MEASUREMENT OF OIL IN PRODUCED WATER

Roberto Lava
Regional Environmental
Protection Agency of Veneto

TAIEX Workshop on Quality

Analysis of Lubricant Oil
(60124)
Cairo (Egypt) 11-12 April 2016
 OUTLINES

- Introduction
- Definitions and Oil Composition
- Sampling and Handling
- Analytical Methods - Reference method (lab)
- Field and on-line
- Calibration and QA/QC
- References and additional informations

2
 PRODUCED WATER

PRODUCED WATER: term used in the oil industry (Neff, Lee, DeBlois)
Largest volume (80%) waste stream in Oil & Gas production (onshore and offshore)

2003 estimated 880 million m3 discharged in the ocean only from offshore
facilities worldwide

Environmental concern potential chronic danger and harm for ecosystem

Composition: complex mixture of organic and inorganic chemicals in water

(freshwater, process water, concentrated salty brine)

Most important contaminants: water-soluble low MW organic acids and low MW PAH,
then high MW alkyl phenols (0.04-3 mg/L), high MW PAH, metals (B, Fe, Mn
Hg, Zn).

3 Discharge in ocean immediate dilution 100-fold within 100 m

 OIL COMPOSITION I

OGP (International Association of Oil and Gas Producers) (2004) Environmental Performance in
the E&P Industry. 2003 Data. Report No. 359. OGP, London, UK, 32 pp

Mean concentration of total petroleum hydrocarbons (TPH) in produced

water discharger offshore in several region of world (report OGP, 2004) from
Neff, Lee, DeBlois
4
 OIL COMPOSITION II

Measurement of oil in produced water is important:

- Process control (optimisation of the process)

Less oil discharged less chemical used process capacity increased

production maximised

- Reporting to regulatory authorities (environmental concern)

Discharge of produced water from Oil & Gas production is generally regulated.
However the main problem is to understand how is possible to determine precisely
the oil content.

OIL IN PRODUCED WATER is a METHOD-DEPENDENT PARAMETER

Without the specification of a method, oil concentration loose its meaning -

5 Many techniques, many methods, often non-reference methods
 OIL COMPOSITION III

Oil in water is made by petroleum compounds. Two main groups:

- Hydrocarbons
- Heteroatom compounds

1) HYDROCARBONS (C, H) normally measured as:

TOTAL PETROLEUM HYDROCARBONS (TPHs) = SATURATED + UNSATURATED
+ AROMATICS
SATURATED both aliphatic (straight or branched) PARAFFINS and
ISOPARAFFINS and alicyclic CYCLOPARAFFINS)

UNSATURATED, less common in crude oil, but produced in a second

phase (cracking) and mainly in OLEFINES

AROMATICS (single, double or multiple benzene ring)

2) HETEROATOM COMPOUNDS (C,H, S, N, O) - part of organic acids

6
 OIL COMPOSITION IV

Total Petroleum Hydrocarbons (TPHs) Yang, 2003

7
 DISPERSED AND DISSOLVED OIL

DISPERSED OIL: oil in the form of small drops (range nm-um), contains
both aliphatic and aromatic hydrocarbons

DISSOLVED OIL: oil in a soluble form in produced water. Less aliphatic, more
aromatic and organic acid

Yang 2006
8
 SOLUBILITY IN WATER
ALIPHATIC HYDROCARBONS

AROMATIC
HYDROCARBONS

9 Fritnopp, 2007
 IMPORTANCE OF DEFINITIONS

OSPAR (Recommendation, 2001):

TOTAL OIL = total hydrocarbons
DISPERSED OIL = hydrocarbons determined according to OSPAR
reference method (Agreement 2005):

US-EPA
OIL AND GREASE = substances extracted by n-hexane
Not evaporated at 70C and capable to being weighed

ISO 9388-2 Determination of the hydrocarbon oil index

(solvent extraction + GC-FID method)

10 DIFFERENT METHODS = DIFFERENT QUANTIFICATION

 SAMPLING AND HANDLING

SAMPLE = representative of the whole situation

GOOD RESULTS = ROBUST METHODS = GOOD SAMPLING METHODOLOGY

(up to 75 % of uncertainty of a measure done by the sampling contribution)

Aspects to consider:

Location of taking the sample

Sampling devices

Iso-kinetic sampling

Sampling bottle
11
 SAMPLING I

LOCATION: depends from the reasons of the analysis

Regulatory compliance monitoring - may be taken in specific location
Process control and optimisation - not so important the location

SAMPLING DEVICE:
Homogeneous sample: taken
downstream of a turbolent
region (better mix), ideal from
vertical pipe to avoid stratifications

Example of oil-in-water sampling probe IMO Resolution MEPC 107.(49) 2003

12
 SAMPLING II

ISO-KINETIC SAMPLING:

samples are taken such that the velocity of fluid in

the sampling pipe is the same as that in the main flow pipe. When a sample is
procured from a sampling line without a continuous flow flow at least 1-2 min
before the sample is taken.

