applied

sciences
Review
Advanced Bioreactor Treatments of
Hydrocarbon-Containing Wastewater
Maria S. Kuyukina 1,2, * , Anastasiya V. Krivoruchko 1,2 and Irena B. Ivshina 1,2
1 Microbiology and Immunology Department, Perm State University, Perm 614990, Russia;
nast@iegm.ru (A.V.K.); ivshina@iegm.ru (I.B.I.)
2 Institute of Ecology and Genetics of Microorganisms, Perm Federal Research Center, Russian Academy of
Sciences, Perm 614081, Russia
* Correspondence: kuyukina@iegm.ru




Received: 29 November 2019; Accepted: 21 January 2020; Published: 24 January 2020


Abstract: This review discusses bioreactor-based methods for industrial hydrocarbon-containing

wastewater treatment using different (e.g., stirred-tank, membrane, packed-bed and fluidized-bed)
constructions. Aerobic, anaerobic and hybrid bioreactors are becoming increasingly popular in the field
of oily wastewater treatment, while high concentrations of petroleum hydrocarbons usually require
physico-chemical pre-treatments. Most efficient bioreactor techniques employ immobilized cultures
of hydrocarbon-oxidizing microorganisms, either defined consortia or mixed natural populations.
Some advantages of fluidized-bed bioreactors over other types of reactors are shown, such as large
biofilm–liquid interfacial area, high immobilized biomass concentration and improved mass transfer
characteristics. Several limitations, including low nutrient content and the presence of heavy metals
or toxicants, as well as fouling and contamination with nuisance microorganisms, can be overcome
using effective inocula and advanced bioreactor designs. The examples of laboratory studies and few
successful pilot/full-scale applications are given relating to the biotreatment of oilfield wastewater,
fuel-contaminated water and refinery effluents.

Keywords: oilfield produced water; refinery wastewater; bioreactor; hybrid systems;

immobilized cells

1. Introduction
Hydrocarbon-containing wastewater is generated in large volumes in petroleum, metallurgical
and transport industries, as well as in other water-intensive industries, agriculture and urban
management. Oil production and refining processes consume large amounts of water and discharge
hydrocarbon-contaminated wastewater streams, which are the main source of organic pollution of the
environment. Petrochemical and metallurgical plants also produce complex wastewater streams, the
volume and composition of which varies greatly depending on the raw materials and technologies
used. Majority of the industrial wastes are hazardous as they contain toxic, mutagenic and carcinogenic
substances. Consequently, industrial waste effluents typically require treatment before reuse or
discharge to open water bodies. Stringent regulations on wastewater discharge are becoming stricter
worldwide, with restrictions applied not only to industrial users but also to municipal wastewater
treatment operations. Industry faces the challenge of reducing the wastewater it generates and
attaining sustainable standards of operation. Water reuse and recycling define final concentrations
of pollutants in wastewater and offer substantial potential for savings, for example, in petroleum
refining [1]. Therefore, environmental legislation, on the one hand, and the needs of industry on the
other, is the driving force in the development of advanced wastewater treatment facilities that provide
high treatment efficiency at low capital, operational and maintenance costs.

Appl. Sci. 2020, 10, 831; doi:10.3390/app10030831 www.mdpi.com/journal/applsci

Appl. Sci. 2020, 10, 831 2 of 19

Urban transport and its services (repair shops, car washes, paint shops and filling stations)
are a growing source of hydrocarbon-containing wastewater. Urban runoffs receive hydrocarbons
mainly from transport but also from small industrial, commercial and domestic activities. Municipal
wastewaters contain thousands organic compounds, among which petroleum hydrocarbons
predominate. Also, emerging micropollutants (e.g., pharmaceuticals, personal care compounds,
flame-retardants, biocides and pesticides) are increasingly detected in urban wastewaters [2].
Industrial and municipal effluents are treated using conventional methods in activated sludge
and aerated lagoon systems. These processes suffer from serious operational problems, while novel
techniques, for example, membrane bioreactors are applied. Treatment of oily wastewater usually
has two stages, firstly, pre-treatment to reduce oil, grease and suspended materials. Secondly, an
advanced treatment stage to degrade and decrease the pollutants to acceptable discharge values.
The complexity of the wastewater composition and stringent discharge limits require combinations
of several treatment methods. There are several reviews published recently on the treatment of
petrochemical wastewater [3–5] including biological methods [6,7]. This review focuses on advanced
bioreactor technologies, including hybrid and integrated physico-chemical and biological systems.

2. Sources and Impacts of Hydrocarbon-Containing Wastewater

Potential sources of hydrocarbon-containing wastewater are petroleum, metallurgical and
transportation industries, which are concerned about the separation and recovery of oil from water
and the treatment of oily wastewater. Large volumes of wastewater having high concentrations of
free and emulsified oil are generated from oil and gas fields, refineries and petrochemical plants, thus
leading to severe contamination of soil and water bodies.
Oilfield wastewater typically includes produced water, used drilling fluid and wastewater after
washing the drilling/extraction equipment and storage tanks. The wastewater volume has increased
worldwide with increasing oil and gas production despite the large proportion of produced water
being reinjected into wells or pumped underground for disposal [8–10]. The amount of produced
water depends on the extraction technology, the reservoir characteristics and the rate of oil extraction.
In different sites, the amount of water may be 2–5 or up to 50 times more than the amount of oil
produced [10].
Oilfield wastewater is a complex mixture of oil, water, suspended and dissolved solids. It may
contain high mineral salt concentrations, heavy metals, naturally occurring radioactive elements and
chemical additives used in drilling and operating the well (surfactants, biocides, pH controlling agents,
etc.) [8,10]. Of the oilfield wastewater constituents, polycyclic aromatic hydrocarbons (PAHs), phenols,
heavy metals and radioactive elements are of environmental concern [8] (Table 1).

Table 1. Toxic Organic and Inorganic Compounds Present in Major Hydrocarbon-Containing

Wastewater Streams.

Type of the Effluent Toxic Organic Components Toxic Inorganic Components References
Benzene, toluene, ethylbenzene, xylene Mineral salts (salinity up to
Oilfield produced water (BTEX), PAHs, phenols, surfactants, 300%), heavy metals, [8,10]
biocides radioactive elements
Ammonia, cyanides, hydrogen
BTEX, PAHs, phenols, MTBE,
sulphide, halides, sulphides,
Refinery wastewater naphthenic acids, methanol, ketones, [3,11]
mercaptans, heavy metals,
ethers, surfactants
radioactive elements
Chlorinated and nitro-benzenes,
phenols, pesticides, brominated organic
compounds, estrogens, PAHs, PCBs,
Heavy metals, ammonia,
Petrochemical phthalates, anilines, tenside, thioanisol,
hydrogen sulphide, [12]
wastewater indole, dimethyl- and
mercaptans, cyanides
trimethylpyrazines,
dimethylpyrimidine, dimethyl- and
trimethylpyridines
Appl. Sci. 2020, 10, 831 3 of 19

Table 1. Cont.

Type of the Effluent Toxic Organic Components Toxic Inorganic Components References
BTEX, phenols, quinolines, PAHs, Heavy metals, acids/alkalines,
Metallurgy wastewater hydrazines and imine-carbohydrazides, radioactive metals, ammonia, [13]
thiophenes cyanide
PCBs, di-(2-ethylhexyl)phthalate
(DEHP), linear alkyl benzene
sulphonates (LAS), nonylphenol
ethoxylates (NPE), dioxins (PCDD),
Urban runoff furans, brominated Heavy metals, salts, acids [2,14]
diphenyl ethers (PBDEs),
pharmaceuticals, personal care
compounds, flame-retardants, biocides
and pesticides

Petroleum refinery effluents are generated in oil refinery processes that convert crude oil into
numerous refined products, such as liquefied petroleum gas, fuels, lubricants and petrochemical
intermediates. These processes consume a large volume of water ranged between 0.2 m3 /t and 25 m3 /t
of feedstock refined for the European refineries [11] with 10% reduction due to efficient water reuse and
recycling [1]. The amount and composition of the refinery wastewater vary considerably depending on
crude oil characteristics, plant configuration and process designs. Regardless of configuration, the main
wastewater stream is generated from cooling systems, distillation, hydrotreating and desalting [3].
In particular, the water used in crude oil processing (e.g., desalting, distillation and cracking) or
washing and cleaning operations comes into direct contact with either crude oil or various hydrocarbon
fractions, and thus representing the main organic load. On the other hand, the water used for cooling
systems and boilers is usually less contaminated but quantitatively represents the largest part (more
than 50% on average) of the wastewater effluent.
Crude oil and hydrocarbons are the main pollutants found in wastewater generated by refineries.
These petroleum compounds consist of three main hydrocarbon groups—paraffins (straight chained
n-alkanes from C1 to C40 and branched isoalkanes), naphthenes or cycloparaffins (naphthene rings
contain typically 5 or 6 carbon atoms; more condensed dicyclonaphthenes C8 and C9 are present
in addition to monocyclonaphthenes) and aromatics (having the benzene ring comprising alternate
double and single bonds with adjacent carbon atoms; monocyclic and polycyclic aromatics). In
addition, naphthenic acids (a mixture of alkyl-substituted acyclic, monocyclic and polycyclic carboxylic
acids with an aliphatic chain of 9 to 20 carbon atoms), which are known to cause toxic effects and
are difficult to remove from refinery wastewater [15]. Other pollutants found in wastewater include
hydrogen sulphide, ammonia, phenols, benzene, cyanides, and suspended solids containing metals
and inorganic compounds (e.g., halides, sulphates, phosphates, sulphides) [11]. Petroleum refinery
effluents are priority pollutants due to their high PAH contents, which are toxic and tend to be more
persistent in the environment [3].
Another major source of oily wastewater is the metallurgical industry. Most of the oily waste
comes from metal-working or metal-forming operations, such as coke quenching, steel rolling, solvent
extraction and electroplating [13]. Oil-in-water and water-in-oil emulsions of different compositions,
ranging from trace of oil in water to trace of water in oil, are used as cooling and lubricating agents;
they also provide corrosion protection for machined parts and machining tools. Such spent oily water
emulsions can be highly viscous and often severely hamper wastewater treatment plant capabilities,
thus causing increased maintenance costs and energy consumption. Also, solvent extraction and
electro-deposition processes used in hydrometallurgy consume myriads of highly toxic organic
substances as extractants, diluents, matrix modifiers, flocculants, brightening agents, acid fog inhibitors.
A general feature of metallurgical process-related effluents is the complex composition and relatively
high toxicity. The primary components of metallurgical oily wastewaters are emulsified oil, emulsifiers,
degreasing agents, surfactants, solvents, suspended solids, metals and acids/alkalines [13]. For example,
the wastewater from rare earth metallurgy contains radioactive metals, such as thorium, uranium,
Appl. Sci. 2020, 10, 831 4 of 19

