UK P&I CLUB

Carefully to Carry SEPTEMBER 2006

The silver nitrate test

A solution of silver nitrate in distilled water is
regularly used as a simple test for the “The carrier
detection of seawater contamination of shall properly
and carefully
ships’ cargoes. Whilst the test is a useful load, handle,
preliminary test for saline contamination it stow, carry,
should be considered as indicative only. It keep, care for
and discharge
has limitations and should not be relied on the goods
as definitive proof of saltwater carried.”
contamination; more detailed laboratory
Hague Rules,
analysis will be required to confirm this.The
Articles iii, Rule 2
reaction is shown below:

This reaction results in the clear test

Carefully to Carry
solution turning a cloudy white as insoluble
Advisory Committee
silver chloride is displaced out of the
solution. This report was produced by the Carefully
to Carry Committee – the UK P&I Club’s
advisory committee on cargo matters.
Silver nitrate + Sodium chloride (salt) . Sodium nitrate + Silver chloride The aim of the Carefully to Carry
(clear solution) (contamination) (clear solution) (insoluble Committee is to reduce claims through
white precipitate) contemporaneous advice to the Club’s
Members through the most efficient
means available.
In order to undertake a ‘spot’ test in situ, surveyors will normally carry a
The committee was established in 1961
small dropping/pipette bottle containing acidified silver nitrate solution. A and has produced many articles on
few drops of the solution should be dropped onto both the suspected cargoes that cause claims and other cargo
contaminated and apparently uncontaminated areas of the subject cargo. related issues such as hold washing,
cargo securing, and ventilation.

Alternative samples of the cargo both apparently contaminated and The quality of advice given has
uncontaminated should be obtained, placed into sealed plastic sample established Carefully to Carry as a key
bags, and removed for later testing. source of guidance for shipowners and
ships’ officers. In addition, the articles
have frequently been the source of
It is essential to use distilled water to wash the test samples as the expertise in negotiations over the
presence of chloride in some waters may produce anomalous results. settlement of claims and have also been
relied on in court hearings.

The test solution should also be acidified with nitric acid to prevent the In 2002 all articles were revised and
formation of other silver salts. published in book form as well as on disk.
All articles are also available to Members
on the Club website. Visit the Carefully to
Laboratory identification of water origins Carry section in the Loss Prevention area
of the Club website www.ukpandi.com for
The source, or origin, of a particular water contamination can be identified more information, or contact the Loss
in the laboratory by a number of different testing procedures. The testing Prevention Department.
procedures are as follows:
● Quantitative chloride determination by titration. related to the concentrations. The peak areas of the
individual anions (i.e. chloride) are compared to
● Quantitative determination of anions (i.e. chloride, standard solutions and the concentration in the actual
nitrate etc) and cations (sodium, potassium etc) by sample calculated. Examples of a typical anion
ion chromatography. chromatogram and standard are shown below. The
● Quantitative determination of metals, such as determination of the cations (i.e. sodium) is done
sodium, magnesium, calcium, potassium and separately using the same instrument but with a
strontium, using either inductively coupled plasma different eluent and column system.
emission spectroscopy (ICPES) or atomic absorption
spectroscopy (AAS). Determination of cations using ICPES or AAS
These two analytical techniques will determine the
Test procedures concentrations of various metals/cations, such as
sodium, calcium, magnesium, potassium, strontium etc
Quantitative chloride determination by titration
in an aqueous solution. The two techniques can be
Two methods are available, one involving titration described as follows:
against standard silver nitrate solution using potassium
chromate as an indicator and the other, involving ● AAS is an analytical technique in which the sample
titrating against a standard solution of a soluble to be analysed is converted into an atomic vapour by
mercury salt using diphenylcarbazone as an indicator. spraying the sample or solution of the sample into a
The chloride concentration is calculated from (i) the flame. The absorbence at a selected wavelength for
volume of standard silver nitrate solution used (ii) the each individual metal/cation is measured and
volume of sample taken and (iii) normality/molarity compared to the absorbence measurements of the
(strength) of the standard solution used. sample and standard.

● ICPES is an analytical technique where the sample

Determination of anions and cations by ion
solution is introduced into an inductively coupled
chromatography
argon plasma at a temperature of approximately
In this instrumental technique a sample (i.e. water) is 8000°C. At this temperature the individual elements
introduced via an injection loop into the eluent passing (cations) become thermally excited and emit light at
through the system. The sample is then pumped their characteristic wavelengths. This light is
through an analytical ion exchange column, which will collected by the spectrometer and amplified to yield
separate the various ions (i.e. anions or cations). The an intensity measurement that can be converted to
separated ions are then detected using a conductivity an elemental concentration by comparison with
detector and the peak areas reported are directly known standards.

5 WS03/1601 Dry cargoes (spot test)

Sample Name: WS03/1601 Injection Volume: 10.0 As noted before, for many dry cargoes such as steel,
Vial Number: 5 Injection Volume: ECD_1
Sample Type: unknown Injection Volume: n.a.
for example, an indication of seawater contamination
Control Program: Anions Injection Volume: n.a. can be achieved on site by the ‘silver nitrate spot test’.
Quantif. Method: Anions_7a Dilution Factor: 1,0000
Recording Time: 8/12/2003 18:55 Injection Volume: 1,0000
The basis of the test is that addition of acidified silver
Run Time (min): 30.00 Injection Volume: 1,0000 nitrate to any solution containing chlorides will produce
a white precipitate of insoluble silver chloride. The
5.00
␮S
chloride content of most seawaters would be expected
4.00
2 - Cl - 7.217
to be around the 20,000 ppm level. Therefore, the
addition of acidified silver nitrate to seawater will
3.00 produce a dense white precipitate making the solution
appear ‘milky’. The test is performed by the attending
2.00
surveyor by adding a small amount of acidified silver
1.00
3 - NO3 - 14,163 4 - SO3 - 23.903 nitrate to any contaminating water found on the dry
cargo. If the resulting solution appears ‘milky’ then it is
0.00
1 - F - 4.053
possible that seawater contamination has occurred.
min