SAMPLE BOTTLE: VERY IMPORTANT!!!

extremely cleaned, with no oil contamination

(wash with soap, dry, solvent)
amber glass bottle (500 mL - 1 L) for a range of
ppm contamination
NO plastic bottle (hydrocarbons may diffuse through)
TEFLON caps
13
 HANDLING I

1) Preserve the samples from degradation by killing bacteria

ACIDIFICATION 2) Dissolve precipitates (Fe compounds, CaCO3) and
stabilisation of emulsion
when produced water is acidified, many of the organic acids
and phenols are converted from water soluble (dissolved) to oil soluble (dispersed),
which are then extracted into a solvent.

Treatment with FLORISIL before analysis usually removes them and they are
not included in the oil measurement.

2.5 mL of HCl concentrated in 1 L

Inside the water just after the sampling

14
 HANDLING II

COOLING
Produced water can be at 80-90 C let cooled before handling and acidification
~ 10 C if necessary to analyse volatile hydrocarbons, to
prevent the loss

TRANSPORTATION
To the laboratory in cooled and dark environment (amber glass)
light may degrade hydrocarbons in the water sample

STORAGE

According to ISO 5667-3 (2003): idea stored in a fridge between 1-5 C,

max storage time is 1 month for oil detection (1 week for volatile compounds)

15
 REFERENCE METHODS

Method-dependant analysis critical to define an available reference method

to compare data

1) INFRARED ABSORPTION (IR)

2) GRAVIMETRIC

3) GAS CHROMATOGRAPHY AND

FLAME IONISATION DETECTION (GC-FID)

16
 INFRARED ABSORPION I

ACIDIFICATION
EXTRACTION
PURIFICATION
QUANTIFICATION

LIQUID - LIQUID with a suitable solvent

Good solvent may include:

1.High power of extraction
2.Safe to use
3.Infrared transparency
4.Environmental friendly Yang, 2002

5.Possibly heavier than water

17 6.Reasonable price and easily available
 INFRARED ABSORPION II

Standard Test Method for S-316 Recoverable Oil and Grease and Non-polar Material by IR
S-316 expensive (350-400 euro/L) implementation of methods for its regeneration
18
 INFRARED ABSORPION III

Single wavelength method: 2930 cm-1 (CH2 stretch vibration frequency)

Quantify all of the CH2 contained in a sample extract (aliphatic)

A = absorbance
A = log IO/I = aLc a = constant
L = path length
C = HC concentration

Triple wavelength method:

3030 cm-1 (C-H stretch aromatic vibration)
2960 cm-1 (CH-H stretch methylene vibration)
2930 cm (CH2-H stretch methyl vibration)

Caromatic = Ctotal - Caliphatic

FT-IR
19
 INFRARED ABSORPION IV

1 L produced water 20 mL S-316

Calibration curve in iso-octane / n-hexadecane
Range determination: 10-120 g/L Total scan 500-4000 cm-1
LOQ: 10 g/L
Specific scan 3200-2700 cm-1

Area selected 3000-2800 cm-1

20
 GRAVIMETRIC METHODS

Based on the measurement of anything extractable by a solvent that is not

removed during a solvent evaporation process can be weighed

Method for a considerable amount of oil in produced water

(mainly for process optimisation)

Up to 50 mg/L

21
 GC-FID I

Gascromatographic separation offer the potential for obtaining details of the

different types of hydrocarbons in the oil fraction.

ISO 9377-2 (2000) or OSPAR GC-FID (OSPAR Agreement 2005)

ACIDIFICATION EXTRACTION PURIFICATION QUANTIFICATION

- 900 mL with 50 mL n-hexane (stirring 30 min)

- Purification with column of Florisil
n-hexane
- Evaporation of the solvent to small volume
- GC separation and quantification

ISO 9377-2 (2000) hydrocarbon index C10 - C40

22
 GC-FID II

ISO 9377-2 (2000) hydrocarbon index C10 - C40

As the hydrocarbons are separated by the GC column, they are burned

by a Flame Ionisation Detector (FID) which responds to all combustibles

Different groups are separated and theoretically same response for the
same concentration

Working range: 50 1000 g/L

23
 GC-FID III

GC chromatogram
of a standard mix
(Diesel Oil / Mineral
Oil)

yellow area as total area

Fraction between
n-decane and n-tetracontane
24
 GC-FID IV

GC chromatogram
of a sample extracted
Integration C12 - C40
excluded
(yellow area)

25
 GC-MS

It is possible to use the MASS SPECTROMETRY

DETECTION SYSTEM,
but there are no reference method available.

