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RECOMMENDED GUIDELINES

FOR
The sampling and analysis of produced
water

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 2

TABLE OF CONTENTS

1
2
2.1
2.2
2.3
2.4
2.5
3
3.1
3.2
3.3
3.4
3.5
4
5
6
7
8

Introduction................................................................................................................... 3
Sampling........................................................................................................................ 3
General.......................................................................................................................... 3
Sampling for the determination of metals ......................................................................... 4
Sampling for the analysis of organic components ............................................................. 4
Sampling for analysis with regard to radioactive elements................................................. 4
Storage and transport of samples.................................................................................... 4
Analysis of organic components...................................................................................... 4
Oil-in-water................................................................................................................... 5
BTEX............................................................................................................................ 5
NPD and PAH .............................................................................................................. 5
Phenols.......................................................................................................................... 5
Organic acids................................................................................................................. 5
Determination of metals .................................................................................................. 5
Determination of radioactive elements............................................................................. 6
Density/salinity............................................................................................................... 6
Blank samples................................................................................................................ 6
Reporting....................................................................................................................... 6

Appendix 1.................................................................................................................................. 7
Appendix 2
Processing and analysis of phenol and alkylised phenols....................................... 11

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 3

Introduction

These are guidelines for the sampling and chemical analysis of produced water relating to inorganic
and organic components, as well as radioactive elements, drawn up by OLF's working committee on
Discharges to Sea. The aim of these guidelines is to achieve comparable results of analysis for water
produced by different production fields, independent of where the samples are taken and which
laboratories carry out the analyses. The guidelines therefore stipulate a number of requirements for
the various analysis techniques with regard to separation, detection limits and accuracy. The
guidelines apply to the sampling and analysis of produced water, regardless of whether the water is
discharged or re-injected.
It is recommended that produced water be sampled and analysed twice a year (at six-month
intervals), and when changes in the production process are expected to lead to changes in the
composition of the discharge. This does not apply to radioactive elements (see item five), which
should be analysed every other year. The results are to be reported to OLF on a continuous basis
for registration in the OLF database for produced water.

Sampling

2.1
General
The sampling must be carried out in such a way that as many representative samples as possible are
obtained from the discharge point. For several of the components the likelihood of contamination or
loss by evaporation is great. Sampling is to take place under normal operational conditions. In case
of changes at the site of sampling, such as extension of the sample stub, or temporary cessation of
produced water discharge, the samples should be taken after a period of normal discharge flow.
Three samples (parallels) are to be taken from each discharge. Because the various analyses require
different conditions, the number of samples will vary according to the type of analyses to be carried
out. The sample bottles must be washed and prepared beforehand at the laboratory that is to carry
out the analyses, as well as labelled with their purpose. A detailed description of how the sampling is
to be done, and a sampling form, is to accompany the sample bottles when they are dispatched. The
sample quantity must be commensurate with the type of analysis to be carried out, and must be
previously agreed upon with the laboratory in question.
During sampling the bottles must be labelled with sample number, as well as date, time, and site of
sampling, and the installation name. These details, as well as any observations made while sampling
(regarding colour, odour, viscosity, etc.), must be recorded on the sampling form.

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 4

2.2
Sampling for the determination of metals
Except for the determination of mercury and arsenic, plastic (polythene) bottles are to be used for
water sampling for the determination of metals. Sample bottles for the determination of mercury and
arsenic must be of colourless glass. The bottles must be cleansed with nitric acid and rinsed with
deionised water. During sampling the water is to run freely into the sample bottle with minimal
distance between bottle and sample stub, avoiding any contact between the two. If possible, a hose
piece of silicone rubber should be connected to the sample stub to prevent direct contact between
metal piece and the sample bottles. The method of conservation is to be evaluated in relation to the
requirements of the individual method used, and is to be specified in advance by the laboratory
performing the analysis.
2.3
Sampling for the analysis of organic components
Water samples for the analysis of organic components are to be taken in dark glass bottles with a
Teflon cap. Prior to sampling, the bottles are to be washed and added concentrated hydrochloric
acid (approx. 1.1 ml per sample litre) at the laboratory where the samples are to be analysed. During
sampling, the jet of produced water must run such that as little air as possible enters the sample. The
bottles are to be filled to the very top, but not to the point of overflow. In cases of sampling for the
analysis of volatile components, gas-tight sample containers or tubes must be used.
2.4
Sampling for analysis with regard to radioactive elements
Water samples for analysis with regard to radioactive elements are to be taken in glass bottles with
Teflon caps. New sample bottles must always be used for sampling. The bottles are to be carefully
rinsed with deionised water prior to use. Prior to sampling the bottles must be rinsed with at least
three batches from the sample jet. Sampling is to take place by water running freely into the bottle.
2.5
Storage and transport of samples
In cases where concentrated acids have been added to sample bottles these maybe transported to
the installations by boat. Data sheets for acids must accompany the samples. After sampling, the
bottles must be stored in a dark and cool environment (corresponding to refrigerator temperatures
unless otherwise specified), and transported as speedily as possible (preferably by helicopter) to the
laboratory where they are to be analysed.