radium, due to the paragenetic relation of these elements with rare earth metals. To treat these oily
wastewaters, the hybrid processes consolidating the advantages of two or more technologies are often
employed because of high metal concentrations and the recalcitrant nature of organic fractions.
Large amounts of oily wastewater are produced by the transportation industry, namely, road,
rail, marine and air transport. The emergence of various kinds of automobiles or vehicles led to the
considerable increase in the use of motor fuels and oils, which are the important sources of hydrocarbon
pollution in wastewater. Furthermore, the car wash, engine wash, paint spraying workshop or petrol
station wastes also contain residual hydrocarbons. Inputs of organic contaminants and metals to
the urban wastewater system occur from three generic sources: domestic, commercial and urban
runoffs. Typical domestic wastewater contains 10–50 mg/L of oil and grease (O&G). Over 6000
organic compounds have been detected in raw water sources within European urban areas, most of
which are due to human activities [14]. While some of these are highly persistent, others are easily
biodegradable. These organic compounds include aliphatic and aromatic hydrocarbons, PAHs, fatty
acids, ketones, phthalate esters, plasticizers and other polar compounds. Solvent extractable organics
are dominated by petroleum hydrocarbons, which arise from motor oil leaks, degraded asphalt and
worn tires from the roads. Most toxic and recalcitrant organic pollutants found in urban wastewaters
include PAHs, polychlorinated biphenyls (PCBs), di-(2-ethylhexyl)phthalate (DEHP), linear alkyl
benzene sulphonates (LAS), nonylphenol ethoxylates (NPE), dioxins (PCDD) and furans (PCDF). Also,
emerging micropollutants (e.g., pharmaceuticals, personal care compounds, flame-retardants, biocides
and pesticides) are increasingly detected in urban wastewaters [2].
While starting in the 1990s, the strict control of organic pollutants from small industrial, domestic
and transport sources in Europe allowed the reduction of the levels of urban contamination; the
concentrations of petroleum hydrocarbons in sewage treatment influents remain quite high. Moreover,
some organic substances, with the potential to exert a health or environmental hazard, were identified
in sludges and sewage treatment effluents [14,16], thus requiring more regulatory, economic and
educational instruments to mitigate the problem of wastewater pollution. According to the Rules of
Cold Water Supply and Sanitation approved by the Russian Federation Government Decree No. 644
(new edition from 26 July 2018), new standards for the concentrations of pollutants in wastewater
allowed to discharge to a centralized sewerage system were established. In particular, the maximum
allowable concentration (mg/L) of petroleum products is 10, fats—50, volatile organic compounds
(toluene, benzene, acetone, methanol, butanol, propanol, their isomers and alkyl derivatives)—20,
suspended solids—300, synthetic surfactants—10, phenols 5, and polychlorinated biphenyls—0.001.
These new regulations have prompted dozens of local treatment facilities to be established by transport,
small industrial and road construction companies, in which the advanced and cost-efficient technologies
of wastewater purification are applied [17].
It is worth noting that the environmental and human health risks of hydrocarbon pollutants are
determined by their toxicity, how they spread if released into the environment, how long they stay
in the environment, and whether they bioaccumulate in the food chain. Therefore, understanding
the fate and transport of contaminants is crucial for risk assessment, while this analysis can be very
complicated because it requires the best approximation of the environmental chemistry of hydrocarbon
contaminants (e.g., biodegradability, hydrophobicity) and the environment at the site (e.g., geology,
geochemistry). At the heart of this problem is the concept of bioavailability [18]. If a pollutant is present
in soil or water but is not available to the biota, then it presents minimal risk (unless chemical conditions
change that can subsequently increase the bioavailability). However, measuring bioavailability is
often a difficult task and cannot be estimated directly from the total pollutant concentration since
the bioavailability level can vary significantly. Bioavailability is indirectly related to partitioning
phenomena, biodegradability and toxicity [19] and it is also dependent on the organism exposed.
While most potential environmental impacts related to oil and gas industry activities are already
well documented, there are several uncertainties concerning the long-term effects of oilfield and refinery
wastewater releases, for example, the effects of endocrine disrupting, carcinogenic and radioactive
Appl. Sci. 2020, 10, 831 5 of 19

components with respect to toxic concentrations, bioaccumulation, fertilization, and so forth [20,21].
A major concern is the release of hydrocarbon- and chloride-rich wastewater into soil, aquatic and
wetland ecosystems [8,22,23].
In general, the hydrocarbon-containing wastewater has various impacts to the soil environment,
which include reduction in crop yield, shortage of oxygen and detrimental effects on wild plants and
animals. The presence of petroleum hydrocarbons in water can reduce soil fertility because of adverse
effects on physicochemical characteristics of soil, microbial populations and plant growth, which could
lead to the reduction in crop yield [24,25]. Also, heavy metal contents in soil repeatedly irrigated with
treated petroleum wastewater can be significantly increased, thus leading to the bioaccumulation of
these toxic elements in the food chain [26]. Major risks associated with treated produced water used
in agricultural irrigation were determined as dissolved formation minerals (i.e., salts and sodium)
and metalloids, while these risks are also related to irrigation with both municipal and industrial
wastewaters that are often saline and sodic [27].
The discharge of hydrocarbon-polluted wastewater into receiving water bodies poses threat to
marine and freshwater environments, especially to vulnerable aquatic ecosystems of northern regions,
where natural biodegradation processes are slower due to low temperatures. Most toxic components,
for example, alkylphenols and PAHs, from produced water can accumulate in phyto- and zooplankton
populations, thus transmitted through the food chain to higher marine organisms and affect their
vital functions [8]. Also, salinization of freshwater resources leads to increasing chloride and sodium
concentrations, which could have toxic effects on fish, macroinvertebrates, amphibians and other
salinity-intolerant species [28].

3. Treatment of Hydrocarbon-Containing Wastewater

It should be noted that concentrations of petroleum hydrocarbons in wastewater may decrease due
to natural processes of decomposition and chemical oxidation, evaporation and biological degradation
by native microflora. In natural environments, however, these processes are relatively slow. To
enhance the oil contaminant removal from wastewater, the mechanical, chemical, physicochemical and
biological methods, as well as their combinations, are employed, providing the required purification
rate at reasonable costs. Importantly, the choice of a treatment method in each case is determined by
the source of wastewater, the diversity and levels of contaminants, and the subsequent intended use of
treated effluents. Recent developments in treatment technologies for petrochemical wastewater and
produced water from oil and gas industries are reviewed by Wei et al. [5]. Treatment of petroleum
wastewater usually involves two stages, firstly, physical (mechanical) pre-treatment to remove free oil
& grease fractions and suspended particles. Secondly, an advanced treatment, usually involving a
combination of different physicochemical and biological methods, to decrease the pollutant level to
acceptable discharge values.
The sedimentation treatment, which is used to separate bulk free oil from water, is mechanically
achieved by gravity in API (American Petroleum Institute) or CPI (Corrugated Plate Interceptor)
separators and dissolved air floatation (DAF) units. During wastewater sedimentation, insoluble solids
are also removed, which prevents clogging and wearing of devices used in subsequent treatment stages.
Mechanical treatment techniques, while allowing the reuse of roughly purified water in the operation
cycle, are inefficient in the recovery of finely dispersed oil, dissolved organics, metals and colloids.
The mechanical step is followed by the physiochemical step, in which small-sized suspended solids
and dispersed oil are further reduced by agglomeration into large-sized particles to ease the removal
by filtration, sedimentation or floatation [3]. However, settling of petroleum products as insoluble
non-utilizable sediments (sludges) performed using expensive chemicals (particularly coagulants and
flocculants) entails costly disposal of the resulting sludge and may lead to secondary contamination of
the treated water [9].
Several techniques that are used as advance treatment methods for reducing the effluent
contamination level to allowable limits for discharge into water bodies include membrane filtration
Appl. Sci. 2020, 10, 831 6 of 19

and electrodialysis [29,30], adsorption [31], biological systems [5], advanced oxidation [5] and
electrochemical processes [32]. Of these, sorption methods are advantageous because their performance
and cost efficiency are compatible with other techniques for petroleum removal, and sorbents are
reusable after regeneration. Sorbents are porous materials, both natural (activated carbon, sawdust,
peat, perlite, clay, sand) and synthetic (polyurethane foam, ceramic materials, synthetic fiber) with high
affinity for the targeted pollutants, good adsorption capacity and hydrophilic-lipophilic properties.
The choice of the material relies on its ecological safety and availability in the region [31,33].
Currently used biological methods are activated sludge systems [34,35], aerated lagoons and
wetlands [36,37]. Laboratory-proved technologies include aerobic [38–41], anaerobic [42–44] and
hybrid [15,45–47] bioreactors. However, because of heavy petroleum hydrocarbon load, high salinity,
low nutrient concentrations and toxicants present, the current activated sludge bioprocesses often
suffer from operation problems, such as low removal rate and high suspended solid concentration [48].
To overcome these problems, advanced bioreactor systems and selected cultures with enhanced
degradative capabilities and tolerance to environmental stresses can be used.

4. Advanced Bioreactors for Hydrocarbon-Containing Wastewater Treatment

4.1. Aerobic Bioreactors

Bioreactor-based technologies allow more precise control and management of biodegradation
parameters, such as temperature, pH, oxygen, nutrient and water contents, homogenous distribution of
hydrophobic contaminants and biomass in the reactor volume, which leads to increased mass transfer
and reaction rates. Aerobic bioreactors are intensively explored for the industrial effluent treatment due
to their easy operation, high microorganism growth and organic carbon oxidation rates and resistance
to toxic effects. Several laboratory and pilot studies were performed to treat oily wastewaters using
aerobic bioreactors of various configurations and different microbial inocula. Selected examples of
aerobic bioreactors used for hydrocarbon-containing wastewater treatment are shown in Table 2.

