NSERC/COSIA/Alberta Innovates Senior Industrial

Research Chair in Oil Sands Process Water Treatment:

Treatment and Toxicity Perspectives

Mohamed Gamal El-Din, Ph.D., P.Eng.Professor

NSERC Senior Industrial Research Chair in Oil Sands Tailings Water Treatment

Theme Co-Lead, Resilient Reclaimed Land and Water Systems, Future Energy Systems (FES)

Department of Civil and Environmental Engineering

University of Alberta, Canada

May 23, 20191

Presentation Outline

2

▪ Overview of NSERC IRC Program

▪ Characterization of Process Water

▪ Selected Treatment Approaches for

Process Water

3

Overview of NSERC

IRC Program

NSERC IRC Program in Oil Sands Tailings Water Treatment

▪ Established in July 2011

▪ First Term: July 2011 to June 2016

▪ Second Term: July 2017 to June 2022

Vision of the NSERC IRC Program

▪ Develop and assess different water treatment strategies and their

applicability to oil sands operations for the safe return of OSPW into the

environment

▪ Contribute broadly to the research base, fundamental engineering and

scientific knowledge, and foundational data that will lead to the

environmentally and economically sustainable development of oil sands

operations

4

safe return of OSPW into the

environment

Long Term

Objectives

NSERC IRC

2nd TermNSERC IRC

1st Term

▪ Understanding of process

fundamentals of active

treatment approaches

▪ Assessment of new

treatment methods

▪ Optimization of selected

treatment processes

▪ Scientific evidence for

developing new regulations

▪ Integration of gained knowledge

into actual water

treatment/reclamation options

by the oil sands industry

▪ Protection of the environment and human health while

the oil sands industry continues to grow

▪ Application of semi-passive

(engineered passive)

treatment/reclamation

approaches

▪ Pilot studies (lab and field)

▪ Scale-up of selected active

and engineered passive

processes

Final Goal

Research Road Map of OSPW Treatment

5

Future Energy Systems (FES) -

Resilient Reclaimed Land and

Water Systems Theme (Canada

First Research Excellence Fund)

▪ Engineered systems often having

relatively high capital costs

▪ Require routine (daily/weekly)

maintenance

▪ Constant, relatively high energy

input

▪ Sophisticated process control

▪ Designed to treat the target

compounds quickly with relatively

low residence times (min/hr)

▪ Combination of natural and

engineered systems

▪ Relatively low capital costs

▪ Require either no maintenance or

minor intermittent maintenance

▪ Little or no anthropogenic energy

input

▪ Designed to treat the target

compounds with relatively high

residence times

▪ Sedimentation

▪ Filtration

▪ Constructed Wetlands

▪ Algae Ponds

Treatment Approaches

▪ Ozonation

▪ Advanced Oxidation

▪ Membrane Filtration

▪ Ion Exchange

▪ Fluidized Bed

Reactors

Hybrid

Processes

6

Potential Reclamation Systems for OSPW

Active approaches Engineered passive approaches

Potential reclamation systems for OSPW

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Coag/flocc using metallic coagulants & polymers

Coag/flocc using crumb rubber or natural coagulants

Natural settling

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sAdsorption using petroleum

cokeAsphaltene-based activated carbon

Cellullose-based adsorbents

Low-cost adsorbents

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Solar-driven photocatalysis

O3 and O3/H2O2

Fenton/photo-Fenton

In-pipe oxidation Catalytic AOP

Bio

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Bio

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Biological active filters

Engineered biofilm system

MBR, IFAS, MBBR

Silica-based microsphere bioreactor

Hybrid constructed wetland

Filt

ratio

nR

O/F

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Soil-based filtration

Membrane filtration

RO/FO

Advanced filtration using self-cleaning filters

NSERC IRC 1st Term NSERC IRC 2nd Term

✓

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7

Wet Reclamation Approach

8

`

Reclamation Criteria

Drivers: Integrated Research

Training HQPProtection of the Environment and

Human Health

Scientific Knowledge

8

www.cbc.ca

Process Water

Pit Lakes

Wetlands

Tailings

Electro-OxidationAdsorption (Petroleum Coke)Biological-Based Treatment

Biofiltration

Life-Cycle Analysis

Pore Water Quality

Low-Cost Materials (Adsorbents, Catalysts)

