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Determination of adsorbable organic

halogen in strongly saline water after solid-
phase extraction (SPE-AOX)

multi X 2000 + SPE

Theory of solid-phase extraction (SPE)

Solid-phase extraction is a reliable sample preparation method that is increasingly

being used. SPE may be applied for sample extraction, sample enrichment and
sample cleanup. Most frequently, however, it is used for the preparation of liquid
samples, for the extraction of low-volatile or semi-volatile analytes. SPE tubes are
available with a huge number of sorbents, with different phases and in different sizes.
SPE can be used in two ways to prepare an analytical sample. With the first method,
the analyte and some other matrix components are retained by the packing material
while the sample itself with the contaminants is allowed to pass through. The
remaining matrix components are washed out by a mild solvent. Then, the analytes
to be determined are eluted.
With the second method, the sample is applied to the tube; the compounds of
interest pass through the adsorbent without noticeable interactions.

Fig. 1: Process of solid-phase extraction

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What is SPE-AOX?

The SPE-AOX does not replace the AOX determination as per DIN EN 1485 used so
far.
Users who so far had to face the problematic analytical task to determine the AOX in
strongly saline water samples will in future be enabled to determine the AOX value
even under such difficult matrix conditions by means of a modified sample
preparation technique. The SPE-AOX is an analytical convention presenting the sum
of organic chlorine, bromine and iodine compounds, which under defined conditions
are adsorbable, both onto styrene divinylbenzene copolymerized resin (= solid
phase) and activated carbon.

In other words:

The basis of this method is the standard DIN EN 1485. With the method, the
adsorption onto activated carbon is preceded by a solid-phase extraction (=SPE)
onto the resin mentioned above. Hence, this also means that all AOX analyzers of
our instrument family used so far can fully be used for this extended AOX analysis
method.

How to measure the SPE-AOX in practice?

In principle, the range of applications for the determination of the SPE-AOX covers all
kinds of water samples (including sea water) with contents of > 10 µg/l of the
dissolved organic halogens chlorine, bromine und iodine. The concentration of
inorganic chloride may amount up to 100 g/l (DIN EN 1485: up to 1g/l) and DOC up
to 1000 mg/l (DIN EN 1485: up to 10 mg/l).

Unlike the DIN EN 1485, in this case insoluble inorganic and organic halogen
compounds as well as halides adsorbed to or included in solids are not covered.
Particulate samples must be filtered by a 0.45 µm membrane filter before the
adsorption process.

This is followed then by the actually new step:

Solid-phase enrichment to styrene divinylbenzene copolymerized resin

This material is commercially available from different sources (e.g. Baker, Supelco),
either loosely or already filled in columns (Fig. 1). Then, an aliquot of the acidified
sample (100 ml) is to be conveyed from top and with overpressure through the
column. Subsequently, as with the conventional AOX method, the system is rinsed
with a 50 nl nitrate wash solution. The flow rate shall be 3 ml/min each.

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For this, the APV 26 Automatic Sample Preparation System is excellently

suitable.
With this equipment, a sample preparation system is available that is equally
suited for the conventional enrichment in compliance with DIN EN 1485 and for
the clean-up step and subsequent adsorption for the SPE method.

Fig. 2: Commercial column for SPE-AOX analysis

The commercial SPE columns are connected via an adapter in place of the standard
activated carbon columns (Fig. 1). The freely selectable sample and wash volume for
every of the 26 possible samples and the strictly sequential operating mode of the
system ensure comfortable and smooth operation. After adsorption and washing, the
SPE columns are removed from the APV 26 and then eluted. This can be done by
means of a customary solid-phase extraction apparatus (Fig. 3) with a total of 5 ml
methanol.

Fig. 3: 12-port solid-phase extraction apparatus

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These easily handled apparatuses are commercially available either for individual
samples or for several samples simultaneously (up to 24) at a reasonable price. The
obtained eluate is then topped up to 100 ml by distilled water and subsequently
subjected to the known adsorption technique as per DIN EN 1485. For this, the now
aqueous eluate is conveyed again as sample to the APV 26, which is equipped now
with the conventional activated-carbon columns. The remaining steps are the same
as with the “normal“ AOX analysis.
If the SPE columns are not used, take care that the already preconditioned columns
are not left in dry condition for a longer period.

Summary (Brief instructions for sample preparation)

Initial use of resin tubes

1. Wash with 10 ml methanol.

2. Wash with 50 ml water.

Sample preparation

1. Let 100ml of the test sample run through the resin column.
2. Wash with 50 ml nitrate wash solution.
3. Discard the liquid run through.
4. Wash with 1ml methanol.
5. Wash again with 4 ml methanol.
6. Wash with 10 ml water.
7. Collect the substance that has passed through in a 50 ml flask and
fill up to the mark.
8. Add 2.5 ml nitrate stock solution and set pH value 2.
9. Transfer the substance that has passed through and let it run
through he duplex columns.
10. Wash with 25 ml nitrate wash solution.

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Order List SPE-AOX (Supelco & J.T. Baker)

SUPELCO
Sigma-Aldrich Chemie GmbH
Grünwalder Weg 30
D-82041 Deisenhofen
Phone: +49 89/65 13-11 30
Fax: +49 89/65 13-11 61

Extraction volume Pack contents Qty. Price Order

[ml] [mg] per box per box (DM) number

SPE columns

ENVI-CHROM P
1ml 100mg 108 441.00 57143
3ml 250mg 54 363.00 57224

Accessories

Adapter 12 81.70 57020-U

SPE vacuum extraction apparatuses 1 1,159.00 57030-U
(12-Port)
SPE vacuum extraction apparatuses 1 1,690.00 57250-U
(24-Port)

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J.T.Baker
Mallinchrodt Baker Deutschland
Im Leuschnerpark 4
D-64347 Griesheim
Phone: +49 6155/60 95 18
Fax: +49 6155/60 95 25

Extraction volume Pack contents Qty. Price Order

[ml] [mg] per box per box (DM) number

SPE columns

SDB-1 Polymer Phase

1ml 50mg 100 260.00 7519-00
3ml 100mg 50 202.00 7519-01
3ml 200mg 50 234.00 7519-02

Zubehör

Adapter 12 103.00 7122-00

Vacuum extraction apparatus 1 1,153.00 7018-00
Baker spe-12G