepts the current option.

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Running a Method

Once selected, the method screen will display the Method number and name, the wavelength and
units.

Pressing 0A/100%T (with the appropriate blank reference sample installed in the instrument) will
zero the instrument and the ‘sample’ box will show reference. During the scanning, a rapid ticking
noise is heard, this is normal.

Pressing GREEN (with the appropriate working sample installed in the instrument) will take a
measurement; the value obtained will be shown in the ‘concentration’ box.

If the instrument shows a value of ‘-----’ in the concentration box, it is because it has detected less
absorbance in the test sample compared to the reference sample. This does happen in some
circumstances.

Connection to a PC

The spectrophotometer has a built in USB communications port that can be used to connect to a
dedicated manufacturers’ printer, manufacturers Bluetooth device or to a PC, but it is pre-set to
communicate with a PC via the enclosed USB cable and software.

The instrument can be used for more sophisticated analytical determinations (UV scanning) and
the connection to a PC enables operators to send spectral data via email for evaluation. It will also
enable software updates to be uploaded remotely.

1V Set up, Operation and Reporting.

Running a Wall Wash Sample on the 1V Spectrometer.
Equipment.

1. UV/Vis Spectrometer.
2. Laptop computer. (PVC Program installed).
3. 10 mm UV Quartz Cell.
4. Laboratory Grade Methanol.
5. Laboratory Grade D.I. Water
6. Box of Tissues.
7. Latex Gloves.
8. Samples.

Set up Instructions.

1. With both Spectrometer and Laptop in ‘Power Off’ mode, connect the
Spectrometer to the computer using the supplied USB cable.
2. ‘Power ON’ the Spectrometer. Allow the unit to perform its self calibration
checks. Once this is done,
3. ‘Power ON’ the connected computer. Once both systems are stable;
4. Click on the ‘PVC’ icon on your computer. The program will search and
find the Spectrometer (You will get a box stating ‘looking to see if Excel is
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present’ and a box screen will pop up entitled ‘PVC Application’. This will
show the product name ‘Lightwave11’, Serial Number (of the Spectrometer
you are connected to,) and ‘Activity’ – Connected.
5. The unit is now waiting for input.

6. From the opening menu screen on the Spectrometer, Select ‘1’

Applications. Then Select ‘3’ Wavescan.
7. The wavescan – Parameters screen will appear. You can scroll around this
screen using the arrow keys on the unit dashboard.
8. Using the ‘back-arrow key’ set the ‘Start Wavelength value down to ‘200
nm’.
9. Using the ‘down arrow key’ scroll down to End Wavelength.
10.Using the ‘back arrow key’ set the End Wavelength to ‘350 nm’.
11.Mode should be set on ‘Absorbance’.
12.Click the ‘Green’ OK key to confirm and set.
13.You will now see the line graph ‘Wavescan’ screen.

UV Scanning.

14.Take the 10 mm Quartz Sample Cell. Note on the open top of one of the
clear panels, there is a ‘Q’ printed. When placing the cell in the cell holder
bracket in the Spectrometer, always have the ‘Q’ facing to the left.
15.Rinse the cell with Lab Grade Methanol, then rinse again with Lab Grade
D.I. Water.
16.Fill the 10 mm cell with D.I. Water. Carefully wipe the clear panels with
soft tissue to ensure they are absolutely clean and the cell is dry. (No
finger marks).
17.Place the cell carefully into the ‘right hand side’ of the cell holder. (There is
a holding lug to hold the cell securely in place).
18.The D.I. Water is used to calibrate the Spectrometer. So we need to use
the ‘BLUE’ calibration reference button. On pressing the BLUE button, the
unit will take this as reference, you will not see a readout.
19.Remove the Quartz cell from the unit. Rinse with pure Lab Grade
Methanol. Fill the cell with pure Lab Grade Methanol and make sure you
wipe and dry it with soft tissue.
20.Replace the methanol filled cell in the cell holder.
21.To read the result, press the GREEN button. You will see a line graph. If
the methanol is pure, without any contamination, you will see a smooth
curve to the left of the read-out panel. On your computer, you will see a
read out screen, recording the data.