Self-Sustaining Landscapes

Bio/Sorption

Solar-Driven and in-situ AOPs

Toolbox of Best Available Treatment/Reclamation

Approaches

Aging

In-Pipe Treatment

Pilots

Bench-Scale Columns

MesocosmSystems

Suspended Growth & Attached Growth Bio. Treatment

Phytoremediation

9

▪ Sludge-Based Biochar as a Catalyst for in situ

Generation of H2O2 to Degrade Naphthenic Acids

▪ Application of Solar-Driven Catalytic Advanced

Oxidation Processes for OSPW Treatment

▪ Photodegradation of Naphthenic Acids Induced by

Natural Photosensitizer in Oil Sands Process Water

▪ Low-Current Electrocatalytic Oxidation for the

Abatement of Organics Present in Process Water

▪ Assessment of the Performance of Solid Fenton

Material to Photodegrade Naphthenic acids

▪ Removal of Organic Constituents from Oil Sands

Process Water Using Low-Cost Adsorbents

▪ In-Pipe Treatment to Assist in OSPW Reclamation

▪ Understand Science of Engineered Passive

Processes for Process Water Reclamation Using

Wetlands and Pit Lakes

Current Projects

10

Characterization of

OSPW

11

Oil Sands Process Water (OSPW)

11

▪ Generated from extraction process

▪ Highly complex mixture of inorganic

and organic compounds, with elevated

pH (8-9)

▪ Organic fraction consists of organic

compounds with different polarities

such as naphthenic acids (NAs), humic

and fulvic acids, benzene, toluene,

ethylbenzene and xylene (BTEX),

phenols and polycyclic aromatic

hydrocarbons, etc.

▪ Inorganic fraction consists of

suspended solids including sand, clay

and silt, dissolved salts and trace heavy

and transitional metals

www.cbc.ca

National Energy Board - Canada - www.neb-one.gc.ca

Raw OSPW

Characteristics of Fresh and Aged OSPWs

Parameters Fresh OSPW Aged OSPW

pH (unit) 8.00 – 8.80 8.13

Total Dissolved Solids (mg/L) 1,900 – 2,500 2,863

Total Suspended Solids (mg/L) 230 – 1,100 200

Conductivity (μS/cm) 3,300 – 4,100 4,280

COD (mg/L) 170 – 420 150

BOD (mg/L) 2.3 – 7.1 16.6

Bicarbonate (mg/L) 580 – 880 1,040

Chloride (mg/L) 400 – 590 925

Acid Extractable Fraction (mg/L) 50 – 75 50

Naphthenic Acids (mg/L) 20 – 45 15

Total Petroleum Hydrocarbons (C10 to C30) (mg/L) 3.7 – 9.4 N/A

Arsenic (μg/L) 3.2 – 7.1 2

Cadmium (μg/L) 0.1 – 0.3 < 0.06

Nickel (μg/L) 7 – 10 5

Selenium (μg/L) 6 – 20 4

Vanadium (μg/L) 5 – 20 10

N/A: not available 12

Analysis of OSPW Analytes

Analysis of Basic Water Parameters pH, TOC, DOC, BOD5, Alkalinity, N (NH3,

total N)

Fourier Transform Infrared

Spectroscopy (FT-IR)

Acid extractable fraction (AEF)

Synchronous Fluorescence

Spectroscopy (SFS)

Qualitative information on fluorophore

compounds and aromatics

Proton Nuclear Magnetic Resonance

(1H-NMR)

Quantitative information on H bound to

aliphatic and aromatic C

Ultra Performance Liquid

Chromatography Time-of-Flight

Mass Spectrometry (UPLC-TOF-MS)

(40,000 Mass Resolution)

Negative mode: Naphthenic acids (NAs)

