Evaluating and Characterizing Oil field

Produced Water of Upper Assam Basin

Subrata Borgohain Gogoi(&), Amarjit Rajbongshi, and Shilpi Sarmah

Department of Petroleum Technology, Dibrugarh University, Dibrugarh, India

[email protected]

Abstract. Large volumes of water are produced (PW) during oil and gas pro-
duction from the various oil fields of Upper Assam Basin, India. PW is a very
complex mixture and contains different toxic compounds that adversely affect the
surrounding environment, the reservoir environment and also the economics of oil
and gas production. PW separated from oil and gas is either injected into the
reservoir for pressure maintenance or discharged to the environment. Therefore
evaluation of PW and its characterization is very important and essential for
environment and reservoir management. This study deals with the complete
evaluation and characterization of PW generated from different depths and hori-
zons of oil reservoirs. The evaluation included the analysis of pH, specific gravity,
salinity, total dissolved solids (TDS), cations, anions, organics and minerals. The
values of specific gravity, salinity, TDS, and some ions such as sodium and
chloride of oilfield PW were increased with increasing the reservoir depths. Useful
relationships were observed between salinity, TDS, cations, anions, organics and
minerals. These results can be used in the design, operation, and optimization of
wastewater treatment systems of petroleum industries for future studies.

Keywords: Evaluation
Characterization
Environment
Produced water

1 Introduction

Currently, it has been well known that the oil industry has to handle more produced
water (PW) than oil which makes the oil industry looks more like a “water industry”
[1]. In the United States, oil wells produce about 7 to 10 barrels of water for each barrel
of oil [2]. It was estimated that, about 210 million bbl of water was produced each day
in 1999 worldwide and is an integral and unavoidable part of oil and gas recovery
processes [1, 3, 4]. This PW includes the formation water and water resulting from
drilling, production and workover activities [5, 6]. Out of various options for man-
agement of PW, mostly adopted options by the hydrocarbon exploration industries are
underground injection for increasing oil recovery in the deep reservoir zone and the
injection to non pay zones in the porous rocks for mere disposal purpose [7, 8]. PW is
sometimes discharged to the surrounding environment or may be used for water
flooding or reservoir pressure maintenance [2, 5]. The quality of PW vary considerably
depending on the geographic location of the reservoir oilfield, the geochemistry of the
producing formation, the type of hydrocarbon product being produced and the char-
acteristics and type of the producing well [2, 5, 9, 10].

© Springer International Publishing AG 2018

D.N. Singh and A. Galaa (eds.), Contemporary Issues in
Geoenvironmental Engineering, Sustainable Civil Infrastructures,
DOI 10.1007/978-3-319-61612-4_14
 Evaluating and Characterizing Oil field Produced Water of Upper Assam Basin 177

The North-East India oil field PWs are the by-products generated during various
operations in the hydrocarbon exploration industries are major sources of pollution in
the area. These pollutants find their way and traverse to various environmental
receptors causing potential danger of polluting the same. The water bodies, both sur-
face and underground are more susceptible to such pollution in oil fields. Management
of oil field PW is a key issue for the oil and gas producers because of its large volume
of generation and high handling cost. The aging oilfields of Upper Assam basin
belonging to Oil India Limited, Duliajan and Oil and Natural Gas Limited, Nazira,
produces crude oil with very high water cuts of more than 90%. Production of PW from
these aging oilfields is also in increasing trend. This PW is highly saline, very rich in
dissolved minerals and has a high temperature than the normal atmospheric water
temperature. The salinities of the PWs from these oil fields range from 1000–3000 mg/l
[7] i.e., 1000–3000 ppm. The oil field in the study area has disposed in an average 3000
m3 of PW on a daily basis from its various oil fields which are an environmental
concern since the injected PW has a potential to migrate and contaminate the ground
water of the area.

2 Experimental

2.1 Materials
Oil samples from Moran, Naharkatiya and Dikom Oil fields were collected from well
heads along with formation water from a depth of more than 3000 m. n-Hexane
(C6H14), NaCl, KCl, Petroleum ether, Conc. HCl, BaCl2 were purchased from Merck
Chemical India, Mumbai.