Table 2. Aerobic Bioreactors Used for Hydrocarbon-Containing Wastewater Treatment.

Bioreactor
Wastewater Type Operational Conditions Treatment Efficiency Reference
Configuration
Acclimatized indigenous
Petroleum refinery Continuously Removal of 95% COD,
microbial consortium. [40]
wastewater stirred tank 97.5% TPH
Experimental period of 225 days
Synthetic Removal of 59–88%
Sludge from municipal AS plant.
petrochemical SBR COD, 76–90% for Hg, [49]
3 cycles at HRT of 15 days.
wastewater 96–98% for Cd
Sludge from domestic sewage
97.5% of COD removal
Petroleum refinery treatment work.
Two-stage SBR and complete O&G [50]
wastewater Two stage operation with
removal
methanol as co-substrate.
Synthetic petroleum Three parallel 10-l reactors. HRT Hydrocarbon removal >
MSBR [51]
wastewater values of 8, 16 and 24 h. 97%
Sludge from municipal AS plant.
Shipboard slop Polyurethane sponges as biofilm
MBR and MBBR 70–85% of TPH removal [52]
wastewater carriers. HRT in the range of
12–15 h.
Sludge from petrochemical
wastewater treatment plant.
Oilfield produced Maximum COD removal
MBBR Sepiolite-modified ceramic foam [53]
water of 74–77%
carriers for biofilm. HRT
ranging from 36 to 10 h.
Appl. Sci. 2020, 10, 831 7 of 19

Table 2. Cont.

Bioreactor
Wastewater Type Operational Conditions Treatment Efficiency Reference
Configuration
Highly packed polymer biofilm
Petrochemical Full-scale CFIC carriers (over 90% filling ratio).
Over 90% COD removal [7]
wastewater biofilm technology COD ranging from 7 to 35 g/L,
flow rate of 240 m3 /day.
Commercial oil-degrading
Removal of 64–78% TOC,
Oilfield wastewater inocula B350M and B350
BAF 86–94% oil and 84–90% [39]
before desalination immobilized on a patented
PAHs
poly-ammoniacum carrier.
Oilfield produced Spent and new GAC carriers for 81% COD removal in
BAF [54]
water indigenous biofilm. 24 h
Oilfield produced Batch stirred tank Acclimated indigenous >60% degradation of
[55]
water bioreactor halophilic microorganisms. crude oil
Carwash wastewater Chitosan-immobilized
Internal loop airlift Removal of 85 ± 5% TPH
with amended Sphingobium sp. P2 (TISTR 2006). [56]
bioreactor and 73 ± 11% COD
lubricant HRT of 2.0 h for over 70 days.
Simultaneous n-alkane
Continuously
Oilfield produced biodegradation and production Alkane removal up to
operated stirred [57]
water of neutral lipids by Alcanivorax 99.6%
tank reactor
borkumensis SK2.
Polypropylene particles
Petroleum refinery
FBB inoculated with refinery 90% COD reduction [38]
wastewater
activated sludge.
Pelleted mycelium of the white
100%removal of 7 out of
Urban wastewaters FBB rot fungus Trametes versicolor [58]
10 pharmaceuticals
ATCC 42530.
Hydrophobized sawdust 70–100% n-alkane
Synthetic petroleum immobilized Rhodococcus ruber removal, 46–70%
FBB [59]
wastewater IEGM 615 and Rhodococcus removal of 2–3-ring
opacus IEGM 249. PAHs
Hydrophobized sawdust
70% removal of alkanes
immobilized Rhodococcus ruber
Oilfield wastewater FBB and PAHs, 75–96% [41]
IEGM 615 and Rhodococcus
removal of heavy metals
opacus IEGM 249.
Poly(vinyl alcohol) cryogel
Highly saline oilfield immobilized Rhodococcus ruber
FBB Removal of 64–82% TPH [60]
wastewater IEGM 231 and Rhodococcus
opacus IEGM 263.

A continuously stirred tank bioreactor was applied to treat hydrocarbon-rich wastewater from a
petroleum refinery site using an acclimatized indigenous microbial consortium [40]. The performance
of the bioaugmented reactor was demonstrated by the reduction of chemical oxygen demand (COD)
rates up to 95% and residual total petroleum hydrocarbon (TPH) concentration to 97.5% (from 320 mg/L
to 8 mg/L). Malakahmad et al. [49] evaluated the performance of a sequencing batch reactor (SBR) with
pre-grown activated sludge microorganisms to treat synthetic petrochemical wastewater containing
mercury and cadmium. They found that COD removal and microbial population growth were inhibited
by high metal concentrations, while metal removal rates were 76–90% for Hg and 96–98% for Cd. A
two-stage SBR system was applied for treatment of refinery wastewater with high COD and O&G
concentrations (up to 7.8 g/L and 13,4 g/L, respectively) using a gradual increase in wastewater load
and methanol as the co-substrate [50]. This strategy enabled a short acclimation period of the sludge,
resulting in 97.5% of COD removal and complete O&G removal.
It should be noted that while the SBR technology is widely used for biotreatment of petroleum
refinery wastewater, it cannot remove suspended solids (SS) completely, so the settleability of the
activated sludge is adversely affected. The application of membrane separation instead of the settling
phase of the SBR realized in a membrane sequencing batch reactor (MSBR) technology results in an
effluent with negligible SS content. However, membrane fouling is a major problem in both membrane
Appl. Sci. 2020, 10, 831 8 of 19

bioreactors and MSBRs, thus increasing considerably the operational costs due to the periodical
physical or chemical membrane cleaning. Dickhout et al. [61] proposed a fouling mechanism for oily
wastewater and they found that oil droplets were coalescing on the membrane surface, forming a
continuous oil layer on the surface, different from a traditional cake layer made of separate particles.
Shariati et al. [51] tested the effect of hydraulic retention time (HRT) on the performance and fouling
characteristics of the MSBR used to treat synthetic petroleum wastewater with an average hydrocarbon
concentration of 60 mg/L. They found that hydrocarbon removal efficiencies higher than 97% were
possible with HRT values of 8, 16 and 24 h. Accordingly, the rate of membrane fouling increased with
the decrease in HRT values.
Campo et al. [52] compared data from three stand-alone treatments of shipboard slop wastewater
produced by the washing of oil tankers with seawater and characterized by high salinity (39 g/L of
NaCl) and hydrocarbon contents (TPH of 135 ± 38 mg/L). The treatments were (1) a chemical treatment
of coagulation-flocculation with aluminum sulphate as coagulant and an anionic flocculant, (2) a
physical treatment of adsorption on granular activated carbon (GAC), (3) two biological treatments
represented by a membrane bioreactor (MBR) and a moving bed biofilm reactor (MBBR) with soft
polyurethane sponges. Both reactors were equipped with ultrafiltration hollow fiber membrane
modules. To limit the fouling, each membrane was periodically backwashed (every 4 min for a period
of 1 min) by pumping a fraction of permeate back through the membrane. The bioreactors operated
continuously with HRT in the range of 12–15 h. As a result, the GAC treatment registered the highest
removal efficiency of TPHs up to 85%, while the coagulation-flocculation treatment reported the lowest
(57%) removal of TPHs. The 70% TPH removal was obtained with the MBBR fed with 100% volume of
slop, thus suggesting a biomass acclimation to salinity and hydrocarbons.
Alternatively, Dong et al. [53] used suspended ceramic foam carriers with a high mechanical
strength, optimum density (close to water) and high porosity to treat oilfield produced water (COD of
343–365 mg/L; TPH of 24–28 mg/L) in MBBRs operating at HRT values ranging from 36 to 10 h. The
highest COD, PAH and ammonia N removal rates were recorded at HRT of 10 h in the MBBR filled
with sepiolite-modified carriers characterized by a larger specific surface area for the biofilm growth,
followed by the MBBR with unmodified carriers, with the lowest removal efficiency in the MBBR with
the activated sludge only.
A full-scale application of continuous flow intermittent cleaning (CFIC) biofilm technology based
on the MBBR concept was performed recently in the Biowater Technology AS in Norway to treat
petrochemical wastewater of fluctuating concentrations with the COD ranging from 7 to 35 g/L [7]. The
CFIC reactor contained highly packed polymer biofilm carriers (over 90% filling ratio) was operated
continuously at the flow rate of 240 m3 /day, resulting in over 90% COD removal. Excess biofilm/sludge
was washed off during periodic washings, thus maintaining a thin and effective biofilm in the reactor.
Zhao et al. [39] investigated the use of biological aerated filter (BAF) reactors inoculated with the
commercial oil-degrading inocula immobilized on a patented poly-ammoniacum carrier to pre-treat
the oilfield wastewater before desalination. By operating the bioreactors for 142 days under low
COD load (1.07 kg COD/m3 ·day) and high salinity conditions, the mean degradation efficiencies of
64–78% for total organic carbon (TOC), 86–94% for oil and 84–90% for PAHs were achieved. More
recently, a bench-scale BAF reactor with GAC was examined for effective removal of organic matter
and solids from produced water using three GAC carriers (one spent and two new) and two nutrient
supplements [54]. The spent GAC with an existing biofilm from the previous treatment of surface water
demonstrated up to 81% COD removal in 24 h (from initial COD values of 1368 ± 312 mg/L), indicating
that appropriate GAC selection and pre-developed biofilm is critical for efficient BAF performance.
Interestingly, recent evaluation of different inocula for treating high salinity produced water in a
batch stirred tank bioreactor [55] revealed a higher efficiency of the acclimated indigenous halophilic
microorganisms compared to that of the commercial inocula used in Reference [39].
Selected bacterial strains with broad hydrocarbon-oxidizing activities and resistance to toxic
petroleum constituents were used as bioreactor inocula. For example, Khondee et al. [56] used an
 water in a batch stirred tank bioreactor [55] revealed a higher efficiency of the acclimated indigenous
halophilic microorganisms compared to that of the commercial inocula used in Reference [39].
Selected bacterial strains with broad hydrocarbon-oxidizing activities and resistance to toxic
petroleum constituents were used as bioreactor inocula. For example, Khondee et al. [56] used an
Appl. Sci. 2020,
internal loop10,airlift
831 bioreactor inoculated with a chitosan-immobilized bacterium Sphingobium 9sp.
of 19
P2
for the removal of automotive lubricants from emulsified wastewater. The reactor operated
continuously at the HRT of 2.0 h for over 70 days, resulting in the removal of 85±5% TPH and 73 ±
internal loop airlift bioreactor inoculated with a chitosan-immobilized bacterium Sphingobium sp. P2 for
11% COD from the carwash wastewater with 25–200 mg/L amended lubricant. Sudmalis et al. [57]
the removal of automotive lubricants from emulsified wastewater. The reactor operated continuously
demonstrated a simultaneous n-alkane biodegradation and production of neutral lipids in a
at the HRT of 2.0 h for over 70 days, resulting in the removal of 85 ± 5% TPH and 73 ± 11% COD from
concentrated produced water stream by Alcanivorax borkumensis SK2 as the sole reactor inoculum. n-
the carwash wastewater with 25–200 mg/L amended lubricant. Sudmalis et al. [57] demonstrated a
Alkane removal efficiency up to 99.6%, with influent alkane COD of 7.4 g/L, was achieved in a
simultaneous n-alkane biodegradation and production of neutral lipids in a concentrated produced
continuously operated stirred tank reactor. The simultaneous process of hydrocarbon biodegradation
water stream by Alcanivorax borkumensis SK2 as the sole reactor inoculum. n-Alkane removal efficiency
and production of mostly extracellular neutral lipids revealed the possibility of bioconversion of toxic
up to 99.6%, with influent alkane COD of 7.4 g/L, was achieved in a continuously operated stirred
industrial wastes into valuable compounds.
tank reactor. The simultaneous process of hydrocarbon biodegradation and production of mostly
Fluidized bed bioreactors (FBBs) (Figure 1), in which the biomass is fixed on bed particles
extracellular neutral lipids revealed the possibility of bioconversion of toxic industrial wastes into
fluidized by liquid up-flow, were successfully applied to aerobic biological treatment of industrial
valuable compounds.
and domestic wastewaters [38,58]. The use of smaller particles than those in MBR and MBBR systems
Fluidized bed bioreactors (FBBs) (Figure 1), in which the biomass is fixed on bed particles fluidized
results in much thicker biofilms and therefore FBBs are proven to be able to withstand large loads
by liquid up-flow, were successfully applied to aerobic biological treatment of industrial and domestic
and operate at lower HRT values compared to typical bioreactor. Large biofilm–liquid interfacial
wastewaters [38,58]. The use of smaller particles than those in MBR and MBBR systems results in much
area, high immobilized biomass concentration and improved mass transfer are the major advantages
thicker biofilms and therefore FBBs are proven to be able to withstand large loads and operate at lower
of this type reactors [62].
HRT values compared to typical bioreactor. Large biofilm–liquid interfacial area, high immobilized
biomass concentration and improved mass transfer are the major advantages of this type reactors [62].