Advantage: identification of peaks,

comparison with a library of MS spectra

Disadvantages: different response and

sensitivity for different hydrocarbons,
response structure-depending and
detector-depending, cleanness of an MS
system (samples with high concentrations)

K. Grob, Kantonales Labor Zurich (2011)

Response increase with the masses

 VOLATILE HYDROCARBONS

EPA Methods hydrocarbon index C6 C10

Separation also of the less volatile fraction
Conservation for a maximum of 48h at +4 C

Different EXTRACTION system:

1) STATIC HEAD SPACE EPA 5021a 10 mL
2) DYNAMIC HEAD SPACE (Purge & Trap) EPA 5030c 40 mL

For separation and quantification:

1) GC-FID EPA 8015d (fraction between the 2-methylpentane and the n-decane
2) GC-MS EPA 8270d (benzene, toluene, ethylbenzene, xilenes (BTEX)

Applicable to groundwater, surface water, wastewater, produced water

LOQ of 50 g/L
NO PURIFICATION but careful with LAB CONTAMINATION !!
 REFERENCE METHODS

- Important for comparison of data from different sources, both for regulatory
purposes (i.e. discharge limits) and performance standards
- For historically reasons, no one specific method is worldwide accepted

- Generally speaking:

METHOD PRO CONS

IR - well established - solvent
- easy - lack info on
- portable composition
Gravimetry - simple -loss of volatile compounds
- cheap - lack info on composition

GC-FID (MS) - info composition - more complex instrumentation

- higher cost

28
 FIELD and ONLINE MEASUREMENTS

Mainly for process optimisation and quick responses

BENCH-TOP methods (for routine oil-in-water analysis)
ONLINE methods (detection of process trend and deviations)

BENCH-TOP ONLINE
Colorimetric Focused Ultrasonic Acoustics
Fibre Optical Chemical Sensor Fibre Optical Chemical Sensor

Infrared Image Analysis

UV absorption Light Scattering and Turbidity
UV fluorescence UV fluorescence

Photoacoustic sensor

To be considered: purpose o measurement, characteristic of produced water, use of solvents,

calibration procedures, compactness and easy-to-use, costs, maintenance
29
 QUALITY ASSURANCE / QUALITY CONTROL

-Importance of reference methods if possible (e.g.: ISO 9388-2, ASTM 7066, )

- Laboratory accreditation according to ISO 17025 standards

- Validated method (calibration curve, working range, LOD and LOQ,

repeatability, reproducibility and intermediate precision, trueness and recovery,
robustness, uncertainty estimation)

Reference methods vs internal methods

For a reference method, usually a calibration oil is defined.

e.g. mix 50:50 of 2 minerals oils (Type A diesel fuel, Type B lubricant) for ISO 9377-2
mix 50:50 of iso-octane / n-hexadecane for ISO 9388-2

- QC samples, procedure under control (e.g. efficiency of Florisil)

30
 QA/QC II

CALIBRATION OIL

Example I
(Yang 2009):

31
 QA/QC III

METHOD TO PREPARE CALIBRATION STANDARDS

Example II
(Yang 2009):

32
 QA/QC IV

Non-reference Methods

Often there is the need to be able to use a non-reference method in the field,
but results are required to be reported.
To be accepted it is necessary to demonstrate that the results are statistically
equivalent to those produced with a reference method.
- statistically significance tests (F-test and Students t-test)
- establishing a valid correlation FULL INTERNAL VALIDATION

CRM (Certified Reference Materials): material that is stable and

homogeneous with respect to one or more specified properties and for
which traceability and uncertainty values at a level of confidence are established
MINERAL OIL HYDROCARBONS in WATER
Unfortunately not a lot available on the market
BAM - HYCREF International Research Project funded by EUROPEAN COMMISSION

33
 REFERENCES and USEFUL READINGS

- M. Yang, Oil in Produced Water, Produced Water K. Lee, J. Neff (eds.)

Springer Science 2011

- J. Neff, K. Lee, E.M. DeBlois, Produced water: overview of composition,

fates and effects, Produced Water K. Lee, J. Neff (eds.) Springer Science 2011

34
 ANY QUESTIONS.?

THANK YOU FOR

YOUR ATTENTIONS

Contact:
Dr. LAVA ROBERTO, PhD
email: roberto.lava@arpa.veneto.it

35
 SUPPLEMENTARY MATERIAL I

SPME - Solid Phase MicroExtraction

- 1990 patented - only spread use with automatisation

- Application for hydrocarbons and PAH in water
- Still few official methods

used as extraction
and purification
system before
a GC analysis

2010 Sigma-Aldrich Co.

36
 SUPPLEMENTARY MATERIAL II

SPME - Solid Phase MicroExtraction

2010 Sigma-Aldrich Co.

37 2010 Sigma-Aldrich Co.

 SUPPLEMENTARY MATERIAL III

SPME - Solid Phase MicroExtraction

Analyte adsorbed
Extraction time

Factors affecting sampling recovery: type of fiber, sample

Modification, extraction time, desorption condition, GC inlet
design, GC column
38