JAN DLUGOSZ UNIVERSITY

BIOREMEDIATION OF OIL HYDROCARBONS

CONTAMINATED SOIL

Iwona Zawierucha

Institute of Chemistry, Environmental Protection and Biotechnology, Jan Dlugosz University in Czestochowa, Poland

(e-mail: i.zawierucha@ajd.czest.pl)

REMEDIATION OF CONTAMINATED LAND AND GROUNDWATER

can appear locally and

periodically as a consequence

of accidental leaks of crude oil

from mining shafts, damaged

pipelines, cisterns, tankers,

and petroleum stations

may also appear

permanently on a definited

area, and as derivatives from

the refineries or engine

industry

OIL HYDROCARBONS IN SOIL (I)

As oil hydrocarbons include hazardous

chemicals, such as benzene, toluene,

ethylbenzene, xylenes and naphthalene,

this contamination can be hazardous to

plants, animals, and humans.

OIL HYDROCARBONS IN SOIL (II)

In response to a growing need to address environmental

contamination, many remediation technologies have been

developed to treat soil and groundwater contaminated with oil

hydrocarbons, including in situ and ex-situ methods.

A contaminated site may require a combination of procedures

allowing for the optimum remediation at prevailing conditions.

Biological, physical and chemical technologies may be used in

combination to reduce the contamination to safe and

acceptable levels.

NATURAL ATTENUATION (I)

NATURAL ATTENUATION (NA)

MONITORED NATURAL

ATTENUATION (MNA)

ENHANCED NATURAL

ATTENUATION (ENA)

Current world trends indicate that the most accessible and

effective in situ extensive remediation technologies are

based on Natural Attenuation (NA). They are

recommended by US EPA, and can be realized as

Monitored Natural Attenuation (MNA) or, in the essential

cases, as Enhanced Natural Attenuation (ENA).

NATURAL ATTENUATION (II)

NA include a variety of physical, chemical, or biological

processes that, under favourable conditions reduce the

concentration of contaminants in the soil and

groundwater.

The mechanisms of natural attenuation can be

classified as destructive and non-destructive

destructive: biodegradation and hydrolysis

non-destructive: sorption, dispersion, dilution,

volatilization

MONITORED NATURAL ATTENUATION

Monitored natural

attenuation (MNA) is a

technique used to monitor or

test the progress of natural

attenuation processes. It

may be used with other

remediation processes as a

finishing option or as the

only remediation process if

the rate of contaminant

degradation is fast enough

to protect human health and

the environment.

The main aim of MNA: to predict/prevent the contaminants

spreading and associated risks to groundwater.

INTRINSIC BIODEGRADATION

Intrinsic biodegradation with

participation of microorganisms - play the

most important role in natural attenuation

of soil contaminated with oil

hydrocarbons

Biodegradation under aerobic conditions

may lead to complete mineralization of oil

hydrocarbons into carbon dioxide, water,

inorganic compounds and cell protein

oil hydrocarbons

bacterial enzymes

CO2 + H2O + energy

O2

H2O

oxidation

PROBLEM

Intrinsic biodegradation rate – low

Factors limiting biodegradation rate:

- activity of microflora

- bioavailability of hyrocarbons

- environmental factors: oxygen, nutrients

ENHANCED NATURAL

ATTENUATION (ENA)

BIOSTIMULATION

the application of a proper agent to soil

to enhance the activity of indigenous

microorganisms

BIOAUGMENTATION

the application of selected oil-

degraders to supplement the existing

microbial population

ENHANCEMENT OF INTRINSIC BIODEGRADATION

Benefits of enhancement of biodegradation

conversion of toxic compounds to non-toxic end products

lower costs of disposal

reduced health and ecological risks

reduced long-term liabilities

the ability to perform the treatment in situ

a very low disturbance of native ecosystems

BIOAUGMENTATION

BIOAUGMENTATION is a promising and low-cost

bioremediation method, in which effective bacterial

isolates or microbial consortia capable of degrading oil

hydrocarbons are introduced to the contaminated soil.

indigenous microorganisms - indigenous microflora from

the target site

exogenous microorganisms – from other remediated or

contaminated sites

commercial suppliers

genetically engineered microrganisms (GEMs)

microbial cultures in an immobilized form

BIOSTIMULATION

water supply

oxygen supply

- tilling

- injection of aerated water, air or pure oxygen

nutrients supply (mainly nitrogen and phosphorus) in

form of organic and/or inorganic fertilizers

surfactants supply

- biosurfactant

- synthetic surfactant

Biostimulation relies on increasing the activity of

indigenous bacteria by providing nutrients, oxygen,

surfactants or water to the contaminated soil or modifying

the environmental conditions.