Figure 1. Different type fluidized-bed bioreactors (FBB): (a) two-phase (liquid–solid); (b) three-phase
(gas–liquid–solid); (c) three-phase (gas–liquid–solid) with particle circulation.

A biotreatment of petroleum refinery wastewater was investigated in the three-phase

(gas–liquid–solid) FBB, in which polypropylene particles were inoculated with the refinery activated
sludge sample and fluidized by an upward flow of air [38]. Clogging and channeling of the bed
were eliminated through the intensive motion of the particles. Approximately a 90% COD reduction
(from 34,250 to 3100 mg/L), was achieved after two weeks of steady-state biomass loading. More
recently, a batch FBB inoculated with the pelleted mycelium of the white rot fungus Trametes versicolor
ATCC 42530 was used to study the degradation of pharmaceutical micropollutants present in urban
wastewaters [58]. Complete removal of 7 out of 10 initially detected pharmaceuticals, including
antibiotics and non-steroid anti-inflammatory compounds, was achieved in a non-sterile treatment.
It should be noted that successful FBB treatments of hydrocarbon-containing water are often
hindered by limitations of mass transfer between three phases: aqueous, hydrophobic (hydrocarbons)
and solid (biocatalyst). Thus, greater requirements apply to the carrier that must have an optimal
particle size and density to be easily fluidized at the operational flow rate, be non-toxic and absorbing
hydrocarbons and microbial cells and be resistant to chemical and mechanical damages. We previously
tested [59] three different materials, namely hydrophobized sawdust, granulated macroporous cryogel
made of poly(vinyl alcohol) and sponge-like poly(acrylamide) cryogel for the immobilization of
Appl. Sci. 2020, 10, 831 10 of 19

Rhodococcus ruber IEGM 615 and Rhodococcus opacus IEGM 249 association (Figure 2). It was found that
hydrophobized sawdust had a largest surface area available for bacterial adhesion, and, as a result,
demonstrated highest level of bacterial cell immobilization. This biocatalyst was used to treat synthetic
petroleum wastewater in FBBs continuously operating at different flow rates (0.6 or 1.2 mL/min) for
3 weeks. The FBB with a faster flow rate was most successful, providing 70–100% removal of n-alkanes
Appl. Sci. 2020, 10, x FOR PEER REVIEW 11 of 20
(C10 –C19 ) and 46–70% removal of 2–3-ring PAHs from contaminated water after two weeks.

(a)

(b)
Figure
Figure 2.
2. SEM
SEM images
images of
of Rhodococcus
Rhodococcus cells
cells immobilized
immobilized (a)
(a) on
on hydrophobized
hydrophobized sawdust
sawdust [41]
[41] and
and (b)
(b) in
in
granulated poly(vinyl alcohol) cryogel [63].
granulated poly(vinyl alcohol) cryogel [63].

More
More recently, we evaluated a feasibility of the FBB process using sawdust co-immobilized
Rhodococcus
Rhodococcus cultures
cultures for
for the
the purification
purification ofof highly
highly concentrated
concentrated (COD
(COD of of 10.3
10.3 g/L;
g/L; TPH
TPH of of 3.74
3.74 g/L)
g/L)
oilfield wastewater
wastewater [41],
[41],resulting
resultinginin70%70%biodegradation
biodegradation efficiencies
efficiencies forfor alkanes
alkanes andandPAHsPAHs
withinwithin
two
two weeks. Furthermore, the 75–96% removal of heavy metals (Al, Cr, Cu, Fe,
weeks. Furthermore, the 75–96% removal of heavy metals (Al, Cr, Cu, Fe, Hg, Zn, Mn) resulted fromHg, Zn, Mn) resulted
from combined
combined effectseffects of physical
of physical sorptionsorption by sawdust
by sawdust and biosorption
and biosorption by the Rhodococcus
by the Rhodococcus biomass.biomass.
While a
While a treatment
treatment of highlyofsaline
highly salinewastewater
oilfield oilfield wastewater was lessinefficient
was less efficient the FBB in theRhodococcus
with FBB with Rhodococcus
co-cultures
co-cultures
immobilized immobilized
in poly(vinylin alcohol)
poly(vinyl alcohol)
granules granules
[60], [60], such gel-encapsulated
such gel-encapsulated cells resistant
cells were more were more to
resistant to salinity
salinity and and hydrocarbons
hydrocarbons and could beand could
easily be easily
recovered recovered
from from the
the bioreactor forbioreactor for further
further reuse.
reuse.
4.2. Anaerobic and Hybrid (Anaerobic-Aerobic) Bioreactors
4.2. Anaerobic and Hybrid (Anaerobic-Aerobic) Bioreactors
Anaerobic digestion has been recognized as the sustainable wastewater treatment because it
requires less space,
Anaerobic generates
digestion haslow sludge
been amount as
recognized compared to aerobicwastewater
the sustainable treatment and produces
treatment methane
because it
as a renewable energy. Currently, anaerobic baffled reactors (ABR), sequencing
requires less space, generates low sludge amount compared to aerobic treatment and produces batch and up-flow
anaerobicassludge
methane blanketenergy.
a renewable (UASB)Currently,
reactors are applied baffled
anaerobic to treat reactors
oily wastewater. Selected examples
(ABR), sequencing batch and of
up-flow anaerobic sludge blanket (UASB) reactors are applied to treat oily wastewater. Selected
examples of anaerobic bioreactors used for hydrocarbon-containing wastewater treatment are shown
in Table 3. Ji et al. [43] studied an ABR start-up and operational performance (total 212 days) in
treating oilfield produced water using mixed acclimated oilfield and urban sewage sludges. Such
long ABR treatment under the COD load of 0.2–0.5 kg/m3·day resulted in COD and oil removals of
Appl. Sci. 2020, 10, 831 11 of 19

anaerobic bioreactors used for hydrocarbon-containing wastewater treatment are shown in Table 3. Ji
et al. [43] studied an ABR start-up and operational performance (total 212 days) in treating oilfield
produced water using mixed acclimated oilfield and urban sewage sludges. Such long ABR treatment
under the COD load of 0.2–0.5 kg/m3 ·day resulted in COD and oil removals of 65% and 88% for heavy
oil produced water with poor nutrient (COD: N: P, 1200:15:1) and high salt concentration (1.15–1.46%).
An UASB bioreactor inoculated with digested sludge from a dairy industry was used to treat petroleum
refinery effluent under mesophilic conditions (38 ± 1 ◦ C) for over120 days [44]. The authors used
response surface methodology to optimize the efficient factors (influent COD of 630 mg/L, upflow
velocity of 0.27 m/h and HRT of 21.4 h). Under these optimum conditions, the COD removal efficiency
was 76.3% and the biogas production rate was 0.25 L biogas/L feed day. More recently, artificial neural
networks were used to model the UASB reactor behavior during 180 d treating petroleum refinery
wastewater under six different organic loads (from 0.58 to 4.14 kg COD/m3 ·day) [64]. The highest COD
removal of 82% shown in the laboratory bioreactor was confirmed by using the best selected model
with the Tansig-Purelin transfer function and 12 neurons.

Table 3. Anaerobic and Hybrid (Anaerobic-Aerobic) Bioreactors Used for Hydrocarbon-Containing

Wastewater Treatment.