Positive mode: Basic and neutral

species, N and S containing

compounds

Ion Mobility Qualitative information on clustering of

NAs, oxidized NAs and heteroatomic

NAs

Gas Chromatography-Mass

Spectrometry (GC-MS)

Polyaromatic hydrocarbons and F1-F4

petroleum fraction

FTICR-MS

(500,000 Mass Resolution)

High resolution MS to distinguish

between S (SxOy), N (NxOy) and Ox – NAs

Inductively Coupled Plasma Mass

Spectrometry (ICP-MS)

Metals

Analysis of OSPW

13

UPLC-QTOFMS system equipped with IMS

QTOFMS (middle) equipped with UPLC (left) and APGC (right)

Supercritical fluid

chromatography (SFC)

Assessment of OSPW Toxicity

Microtox Assay

In vitro Assays using

Fish Cells or

Mammalian Cells

Acute and Screening

Chronic Ecotoxicity

Assays (Commercial Lab)

Toxicological Assessment

using Zebrafish (Develop.

and Lifetime Exposures)

Immunotoxicity

Assessment (in vivo)

using Goldfish and Mouse

Mouse Development

& Reproduction

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req

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cy

Chronic Ecotoxicity

Assays (Commercial

Lab)

Routine analyses conducted

after each treatment process

Potential return of treated

OSPW into the environment

Analyses conducted after

each treatment process at

optimum conditions

Analyses conducted after

treatment processes

involving chemical and

biological transformations at

optimum conditions

14

15

Ozonation as an Active

Treatment for Process Water

Reclamation

Ozonation

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Has a very strong oxidizing

power with a short reaction

time

Reacts with a large variety

of organic compounds

Increases process water

biodegradability

Ozonation of OSPW

0

10

20

30

40

50

60

70

80

90

0 50 100 150 200 250 300 350

Co

nc

en

tra

tio

n o

f A

cid

Ex

tra

cta

ble

Fra

cti

on

(m

g/L

)

Utilized Ozone Dose (mg/L)

pH 8.3

pH 6.5

pH 10.0

Reference: Gamal El-Din et al. (2011), Sci. Total Environ., 409(23), 5119-5125.

Effect of Ozonation on the Levels of Acid Extractable Fraction

About 0.5 mg/L total

NAs were oxidized per

mg/L of utilized ozone

dose, at utilized ozone

doses lower than 50

mg/L

About 0.6 mg/L of total acid-

extractable organics were oxidized

per mg/L of utilized ozone dose (doses lower than 80 mg/L)

0.3 mg/L of total acid-

extractable organics were

oxidized per mg/L of utilized ozone dose

17

About 0.05 mg/L total

NAs were degraded

per mg/L of utilized

ozone dose, at higher

utilized ozone doses

Effect of Ozonation on Naphthenic Acids (NAs) Speciation

▪ NAs with high carbon numbers (n)

are degraded more effectively than

NAs with less carbon numbers

▪ Ozone degrades NAs with high

number of rings more effectively

than NAs with small Z numbers

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0 20 40 60 80 100

[NA

s]

/In

itia

l [N

As

]

Utilized Ozone Dose (mg/L)

Z = -2

Z = -4

Z = -6

Z = -8

Z = -10

Z = -12

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0 20 40 60 80 100

[NA

s]

/In

itia

l [N

As

]

Utilized Ozone Dose (mg/L)

n = 10

n = 12

n = 14

n = 16

n = 18

n = 19

Carbon NumberNumber of Rings

Reference: Wang et al., Environ. Sci. Technol., 47(12), 6518-6526 (2013). 18

Mammalian Toxicity of RAW and Ozonated OSPW

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Monitoring OSPW-Mediated Influences on Immune Cellular Viability

and Functions

• OPSW• OSPW-O3

• OSPW-OF• OSPW-OF-O3

FEEDBACKhttp://www.wisegeekhealth.com/what-are-macrophages.htm#monocyte

• Health Status• Gene Expression• Protein Levels• Cellular Activity

Cell LineMammalian Immune Cell-

line (RAW 264.7)Treatments

OSPW Waters

AssaysBioindicators

Fu et al., Environ. Sci. Technol., 51(15), 8624-8634 (2017).

