Bio-remed Oil spills - Indian Coast Guard

Bio-remediation Bio remediation techniques for
responding to Oil spills at Sea
Dr Pradeep Kumar
Naval Materials Research Laboratory (NMRL)
DRDO, Min. of Defence, Defence,
Ambernath 421506,
Thane, Maharashtra

EFFECTS OF SPILLED OIL ON
BIRDS
ANIMALS
TURTLES
Short-term Short term effects
Tarring of beaches,
Damage to fisheries
Water Contamination
Long-term Long term effects
Persistent toxic chemical in water & soil
Permanent genetic mutation on entry through food
chain
Oil Pollution
EELS

Methods
a) Natural
Evaporation, Dissolution
Photo-oxidation
Photo oxidation
Biodegradation
Sedimentation, Dispersion,
Spreading and Drifting
d) Bioremediation
ODB, Bioemulsifier, Bioemulsifier,
other
mediators
Possible methods of oil spill removal
b) Physical
Mechanical recovery (Skimmers,
Booms, Suctions, Separation)
c) Chemical
Sorbents – inorganic/organic
(Vermiculites,Glass wool,Carbon
Wool, foam)
Limitations
Limited to low MW
Fractions.
Slow and controlled by
environmental factors.
Limited Efficiency.
Environmentally controlled.
Clumsy, time consuming
and costly.
Requires other physical
methods
Reuse of
chemicals/sorbents
chemicals/ sorbents
impractical.
Requires supply of
nutrients
Adaptability
Restricted
Restricted
Restricted
Restricted and
Unacceptable.
Restricted
Not ecofriendly.
ecofriendly
Ecofriendly and
easy application.

Bioremediation
What is bioremediation?
Management of pollution through Biological means
Bioremediation of pollutant oil
– microorganisms (fungi or bacteria)
– to decompose toxic pollutants
– Enhanced biodegradation of petroleum hydrocarbons
– Biodegradation
a natural process by which microbes alter and break
down petroleum hydrocarbons into other substances.
– Resultant products: products:
CO 2, , water, and partially oxidized biologically inert by-
products (Bragg et al. 1992).

AD/ABSORPTION
BIOREMEDIATION
TECHNOLOGIES
BIOREMEDIATION
PLANT MATERIALS BIOSURFACTANTS BIOPOLYMERS
STRAW, SAW DUST, WOODSHAVINGS
LOW MW BIOCHEMICALS
TO CLEAN OILED SURFACE
BIOEMULSIFIERS & ENZYMES

Bioremediation: Advantages
Minimal physical disruption of site.
No adverse effect, when used correctly.
Helpful in removing - toxic components
of oil.
Simple and more thorough approach
than mechanical technologies.
Relatively less costly.

Bioremediation: Limitations
Effectiveness may vary for different
types of Oil (Oil Crude, HSD, FFO)
May not be convenient during heavy
rains & low visibility.
Quick & specifically tailored approach
for each polluted site.
May require 2-3 2 3 periodic spraying of
Nutrient depending upon the density of
spilled oil.

DRDO
OIL SPILL CONTROL TECHNOLOGY

Schematic representation
Bioremediation of oil in marine environments
HSD+
Bacteria+
BE. HSD+
Bacteria+
BE+
Nutrient
HSD+
Bacteria+
BE+
Nutrient+
Oxygen

Infra-red Infra red
signals
(FTIR)
Solubility
Toxicity
Characteristics : NMRL Bioemulsifier
Thermal
properties
(TGA, under
N2 ENV.)
Molecular
Weight (GPC)
IDT 200°C. 200 C.
STABLE UP
199°C 199 C
Peak Mw.5919;
Polydispersity
1.11.
Alcohol, ester,
carboxyl and
proteins.
Alcohol,
Seawater and
HSD
Non toxic
(Endotoxin Endotoxin free).
80
SURFACE TENSION
(mN/m)
70
60
50
40
30
20
SURFACE TENSION REDUCTION BY BE
Sea water
Syn. Sea water
Distilled Water
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
BE CONC. (%)
OIL Eating Bacteria
Hallomonas cupida
Pseudomonas stutzeri
Bacillus pumilus
Bacillus sphericus
Micrococcus roseus
Micrococcus varians. varians
Characterized by Genetic
engineering techniques and genes
involved in biodegradation are
sequenced.

Trials on Bioremediation of floating oil using
Bioemulsifier
• First Bioremediation Trial :
• NMRL Bioemulsifier, Oil degrading bacteria and
Nutrient compound as compared to control.
• Naval harbour, Mumbai,(April 20th 2001),
• Area of 25 m2 • Fast and effective dispersion (90 – 95% dispersion) and
degradation of HSD (10 days) .
• Extended Trials: 40 lit of weathered oil (Dec.21st to 31,
2001): in an extended area of 100 m2 80-85% dispersion in 8-
10days.
• Conclusion: The results indicated effective dispersion of
floating oil within 8-10 days.