Bioreactor Treatment
Wastewater Type Operational Conditions Reference
Configuration Efficiency
Start-up and operational
COD and oil
Oilfield produced performance (total 212 days) with
ABR removals of 65% [43]
water mixed acclimated oilfield and
and 88%
urban sewage sludges.
Mesophilic conditions (38 ± 1 ◦ C) 76.3% COD
Petroleum refinery
UASB for over120 days. Digested sludge removal, 0.25 L [44]
effluent
from a dairy industry. biogas/L feed d
Treating under six different
Petroleum refinery COD removal of
UASB organic loads (from 0.58 to 4.14 kg [64]
wastewater 82%
COD/m3 ·day) during 180 days.
Sludge from anaerobic and aerobic
tanks of petroleum refinery AS 95.8, 98.9 and 94.4%
Heavy oil HA-MBBR
plant. Effluent concentrations of removals of COD, [47]
wastewater O3-BAC
COD, oil and ammonia were 48, oil and ammonia
1.3 and 3.5 mg/L.
The wastewater was treated for
Acrylonitrile Stirred-tank HA COD, NH3-N and
36 h in a batch process and the
butadiene styrene with a series of phosphorus
effluent was applied to the algal [65]
resin-manufacturing algal removal of 83, 100
microcosm treatment using
wastewater photobioreactors and 89%
Chlorella sp.
Filamentous microalgae Tribonema
Open sp. Aeration and mixing by
photobioreactors sparging air enriched with 1.5%
Petrochemical COD
integrated with CO2, gas flow rate 0.5 vvm, light [66]
wastewater removal of 97.8%
anaerobic/oxic intensity 300 µmol/m2 ·s,
process temperature
25 ◦ C.
Granular sludge from paper and
86% of the total
pulp wastewater treatment facility.
Petroleum refinery COD and 91% of
Pilot HyVAB Continuously operating at [15]
wastewater the soluble COD
varying organic loading rates for
removal
92 days.
Granular sludge from
petrochemical wastewater
Metformin- 98% COD removal
treatment bioreactor. Co-digest
containing Pilot HyVAB and 100% [67]
pharmaceutical- containing
wastewater metformin removal
wastewater with the wastewater
rich of easily degradable organics.

However, anaerobic treatment alone does not always meet the requirements of water discharge
and requires subsequent treatment using, for example, an aerobic process [15]. A laboratory treatment
Appl. Sci. 2020, 10, 831 12 of 19

system consisted of UASB and aerobic packed-bed biofilm (PBB) reactors was applied to remove PAHs
from refinery wastewater (COD of 435 mg/L; TPH of 1520 mg/L; PAH of 10.33 mg/L), resulting in
the total COD removal efficiency of 81.07% and the complete removal of three PAHs (naphthalene,
phenanthrene and pyrene) after 118 days [68]. In other study, a combination of UASB and BAF
reactors was used by Liu et al. [45] in a field pilot study of the treatment of heavy oil wastewater with
high organic loads (COD of 129.8–1238 mg/L; oil of 24.5–315.5 mg/L) and low N and P contents. By
operating the system for 252 days (including the start-up of 128 days), the COD, ammonia nitrogen
(NH3-N) and SS were removed by 74%, 94% and 98%, respectively. The authors suggested that most
of the alkanes were degraded by the UASB process, while the BAF played important roles both in
degrading organic compounds and removing NH3-N and SS. Lu et al. [46] used two MBBRs filled
with suspended ceramsite for the sequential anaerobic–aerobic treatment of refinery wastewater (COD
of 675–742 mg/L; O&G of 42–48 mg/L) at the continuous flow mode for 124 days. The results showed
that COD and NH3-N removal efficiencies were higher than 85% at the HRT values of 72 and 36 h.
Additionally, the removal of 16 PAHs detected in the influent was 39.4 and 74.6% for anaerobic and
aerobic MBBRs, respectively.
More complex hybrid system integrating a hydrolysis acidification (HA) reactor, a MBBR and
an ozonation-biologically activated carbon (O3 -BAC) unit was used to treat heavy oil wastewater
(COD of 1020–1250 mg/L; oil of 108–127 mg/L), resulting in 95.8 98.9 and 94.4% removals of COD, oil
and ammonia, respectively [47]. The HA process improved the biodegradability of complex organics,
while the MBBR process played an important role in the oxidative removal of hydrocarbons. The
ozonation process further enhanced the biodegradability of the MBBR effluent and, finally, deep
treatment was completed in the BAC reactor. Another novel two-stage system coupling a stirred-tank
HA reactor with a series of algal photobioreactors was investigated for the treatment of acrylonitrile
butadiene styrene resin-manufacturing wastewater (COD of 856 ± 11 mg/L) [65]. The coupling system
achieved deep cleaning of the benzene-containing wastewater (COD, NH3 -N and phosphorus removal
rates were 83, 100 and 89%, respectively) while producing a considerable Chlorella sp. biomass at
low cost. A filamentous microalgae Tribonema sp. was used by the same research group in open
photobioreactors integrated with the traditional anaerobic/oxic process to treat low-concentration
petrochemical wastewater (COD of 312.8 ± 15.6 mg/L) [66]. It was found that the algal post-treatment
step was efficient in the removal of pollutants (COD removal rates were 71.7–97.8%) as well as in
biomass and oil accumulations.
The above laboratory and pilot studies clearly demonstrate that integrated bioreactor systems
provide generally better performance for treating oily wastewater because of the synergistic effects
of anaerobic and aerobic microorganisms enabling sequential degradation of recalcitrant organic
compounds. However, such multi-module combinations of anaerobic and aerobic processes require
large space and energy and can lead to methane emission. Recently, Wang et al. [15] tested on a
pilot scale a hybrid vertical anaerobic biofilm (HyVAB) reactor, which integrated a bottom anaerobic
sludge bed and a top aerobic biofilm stage [69]. The reactor was operated continuously at reducing
HRT (from 55 to 12 h) and increasing organic loading rate (from 3 to 33 kg COD/m3 ·day) for 92
days, treating high strength refinery wastewater, that resulted in 86% of the total COD and 91% of
the soluble COD removal [15]. An advantage of this system is that due to the close integration of
anaerobic and aerobic processes, dissolved gases (methane, H2 S etc.) generated in the anaerobic
stage are captured and oxidized by aerobic microorganisms, thus avoiding a methane emission and
providing odorless discharges to air and water. Moreover, returning the excess aerobic sludge to
the bottom anaerobic part simply by gravity simplifies the sludge treatment and contributes to a
methane production. Therefore, the HyVAB reactor represents a compact integrated system with
low footprint, low capital expenditures and high efficiency in organic removal, energy recovery and
emission prevention. Very recently, the same research group tested a pilot HyVAB reactor for the
treatment of wastewater containing metformin, a widely used antidiabetic drug [67]. To achieve
complete metformin removal, it was proposed to co-digest pharmaceutical-containing wastewater
Appl. Sci. 2020, 10, 831 13 of 19

with the wastewater rich of easily degradable organics. After a period of adaptation, the reactor was
able to manage organic loads of 11 g COD/day and above 10 mg/L metformin, resulting in the removal
of 98% COD and 100% metformin.
It should be noted that despite numerous successful laboratory and pilot-scale applications of
advanced bioreactors for the treatment of oily wastewaters, their full-scale implementation is still
rare. Biological processes to treat the petroleum wastewater are usually conducted in traditional
activated sludge (fixed bed or suspended bed) systems or in aerated lagoons [11]. Some companies
also incorporate MBRs into their treatment trains for discharge of produced waters [70].

5. Sequentially Coupled Physico-Chemical and Biological Treatments

In recent years, great efforts and progress has been made in the combination of biological treatment
with cutting-edge physico-chemical technologies, including advanced oxidation, electrocoagulation
and electroflotation, UV irradiation, sonication, bioelectrochemical processes, innovative membrane
and sorption materials. Most of these technologies are used as pre-treatment methods aimed at
reducing a toxic shock from concentrated wastewater to microorganisms operating in bioreactors [71].
Bahri et al. [72] reviewed four advanced oxidation processes (AOPs)—photocatalytic oxidation,
Fenton/photo-Fenton oxidation, wet air oxidation and catalytic wet air oxidation, which can be
used as pre-treatment methods to increase the performance capability of the biological treatment.
Depending on wastewater characteristics and operational conditions, the AOP converts recalcitrant
organic components into lower molecular weight compounds, which are more amenable to biological
degradation and hence an easier decomposition in a biological treatment plant can be achieved. Kang
et al. [73] applied a vacuum ultraviolet (VUV, 185 nm) and TiO2 oxidation system for the pre-treatment
of oily wastewater. The results indicated that the VUV/TiO2 process reduced significantly COD,
BOD and oil content and improved the biodegradability of oily wastewater, thus paving the way for
subsequent biological treatment.
Pérez et al. [74] studied a sequentially coupled electrocoagulation (EC) and a fixed film aerobic
bioreactor to treat highly concentrated (COD of 19.4 g/L; TPH of 10.2 g/L) petroleum refinery wastewater.
Under the optimized EC conditions (6.5 V, 0.1 M NaCl, 4 electrodes without initial pH adjustment),
over 88% of COD and >80% of TPH were removed and the effluent biodegradability increased from
the BOD/COD value of 0.015 up to 0.5. Further bioreactor treatment using bacteria isolated from the
wastewater and immobilized on tezontle, a red basaltic scoria, resulted in the overall removal of 95 and
98% for COD and TPH respectively after 30 days.
A combination of surfactant-modified zeolite (SMZ) adsorbent beds and an MBR was used to
reduce the organic carbon content of produced water prior to reverse osmosis (RO) [75]. In the pilot
plant, pre-treated produced water from gas and oil fields was cycled through the SMZ adsorbent column
to remove volatile organic compounds (BTEX, acetone) and semi-volatile organics (e.g., napthalene).
The effluent from the SMZ column was fed to the submerged MBR for the removal of organic acid
components of TOC. Continuous operation of the SMZ/MBR system at 9.6-h HRT resulted in the overall
92% removal efficiency of the influent TOC. BTEX concentrations were reduced from the initial input
level of 70 mg/L to 5 mg/L by the SMZ units and to an average of 2 mg/L after the MBR. Fakhru’l-Razi
et al. [76] compared the MSBR and MSBR/RO efficiencies in treating oilfield produced water (COD of
1240 ± 119 mg/L; O&G of 15 ± 1.8 mg/L). Different HRT values of 8, 20 and 44 h were investigated in the
MSBR operations and the results demonstrated that for the HRT of 20 h, the combined COD, TOC and
O&G removal efficiencies were 90.9%, 92% and 91.5%, respectively. The MSBR effluent concentration
levels met the requirements for oil well reinjection. The RO treatment decreased the salt and organic
contents to acceptable levels for irrigation and industrial re-use. Fouling of the membrane surface
consisted mainly of inorganic (salts) and organic (microorganisms and their products, hydrocarbon
components) substances.
A full-scale application of the integrated treatment process, including a pre-treatment (microaerobic
hydrolysis and acidification, MOHA), biological treatment (A/O process) and advanced treatment
Appl. Sci. 2020, 10, 831 14 of 19

