Environmental Technology

ISSN: 0959-3330 (Print) 1479-487X (Online) Journal homepage: http://www.tandfonline.com/loi/tent20

Oilfield Water Treatment by Electrocoagulation-

Reverse Osmosis for Agricultural Use: Effects on
Germination and Early Growth Characteristics of
Sunflower.

Paulo S. A. de Souza, Alexandre A. Cerqueira, Michelle M. Rigo, Julieta L.

de Paiva, Rafael S. P. Couto, Fábio Merçon, Daniel V. Perez & Monica R. C.
Marques

To cite this article: Paulo S. A. de Souza, Alexandre A. Cerqueira, Michelle M. Rigo, Julieta L.
de Paiva, Rafael S. P. Couto, Fábio Merçon, Daniel V. Perez & Monica R. C. Marques (2016):
Oilfield Water Treatment by Electrocoagulation-Reverse Osmosis for Agricultural Use: Effects
on Germination and Early Growth Characteristics of Sunflower., Environmental Technology,
DOI: 10.1080/09593330.2016.1218941

To link to this article: http://dx.doi.org/10.1080/09593330.2016.1218941

Accepted author version posted online: 02

Aug 2016.
Published online: 02 Aug 2016.

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 1

Publisher: Taylor & Francis & Informa UK Limited, trading as Taylor & Francis Group
Journal: Environmental Technology
DOI: 10.1080/09593330.2016.1218941

Oilfield Water Treatment by Electrocoagulation-Reverse Osmosis for

Agricultural Use: Effects on Germination and Early Growth Characteristics
of Sunflower.

Paulo S. A. de Souza,a,b Alexandre A. Cerqueira,a Michelle M. Rigo,a Julieta L.

de Paiva,a Rafael S. P. Couto,a Fábio Merçon,c Daniel V. Perez,d Monica R. C.
Marques*a.
a
Environmental Technology Laboratory, State University of Rio de Janeiro, Rio de Janeiro, Brazil. b Osorio
Foundation, Ministry of Defense of Brazil, Rio de Janeiro, Brazil. c Department of Biochemical Process
Technology, State University of Rio de Janeiro, Rio de Janeiro, Brazil.d Brazilian Agricultural Research
Corporation; Ministry of Agriculture, Livestock and Supply of Brazil; Rio de Janeiro; Brazil.

*Corresponding author – Address: Rua São Francisco Xavier, 524, Rio de Janeiro,RJ, Brazil, CEP:
20550-900; Telephone: +55(21)2334-0563; Fax: +55(21)2334-0563; E-mail: monicamarques@uerj.br
 2

Oilfield Water Treated by Electrocoagulation-Reverse Osmosis for

Agricultural Use: Effects on Germination and Early Growth Characteristics
of Sunflower.
This study aims to evaluate the effects of oilfield water from, treated by a hybrid process of
electrocoagulation and reverse osmosis (EC-RO), on seed germination and early growth
characteristics sunflower (Heliantus annus L.). In electrocoagulation (EC) step, tests were
conducted with 28.6 A m-2 current density and 4 min. reaction time. In reverse osmosis (RO)
step, system was operated with 1 L min-1 constant flow and 2 MPa, 2.5 MPa and 3 MPa feed
pressures. In all feed pressures, RO polymeric membranes achieved very high removals of
chemical oxygen demand (COD) (up to 89%) and oils and greases (O&G) (100%) from EC
treated effluent. In best feed pressure (2.5 MPa), turbidity, total dissolved salts, electrical
conductivity, salinity, toxic ions and sodium adsorption ratio values were attained into
internationally recognized standards for irrigation water. Using EC-RO (feed pressure:2.5 MPa)
treated OW, germinated sunflower seeds percentage (86±6%), speed of germination (30±2) and
biomass production (49±5 mg) were statistically similar to control (distilled water) results.
Vigor index average values obtained using OW treated by EC-RO (3,871), was higher than
obtained by OW water treated by EC (3,300). The results of this study indicates that EC-RO
seems to be a promising alternative for treatment of oilfield water aiming sunflower crops
irrigation, since the use of this treated effluent did not affect adversely seed germination and
seedling development, and improved seedling vigor. Furthermore, oilfield water treatment by
EC-RO reduces sodium levels into acceptable standards values avoiding soil degradation.
Keywords: electrocoagulation; oilfield water; reverse osmosis; sunflower; irrigation