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Saving your Data.

0. Create a folder on the desktop where you want to store the data and
work on the files.
1. On the PVC Application Screen, open the options screen by clicking on
the Icon next to the Connected unit.

24. This will open up the ‘PVC Instrument Configuration

Box’.

Selection

The screen should be set up as you see above. However, you will need to
specify the location of the folder you have created to save your data.

This is done in ‘Data Directory’ > ‘Directory Excel Data’ Row.

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Click on ‘Directory Excel Data’ and it will be highlighted in blue. A
Selection Box will appear. Click the Selection box.

This will open up the ‘Browse for Folder’ Box. You can either create your
new ‘Folder’ here, or just select the folder you have created previously in
which to store your files.

Select the folder and click OK on the ‘Browse For Folder’ Box.
Click OK on the ‘PVC Instrument Calibration Box.
The UV data will be automatically exported to the specified folder.

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25.Open the specified folder. Each time you press the GREEN button to scan
a sample, the excel data will be sent to this folder.
26.Exported files are automatically named:
“WAVE SCAN (Date and time).”
Rename the files as it goes into the folder, so it is easily identified later,
e.g. Tk 1P (Date/time).

Building a Comparative Scan Graph Sheet.

During cleaning operations, it can be useful to see the effectiveness,

improvement (or lack of it) in the Chemical condition of the tank
coating. The UV Spectrometer allows us to profile this, by layering the
Scans onto one Graph Sheet.

Within the Folder you select to store your UV data files, Save the Excel
File ‘Nordic Ship WW & UV Report’. This Excel Workbook file contains a
Worksheet for report on your Wall Wash Analysis. It also contains
Worksheets for tank by tank cumulative data storage and graph display.

1. Open the Wavescan excel file you saved

from the UV Scan.
2. There are 3 worksheets. Click on the Chart
Data 1.
3. Note the data in columns ‘Wavelength nm
& Absorbance (A).
4. Select the data from these 2 columns from
top (200 nm) to bottom (350 nm).
5. Select Copy.
6. Open the Excel File ‘Nordic Ship WW & UV
Report and select the relevant tank
number. (Copy a sheet for additional
tanks).
7. Go to column 1 and paste the data for the
1st set of results.
8. Columns 2, 3 etc will be for subsequent
wall wash scan results for the same tank,

The line graph will automatically be

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Each Graph line name (appearing on the Graph) can be renamed by right
clicking on the Graph Box.
Choose option ‘Select Data’.

To allow you to make effective comparison of your data, you can proceed
as follows;

Tel: +9711.(0)9Run
2220a262
UV Fax:‘Blank’
Scan on your +971 (0)9Pure
2221 252 Email:
Lab Grade [email protected]
Methanol. Copy
and Past the Data from this sample as your first entry ‘Pure
Methanol’. So you will not need to rename this.
2. For your first Wall Wash sample, Copy and Paste your data to
Columns No. 2.

1. In the ‘Select Data Box’, Select the line data you wish to rename
and click on ‘Edit’.
2. Enter the Series Name only. (Do not change the series values –
unless you know what you are doing!)
3. In the Series Name, enter the description for that line. (ie. 1P
18/04/12). Click OK
4. Click OK in the Data Source Box. The line will be renamed
as appropriate.
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By adding the progressive Data in this way, you will develop a Graph of your
Scans which can show a development as in the below Graph. This Graph will
show the development of your cleaning. IE. Your methanol wall wash is
picking up reduced amounts of contamination from the tank coatings.

3. Rename the Graph line description by ‘Right Clicking’ on the graph area.

L&I Maritime
Services. UK/UAE.

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