Analysis of organic components

Organic components to be analysed are oil-in-water, BTEX (benzene, toluene, ethylbenzene, and
xylene), NPD (naphtalene, phenanthrene and dibenzothiophene)/PAH (polycyclic aromatic
hydrocarbons), phenols and organic acids. All parallel samples are to be analysed. See Appendix 1
for further specification of individual compounds in these groups. The list in Appendix 1 is identical
with the format used in OLF's database of produced water configurations, and SFT's report format
(Appendix to the Information Duty Regulations, Reporting requirements from offshore petroleum
activities).

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 5

3.1
Oil-in-water
The hydrocarbon content is to be analysed in accordance with the existing standard, which as of 1
January 2003 is ISO NS-EN 9377-2. Other methods can also be used (for instance on-line analysis
equipment) providing it can be documented that these methods are calibrated in line with standard
methods.
3.2
BTEX
In order to avoid evaporation of BTEX during sample processing, headspace or purge-and-trap
techniques must be used. The analysis should preferably be carried out with GC-MS (gas
chromatography with mass spectrometric detector), but GC-FID (gas chromatography with flameionisation detector) can also be used. The quantification limit is 1.0 g/l.
3.3
NPD and PAH
NPD and PAH are to be determined by GC-MS (see Appendix 1). The quantification limit is 0.1
g/l.
3.4
Phenols
Phenols and C1-C9 alkyl phenols are to be determined by GC-MS. Methodology that avoids
interference from benzoic acids must be used. The specification of the time window for the
integration and use of standards can be found in Appendix 2. The quantification limit is 0.1 g/l.
3.5
Organic acids
Organic acids are to be analysed individually (see Appendix 1). Possible methods are ionic
chromatography, isotachophoresis (ITP), or GC-MS. The calibration standard must be documented.
The quantification limit is 2 mg/l.

Determination of metals

With regard to the determination of metals, methods indicating the total content of each metal must
be used. Additional information on the chemical state (speciation) is also desirable if available. This is
connected to knowledge of bioaccessibility and potential for harmful impact on marine life. For
determination of metals a method that can detect the individual metal down to its background level in
the seawater is required. Requirements as to the detection limit for the method (total content of each
metal) have been set based on knowledge of the background levels of metals in the North Sea.

Metal
Chrome
Nickel
Copper
Zinc
Cadmium

Requirement re: quantification limit (g/l)


1.5
9
6
15
6

Possible methods
____________
AAS / ICP-MS / DRC-ICP-MS / HR-ICP-MS
AAS / ICP- MS / DRC-ICP-MS / HR-ICP-MS
AAS / ICP- MS / DRC-ICP-MS / HR-ICP-MS
AAS / ICP- MS / DRC-ICP-MS / HR-ICP-MS
AAS / ICP- MS / DRC-ICP-MS / HR-ICP-MS

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Lead
Mercury
Arsenic
Barium
Iron

1.5
0.1
1
10
1

Revision no:

Date revised:

Page: 6

AAS / ICP- MS / DRC-ICP-MS / HR-ICP-MS


CV-AAS/Au-amalgamation
HG-AAS / ICP-MS / DRC-ICP-MS
AAS / ICP- MS / DRC-ICP-MS / ICP-AES
AAS / ICP- MS / DRC-ICP-MS / ICP-AES