Introduction

Oilfield waters (also called “produced waters”) is a by-product of various processes in oil and gas

production.[1] At production phase, for each barrel of oil produced, three barrels of oilfield water are

generated per day and, as oil wells mature, this ratio increases and may reach 7 to 10 barrels per oil

barrels per day.[2] This effluent may contain various toxic compounds, such as volatile aromatic

compounds (VOCs), polycyclic aromatic hydrocarbons (PHA´s), organic acids, phenols, metals, ions

and radionuclides.[1,2]

Depending on the treatment technology used, oilfield water can be framed as irrigation water.
 3

For this purpose, the treated effluent should meet internationally recognized standards such as that

reported by Westcot and Ayers (1985) [3] and United States Environmental Protection Agency, US EPA

(2004) [4], that refers to salinity, sodium, excessive chlorine residual, nutrients and heavy metals, which

are related to the main constraints associated with reclaimed water irrigation, like crop yield and soil

properties.[3-5]

Electrocoagulation (EC) is a process for water or wastewater treatment that uses

sacrificial anodes in order to produce metal cations for coagulation.[6] The metal hydroxide

formed coagulate liquid impurities and hydrogen bubbles evolved at the cathode allow flotation

of foam that drags organic matter. Subsequently, the aggregates formed may be removed by

decantation or flotation.[7-9]

In comparison to traditional chemical coagulation, electrocoagulation has the

advantages of removing the smallest coloidal particles and not add chemicals to conduct

coagulation and precipitation, as they occur as consequence of electrode reactions.[9-11].

Electrocoagulation units are small, compact, requires low maintenance, reduced operating costs

when compared to other flotation units and still has the advantage of producing relatively low

amount of residue.[9,11] Several studies have reported that this technology is feasible to treat,

for example, potable water, urban wastewater, oil wastes,[9-12] textile wastewater ,[13]

suspended particles, chemical and mechanical polishing waste ,[14] fluoride-containing water

,[10,15,16] heavy metal containing solutions ,[17,18] pesticides from polluted solutions and

groundwater [19,20], boron in seawater desalination [21].

Sunflower (Heliantusannus L.) crops have attracted attention worldwide since can be

used for biodiesel production and because of its peculiar agronomic characteristics such as,

drought tolerance as well as acceptance of moderated salinity levels in irrigation waters. [22]

Using untreated oilfield water, Marques et al. [23] observed that, normal seedlings

percentage and seedling vigor tended to decrease more intensely in oils and greases (O&G) and

chemical oxygen demand (COD) levels higher than 337.5 mg L-1 and 1,321 mgO2 L-1,
 4

respectively, possibly due to toxic effects caused by oil and recalcitrant organic compounds.

According to these authors [23], EC technique with alternating current, using iron electrodes,

due to aluminum toxicity to plants [24], appears to be a viable technology to remove O&G

(96%), COD (94%), color (97%) and turbidity (99%) from oilfield water and improve

sunflower seeds germination and seedling development, indicating the potential use of this

treated wastewater in irrigation of sunflower crops.

However, EC is not a suitable technique for reducing excessive salinity and ions levels

from oilfield water. On the contrary, EC may increase effluent salinity, due to anode oxidation.

[9] Salinity, which is the amount of salt dissolved in water, directly affects plant growth,

generally has an adverse effect on agricultural crop performance and can also affect soil

properties.[3,25].

Membrane separation processes, such as reverse osmosis (RO), has the characteristics

of removing salts and all dissolved especeis in solution, even monovalent ions. [25]. Thus, this

technology should be an interesting option to compose a hybrid system with EC, for oilfield

water treatment agricultural irrigation [25,26]. Furthermore, it is well known that the RO

membranes are expected to foul faster at high oil contamination and a pretreatment like

electrocoagulation before reverse osmosis is recommended to remove large diameter and free

oil particles. [26,27]

The present study aimed to assess the effects of oilfield water treated by combined

Electrocoagulation-Reverse Osmosis for agricultural irrigation purposes on seed germination and early

growth characteristics of sunflower (H. annuus L.).