THE GOALS OF THE STUDY

the effect of bioaugmentation,

biostimulation and their combination on

the biodegradation rate in oil

hydrocarbons contaminated soil

the comparison of methods of

biodegradation enhancement to select

the best treatment option for optimal

soil remediation

THE RANGE OF RESEARCH

Determination of soil parameters and intrinsic biodegradation rate

under aerobic conditions

Biodegradation enhancement by:

addition of indigenous or exogenous bacterial consortium

addition of oxygen

addition of nutrients

addition of surfactant

combined method

The comparison of methods of biodegradation enhancement

COLLECTING OF SOIL SAMPLES

THE LOCATION

OF SOIL SAMPLES

COLLETING

KLUCZEWO AIRPORT

EXPERIMENTS

BATCH TESTS

Mass of soil sample: 30 g

Temperature: 20±5oC

Soil: TPH contaminated with oil

hydrocarbons (“historical” - aged

contamination) originated from the

former military airport in Kluczewo,

Poland (from depths of 1.5 m - G1 and

2.0 m – G2)

The reactors with soil

samples

RESPIROMETER TEST

• on-line measurements of the

O2 consumed and CO2

produced during hydrocarbons

biodegradation

10-chamber Micro-Oxymax

respirometer O2/CO2

The Micro-Oxymax system is

a highly adaptable general

purpose closed circuit

respirometer. The system

monitors the concentration of

gas contained within an

enclosed head space into which

the soil being monitored is

respiring. Periodic sensing of the

gas concentration, along with an

equally accurate measurement

of the volume of the head space,

allows calculations of

incremental and accumulated

values for O2 consumption and

CO2 production.

MICROBIAL TESTS

Microbial enumeration of bacteria

was measured as the number of colony

– forming units (CFU) per gram, using

the standard agar-plate technique.

Hydrocarbon – degrading bacteria

isolated from contaminated soil

samples were grown on the solid agar

media with monoaromatic

hydrocarbons (mix of benzene, toluene

and xylene) as the sole carbon source.

Isolated bacterial strains were transferred from agar cants to a liquid

nutrient medium with monoaromatic hydrocarbons. The aerobic bacteria

were grown in flasks of 0.5 L, aerated by mechanical mixing. Bacteria were

grown as a consortium (i.e. several strains in one liquid medium) without

identifying the strains. The separation of bacterial suspension from the liquid

medium was achieved by centrifuging (at 2000 rpm for 5 minutes).

Concentrations of a bacterial consortium (numbers of cells in 1 mL of a

suspension) were checked using the Thom’s chamber.

BIOAUGMENTATION: soil + 8 mL of indigenous or exogenous bacterial consortium

containing 2.4 or 4.8×1015 CFU/mL

BIOSTIMULATION – OXYGEN SUPPLY: soil + 8 mL of aerated water

BIOSTIMULATION – SURFACTANT SUPPLY: soil + 0.15 mL of Tween 80 (dose =

1.0% v/v)

BIOSTIMULATION – NUTRIENTS SUPPLY: soil + 8 ml nutrient medium

COMBINED METHOD: soil + 7.85 mL of the indigenous bacterial consortium + 0.15 mL

of Tween 80

CONTROL SAMPLES:

control 1 (uncontaminated soil samples G1R and G2R)

THE OBJECTIVE: to determine the basal respiration which is the result of

soil organic matter (SOM) decomposition

control 2 (contaminated soil samples G1 and G2 without any enhancement)