AAS: Atomic absorption spectroscopy


DRC-ICP-MS: Dynamic reaction cell inductively coupled plasma mass spectroscopy
HR-ICP-MS: High resolution inductively coupled plasma mass spectroscopy
CV-AAS: Cold vapour atom absorption spectroscopy
HG-AAS: Hydride generation atomic absorption spectroscopy
ICP-MS: Inductively coupled plasma mass spectroscopy
ICP-AES: Inductively coupled plasma atomic emissions spectroscopy

Determination of radioactive elements

Determination of radioactive elements is done by high resolution germanium detector gamma


spectroscopy. The method proves all radioactive substances emitting gamma rays. The samples are
placed in Marinelli beakers, and left to rest for 14 days in order to achieve equilibrium between the
nuclides in the natural chains. The samples are then measured for 17 to 24 hours, and the
radioactivity level of radium-226 is calculated from the activity of lead-214 and bismuth-214. The
quantification limit is 0.2 Bq/l.

Density/salinity

Density and salinity are determined by standard methods. There is no requirement as to quantification
limit, but the methodology used must be documented.

Blank samples

In order to identify any contamination of the samples during sampling and analysis, at least one blank
sample (field blank sample) must be part of every group of components to be analysed. As a blank
sample, high-purity water (deionised water (MilliQ-water) for metal analyses and MilliQ-/Romilwater or similar water for analysis of organic compounds) is to be used. This blank sample is to be
treated in the same way as the samples, i.e. it is to be sent to the installation together with the sample
bottles in question, and analysed in exactly the same way as the genuine samples.

Reporting

All results of analyses are to reported continuously to OLF for registration in the OLF produced
water database with reference to the report format enclosed in Appendix 1.

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 7

Appendix 1
Method

Oil in water
(Installation)
Benzene
Toluene
Ethylbenzene
Xylene
Sum BTEX
Naphtalene*
C1-naphtalene
C2-naphtalene
C3-naphtalene
Phenanthrene*
Anthracene*
C1-Phenanthrene
C2-Phenanthrene
C3-Phenanthrene
Dibenzothiophene
C1-dibenzothiophene

Technique

Unit

Detection
limit

Concentration
in sample

Laboratory
Date of
where analysis sampling
is carried out

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

C2-dibenzothiophene
C3-dibenzothiophene
Sum NPD
Acenaphthylene*
Acenaphthene*
Fluorene*
Fluoranthene*
Pyrene*
Chrysene*
Benzo(a)anthracene*
Benzo(a)pyrene*
Benzo(g,h,i)perylene*
Benzo(b)fluoranthene*
Benzo(k)fluoranthene*
Indeno(1,2,3c,d)pyrene*
Dibenz(a,h)anthracene*
Sum 16 EPA-PAH
(marked with star)
Phenol
C1-Alkylphenols
C2-Alkylphenols
C3-Alkylphenols
C4-Alkylphenols
C5-Alkylphenols

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OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

C6-Alkylphenols
C7-Alkylphenols
C8-Alkylphenols
C9-Alkylphenols
Sum Alkylphenols
C0-C3
Sum Alkylphenols
C4-C5
Sum Alkylphenols
C6-C9
Formic acid
Glacial acetic acid
Propionic acid
Butyric acid
Valeric acid
Sum organic acids
Naphthenic acid
Barium**
Arsenic
Lead
Cadmium
Chrome
Iron**
Copper
Mercury

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OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 10

Nickel
Zinc
226Ra (radioactivity)
PAH-compunds which are part of EPA's list of 16 prioritised PAH-compounds. These are the compounds which are usually reported when PAH is reported.
** Optional; is reported if analysis results exist

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

APPENDIX 2

Revision no:

Date revised:

Page: 11

PROCESSING AND ANALYSIS OF PHENOL AND


ALKYLISED PHENOLS

The description of methodology given below builds on results from a comparison of methodology
carried out by four laboratories in 2002. Significance has been attached to the greatest possible
standardisation of the analyses.
Phenol and the C1 -C9 phenols are to be analysed using solvent extraction followed by GC-MS. The
method makes it possible to combine analysis with regard to alkylphenols and PAH.
Processing