Materials and methods

Simulated Oilfield Water Preparation

A synthetic oilfield water (OW) was prepared according methodology described in Marques et al. [23]

as follows. In a 2 L becher containing 1 g of petroleum (supplied by Petrobras-Brazil), 0.1 g L-1 of the

emulsifiers SP-60® and TW-60® (1:1 ratio - Oxiteno Corp.) and 0.9 L of distilled water in which was
 5

added synthetic sea salt (3 g L-1-Coralife Corp.). Subsequently, mechanical stirrer (Wigen Hauser D-

500 homogenizer) of 10,000 rpm stirred OW vigorous during 20 min to form a stable emulsion.

Electrocoagulation system

Electrocoagulation (EC) step of OW treatment was carried out in a bench scale electrolytic reactor unit

consisting of a 1 L capacity electrolytic glass cell, a monopolar electrode comprising seven rectangular

(10 cm x 5 cm x 0.3 cm) iron plates (99.9% pure) accomplishing a total of 700 cm2 electrode area and

1.0 cm distance between each electrode, vertically placed. The alternating current (AC) unit had 15 V

output and 60 Hz frequency, was obtained from an AC/AC frequency converter (CFW0800, WEG),

connected to a voltage step-down transformer (PLTN 100/15, Tecnopeltron).[9] In this study, all tests

were conducted with 2A current intensity (providing a current density of 28.6 A m-2) during 4 min

reaction time. [23]

Reverse osmosis system

After EC treatment, treated OW was transferred to a reverse osmosis system (PAM Membranes) feed

tank and pumped by a high pressure pump into the membrane module with tangential flow (Figure

1).[28] A commercial aromatic polyamide membrane (4040-X201—TSA; Trisep Corporation®) with

116.9 cm2 area of effective permeation was used. This membrane has 99.50% average for salts rejection

rate and was originally compressed with ultrapure water until the water flow was kept constant. The

flat-sheet membrane sample used in the study was cut from spiral wound element. Membrane pure water

permeability was 1.4 L h m-2 bar-2.

 6

Figure 1. Reverse osmosis system

flowchart. Reference: Da Silva et al. [28].

The system was operated using a 1 L min-1 constant flow and three different pressures: 2 MPa,

2.5 MPa and 3 MPa. An initial volume of about 5L was treated in RO system, the permeate samples

were collected and immediately analyzed. After each test, the membrane was cleaned by feeding

deionized water for 30 minutes.

EC-RO hybrid system performance was assessed by monitoring the following parameters:

COD, O&G, turbidity, color, conductivity, pH, TDS, metals (Al, Cr, Cu, Fe, Mn, Ni, Pb e Zn) and ions

(Na+, K+, Mg2+, Ca2+, Cl-, NO3-, PO43-, SO42-).

Sodium adsorption ratio (SAR) was calculated by Equation (1):

[ ]
= (1)

where the brackets refer to the cation concentrations in mmol L−1 units

The removal efficiency of the physical-chemical parameters analyzed in the effluents was
calculated by Equation (2):

( − ) (2)
E(%) = .100
 7

Where Po represents the physical-chemical parameters values before treatment and Pf after treatment.

Permeate flows (Jw) was calculated according to Equation (3) as described by Lee et al. [36]:

= (3)
.∆

Where V is the permeate volume (m), A is the effective permeation membrane area (m2) and ∆t is the
observed time interval (h).

Effluents characterization

All treated effluents were characterized immediately after the experiments conduction. pH, total

dissolved solids (TDS), salinity, conductivity, turbidity, color, O&G and COD were determined

according to Standard Methods for the Examination of Water and Wastewater.[29] Total dissolved

solids (TDS), pH, salinity and conductivity were measured with a multi-parameter analyser (PCS Testr

35 – OAKTON). Turbidity was measured by a turbidimeter (TB 1000–Tecnopon). Color was analyzed

by spectrophotometry (DR 5000 - HACH) and measured using 400 nm range in absorbance curve. COD

values were obtained using a spectrophotometer (DR 5000 - HACH) and a COD reactor (DRB 200 -

HACH). O&G measurements were performed with a Soxhlet extractor. The ions concentrations (Na+,

K+, Mg2+, Ca2+, Cl-, NO3-, PO43- e SO42-), was determined by ion chromatography (ICS 3000, DIONEX),

equipped with a IonPac® CS16 Analytical (3x250 mm) cation column, preceded by two pre-columns

and a cation suppressor CSRS 300 (2 mm) and also a AS23 Analytical (2X250 mm) anion column,

preceded by a pre-column and a 300 ASRS anion suppressor (2mm). The metals concentrations: Al, Cr,

Cu, Fe, Mn, Ni, Pb and Zn were determined by flame atomic absorption spectroscopy using an analytical

FAAS VARIAN AAS 240 spectrometer. The reported concentration for each parameter was the average

of 3 times measurement.