Mammalian Toxicity of RAW and Ozonated OSPW

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▪ Raw OSPW was acutely

toxic in a dose-dependent

manner, whereas

reconstituted OSPW

Organic Fraction was not

toxic

▪ Ozonation of raw OSPW did

not ameliorate acute toxicity

▪ Raw OSPW at doses of 10

mg/L NA significantly up-

regulated genes belonging

to the DNA damage and

oxidative stress pathways

Fu et al., Environ. Sci. Technol., 51(15), 8624-8634 (2017).

Developmental Effects of OSPW Exposure on Zebrafish

21

▪ Survival of zebrafish embryos was not

impacted by raw or ozonated OSPW

exposure

▪ Heart development and function genes

were downregulated by OSPW exposure

▪ Cardiac function was largely unaffected by

exposure

▪ Exposure did not induce craniofacial

abnormalities or apoptosis Heart

rate

(bpm

)

0

50

100

150

200

EmbryoMedia

(Control)

OSPW Ozonated

OSPW

*

OSPW exposure increased heart rate in 2 dpf

embryos, however, heart rate remains in a

‘normal’ range for this life

Exposure to raw and ozonated OSPW

exposure had no impact on jaw morphology

dpf: Days post fertilization

Lyons et al., Environ. Pollut., 241, 959-968 (2018).

22

Application of Electro-

Oxidation for the Degradation

of Organics in OSPW

23

▪ Considering the nature of OSPW (high TDS and electrical conductivity),electro-oxidation (EO) can be effective and cost-efficient option forOSPW treatment

▪ If can be applied at low current densities, EO can achieve high currentefficiencies and, therefore, energy cost can be reduced significantly

▪ EO by active anode and at low current densities should preferentiallydegrade the more recalcitrant NAs without wasting energy in achievingcomplete mineralization

▪ Low current electro-oxidation = Effective + Low (energy) cost +Relatively low-cost anode material

▪ At low current densities the problems of the anodes severe corrosioncan be avoided

Rationale

Project Significance and Potential Applications

24

Solar-powered

Electro-

oxidation

Solar UV/Chlorine

Solar photo-catalysis

OSPW highly suitable for electro-oxidation (EO) process

▪ Excellent conductivity without adding supporting electrolyte

▪ Electrogeneration of strong oxidants - •OH, S2O82‒, SO4

•‒, ClO‒/HOCl

▪ Limited/no hazardous or toxic waste byproducts

25

Concluding Remarks

Concluding Remarks

▪ Tailings water treatment and reclamation are

among the most difficult environmental

challenges facing the oil sands mining

sector

▪ Through multidisciplinary research, we have

develop innovative approaches for the

decontamination and detoxification of

process water

▪ In situ catalytic oxidation may play a critical

role in enhancing the remediation of OSPW

when applied as a pre-treatment step to

accelerate the degradation of NAs among

other organics in OSPW

▪ Novel materials (waste by-products) are

being used for treatment, reclamation and

resource recovery

26http://osqar.suncor.com/2014/03/tailings-ponds-what-theyre-made-of.html

Future Work

27http://osqar.suncor.com/2014/03/tailings-ponds-what-theyre-made-of.html

27

Engineered and Passive Treatment/ Reclamation

Success Indicators

Life-Cycle Analysis

Field Pilots(Wetlands and Pit Lakes)

Acknowledgments

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Thank You!

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For Additional Information:

Mohamed Gamal El-Din, Ph.D., P.Eng.Professor

NSERC Senior Industrial Research Chair in Oil Sands Tailings Water Treatment

Theme Co-Lead, Resilient Reclaimed Land and Water Systems, Future Energy

Systems (FES)

Department of Civil and Environmental Engineering

University of Alberta

Email: mgamalel-din@ualberta.ca

Tel: (780) 492-5124