THE OBJECTIVE: to determine the overall respiration, due to organic

matter and hydrocarbons biodegradation

METHODS

Cumulative curves of O2 uptake and CO2

production

The equation of linear regression of cumulative

curves

y = a∙x

a/60 = the mean rate of

[ml/min] O2 consumption/CO2 production

DATA PROCESSING

DATA PROCESSING: cumulative curves of O2 uptake and CO2 production

O2 consumption

CO2 production

y = 8,8186x

R2 = 0,9924

y = 21,227x

R2 = 0,9974

0

500

1000

1500

2000

2500

3000

0 18 36 54 72 90 108 126 144 162 180

time, h

cu

mu

lati

ve O

2, m

l

G1R

G1

y = 8,3444x

R2 = 0,9902

y = 20,872x

R2 = 0,9987

0

500

1000

1500

2000

2500

3000

0 18 36 54 72 90 108 126 144 162 180

time, h

cu

mu

lati

ve C

O2, m

l

G1R

G1

CALCULATION OF BIODEGRADATION RATE

MASS BALANCE EQUATION CnHm + a O2 = nY CH2O + b CO2 + c H2O

ASSUMING: m/n = 1,5 Y = 0,5

m – number of hydrogen atoms, n – number of carbon atoms, a, b, c – stoichiometric

coefficients of reaction, Y – microbial yield (TPH formula = CH1,5, Y = 0,5)

k’NA/ENA - intrinsic/enhanced biodegradation rates calculated on the basis of O2 consumption

rates [mg of TPH kg of soil-1 day-1]

kO2 - O2 consumption rates [μL/min],

2.144 – a conversion coefficient for the O2 consumption rate [mmol of O2 kg of soil-1 day-1]

The comparative analysis of biodegradation enhancement – the ratio kENA/kNA

2

14

124

144,2/ OENANA k

n

mY

n

m

k

daysoilofkg

nshydrocarboofmg

Soil sample

the overall respiration

(hydrocarbons

biodegradation

+ SOM decomposition)

the basal respiration (SOM

decomposition)

hydrocarbons

biodegradation

Mean rate [ml/min]

O2

consumption

CO2

production

O2

consumption

CO2

production

O2

consumption

CO2

production

G1 0,35 0,34 0,15 0,14 0,20 0,20

G2 0,22 0,19 0,10 0,09 0,12 0,10

RESULTS: intrinsic biodegradation

Mean rates of O2 consumption and CO2 production

mean biodegradation rate calculated based

on the O2 consumption rate THE O2 CONSUMPTION

RATE – MORE RELIABLE

INDICATOR TO EVALUATE

THE IN SITU

BIODEGRADATION

for G1 = 7

for G2 = 4

daysoilofkg

nshydrocarboofmg

Higher values of mean rates of O2 consumption and CO2 production in

contaminated compared to uncontaminated soil samples indicated aerobic

biodegradation of oil hydrocarbons.

RESULTS: the effect of bioaugmentation

Notation: G1, G2 – contaminated soil without enhancement - depths of 1.5 and 2.0 m;

1A/2A – addition of exogenous/indigenous bacterial consortium (2.4×1015 CFU mL-1);

1B/2B – addition of exogenous/indigenous bacterial consortium (4.8×1015 CFU mL-1)

20

103

121125

141

18

97

114 116

132

0

20

40

60

80

100

120

140

160

G1 1A 2A 1B 2B G2 1A 2A 1B 2B

bio

deg

rad

ati

on

rate

,

mg

of

hyd

rocarb

on

s k

g-1

day

-1

The highest biodegradation rate - addition of indigenous

bacterial consortium (4.8×1015 CFU mL-1)

RESULTS: the effect of biostimulation

9

35

28

20

6

29

20

16

0

5

10

15

20

25

30

35

40

G1 C D E G2 C D E

bio

deg

rad

ati

on

rate

,

mg

of

hyd

rocarb

on

s k

g-1

day -1

Notation: G1, G2 – contaminated soil without enhancement - depths of 1.5 and 2.0 m;

C – addition of nutients, D – addition of surfactant, E – addition of aerated water

The highest biodegradation rate - addition of nutrients

ANALYSIS OF BIODEGRADATION ENHANCEMENT

7

4

3

2

15

0 2 4 6 8 10 12 14 16

the increase of biodegradation rate (kENA/kNA)

combined method -

bioaugmentation +

addition of surfactant

biostimulation by

aerated water supply

biostimulation by

surfactant supply

biostimulation by

nutrients supply

bioaugmentation

The highest increase of biodegradation rate – combined

method (bioaugmentation + addition of surfactant)

CONCLUSIONS

1. Each of the studied enhancement methods resulted in an increase of the

biodegradation rate in oil hydrocarbons contaminated soil.