0.0 5.0 10.0 15.0 20.0 25.0 30.0

However, as stated previously, to confirm the presence
of seawater further laboratory analysis will be required.
No. Ret. Time Peak Name Height Area Rel. Area Amount Type An alternative to the silver nitrate spot test is to take
min ␮S ␮S* min % ppm
1 4.05 F 0.036 0.005 0.22 0.040 BMB* swabs of the contaminating water, which should then
2
3
7.22
14.16
Cl
NO3
4.093
0.993
0.946
0.464
42.88
21.01
10.759
9.752
BMB*
BMB*
be placed in a suitable airtight container and submitted
4 23.90 SO4 0.926 0.792 35.88 12.370 BMB* to the laboratory for further analysis.
Total: 6.048 2.207 100.00 32.920
It is important to note that certain other water sources, ● Production (oilfield) waters have very high sodium
such as brackish or river water, will contain chlorides and chloride levels, which are significantly higher
and would also produce a ‘milky’ solution with the than the levels found in seawater.
addition of acidified silver nitrate. Even domestic tap
water contains enough chlorides to give a slightly
● The calcium levels in production waters are
‘milky’ solution when tested with acidified silver nitrate. significantly higher than the magnesium levels,
which are the reverse for seawater, where the
The silver nitrate spot test should be applied to magnesium levels are higher. The calcium/
galvanised goods with caution as it gives a black magnesium ratio is a useful indicator as to whether
precipitate due to interference from the zinc present. In the water is seawater or production origin.
addition, the silver nitrate spot test can be misleading ● River waters will vary in cation and anion levels,
when applied to certain types of packaging, leather depending on whether it is tidal and the levels will
goods etc, which may, themselves, contain chlorides. vary during the day depending upon the state of the
Control samples of uncontaminated cargo should, tide.
where possible, always be obtained and/or tested in
situ. ● Domestic tap water would be expected to have a
chloride level of less than 100 ppm. However, other
Liquid petroleum cargoes (laboratory test) salts, such as magnesium, calcium etc, will vary,
depending upon whether a hard or soft water area.
Unlike dry cargoes, any water contamination of a liquid
petroleum cargo will become either suspended within ● The individual metal/cation concentrations will vary
the cargo and/or percolate through and settle on the in seawater, depending upon the geographical
tank bottoms. The nature of the petroleum cargo will location and it is possible that this type of analysis
dictate whether the contaminating water will settle to can indicate the location of the seawater. For
the bottom of the cargo tanks. For example, a viscous example, the typical concentrations noted below
fuel oil cargo is more likely to retain the water in vary significantly and the levels found say, in the
suspension than a gasoline or kerosene cargo. Black Sea, are very much lower.
Unfortunately, water contamination of a petroleum
cargo will almost certainly not be spread ● The major cations and anions of seawater and some
homogeneously throughout the entire cargo, which typical values are as shown below:
makes representative sampling extremely difficult.
However, the identification of the type of water present Chloride (Cl) 18,980 mg/kg
can be achieved using either the AAS or ICPES
Sodium (Na) 10,561 mg/kg
techniques described previously. Prior to the use of
either of these techniques, the petroleum/water sample Magnesium (Mg) 1,272 mg/kg
will have to be ignited and burnt until only an ash
remains. This ash is then dissolved in either an acid or Sulphate (SO4) 884 mg/kg (as S)
a flux and an aqueous solution is prepared, which is but 2,652 mg/kg (as SO4)
then examined using
either AAS or ICPES to determine the concentrations Calcium (Ca) 400 mg/kg
of the metals/cations present. The analysis of samples
Potassium (K) 380 mg/kg
taken from various stages of the voyage (i.e. loadport
shore tanks, after loading and before discharge) can be Bromide (Br) 65 mg/kg
determined. In conjunction with the actual water
content, it is then possible to produce a ‘cation Carbonate (CO3) 140 mg/kg
fingerprint’ of the water present in the samples taken at
various stages of the voyage, which can then be used
Strontium (Sr) 13 mg/kg
to try and identify the source of the contamination.
● Brackish water is defined as water having a chloride
Water sources (fingerprinting) content in excess of 2,000 ppm.

There are a number of different possible sources of

water, such as seawater, domestic water, distilled
Glossary of terms
water, brackish water, river water, spring water,
production (oilfield) water etc, and each source of Anion: A negative ion.
water will vary depending on the geographical Cation: A positive ion, molecule or radical.
location. The following comments are useful in
determining the type/source of any water associated Chromatography: A method for the separation of
with a dry or liquid cargo: trace constituents of the sample by passing gaseous
mixture through a column of finely divided powder
which selectively absorbs the constituents in one or
more sharply divided bands.

Chromatogram: The array of distinctive bands

produced by chromatography.

Eluent: The aqueous carrier of the sample through an

ion chromatography system.

Ion: An electrically charged atom, radical or molecule

formed by the dissolution of an electrolyte.

Molarity: Gram molecular weight, concentration of a

solution.

ppm: Parts per million.

Spectroscopy: The science and practice of using

spectrometers and spectroscopes in chemical analysis
and studies of atoms, molecules, ions etc.

UK P&I CLUB For further information please contact:

IS MANAGED Loss Prevention Department, Thomas Miller P&I Ltd
BY THOMAS Tel: +44 20 7204 2307. Fax +44 20 7283 6517
MILLER Email: lossprevention.ukclub@thomasmiller.com