(micro-flocculation dynasand filtration and catalytic ozonation, MFDF-CO) was demonstrated in the
Chinese biggest petrochemical wastewater treatment plant [77]. The performance of the integrated
process was stable and resulted in the COD reduction from 84.7 to 47.0 mg/L and removing most organic
micropollutants. The final effluent showed low acute toxicity and genotoxicity. The energy demand,
however, increased by 44.1% with the electricity consumption mainly from the ozone generator, leading
to increased operational cost and indirect carbon emission.
Several recent studies reported a performance of microbial fuel cells (MFCs) and their reactor
systems for simultaneous energy production and wastewater treatment using single bacterial cultures
and microbial consortia. Using a wild-type bacterium Pseudomonas putida BCRC 1059, refinery
wastewater (COD of 2213 mg/L) was treated in a single chamber air-cathode MFC and generated
electric current over four-batch cycles for 63 cumulative days [78]. A maximum voltage of 355 mV
was obtained with the highest power density of 0.005 mW/cm2 in the third cycle with a maximum
current density of 0.015 mA/cm2 regarding the external resistor of 1000 Ω. A maximum coulombic
efficiency of 6 × 10−2 % was obtained in the fourth cycle and the COD removal efficiency of 30% was
reached as a function of time. Very recently, a bioelectrochemical treatment of synthetic produced water
(contained o.8 g/L of engine oil; TPH of 124–130 mg/L) and simultaneous bioelectrogenesis was studied
in single and dual chamber MFCs [79]. Among both configurations, dual chamber MFC showed
higher efficiency with respect to bioelectrogenesis, sulfate removal, COD and TPH reductions. The
estimated polarization behavior of both MFCs also indicated an effective response of the electroactive
anode biofilm.
Microbial communities and bioelectrochemical activities were evaluated in two laboratory-scale
MFC reactors inoculated by petrochemical industrial or domestic microbial consortia for degrading
2,4-dichlorophenol and producing electricity [80]. Wastewater-inoculated MFCs were capable of
simultaneous energy generation and phenolic degradation. Members of bacterial genera Arcobacter,
Aeromonas, Pseudomonas, Acinetobacter, Cloacibacterium and Shewanella were found to be important
bacteria for 2,4-DCP degradation while Bacillus sp. dominated in the industrial consortium was
contributing to higher electricity production. Cloacibacterium sp. was identified for the first time to
contribute to phenol degradation in MFC.
A laboratory performance of integrated constructed wetland and MFC reactors (CW-MFC) to
treat oil-contaminated wastewater (COD of 520 ± 42 mg/L; oil content of 235 ± 12 mg/L) was compared
with the MFC and CW alone [81]. The COD removals of three reactors were between 73% and 75%
and oil removals were over 95.7%. Compared with MFC, the CW-MFC with a MnO2 modified cathode
produced higher power density and output voltage. Maximum power densities of CW-MFC and
MFC were 3868 mW/m3 (102 mW/m2 ) and 3044 mW/m3 (80 mW/m2 ), respectively. Wetland plants in
CW-MFC play a positive role for the reactor cathode potential.

6. Conclusions
Bioreactor-based methods are proved as suitable techniques for the treatment of industrial
hydrocarbon-containing wastewater due to their substantial advantages over traditional activated
sludge systems, such as more precise control and management of biodegradation parameters, increased
mass transfer between aqueous, hydrophobic (hydrocarbons) and solid (biocatalyst) phases and higher
resistance of the immobilized biomass to toxic effects. However, their extensive implementation
is hindered by relatively high operational and maintenance costs. This leads to the search for
economical compact bioreactor designs, which however retain sufficient treatment efficiency. There
are a great variety of advanced constructions, for example, stirred-tank, membrane, packed-bed and
fluidized-bed bioreactors that can be operated in aerobic, anaerobic or coupled anaerobic-aerobic mode.
Several laboratory and pilot studies demonstrated better performance of hybrid anaerobic-aerobic
systems because of the synergistic effects of anaerobic and aerobic microorganisms in degrading
complex recalcitrant organics. Therefore, future efforts may be focused on improving such hybrid
systems to reduce space and energy consumption as well as gas and odor emissions [15]. It exposes
Appl. Sci. 2020, 10, 831 15 of 19

new requirements to microbial inocula, emphasizing the need for a deeper study of interactions in
anaerobic and aerobic microbial communities under anaerobic, microaerophilic and aerobic conditions
using genomics and metabolomics tools [82,83]. Genetic tools can also be useful for detecting
possible pathogens in bioreactor effluents and sludges. Considering the main challenges of oily
wastewater treatment arising from high strength and a complexity of effluents, a pre-treatment using
physico-chemical technologies aimed at reducing a toxic shock from concentrated wastewater to
microorganisms operating in bioreactors, is essential [71]. Therefore, a complex physico-chemical and
biological approach seems promising for the removal of many contaminants with diverse chemical
structures and biodegradabilities.

Funding: This research was funded by the Ministry of Science and Higher Education of the Russian Federation
(State Tasks 6.3330.2017/4.6, AAAAA19-119112290010-7) and the Russian Science Foundation (18-14-00140).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Alva-Argáez, A.; Kokossis, A.C.; Smith, R. The design of water-using systems in petroleum refining using a
water-pinch decomposition. Chem. Eng. J. 2007, 128, 33–46. [CrossRef]
2. Wastewater Management—A UN-Water Analytical Brief. 2015. Available online: https://www.unwater.org/
publications/wastewater-management-un-water-analytical-brief/ (accessed on 14 November 2019).
3. Diya’uddeen, B.H.; Daud, W.M.A.W.; Abdul Aziz, A.R. Treatment technologies for petroleum refinery
effluents: A review. Process Saf. Environ. Prot. 2011, 89, 95–105. [CrossRef]
4. Jamaly, S.; Giwa, A.; Hasan, S.W. Recent improvements in oily wastewater treatment: Progress, challenges,
and future opportunities. J. Environ. Sci. 2015, 37, 15–30. [CrossRef] [PubMed]
5. Wei, X.; Zhang, S.; Han, Y.; Wolfe, F.A. Treatment of petrochemical wastewater and produced water from oil
and gas. Water Environ. Res. 2019, 91, 1025–1033. [CrossRef] [PubMed]
6. Sanchez-Salas, J.L.; Raynal Gutierrez, M.E.; Bandala, E.R. Aerobic treatment of petroleum industry effluents.
In Current Developments in Biotechnology and Bioengineering: Biological Treatment of Industrial Effluents; Lee, D.-J.,
Hallenbeck, P., Ngo, H.H., Jegatheesan, V., Pandey, A., Eds.; Elsevier: Amsterdam, The Netherlands, 2016;
Chapter 3; pp. 79–102.
7. Ghimire, N.; Wang, S. Biological treatment of petrochemical wastewater. In Petroleum Chemicals—Recent Insight;
Zoveidavianpoor, M., Ed.; IntechOpen: London, UK, 2018. Available online: https://www.intechopen.com/
books/petroleum-chemicals-recent-insight/biological-treatment-of-petrochemical-wastewater (accessed on
11 November 2019). [CrossRef]
8. Bakke, T.; Klungsøyr, J.; Sanni, S. Environmental impacts of produced water and drilling waste discharges
from the Norwegian offshore petroleum industry. Mar. Environ. Res. 2013, 92, 154–169. [CrossRef]
9. Ottaviano, J.G.; Cai, J.; Murphy, R.S. Assessing the decontamination efficiency of a three-component
flocculating system in the treatment of oilfield-produced water. Water Res. 2014, 52, 122–130. [CrossRef]
10. Veil, J.A. U.S. Produced Water Volumes and Management Practices in 2012; Veil Environmental, LLC: Annapolis,
MD, USA, 2015; 119p.
11. Barthe, P.; Chaugny, M.; Roudier, S.; Sancho, L.D. EU Best Available Techniques (BAT): Reference Document for
the Refining of Mineral Oil and Gas; Publications Office of the European Union: Luxembourg, 2015. [CrossRef]
12. Botalova, O.; Schwarzbauer, J.; Frauenrath, T.; Dsikowitzky, L. Identification and chemical characterization
of specific organic constituents of petrochemical effluents. Water Res. 2009, 43, 3797–3812. [CrossRef]
13. Wu, P.; Jiang, L.Y.; He, Z.; Song, Y. Treatment of metallurgical industry wastewater for organic contaminant
removal in China: Status, challenges, and perspectives. Environ. Sci. Water Res. Technol. 2017, 3, 1015–1031.
[CrossRef]
14. Thornton, I.; Butler, D.; Docx, P.; Hession, M.; Makropoulos, C.; McMullen, M.; Nieuwenhuijsen, M.;
Pitman, A.; Rautiu, R.; Sawyer, R.; et al. Pollutants in Urban Waste Water and Sewage Sludge; EU Final Report;
ICON: London, UK, 2001; 244p.
15. Wang, S.; Ghimire, N.; Xin, G.; Janka, E.; Bakke, R. Efficient high strength petrochemical wastewater treatment
in a hybrid vertical anaerobic biofilm (HyVAB) reactor: A pilot study. Water Pract. Technol. 2017, 12, 501–513.
[CrossRef]
Appl. Sci. 2020, 10, 831 16 of 19