MATERIALS REQUIRED FOR BIOREMEDIATION OF
FLOATING OIL (30 gallons) IN AN AREA OF 500 m 2
BIOEMULSIFIER
NUTRIENT MIXTURE
OIL DEGRADING
BACTERIA (ODB)
50 grams
10 litres.
40 litres
(10g powder)
TOTAL RECURRING COAST
(BE+NUTRIENT+ODB)
Approximately Rs.50,000 / tonne of oil
Rs2500/-
Rs2000/-
Rs500/-
Rs5000/

Bioremediation process -Flow chart
Spray all the ingredients evenly and sequentially as given below
Day ‘0’ 3 rd Day 6th Day 9th Day
Spray Nutrient
Mixture uniformly
over oil film on ‘0’ day
Followed by
Bioemulsifier
(concentration 0.25% w/v)
Followed by
oil degrading
bacteria
Spray
Nutrient
Mixture
alone
Spray
Nutrient
Mixture
alone
Spray Nutrient
Mixture alone

OIL BIODEGRADATION CYCLE
FUEL OIL
FATTY ACIDS + CO 2 + H 2 O
ALDEHYDES
BIOREMEDIATION
OXIDATION BY
MONOOXYGENASES
PRIMARY ALCOHOLS

EFFECTS OF BIOREMEDIATION
1. Initial oil film (HSD). 2. Complete emulsification.
3. Fragmentation & precipitation.
4. Dispersion of oil film.

BIOREMEDIATION AT VIZAG HARBOUR WATERS
Spraying at N-10
1100h
Oil Slick N-9 N 9 OIL
EMULSIFICATION,
15-20 15 20 min after spraying 1115h
Day “0”
27 Apr 03

DO’S
1. Boats and floating structures be preferably removed to facilitate facilitate
easy accessibility and to ensure total coverage.
2. BIOEMULSIFIER ALWAYS BE DISSOLVED IN SEAWATER as
it contains required divalent metal cations, cations,
necessary for
solubilization.
solubilization.
3. Normal safety precautions must be observed during spraying of
bioemulsifier ( such as use of face mask, gloves and apron etc ) .
4. Movement of boats etc over the site be restricted.
5. Spraying hardware should be washed immediately after use (with
fresh water).
6. Bioremediation exercise may be repeated in the areas where fresh
oil is invading the treated site.
7. In case of profuse skin contact wash immediately with excess of
water.

DON’TS
1. Do not undertake bioremediation during dredging
activity.
2. Do not spray bioemulsifier on floating non oil dirt to
avoid wastage and inconsistent results.
3. Do not spray bioemulsifier during heavy rains to
avoid wastage and inconsistent results.

Bioremediation
of HSD, FFO & Crude Oil
BIOREMEDIATION
DIESEL FFO CRUDE OIL
TEST-1 HSD CONTROL-1 TEST-2 CONTROL-2 TEST-3 CONTROL-3
HSD+NP+BE+ODB FFO+NP+BE+ODB CRUDE+NP+BE+ODB
TEST-1 (HSD)
SEAWATER : 5L
HSD : 25g
NP (0.05%) : 2.5g;
BE (0.25%) : 2.5g
ODB : 15X105 TEST-2 (FFO)
SEAWATER : 5L
FFO : 25g
NP (0.05%) : 2.5g;
BE (0.25%) : 2.5g
ODB : 15X105
TEST-3
SEAWATER : 5L
CRUDE : 25g
NP (0.05%) : 2.5g;
BE (0.25%) : 2.5g
ODB : 15X105

Bioremediation - HSD
TEST-1: Seawater + HSD + NUTRIENT + BE + ODB
CONTROL-1:Seawater+HSD

Bioremediation – Crude Oil

Bioremediation – FFO

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Optical Density and Bacterial Growth
0 DAY 3 DAY 6 DAY
HSD-T1
FFO-T2
CRU-OIL-T3
DAY
0
3
6
HSD
CFU / ml
76 X 10 -5
187 X 10 -5
67 X 10 -5
FFO
CFU / ml
67 X 10 -5
133 X 10 -5
43 X 10 -5
CRUDE
OIL
CFU / ml
71 X 10 -5
155 X 10 -5
51 X 10 -5

Oil Bioremediation technology :Market
Probable users
IOC,
BPCL,HPCL,
ONGC, OIL,
IPCL, Reliance
& ESSR
Navy : 4
Commands
Annual requirements
For 6 tonnes of spilled oil
per annum each during
drilling & refining
(3x8 firms=24t)
8 tonnes
Cost/tonne Cost/ tonne
of oil spilled
@0.5 lacs/t lacs/t
24 lacs
4.0 lacs
Initial Investment : 60 lacs on fermentor+separator+evaporator+overheads

ACKNOWLEDGEMENTS
(A) WESTERN NAVAL COMMAND MUMBAI
(B) COAST GUEST REGION WEST
(C) CGPRT MAZGOAN DOCK
(D) NMRL (DRDO)
1. Dr Susan Titus, Sc. ‘E’
2. Dr S.N. Gaonkar, Gaonkar
Sc. ‘D’
3. Mr B.S. Swami Sc. ‘D’
4. Mrs Shobhana Chongdar Sc. ‘C’
5. Mrs. Sapna Pavitran Sc. ‘C’
6. Dr C.B. Jagtap Sc. ‘C’
7. Mr. Udhay Kumar T.O. ‘C’
8. Ku. Chitra Deshmukh T.A. ‘B’
9. Shri R. Mohan Ram T.A. ‘A’