Plant material
 8

Certified sunflower seeds (Helianthus annuus L.) (Var. BRS-324) provided by EMBRAPA (Brazilian

Agricultural Research Corporation-Brazil) were stored in desiccators containing anhydrous calcium

chloride. Before sowing, seed dormancy was broken by maintaining the seeds immersed in a 90oC

heated water during one minute and surface decontamination was taken using sodium hypochlorite 5%

solution for two minutes, followed by washing in running water for 3 minutes, then in distilled water

for 1minute. After this procedure the seeds were dried at ambient temperature.[30]

Germination tests

The seeds were treated by two kinds of irrigation waters (treatments): distilled water (control) and the

OW treated by combined electrocoagulation flocculation reverse osmosis (EC-RO-OW) in the best

condition. Four replications containing 50 seeds per assay germinated in germination papers

(Germitest®) previously moistened by the treatments solutions (control and EC-RO). The amout of

treatment solutions, in mL, corresponded to 2.5 times the weightof the dry paper, in grams. The

germination papers were carefully rolled and wrapped in polyethylene bags to reduce evaporation and

placed in a germination incubator (ETHIK, 411FPD) at 25 oC temperature, in upright position for a

12 hours photoperiod.[31,32]

Speed of germination

A daily count of the germination incubated seeds was taken until there was no more seeds to germinate

and the speed of germination was calculated according to Maguire [33], by using the formula:

= ∑( ) (4)

Where n is the number of seeds newly germinated at time t, and t is days from sowing.
 9

Seedling development, biomass production and vigor index

Seedling development was observed throughout the experiments and on the 10th counting day, normal

seedlings percentages determined.[31]

Ten normal seedlings from each treatment were randomly selected, dried overnight in an oven

at 90oC temperature. Biomass production was measured and expressed as seedling dry weight.[34]

Vigor index was calculated by Equation (5) according to Abdul-Baki and Anderson [35]:

= (%) ℎ (5)

Results and discussion

Oilfield water treatment using combined Electrocoagulation-Reverse Osmosis process

In all feed pressures tested, the use of RO membranes promoted significant COD removals

(Figure 2A) from OW treated only by EC.[23] These removal efficiencies were 89% (2.0 MPa), 90%

(2.5 MPa) and 82% (3.0 MPa), ensuring the reduction to a minimum level of possible recalcitrant

organic compounds, which can affect germination adversely.[36]

 10

(A) (B)
160

2500
140

120
2000
COD / (mgO2 L )

100
-1

TDS / (mg L )
-1
1500
80

60
1000

40
500
20

0 0
EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0) EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0)

(C) (D)
4,0
3500

3,5
3000

3,0
Conductivity / (uC cm )
-1

2500

2,5

Fe / (mg L )
2000 -1

2,0
1500
1,5
1000
1,0

500
0,5

0
0,0
EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0)
EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0)

Figure 2. Results for OW treated by EC* and EC-RO: (A) COD; (B) TDS; (C) conductivity and (D) Fe.

(2.0): RO feed pressure=2.0 MPa; (2.5): RO feed pressure=2.5 MPa and (3.0): RO feed pressure=3.0

MPa. Average values; n=3. *Reference: Marques et al. [23].

Table 1 shows that EC step promotes significant reductions in O&G and turbidity values

from OW, obtaining removal rates of 97% and 99.9% of these parameters, respectively. These

results (Table 1) demonstrate the high effectiveness of EC technique as pretreatment step of

RO for treatment of oilfield water. The significant reduction in oil and suspended particles

contents reduces membranes fouling, which increases its useful life and reduces maintenance

costs. [26,27]

After EC-RO treatment O&G levels were completely removed from raw efluent in all

feed pressures tested, eliminating the possibility of inhibitory effects of oil in germination.[37]
 11

Salinity (expressed as conductivity and TDS) is a key factor for wastewater reuse in

agriculture [3], since when subjected to salt stress, plant metabolism is interrupted or inhibited

by increasing reactive oxygen species and lipid peroxidation, resulting in reduced germination,

weaker root and shoot growth and even mortality. [3,38] After EC-RO combined treatment,

TDS (maximum average value: 278 mg L-1) (Figure 2B) and conductivity (maximum average

value: 353 μS cm-1) (Figure 2C) of the OW treated (EC-RO-OW) attained into salinity irrigation

standards (Table 2) reported by Westcot and Ayers [3] and US EPA [4] in all feed pressures

tested .