16. Rizzardini, C.B.; Goi, D. Sustainability of domestic sewage sludge disposal. Sustainability 2014, 6, 2424–2434.
[CrossRef]
17. Varyushina, G. Solutions for the disposal of industrial and rain wastewater of transport enterprises in
Moscow. MATEC Web Conf. 2018, 144, 05007. [CrossRef]
18. Kuyukina, M.S.; Ivshina, I.B.; Makarov, S.O.; Philp, J.C. Risk assessment and management of terrestrial
ecosystems exposed to petroleum contamination. In Environmental Contamination; Srivastava, J.K., Ed.;
InTech: London, UK, 2012; Chapter 10; pp. 177–198.
19. Philp, J.; Stainsby, F.; Dunbar, S. Partitioning and Bioavailability. In Water Encyclopedia; Hoboken, N.J., Ed.;
Wiley: Hoboken, NJ, USA, 2005. [CrossRef]
20. Disko West. A Strategic Environmental Impact Assessment of Hydrocarbon Activities; Scientific Report from
DCE—Danish Centre for Environment and Energy; Mosbech, A., Schiedek, D., Dünweber, M., Eds.; Aarhus
University, DCE: Aarhus, Denmark, 2013; No. 71; 306p.
21. Kassotis, C.D.; Tillitt, D.E.; Lin, C.H.; McElroy, J.A.; Nagel, S.C. Endocrinedisrupting chemicals and oil and
natural gas operations: Potential environmental contamination and recommendations to assess complex
environmental mixtures. Environ. Health Perspect. 2016, 124, 256–264. [CrossRef] [PubMed]
22. Neff, J.; Lee, K.; DeBlois, E.M. Produced Water: Overview of Composition, Fates, and Effects. In Produced
Water; Lee, K., Neff, J., Eds.; Springer: Berlin/Heidelberg, Germany, 2011; pp. 3–54. [CrossRef]
23. Neuparth, T.; Moreira, S.M.; Santos, M.M.; Reis-Henriques, M.A. Review of oil and HNS accidental spills in
Europe: Identifying major environmental monitoring gaps and drawing priorities. Mar. Pollut. Bull. 2012,
64, 1085–1095. [CrossRef]
24. Osuji, L.C.; Nwoye, I. An appraisal of the impact of petroleum hydrocarbons on soil fertility: The Owaza
experience. Afr. J. Agric. Res. 2007, 2, 318–324.
25. Sutton, N.B.; Maphosa, F.; Morillo, J.A.; Al-Soud, W.A.; Langenhoff, A.A.M.; Grotenhuis, T.; Rijnaarts, H.H.M.;
Smidt, H. Impact of long-term diesel contamination on soil microbial community structure. Appl. Environ.
Microbiol. 2013, 79, 619–630. [CrossRef] [PubMed]
26. Hayat, S.; Ahmad, I.; Azam, Z.M.; Ahmad, A.; Inam, A.; Samiullah. Effect of long-term application of oil
refinery wastewater on soil health with special reference to microbiological characteristics. Bioresour. Technol.
2002, 84, 159–163. [CrossRef]
27. Echchelh, A.; Hess, T.; Sakrabani, R. Reusing oil and gas produced water for irrigation of food crops in
drylands. Agric. Water Manag. 2018, 206, 124–134. [CrossRef]
28. Tasker, T.L.; Burgos, W.D.; Piotrowski, P.; Castillo-Meza, L.; Blewett, T.A.; Ganow, K.B.; Stallworth, A.;
Delompré, P.L.M.; Goss, G.G.; Fowler, L.B.; et al. Environmental and human health impacts of spreading oil
and gas wastewater on roads. Environ. Sci. Technol. 2018, 52, 7081–7091. [CrossRef]
29. Campos, J.C.; Borges, R.M.H.; Oliveira Filho, A.M.; Nobrega, R.; Sant’anna, G.L., Jr. Oilfield wastewater
treatment by combined microfiltration and biological processes. Water Res. 2002, 36, 95–104. [CrossRef]
30. Sirivedhin, T.; McCue, J.; Dallbauman, L. Reclaiming produced water for beneficial use: Salt removal by
electrodialysis. J. Membr. Sci. 2004, 243, 335–343. [CrossRef]
31. El-Naas, M.H.; Al-Zuhair, S.; Alhaija, M.A. Reduction of COD in refinery wastewater through adsorption on
date-pit activated carbon. J. Hazard. Mater. 2010, 173, 750–757. [CrossRef] [PubMed]
32. dos Santos, E.V.; Bezerra Rocha, J.H.; de Araújo, D.M.; de Moura, D.C.; Martínez-Huitle, C.A. Decontamination
of produced water containing petroleum hydrocarbons by electrochemical methods: A minireview. Environ.
Sci. Pollut. Res. 2014, 21, 8432–8441. [CrossRef] [PubMed]
33. Kalmykova, Y.; Moona, N.; Strömvalla, A.-M.; Björklund, K. Sorption and degradation of petroleum
hydrocarbons, polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill
leachate using sand, activated carbon and peat filters. Water Res. 2014, 56, 246–257. [CrossRef] [PubMed]
34. Tellez, G.; Nirmalakhandan, N.; Gardea-Torresdey, J.L. Kinetic evaluations of a field-scale activated sludge
system for removing petroleum hydrocarbons from oilfield-produced water. Environ. Prog. 2005, 24, 96–104.
[CrossRef]
35. Huang, C.; Shi, Y.; Gamal El-Din, M.; Liu, Y. Treatment of oil sands process-affected water (OSPW) using
ozonation combined with integrated fixed-film activated sludge (IFAS). Water Res. 2015, 85, 167–176.
[CrossRef] [PubMed]
36. Ji, G.D.; Sun, T.; Zhou, Q.X.; Sui, X.; Chang, S.J.; Li, P.J. Constructed subsurface flow wetland for treating
heavy oil-produced water of the Liaohe Oilfield in China. Ecol. Eng. 2002, 18, 459–465. [CrossRef]
Appl. Sci. 2020, 10, 831 17 of 19

37. Kanagy, L.E.; Johnson, B.M.; Castle, J.W.; Rodgers, J.H., Jr. Design and performance of a pilot-scale constructed
wetland treatment system for natural gas storage produced water. Bioresour. Technol. 2008, 99, 1877–1885.
[CrossRef]
38. Sokół, W. Treatment of refinery wastewater in a three-phase fluidised bed bioreactor with a low density
biomass support. Biochem. Eng. J. 2003, 15, 1–10. [CrossRef]
39. Zhao, X.; Wang, Y.; Ye, Z.; Borthwick, A.G.L.; Ni, J. Oil field wastewater treatment in Biological Aerated
Filter by immobilized microorganisms. Process Biochem. 2006, 41, 1475–1483. [CrossRef]
40. Gargouri, B.; Karray, F.; Mhiri, N.; Aloui, F.; Sayadi, S. Application of a continuously stirred tank bioreactor
(CSTR) for bioremediation of hydrocarbon-rich industrial wastewater effluents. J. Hazard. Mater. 2011, 189,
427–434. [CrossRef]
41. Kuyukina, M.S.; Ivshina, I.B.; Serebrennikova, M.K.; Krivoruchko, A.V.; Korshunova, I.O.; Peshkur, T.A.;
Cunningham, C.J. Oilfield wastewater biotreatment in a fluidized-bed bioreactor using co-immobilized
Rhodococcus cultures. J. Environ. Chem. Eng. 2017, 5, 1252–1260. [CrossRef]
42. Parker, W.; Farquhar, G.J. Treatment of a petrochemical wastewater in an anaerobic packed bed reactor. Water
Qual. Res. J. 1989, 24, 195–206. [CrossRef]
43. Ji, G.D.; Sun, T.H.; Ni, J.R.; Tong, J.J. Anaerobic baffled reactor (ABR) for treating heavy oil produced water
with high concentrations of salt and poor nutrient. Bioresour. Technol. 2009, 100, 1108–1114. [CrossRef]
[PubMed]
44. Rastegar, S.O.; Mousavi, S.M.; Shojaosadati, S.A.; Sheibani, S. Optimization of petroleum refinery effluent
treatment in a UASB reactor using response surface methodology. J. Hazard. Mater. 2011, 197, 26–32.
[CrossRef] [PubMed]
45. Liu, G.; Ye, Z.; Tong, K.; Zhang, Y. Biotreatment of heavy oil wastewater by combined upflow anaerobic
sludge blanket and immobilized biological aerated filter in a pilot-scale test. Biochem. Eng. J. 2013, 72, 48–53.
[CrossRef]
46. Lu, M.; Gu, L.P.; Xu, W.H. Treatment of petroleum refinery wastewater using a sequential anaerobic-aerobic
moving-bed biofilm reactor based on suspended ceramsite. Water Sci. Technol. 2013, 67, 1976–1983. [CrossRef]
[PubMed]
47. Zheng, T. A compact process for treating oilfield wastewater by combining hydrolysis acidification, moving
bed biofilm, ozonation and biologically activated carbon techniques. Environ. Technol. 2016, 37, 1171–1178.
[CrossRef]
48. Seo, D.C.; Lee, H.J.; Hwang, H.N.; Park, M.R.; Kwak, N.W.; Cho, I.J.; Cho, J.S.; Seo, J.Y.; Joo, W.H.; Park, K.H.;
et al. Treatment of non-biodegradable cutting oil wastewater by ultrasonication-Fenton oxidation process.
Water Sci. Technol. 2007, 55, 251–259. [CrossRef]
49. Malakahmad, A.; Hasani, A.; Eisakhani, M.; Isa, M.H. Sequencing batch reactor (SBR) for the removal of Hg2+
and Cd2+ from synthetic petrochemical factory wastewater. J. Hazard. Mater. 2011, 191, 118–125. [CrossRef]
50. Lee, L.; Hu, J.Y.; Ong, S.L.; Ng, W.J.; Ren, J.H.; Wong, S.H. Two-stage SBR for treatment of oil refinery
wastewater. Water Sci. Technol. 2004, 50, 243–249. [CrossRef]
51. Shariati, S.R.P.; Bonakdarpour, B.; Zare, N.; Ashtiani, F.Z. The effect of hydraulic retention time on the
performance and fouling characteristics of membrane sequencing batch reactors used for the treatment of
synthetic petroleum refinery wastewater. Bioresour. Technol. 2011, 102, 7692–7699. [CrossRef] [PubMed]
52. Campo, R.; Giustra, M.G.; De Marchis, M.; Freni, G.; Di Bella, G. Characterization and treatment proposals of
shipboard slop wastewater contaminated by hydrocarbons. Water 2017, 9, 581. [CrossRef]
53. Dong, Z.; Lu, M.; Huang, W.; Xu, X. Treatment of oilfield wastewater in moving bed biofilm reactors using a
novel suspended ceramic biocarrier. J. Hazard. Mater. 2011, 196, 123–130. [CrossRef] [PubMed]
54. Riley, S.M.; Ahoor, D.C.; Cath, T.Y. Enhanced biofiltration of O&G produced water comparing granular
activated carbon and nutrients. Sci. Total Environ. 2018, 640–641, 419–428.
55. Pendashteh, A.R.; Chaibakhsh, N.; Ahmadun, F.-R. Biological treatment of high salinity produced water by
microbial consortia in a batch stirred tank reactor: Modelling and kinetics study. Chem. Eng. Commun. 2018,
205, 387–401. [CrossRef]
56. Khondee, N.; Tathong, S.; Pinyakong, O.; Powtongsook, S.; Chatchupong, T.; Ruangchainikom, C.;
Luepromchai, E. Airlift bioreactor containing chitosan-immobilized Sphingobium sp. P2 for treatment
of lubricants in wastewater. J. Hazard. Mater. 2012, 213–214, 466–473. [CrossRef] [PubMed]
Appl. Sci. 2020, 10, 831 18 of 19