Prior to extraction, pH is checked in the samples. This should be approximately 2. The water samples are
transferred quantitatively from the bottles to suitable extraction containers (separating funnel) and then
extracted three times by respectively 100 ml, 50 ml and 30 ml dichloromethane. The solvent for the first
extraction is used to wash the inside of the sample bottle and the Teflon cork before it is added to the
extraction container. Surrogate internal standards (SIS), deuterated C1 , C2 and C3 phenol are added, before
the solvent is added. An estimated level of these is 100 g C1 phenol and 50 g C2 and C3 phenol per litre
of water.
Extracts are combined and purified with gel permeation chromatography (exclusion volume 1000 ). This
will remove background noise and benzoic acids from the sample. The extracts will be concentrated to
approx. 1 ml (e.g. using Turbo Vap) and added internal standards for recovery (RIS) (approx. 2.5 g to 1
ml sample). If necessary the samples can be diluted and more RIS added if the analyses show that
components are being saturated.

Instrumental Analysis
The samples are analysed using GC-MS SIM on a non-polar capillary column or a capillary column of
weak polarity. Recommended conditions for analysis:

Start temperature
Duration of start temperature
Temperature programme
Final temperature
Duration of final temperature
Injector temperature
Ion source temperature
Gas velocity

40C
1 min
6 /min
300C
20 min
300C (alternatively on-column)
280C
1 ml/min (He)

The components to be included in the analysis with respective ions for GC-MS SIM are listed in Table 1.
Quantification

Phenol is quantified by integrating the specific maximum and making use of the relative response factor
(RRF) for phenol in relation to the internal standard.

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Date revised:

Page: 12

C1 phenols are quantified in the same way as the sum of the individual components o-cresol and m/pcresol. RRF is used for o-cresol.
C2-C5 phenols are quantified by the base line integration of all components for the respective groups. The
parent component phenol is used as a basis for the calculation of response factors.
Due to the risk of interference with other components the C6-C9 phenols are quantified as the sum of the
single components of each group (see Table 1).
Quality Control

The laboratory that carries out the analyses is to produce documentation showing that the analyses are
carried out with a quality level equivalent to accreditation or GLP. An example is given below of how such
quality control can be carried out.
For every set of genuine tests, samples to document the background levels from the laboratory, as well as
the degree of accuracy and precision, should be produced and analysed. This is to be done for at least
every twenty samples being processed.
Tests for quality control:
A sample blankis to be made by carrying out all steps in the processing and analysis for pure solvent
from the same batch as the extraction agent.
A laboratory control test is made by adding all analytes to pure solvent that is processed and analysed
in the same manner as the samples.
"Matrix spike" test: a genuine sample where all analytes to be determined are added.
Reproducibility is tested by processing and analysing a parallel of a genuine sample or a parallel of the
"Matrix spike" test.
Accuracy is tested by adding a selection of the analytes to a GC-vial with a solvent which is then
analysed, SIS or RIS
Quality requirements:
The level in the blank sample must be lower than the lowest result reported
70-130% recovery from the laboratory control sample and the "Matrix spike" sample
< 30% per cent deviation in parallel of sample or "Matrix spike" 30-130% recovery of SIS

Table 1: Summary of analytes and quantification parameters

Compound
Phenol

~RT (min.)

RF for
Ions Homologue

SIS

RIS

13.25

94, 66

2-methtylphenol

15.31

108, 107

4-Methylphenol-d8 Acenaphthene -d10

4-methylphenol

15.86

107, 108

4-Methylphenol-d8 Acenaphthene -d10

C1-Phenols

Phenol-d5 Acenaphthene -d10


4-Methylphenol-d8 Acenaphthene -d10

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

C2-Phenols

Revision no:

Date revised:

Page: 13

107, 122

Phenol 2,4-Dimethylphenol -d3 Acenaphthene -d10

4-ethylphenol

18.24

107, 122

2,4-Dimethylphenol -d3 Acenaphthene -d10

2,4-dimethylphenol

17.83

122, 107

2,4-Dimethylphenol -d3 Acenaphthene -d10

3,5-dimethylphenol

18.33

122, 107

2,4-Dimethylphenol -d3 Acenaphthene -d10

121, 107

Phenol 4-n-Propylphenol - d12 Acenaphthene -d10

C3-Phenols
4-n-propylphenol

20.56

107, 136

4-n-Propylphenol - d12 Acenaphthene -d10

2,4,6-trimethylphenol

19.43

121, 136

4-n-Propylphenol - d12 Acenaphthene -d10

2,3,5-trimethylphenol

20.95

121, 136

C4-Phenols

135, 150

4-n-Propylphenol - d12 Acenaphthene -d10


Phenol

Phenanthrene-d10 Acenaphthene -d10

4-n-butylphenol

22.92

107, 150

Phenanthrene-d10 Acenaphthene -d10

4-tert-butylphenol

21.40

150, 107

Phenanthrene-d10 Acenaphthene -d10

4-isopropyl-3-methylphenol

22.30

150, 135

Phenanthrene-d10 Acenaphthene -d10

C5-Phenols

149, 164

Phenol

Phenanthrene-d10 Acenaphthene -d10

4-n-pentylphenol

25.13

107, 164

Phenanthrene-d10 Acenaphthene -d10

2-tert-butyl-4-methylphenol

22.72

149, 164

Phenanthrene-d10 Acenaphthene -d10

4-tert-butyl-2-methylphenol

22.89

149, 121

Phenanthrene-d10 Acenaphthene -d10

C6-Phenols

Phenanthrene-d10 Acenaphthene -d10

4-n-hexylphenol

27.27

107, 178

Phenanthrene-d10 Acenaphthene -d10

2,5-diisopropylphenol

24.54

163, 178

Phenanthrene-d10 Acenaphthene -d10

2,6-diisopropylphenol

22.98

163, 107

Phenanthrene-d10 Acenaphthene -d10

2-tert-butyl-4-ethylphenol

24.34

163, 135

Phenanthrene-d10 Acenaphthene -d10

6-tert-butyl-2,4-dimethylphenol

23.62

163, 135

Phenanthrene-d10 Acenaphthene -d10

4-n-heptylphenol
2,6-dimethyl-4-(1,1dimethylpropyl)phenol
4-(1-ethyl-1-metylpropyl)-2methylphenol

29.30

107, 192

Phenanthrene-d10 Acenaphthene -d10

26.04

163, 192

Phenanthrene-d10 Acenaphthene -d10

27.04

163, 121

Phenanthrene-d10 Acenaphthene -d10

(2,6-diisopropyl-4-methylphenol)

26.37

177, 192

Phenanthrene-d10 Acenaphthene -d10

4-n-octylphenol

31.22

107, 206

Phenanthrene-d10 Acenaphthene -d10

4-tert-octylphenol

28.20

135, 107

Phenanthrene-d10 Acenaphthene -d10

2,4-di-tert-butylphenol

26.93

177, 206

Phenanthrene-d10 Acenaphthene -d10

2,6-di-tert-butylphenol

24.78

191, 206

Phenanthrene-d10 Acenaphthene -d10

4-n-nonylphenol

33.05

107, 220

Phenanthrene-d10 Acenaphthene -d10

2-methyl-4-tert-octylphenol

28.97

149, 121

Phenanthrene-d10 Acenaphthene -d10

2,6-di-tert-butyl-4-methylphenol

26.17

205, 220

Phenanthrene-d10 Acenaphthene -d10

4,6-di-tert-butyl-2-methylphenol

26.67

205, 220

Phenanthrene-d10 Acenaphthene -d10

C7-Phenols

Phenanthrene-d10 Acenaphthene -d10

C8-Phenols

Phenanthrene-d10 Acenaphthene -d10

C9-Phenols

Phenanthrene-d10 Acenaphthene -d10

Internal stadnards
SIS
Phenol-d5

13.21

99, 71

Acenaphthene -d10

4-Methylphenol-d8

15.76

115, 85

Acenaphthene -d10

2,4-Dimethylphenol -d3

17.81

125, 110

Acenaphthene -d10

4-n-Propylphenol - d12

20.38

113, 147

Acenaphthene -d10

26.85

164, 162

Phenanthrene-d10
RIS
Acenaphthene-d10
Note:

OLF Recommended Guidelines for The sampling and analysis of produced water
No.: 085

Date effective: 11.06.03

Revision no:

Benzoic acid (ion 122) can potentially interfere with C2-phenols


C1-benzoic acid (ion 136) can potentially interfere with C3-phenols

Date revised:

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