The use of RO membranes was also effective in reducing Fe concentration increased by

EC treatment, as a consequence of the anode oxidation (Figure 2D). Fe removal rates obtained

by RO step were 99% (2.0 MPa) and 98% (2.5 and 3.0 MPa). In all operating conditions

evaluated, Fe concentrations were below irrigation standards required by U.S. EPA [4] (Table

2). Thas is an important feature for irrigation waters, since high Fe concentrations may cause

pipes cloguing due precipitation of low soluble salts that can reduce the absorption by plants of

essential nutrients such as P, K, Ca, Mg and Mn. [39]

In all operating feed pressures investigated, the average values for pH in permeates

(pH=6.0) were similar to EC treated and untreated OW and were within the ranges established

by Westcot and Ayers [3] and US EPA [4] for irrigation waters (Table 2). pH is also an

important parameter when assessing irrigation water quality since it affects nutrients and toxic

substances availability as well as plays an important role in plant growth.[3,39] Furthermore,

pH values above 8.4 can cause blockages in the irrigation system due to calcium carbonate

precipitation as well as waters with low pH values can rapidly corrode the metal components

of irrigation pipe system.[3]

Na+ and Cl- concentrations (Figure 3A) were also focused since they are toxicity

parameters for irrigation waters. The excess presence of these ions can cause necrosis and burns
 12

in the leaves.[39] After EC-RO treatment, these ions concentrations in permeate, were found

below the irrigation standards (Table 1) in all operating pressures tested.

(A) +
2000 Na
-
Cl

1500

-1
mg L 1000

500

0
EC* EC-RO(a) EC-RO(b) EC-RO(c)

(B)
16 SAR

14

12

10
-1 0.5
(mmolc L )

0
EC* EC-RO(a) EC-RO(b) EC-RO(c)

Figure 3. Results for OW treatment by EC* and EC-RO: (A) Na+/Cl- concentrations and (B) SAR. RO

feed pressures: (a)= 2.0 MPa; (b)= 2.5 MPa and (c)= 3.0 MPa. Average values; n=3. *Reference:

Marques et al. [23]

SAR expresses Na+ ion tendency of being adsorbed by ion exchange sites in the

soil,taking Ca2+ and Mg2+ ions place. At higher SAR values, the water quality is less proper for

irrigation, due to increasing infiltration rate which results in reduction of the amount of water

available to plants in soil.[3,40] Regarding SAR, the results obtained for this parameter (Figure

3B), in all evaluated operating pressures are within the recommended standards for water

irrigation, settled down by Westcot & Ayers [3] (Table 1).

The results presented in Figures 2 and Figure 3, shows that in the pressure range studied

for RO step, a great reduction in COD, TDS, conductivity, Fe, Na+, Cl- and SAR was obtained,
 13

but with no significant differences, demonstrating the ability of RO membrane to remove

residual contaminants form EC step. The obtained values for EC-RO-OW parameters were also

below the irrigation standards used as reference in this work (Table 1) in the pressure range

studied. Among these operating conditions, taking acount these results and permeate flows

values calculated by Eq. (4) ( 2.0 MPa: 13.75 L h-1 m-2 ; 2.5 MPa: 16.57 L h-1 m-2 and 3.0 MPa:

20.60 L h-1 m-2), the optimal feed pressure chosen for RO step of EC-RO treatment was 2.5

MPa. This choice is justified since, in this work, the use of this feed pressure provided higher

permeate flows and similar removal rates of O&G, COD, salinity (conductivity and TDS), Na+

and Cl- ,which are important parameters to be considered in treatment of waters aiming

irrigation purposes than that obtained by the use of 2.0 MPa.[3-5] Furthermore, the use of the

maximum feed pressure (3.0 MPa), tends to reduce the rejection of this parameters due to

excessive membrane mechanical deformation and fouling.[26-28]