2. The highest biodegradation rate due to bioaugmentation was achieved when the

bacterial consortium containing 4.8x1015 CFU mL-1 was applied. Moreover, application

of indigenous bacterial consortia was more efficient in comparison to the exogenous

bacteria, as the 7-fold increase of the biodegradation rate was achieved. Native

microorganisms are well adapted to their environment, and a rapid growth of

population guarantees better biodegradation.

3. In the case of biostimulation the highest increase of biodegradation was observed

when nutrients were added to soil - the enhanced biodegradation rate was 4 times

higher than the intrinsic biodegradation rate.

4. Both: bioaugmentation and biostimulation appeared to be effective in enhancing

intrinsic biodegradation of oil hydrocarbons in soil; however, the combined

enhancement increased the biodegradation rate more efficiently. In the case of aged

contamination, the best enhancement performance was achieved by the use of

bioaugmentation + addition of a surfactant. When such treatment was applied, the

enhanced biodegradation rate was 15 times higher than the intrinsic biodegradation

rate. Inoculating of soil with indigenous microorganisms seems to be the most

effective option, while applying a surfactant makes a substrate more available for

microorganisms.

JAN DLUGOSZ UNIVERSITY

PERMEABLE REACTIVE BARRIER (PRB) AND

POLYMER INCLUSION MEMBRANE (PIM) TECHNOLOGIES FOR REMOVAL OF HEAVY

METALS FROM GROUNDWATER AND LANDFILL LEACHATE

Iwona Zawierucha

Institute of Chemistry, Environmental Protection and Biotechnology, Jan Dlugosz University in Czestochowa, Poland

(e-mail: i.zawierucha@ajd.czest.pl)

REMEDIATION OF CONTAMINATED LAND AND GROUNDWATER

Since the industrial revolution, pollution by heavy metals has

substantially increased through:

industrial effluents and landfill leaching

mining activities

use of fertilizers and pesticides in agriculture

burning of waste and fossil fuels

municipal waste treatment

HEAVY METALS (I)

Because of their threat to human health and the extend of the problems related to

both natural and anthropogenic contamination by heavy metals and metalloids,

major efforts are undertaken to develop remediation technologies for treatment of

metal-contaminated soils, sediments and groundwater, which are based either on

physical or chemical principles, or on biological processes. Conventionally, heavy

metal pollution in soil and water is removed by methods based on physical and/

or chemical processes.

HEAVY METALS (II)

The most hazardous heavy metals

cadmium (Cd) copper (Cu)

lead (Pb) mercury (Hg)

nickel (Ni) zinc (Zn)

arsenic (As)

Possible remediation methods are based on removal

of heavy metals from soil and groundwater or a

decrease in bioavailability of them by in-situ

immobilization processes. The immobilization of

heavy metals in the unsaturated zone is based on the

addition of soil additives to immobilize the metals by

sorption or precipitation.

REMEDIATION – UNSATURATED ZONE

Pump and treat, using precipitation or flocculation

techniques followed by sedimentation and disposal of the

resulting contaminated sludge is frequently used for treating

heavy metal contamination in groundwater

Other methods for heavy metal removal from groundwater

involve ion exchange, reverse osmosis and microfiltration

For the in situ treatment of groundwater, a reactive barrier

may be installed where metals are transformed into insoluble

metal sulfides or on the binding of heavy metals to sorptive

materials of barrier.

GROUNDWATER REMEDIATION METHODS

installed in a natural aquifer perpendicular to the

groundwater flow direction

heavy metals removed from groundwater by sorption,

precipitation and biological processes

PERMEABLE REACTIVE BARRIERS (PRBs)

EPA (1999), Remedial Technology Fact Sheet, 542-R-99-002

Definition:

Permeable Reactive Barriers are

"passive in situ treatment zones of reactive material that

degrades or immobilizes contaminants as groundwater

flows through it. PRBs are installed as permanent, semi-

permanent, or replaceable units across the flow path of a

contaminant plume. Natural gradients transport cont-

aminants through strategically placed treatment media.