57. Sudmalis, D.; Da Silva, P.; Temmink, H.; Bijmans, M.M.; Pereira, M.A. Biological treatment of produced
water coupled with recovery of neutral lipids. Water Res. 2018, 147, 33–42. [CrossRef]
58. Cruz-Morató, C.; Ferrando-Climent, L.; Rodriguez-Mozaz, S.; Barceló, D.; Marco-Urrea, E.; Vicent, T.;
Sarrà, M. Degradation of pharmaceuticals in non-sterile urban wastewater by Trametes versicolor in a fluidized
bed bioreactor. Water Res. 2013, 47, 5200–5210.
59. Kuyukina, M.S.; Ivshina, I.B.; Serebrennikova, M.K.; Krivorutchko, A.B.; Podorozhko, E.A.; Ivanov, R.V.;
Lozinsky, V.I. Petroleum-contaminated water treatment in a fluidized-bed bioreactor with immobilized
Rhodococcus cells. Int. Biodeterior. Biodegrad. 2009, 63, 427–432. [CrossRef]
60. Serebrennikova, M.K.; Golovina, E.E.; Kuyukina, M.S.; Ivshina, I.B. A consortium of immobilized rhodococci
for oilfield wastewater treatment in a column bioreactor. Appl. Biochem. Microbiol. 2017, 53, 435–440.
[CrossRef]
61. Dickhout, J.M.; Moreno, J.; Biesheuvel, P.M.; Boels, L.; Lammertink, R.G.H.; de Vos, W.M. Produced water
treatment by membranes: A review from a colloidal perspective. J. Colloid Interface Sci. 2017, 487, 523–534.
[CrossRef] [PubMed]
62. Nelson, M.J.; Nakhla, G.; Zhu, J. Fluidized-bed bioreactor applications for biological wastewater treatment:
A review of research and developments. Engineering 2017, 3, 330–342. [CrossRef]
63. Kuyukina, M.S.; Ivshina, I.B.; Gavrin, Y.A.; Podorozhko, E.A.; Lozinsky, V.I.; Jeffree, C.E.; Philp, J.C.
Immobilization of hydrocarbon-oxidizing bacteria in poly(vinyl alcohol) cryogels hydrophobized using a
biosurfactant. J. Microbiol. Methods 2006, 65, 596–603. [CrossRef] [PubMed]
64. Gasim, H.A.; Kutty, S.R.M.; Hasnain Isa, M.; Alemu, L.T. Optimization of anaerobic treatment of petroleum
refinery wastewater using artificial neural networks. Res. J. Appl. Sci. Eng. Technol. 2013, 6, 2077–2082.
[CrossRef]
65. Huo, S.; Zhu, F.; Zou, B.; Xu, L.; Cui, F.; You, W. A two-stage system coupling hydrolytic acidification with
algal microcosms for treatment of wastewater from the manufacture of acrylonitrile butadiene styrene (ABS)
resin. Biotechnol. Lett. 2018, 40, 689–696. [CrossRef]
66. Huo, S.; Chen, J.; Chen, X.; Wang, F.; Xu, L.; Zhu, F.; Guo, D.; Li, Z. Advanced treatment of the low
concentration petrochemical wastewater by Tribonema sp. microalgae grown in the open photobioreactors
coupled with the traditional Anaerobic/Oxic process. Bioresour. Technol. 2018, 270, 476–481. [CrossRef]
67. Janka, E.; Carvajal, D.; Wang, S.; Bakke, R.; Dinamarca, C. Treatment of metformin-containing wastewater
by a hybrid vertical anaerobic biofilm-reactor (HyVAB). Int. J. Environ. Res. Public Health 2019, 16, 4125.
[CrossRef]
68. Nasirpour, N.; Mousavi, S.M.; Shojaosadati, S.A. Biodegradation potential of hydrocarbons in petroleum
refinery effluents using a continuous anaerobic-aerobic hybrid system. Korean J. Chem. Eng. 2015, 32, 874–881.
[CrossRef]
69. Phattaranawik, J.; Leiknes, T. Study of hybrid vertical anaerobic sludge-aerobic biofilm membrane bioreactor
for wastewater treatment. Water Environ. Res. 2010, 82, 273–280. [CrossRef]
70. U.S. Environmental Protection Agency. Detailed Study of the Centralized Waste Treatment Point Source Category
for Facilities Managing Oil and Gas Extraction Wastes. EPA-821-R-18-004; U.S. EPA: Washington, DC, USA,
2018; 262p.
71. Prabakar, D.; Suvetha, K.S.; Manimudi, V.T.; Mathimani, T.; Kumar, G.; Rene, E.R.; Pugazhendhi, A.
Pretreatment technologies for industrial effluents: Critical review on bioenergy production and environmental
concerns. J. Environ. Manag. 2018, 218, 165–180. [CrossRef]
72. Bahri, M.; Mahdavi, A.; Mirzaei, A.; Mansouri, A.; Haghighat, F. Integrated oxidation process and biological
treatment for highly concentrated petrochemical effluents: A review. Chem. Eng. Process. Process Intensif.
2018, 125, 183–196. [CrossRef]
73. Kang, J.; Lu, L.; Zhan, W.; Li, B.; Li, D.; Ren, Y.; Liu, D. Photocatalytic pretreatment of oily wastewater
from the restaurant by a vacuum ultraviolet/TiO2 system. J. Hazard. Mater. 2011, 186, 849–854. [CrossRef]
[PubMed]
74. Pérez, L.S.; Rodriguez, O.M.; Reyna, S.; Sánchez-Salas, J.L.; Lozada, J.D.; Quiroz, M.A.; Bandala, E.R.
Oil refinery wastewater treatment using coupled electrocoagulation and fixed film biological processes.
Phys. Chem. Earth Parts A/B/C 2016, 91, 53–60.
Appl. Sci. 2020, 10, 831 19 of 19

75. Kwon, S.; Sullivan, E.J.; Katz, L.; Kinney, K.A.; Bowman, R.S. Pilot scale test of a produced water-treatment
system for initial removal of organic compounds. In Proceedings of the SPE Annual Technical Conference
and Exhibition, Denver, CO, USA, 21–24 September 2008. SPE-116209-MS. [CrossRef]
76. Fakhru’l-Razi, A.; Pendashteh, A.; Abidin, Z.Z.; Abdullah, L.C.; Biak, D.R.A.; Madaeni, S.S. Application
of membrane-coupled sequencing batch reactor for oilfield produced water recycle and beneficial re-use.
Bioresour. Technol. 2010, 101, 6942–6949. [CrossRef] [PubMed]
77. Wu, C.; Li, Y.; Zhou, Y.; Li, Z.; Zhang, S.; Liu, H. Upgrading the Chinese biggest petrochemical wastewater
treatment plant: Technologies research and full scale application. Sci. Total Environ. 2018, 633, 189–197.
[CrossRef] [PubMed]
78. Majumder, D.; Maity, J.; Tseng, M.-J.; Nimje, V.; Chen, H.-R.; Chen, C.-C.; Chang, Y.-F.; Yang, T.-C.; Chen, C.-Y.
Electricity generation and wastewater treatment of oil refinery in microbial fuel cells using Pseudomonas
putida. Int. J. Mol. Sci. 2014, 15, 16772–16786. [CrossRef] [PubMed]
79. Mohanakrishna, G.; Al-Raoush, R.I.; Abu-Reesh, I.M.; Aljaml, K. Removal of petroleum hydrocarbons and
sulfates from produced water using different bioelectrochemical reactor configurations. Sci. Total Environ.
2019, 665, 820–827. [CrossRef]
80. Hassan, H.; Jin, B.; Donner, E.; Vasileiadis, S.; Saint, C.; Dai, S. Microbial community and bioelectrochemical
activities in MFC for degrading phenol and producing electricity: Microbial consortia could make differences.
Chem. Eng. J. 2018, 332, 647–657. [CrossRef]
81. Yang, Q.; Wu, Z.; Liu, L.; Zhang, F.; Liang, S. Treatment of oil wastewater and electricity generation by
integrating constructed wetland with microbial fuel cell. Materials 2016, 9, 885. [CrossRef]
82. Tang, Y.; Shigematsu, T.; Ikbal; Morimura, S.; Kida, K. The effects of micro-aeration on the phylogenetic
diversity of microorganisms in a thermophilic anaerobic municipal solid-waste digester. Water Res. 2004, 38,
2537–2550. [CrossRef]
83. Yang, C.; Zhang, W.; Liu, R.; Li, Q.; Li, B.; Wang, S.; Song, C.; Qiao, C.; Mulchandani, A. Phylogenetic diversity
and metabolic potential of activated sludge microbial communities in full-scale wastewater treatment plants.
Environ. Sci. Technol. 2011, 45, 7408–7415. [CrossRef] [PubMed]

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