Table 1 shows the characterizations of untreated synthetic oilfield water (OW) and treated by

EC oilfield water (EC-OW), according to Marques et al., [23] as well as the characterization of treated

by EC-RO oilfield water (EC-RO-OW) in the best operating condition (2.5 MPa) adopted by this study:

Table 1. Characterizations of untreated simulated oilfield produced water (OW), treated by EC oilfield
water (EC-OW)a and treated by EC-RO oilfield water (EC-RO-OW)
 14

Irrigation standards limits

Parameter OWa EC-OWa EC-RO-OWb
Westcot & Ayers [3] U.S. EPA [4]

pH 6.0 6.0 6.0 6.5 – 8.4 6–9

-1
Conductivity (μS cm ) 3,583 3,448 247 3,000 ----
-1
TDS (mg L ) 2,614 2,634 215 2,000 2,000
Turbidity (NTU) 4,780 6.6 1.0 ---- 2
Color (Abs.400 nm) 2.5 0.06 0.0 ---- ----
-1
COD (mg O2 L ) 2,642 152 16 ---- ----
-1
O&G (mg L ) 675 21 0.0 ---- ----
Na (mg L-1) 2,158 2,022 94 207 ----
K (mg L-1) 1,179 1,205 193 ---- ----
-1
Ca (mg L ) 1,301 1,236 195 ---- ----
-1
Mg (mg L ) nd nd nd ---- ----
-1
Al (mg L ) 0.40 0.30 0.1 ---- 20
Fe (mg L-1) 0.12 3.77 nd ---- 3
-1
Mn (mg L ) 0.18 0.02 nd ---- 10
-1
Cr (mg L ) 0.01 nd nd ---- 1
-1
Ni (mg L ) 0.05 0.04 nd ---- 2
Pb (mg L-1) 0.11 0.09 nd ---- 10
Cu (mg L-1) 0.015 nd nd ---- 5
-1
Zn (mg L ) 0.02 0.02 nd ---- 10
- -1
Cl (mg L ) 1,615 1,503 118 355 ----
- -1
NO3 (mg L ) 708 574 27 30 ----
SAR (mmolc L-1)1/2 14 15.8 2 15 ----
TDS: total dissolved salts; COD: chemical oxygen demand; O&G: oils and greases; SAR: Sodium Adsorption
Ratio. nd: not detected. (----): not availed. aReference: Marques et al. 2015 [23]. bFeed pressure: 2.5 MPa

The results presented in Table 1 indicates that the combination of electrocoagulation

and reverse osmosis technologies is a promising alternative for treatment of oilfield water

aiming irrigation puposes. In addition, electrocoagulation and revers osmosis systems are

compact, simple to design and operate, have low maintenance requirements and its modules

can be easily associated, enabling not only the integration of the two processes, as its use in

large scale, making expansion of the systems easy.[9,11,26-28]

Sunflower seed germination, seedling development, biomass production and vigor index
 15

Germination test is a complementary tool for physico-chemical analysis of wastewater

that evaluates the phytotoxic effects on seed germination process, which is a period where

numerous physiological processes occurs.[41,42] Figure 4A shows that germinated seeds

percentage was 86±6% and Figure 4B shows that speed of germination was 30±2, using EC-

RO treated oilfield water (EC-RO-OW). These results indicates that there was no statistical

difference between treatments (distilled water) and EC-RO-OW, in spite of differences in

soluble organic matter (COD) and salinity (EC and TDS) between these treatments (Table 1).

Therefore, can be inferred that these diferences did not influenced the germination process and

its velocity which, according to Beweley and Black,[41] is regulated by internal seeds balance

factors and external environmental factors, such as, light, humidity, temperature and oxygen

concentration.
 16

100
(A)

80

Germination (%)
60

40

20

0
Control EC-RO-OW

35 (B)

30

Speed of germination (seed day )

-1
25

20

15

10

0
Control EC-RO-OW

100
(C)

80
Normal seedlings (%)

60

40

20

0
Control EC-RO-OW

(D)
50
Seedling dry wt (mg seedling )
-1

40

30

20

10

0
Control EC-RO-OW

4500 (E)
4000

3500

3000
Vigor index

2500

2000

1500

1000

500

0
Control EC-RO-OW

Figure 4. Germination percentage (A), Speed of germination (B), normal seedlings percentage
(C), seedling dry weight (D) and (E) vigor index. EC-RO-OW: OW treated by EC-RO. RO feed
pressure: 2.5 MPa.