The media degrade, sorb, precipitate, or remove chlo-

rinated solvents, metals, radionuclides, and other

pollutants."

PERMEABLE REACTIVE BARRIERS (I)

PERMEABLE REACTIVE BARRIER (II)

A permeable reactive barrier material consisting of permanent, semi permanent or

replaceable reactive media is placed in the subsurface across the flow of path of a plume of

contaminated groundwater, which must move through it as it flows, typically under its natural

gradient, thereby creating a passive treatment system. As the contaminant moves through the

material, reaction occur that transform the contaminants into less harmful (non-toxic) or

immobile species. The PRB is not a barrier to the groundwater, but it is a barrier to the

contaminants. PRBs are designed to be more permeable than the surrounding aquifer

materials so that contaminants are treated as groundwater readily flows through without

significantly altering groundwater hydrogeology.

"Emission oriented remediation

approach"

Clean-up of the plume, not

the source

Passive system

No active pumping of

groundwater

Low maintenance following

installation

PRB CONCEPT

Application:

Unclear location of source(s)

Slow contaminant release from

source

Low solubility of contaminants

Large volumes of contaminated

soil

Built-up areas

TYPES OF REACTIVE WALLS

a) Continuous Barrier b) Funnel-and-gate system

The continuous PRB configuration consists of a single reactive zone

installed across the contaminant plume, while the funnel-and-gate

system consist of a permeable gate (reactive zone) placed between

two impermeable walls that direct the contaminated plume towards

the reactive zone.

PRBs treat contaminants by two general

processes, either destructive processes

where the contaminant is transformed

into non-toxic end products, or non-

destructive processes where the

contaminant is removed by processes

such as sorption or transformation to less

mobile or less toxic forms.

PERMEABLE REACTIVE BARRIER (III)

1. Sorption - removal from groundwater through

adsorption or complexation

2. Chemical precipitation - fixation of

contaminants in insoluble compounds

3. Biological treatment (mainly bioprecipitation)

- using of organic carbon to stimulate

biologically mediated sulphate reduction

SEPARATION PROCESSES USED IN PRBs FOR

HEAVY METALS

REACTIVE MATERIALS USED IN PRBs

PERMEABLE REACTIVE BARRIERS

SORPTION

PRECIPITATION

BIOLOGICAL BARRIER

Activated carbon

Zeolite

Ion-exchange resin

Zero-valent iron

Molasses

Lactate

Compost

Soybean oil

Iron sorbents

Complexing agents

Atomised Slag

Caustic magnesia

High contaminant attenuation

Good selectivity for target contaminants

Fast reaction rates

High hydraulic permeability

Long-term stability

Environmental compatibility

Sufficient availability in homogenous quality

Cost-effectiveness

REACTIVE MATERIAL REQUIREMENTS

PRB ADVANTAGES AND LIMITATIONS

ADVANTAGES

• Contains the plume while source is

remediated

• Reduces mass discharge and

accelerates monitored natural

attenuation (MNA)

• Treats broad spectrum of

contaminants

• Green and sustainable – low energy

requirements

• Low operations and maintenance cost

• Long-term effectiveness

• System is unobtrusive once installed

LIMITATIONS

• Existing infrastructure

• Depth, hydraulic limits

• Performance may

decrease over time

PRBs WITH SELECTED REACTIVE MATERIALS FOR

HEAVY METALS – COMPARATIVE OVERVIEW (I)

Material Advantage Disadvantage Mechanism and

process

Activated

carbon

High adsorption

capacity

Regeneration possible

More field-scale

studies on metal

adsorption is needed

Adsorption by high

surface area (1000

m2/g) and presence

of surface functional

groups

Zeolites Very high adsorbing

capacity

Hundreds of natural

zeolites are available

Selective adsorption

capacity

Adsorption, ion

exchange, catalytic

and molecular sieving

through 3D

aluminosilicate

structure

THE PRBs WITH SELECTED REACTIVE MATERIALS FOR

HEAVY METALS – COMPARATIVE OVERVIEW (II)

Material Advantage Disadvantage Mechanism and

process

Zero-valent iron

(ZVI)