2.2 Methods
Characterization of PW by determination of the physical properties:
The PWs were characterized by determining experimentally the physical properties
like pH, salinity by Mettler Toledo pH meter, conductivity and resistivity by Ecotester,
quantifying the crude oil presence in PW, total dissolved solids and presence of sul-
phate by analytical methods and inorganics by Induced coupled plasma optical emis-
sion spectrometry (ICP-OES). The determinations of organic components in PWs were
done by Thin-layer chromatography and flame ionization detection (TLC-FID) and
GC-MS (Gas Chromatography Mass Spectroscopy).
Characterization of PW by Geochemical properties of formation water by core
sample analyses:
To understand the relationship of the components in PWs with the subsurface
geological formation of the oil producing reservoirs a study on the clay minerals and
other minerals present in the core samples obtained from M#1 (depth = 3928.2 m) and
M#2 (depth = 3905.3 m) were studied. Clay minerals were examined by X-ray
diffraction (XRD) and minerals by microscopically examining thin slides of the core
samples (Table 3).
178 S.B. Gogoi et al.

3 Results and Discussion

Samples of crude oil and formation water were collected from Moran, Naharkatiya and
Dikom Oil Fields of Upper Assam Basin. It was observed that the wells M#1 (depth =
3928.2 m) and M#2 (depth = 3905.3 m) belonging to Moran oil field have been
producing crude oil with 98% water cut. Therefore the PW from these wells were
separated easily in separating funnels by ethyl ether and all further experiments were
done in these PWs. pH was found to be 6.89 and 6.76 for M#1 and M#2 respectively
and the salinity was found to be 2760 ppm (2760 mg/l) and 3020 ppm (3020 mg/l) for
M#1 and M#2 respectively. The conductivity was 13.3 mS/cm and 12.9 mS/cm for
M#1 and M#2 respectively, while the resistivity was 75.2 Ohm-cm and 77.5 Ohm-cm
for M#1 and M#2 respectively. Since PW has ions so the conductivity is well above
pure water whose conductivity is 0.55 mS/cm. The crude oil fraction per ml of PW was
0.01676 gm and 0.01712 gm for M#1 and M#2 respectively. While the total dissolved
solids (TDS) per ml of PW were 0.00286 gm and 0.00477 gm for M#1 and M#2
respectively. The inorganics per litre of PW were found to be Ca = 7.817 mg & 6.792
mg; Fe = 0.016 mg & 0.19 mg; Mg = 2.285 mg & 3.104 mg; Mn = 0 & 0; Mo = 0 &
0.013 mg; Ni = 0.010 mg & 0.017 mg; Pb = 0 & 0; Sr = 0.402 mg & 0.398 and
Zn = 0.006 mg & 0.007 mg for M#1 and M#2 respectively. The total inorganics was
10.536 mg/l and 10.521 mg/l for M#1 and M#2 respectively.
(a) The results of the organics in PW measured by TLC-FID are shown in Table 2
Determinations of organics in PWs are shown in Figure 1 which shows the majority of
n-alkane distributions for whole-oil gas chromatograms. A broad spectrum of n-alkanes
ranging from n-C10 through n-C35 was observed. Modest odd-carbon preference in the
n-C15 through n-C19 range was also observed. The presence of isoprenoidspristane
(C19H40) and phytane (C20H42) was also detected. The heavy hydrocarbons from C18 to
C20 can also be seen.

Fig. 1. Shows the GC fingerprints of PW from M#1 & M#2.

 Evaluating and Characterizing Oil field Produced Water of Upper Assam Basin 179

(b) To understand the relationship of the components in PWs with the subsurface
geology the results of the XRD and thin slides examination are in Table 2 and the
pictures of the slides is in Fig. 2.

Fig. 2 Showing the pictures of the thin slides

180 S.B. Gogoi et al.

Fig. 2 (continued)
Evaluating and Characterizing Oil field Produced Water of Upper Assam Basin 181

Fig. 2 (continued)
182 S.B. Gogoi et al.

Table 1. Different water samples collected from Oil Fields

Sample No./ Well no./ Geologic Res. Res. Water cut
Oil field Year of formation/depth pressure Temp. (oC) i.e. water in
producing (m) (kg/cm2) crude oil
(%)
IV/Dikom D#1/1993 Eocene/3800 240 100 40
III/Moran M#1/1965 Barail/3100 200 88 98
III/Moran M#2/1963 Barail/3250 190 85 98
I/Moran M#3/1969 Barail/3200 240 87 26
II/Nahorkatiya N#1/2006 Eocene/4400 450 110 2
CW Chemically treated water collected from the manifold of Moran OCSa
F Pond water from Moran OCSa
V(W) Chemically treated water collected from the manifold of Dikom OCSa
a
Oil Collecting Station