In order to complement germination tests and predict subsequent plant development,

seedling emergence and biomass production in a very early stage of plant development are
 17

options to the use of greenhouses that takes several months and considerable space.[37] Figure

4C shows that normal seedlings percentage obtained by EC-RO-OW was high (79±4%), but

minor than that obtained by control (91±2%). This difference may be related to residual COD

content (Table 1) of EC-RO-OW effluent. This parameter indicates the presence of minimum

levels of recalcitrant organic compounds that may promote physico-chemical interactions

which reduces metabolism and carbon fixation processes.[36,37]

The average value for biomass production, expressed by seedling dry wheight (Fig.

4D), obtained by EC-RO treatment (49±5 mg) was higher than that obtained by control

treatment (45±3 mg), however not differing statistically. Therefore, biomass production was

not influencied by the differences in soluble organic matter (COD), salinity (conductivity and

TDS) and toxic ions levels, like Na+ and Cl-, in EC-RO-OW efluent (Table 1) and control,

similarly to what was observed for germination percentages and speed of germination (Figures

4A and 4B).

Seed vigor index can be defined as that property which determines the seed emergence

under unfavorable conditions.[31] Figure 4E shows that vigor index (calculated by Eq. 5)

obtained by EC-RO-OW treatment (3,871±155) was a little inferior than that obtained by

control (4,077±122), but do not differ statistically. Indicating that this parameter was also

unaffected by differences in COD, salinity and ions of EC-RO-OW efluent and control (Table

1).

However, when comparing these results (Figure 4E) with those obtained previously by

Marques et al. [23], who treated the same variety of sunflower seeds (EMBRAPA var. BRS-

324) with the same simulated oilfield water, but only treated with electrocoagulation process

(EC-OW), the average vigor index obtained was lower (3.300). This results suggests that vigor

index of sunflower seeds (var. EMBRAPA BRS-324) is negatively influencied by very higher

levels of O&G, COD, salinity and toxic ions (mainly Na+, Cl-) and Fe in OW treated only by
 18

EC (Table 1).

Thus, EC-RO appears as an effective technology for treatment of oilfield water to

improve sunflower seedlings development, as well as promotes a reduction in residual levels of

COD and O&G derived from EC treatment, fitting salinity, toxic ions and Fe concentrations

into acceptable levels for irrigation purposes. Furthermore, the lower Na+ concentrations and

RAS values of oilfield water treated by EC-RO (Table 1) may prevent soil degradation.[3,25]

Conclusions

Electrocoagulation is an efficient technique as pretreatment step of reverse osmosis for

treatment of oilfield water. The significant reduction in O&G and turbidity contents reduces

membranes fouling, which increases its useful life and reduces maintenance costs.

All parameters analyzed in membrane permeates in best operating condition (2.5 MPa)

were within established international standards for irrigation, indicating that combined

Electrocoagulation-Reverse Osmosis is a promising alternative for treatment of oilfield water

aiming irrigation puposes, preserving crop yield and soil structural stability.

Since electrocoagulation and reverse osmosis units are compact, its modules can be

associated, making expansion and use in large scale of the systems easy.

The use of oilfield water treated by combined Electrocoagulation-Reverse Osmosis, in

best operating condition (of 2.5 MPa), did not influence adversely germination percentage,

speed of germination, and biomass sunflower production.

Vigor index obtained using oilfield water treated by combined Electrocoagulation-Reverse

Osmosis, was higher than that obtained by using simulated oilfield water treated only by

Electrocoagulation, indicating that this hybrid technology is a promising alternative to remove oil,

soluble organic matter, salts, metals and toxic ions in excessive levels, in order to not affect adversely

sunflower seedling development.

 19

Disclosure statement

No potential conflict of interest was reported by the authors.

Funding

This study was funded by Rio de Janeiro State Research Foundation-FAPERJ [grant number E-

26/112.211/2012].

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 23

List of Figures

Figure 1. Reverse osmosis system flowchart. Reference: Da Silva et al. [28].

Figure 2. Results for OW treated by EC* and EC-RO: (A) COD; (B) TDS; (C) conductivity and (D) Fe.

(2.0): RO feed pressure=2.0 MPa; (2.5): RO feed pressure=2.5 MPa and (3.0): RO feed pressure=3.0

MPa. Average values; n=3. *Reference: Marques et al. [23].

23
 24

(A) (B)
160

2500
140

120
2000
COD / (mgO2 L )

100
-1

TDS / (mg L )
-1
1500
80

60
1000

40
500
20

0 0
EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0) EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0)

(C) (D)
4,0
3500

3,5
3000

3,0
Conductivity / (uC cm )
-1

2500

2,5
Fe / (mg L )
-1

2000
2,0
1500
1,5
1000
1,0

500
0,5

0
0,0
EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0)
EC* EC-RO(2.0) EC-RO(2.5) EC-RO(3.0)

Figure 3. Results for OW treatment by EC* and EC-RO: (A) Na+/Cl- concentrations and (B) SAR. RO

feed pressures: (a)= 2.0 MPa; (b)= 2.5 MPa and (c)= 3.0 MPa. Average values; n=3. *Reference:

Marques et al. [23]

24
 25

(A) +
2000 Na
-
Cl

1500

-1
mg L
1000

500

0
EC* EC-RO(a) EC-RO(b) EC-RO(c)

(B)
16 SAR

14

12

10
-1 0.5
(mmolc L )

0
EC* EC-RO(a) EC-RO(b) EC-RO(c)

Figure 4. Germination percentage (A), Speed of germination (B), normal seedlings percentage
(C), seedling dry weight (D) and (E) vigor index. EC-RO-OW: OW treated by EC-RO. RO feed
pressure: 2.5 MPa.

25
 26

100
(A)

80

Germination (%)
60

40

20

0
Control EC-RO-OW

35 (B)

30

Speed of germination (seed day )

-1
25

20

15

10

0
Control EC-RO-OW

100
(C)

80
Normal seedlings (%)

60

40

20

0
Control EC-RO-OW

(D)
50
Seedling dry wt (mg seedling )
-1

40

30

20

10

0
Control EC-RO-OW

4500 (E)
4000

3500

3000
Vigor index

2500

2000

1500

1000

500

0
Control EC-RO-OW

[43]

26
 27

Table 1. Characterizations of untreated simulated oilfield produced water (OW), treated by EC oilfield
water (EC-OW)a and treated by EC-RO oilfield water (EC-RO-OW)

Irrigation standards limits

Parameter OWa EC-OWa EC-RO-OWb
Westcot & Ayers [3] U.S. EPA [4]

pH 6.0 6.0 6.0 6.5 – 8.4 6–9

Conductivity (μS cm-1) 3,583 3,448 247 3,000 ----
TDS (mg L-1) 2,614 2,634 215 2,000 2,000
Turbidity (NTU) 4,780 6.6 1.0 ---- 2
Color (Abs.400 nm) 2.5 0.06 0.0 ---- ----
-1
COD (mg O2 L ) 2,642 152 16 ---- ----
O&G (mg L-1) 675 21 0.0 ---- ----
Na (mg L-1) 2,158 2,022 94 207 ----
-1
K (mg L ) 1,179 1,205 193 ---- ----
-1
Ca (mg L ) 1,301 1,236 195 ---- ----
-1
Mg (mg L ) nd nd nd ---- ----
Al (mg L-1) 0.40 0.30 0.1 ---- 20
-1
Fe (mg L ) 0.12 3.77 nd ---- 3
-1
Mn (mg L ) 0.18 0.02 nd ---- 10
-1
Cr (mg L ) 0.01 nd nd ---- 1
Ni (mg L-1) 0.05 0.04 nd ---- 2
Pb (mg L-1) 0.11 0.09 nd ---- 10
-1
Cu (mg L ) 0.015 nd nd ---- 5
-1
Zn (mg L ) 0.02 0.02 nd ---- 10
Cl- (mg L-1) 1,615 1,503 118 355 ----
NO3- (mg L-1) 708 574 27 30 ----
SAR (mmolc L-1)1/2 14 15.8 2 15 ----
TDS: total dissolved salts; COD: chemical oxygen demand; O&G: oils and greases; SAR: Sodium Adsorption
Ratio. nd: not detected. (----): not availed. aReference: Marques et al. 2015 [23]. bFeed pressure: 2.5 MPa

27