Table 2. Composition of PW using TLC-FID

Depth (m) %Saturates %Aromatics %Res + Asphalts Interpretation
3928.2 21.9 52.7 25.4 Heavy oil
3905.3 28.2 58.4 13.4 Heavy oil

(c) Pollutants in terms of toxicity

pH effects the chemical and biological properties of water. PWs pH is governed by
the carbon dioxide/ bicarbonate/ carbonate equilibria and ranges between 4.5 and 8.5
although mostly basic. pH of the PWs obtained was almost neutral. Electrical Con-
ductivity, which is a measure of the ionic properties of the water body, showed values
much higher than pure water. Total hardness, predominantly caused by divalent cations
such as Calcium, Magnesium, and others is the sum of total cations present in the
water, which is perhaps due to minerals coming from the drilling activities and from
underground reservoir. The concentration of sodium in water in terms of salinity is
about 3000 mg/l, which is detrimental for the nearby agricultural fields. The aromatics
detected in TC-FID (Table 1) behave as a bioaccumulate in marine organisms and may
threaten the environment. A broad spectrum of n-alkanes ranging from n-C10 through
n-C35 was observed in GCMS (Fig. 1) where the modest odd-carbon preference in the
n-C15 through n-C19 range is present. The presence of isoprenoidspristane (C19H40) and
phytane (C20H42) was also detected in GCMS. The heavy hydrocarbons from C18 to
C20 can also be seen. These molecules are used as biomarkers and their analysis is
applied in studies of biodegradation.
 Evaluating and Characterizing Oil field Produced Water of Upper Assam Basin 183

Table 3. Experimental results of XRD and Thin slides

Sl Sample Mineral Chemical formula
no (Well
no.)
1 M#1 & Clay types
M#2 Kaolinite Al2Si2O5(OH)4
Illite (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)],
Chlorite present NaClO2 or Mg(ClO2)2
as
2 M#1 & Quartz SiO2
M#2 Feldspar KAlSi3O8 – NaAlSi3O8 – CaAl2Si2O8
3 M#1 Mica X2Y4–6Z8O20(OH,F)4 in which X is K, Na, or Ca or
less commonly Ba, Rb, or Cs
Y is Al, Mg, or Fe or less commonly Mn, Cr, Ti, Li
Z is chiefly Si or Al, but also may include Fe3+ or Ti
4 M#2 Calcite cement Calcite and Aragonite. Aragonite is a carbonate
crystals mineral, one of the two common, naturally
occurring, crystal forms of calcium carbonate,
CaCO3 (the other form being the mineral calcite). It
is formed by biological and physical processes,
including precipitation from marine and freshwater
environments
5 M#2 Haematite Hematite is the mineral form of iron (III) oxide
cement (Fe2O3), one of several iron oxides
6 M#1 Isolated patches As in Sl.no. 1
of clay minerals
7 M#2 Feldspar grains As in Sl.no. 2, Feldspar grains which has started
getting sericitised. Sericite is a very fine grained
clay which is formed by diagenetic transformation
of feldspar

4 Conclusion

PWs obtained was almost neutral and conductivity higher than water. Hardness was
due to divalent cations which may be due to drilling activities. The salinity and min-
erals are detrimental for agricultural fields. The aromatics may behave as a bioaccu-
mulate in marine organisms and threaten environment. A broad spectrum of n-alkanes
ranging from n-C10 through n-C35 together with isoprenoidspristane (C19H40) and
phytane (C20H42) and heavy hydrocarbons (C18 to C20) were observed. The heavy
hydrocarbons can be used as biomarkers and their analysis will be applied in studies of
biodegradation.
184 S.B. Gogoi et al.

Acknowledgment. The authors are also greatly indebted to the anonymous reviewers whose
comments will significantly improve this manuscript. This work was funded by the Department
of Biotechnology, Government of India in the form of Joint R&D activities under the twinning
programme for scientists working in Dibrugarh University in the form of a Twinning project no.
DBT-ENV/2013/222 (Twin 2013).

Nomenclature
PW Formation Water
TDS Total Dissolved Solid
RSM Response Surface Methodology
XRD X - Ray Diffraction
ICP-OES Induced Coupled Plasma Optical Emission Spectrophotometer
TLC-FID Thin Layer Chromatography and Flame Ionization Detection
GC Gas Chromatography
GC-MS Gas Chromatography Mass Spectroscopy

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