ZVI is cheap

Handling is easy

Clogging of barrier by

metal hydroxides and

carbonates

ZVI gets corroded

With corrosion of ZVI, pH

increased, redox

potential decreased, and

Fe(II) was generated

with reduction and

precipitation of other

metals

Ion-exchange

resins

High capacity

Fast reaction rate

Smaller amount

required to treat a given

volume of groundwater

Can be regenerated and

reused

High costs in

comparison with other

materials

Adsorption and ion

exchange

REMOVAL OF Cd2+, Zn2+ AND Pb2+ IONS FROM MODEL

GROUNDWATER USING SELECTED REACTIVE MATERIALS

THE EFFECT OF MATERIAL

DOSE ON THE REMOVAL

EFFICIENCY

THE EFFECT OF CONTACT

TIME ON THE REMOVAL

EFFICIENCY

COMPARATIVE ANALYSIS OF USED REACTIVE MATERIALS AND

THE CHOICE OF THE BEST MATERIAL DEPENDING ON THE

AMOUNT AND CONTACT TIME

THE SCOPE OF STUDY – BATCH TESTS

REACTIVE MATERIALS

Material Activated

carbon Baqua 1 Zeolite Fe0

Ion-exchange resin

Amberlite IR 120 H

Particle size [mm] 1,0 0,5-1,0 0,4-0,8 0,6-0,8

Granular activated

carbon (GAC)

Zeolite Zero-valent iron

(Fe0)

Ion-exchange

resin

EXPERIMENTAL

synthetic

groundwater

reactive

material

BATCH TESTS

- groundwater: 100 ml (initial metals

concentration = 25 mg/L)

- reactor volume: 250 ml

- dose of material: 0,5; 1; 2 g

- contact time: 5-120 min

- analysis of filtrate: concentration of

Zn, Cd, Pb (Unicam Solaar 939)

RESULTS: the effect of reactive material dose

The removal degrees (in %) were increased with

increasing amounts (dose) of reactive materials

Above 99,9% removal efficiency of metal ions for activated

carbon and ion-exchange resin (in case of dose = 2 g)

0

10

20

30

40

50

60

70

80

90

100

% r

em

oval

zeolite iron activated

carbon

resin

Cd

Zn

Pb

0

10

20

30

40

50

60

70

80

90

100

% r

em

oval

zeolite iron activ ated

carbon

resin

Cd

Zn

Pb

dose = 0,5 g dose = 2 g

RESULTS: the effect of contact time

Rapid decrease of metals

concentration in the first 10

minutes of groundwater contact

with reactive materials

The best results for all metals

achieved for activated carbon and

resin

0

5

10

15

20

25

30

0 20 40 60 80 100 120 140

contact time, min

Zn

, m

g/L

zeolite

iron

activated carbonl

resin

0

5

10

15

20

25

30

0 20 40 60 80 100 120 140

contact time, min

Cd

, m

g/L

zeolite

iron

activated carbon

resin

0

5

10

15

20

25

30

0 20 40 60 80 100 120 140

contact time, min

Pb

, m

g/L

zeolite

iron

activated carbon

resin

COLUMN TESTS: AIM AND MATERIALS

AIM OF THE STUDY: to investigate the performance of permeable

sorption barriers for the removal of cadmium and zinc from synthetic

groundwater

REACTIVE MATERIALS SYNTHETIC GROUNDWATER

COLUMN TESTS: EXPERIMENT METHODOLOGY

COLUMN TESTS

- columns: length 250 mm, internal

diameter ≈10 mm

- volume of media: ≈ 20 mL

- porosity: resin - 0.49, zeolite - 0.43,

GAC - 0.39

- flow rate: 9,6 mL/h

1 – resin 2 – zeolite 3 - GAC

COLUMN TESTS: RESULTS

Column effluent concentrations of Cd and Zn in treatment of contaminated

groundwater using reactive materials

Cd and Zn – the breakthroughs occured for zeolite and

GAC

COLUMN TESTS: RESULTS

Column effluent concentrations of Na and NO3- Cd and Zn in treatment of

contaminated groundwater using reactive materials

The ion exchange resin – high efficiency for removal of

heavy metals; simultaneous removal of Na did not impact on

its activity

The initial increase of Na concentration for zeolite – result of

ion exchange in structure of this material

COLUMN TESTS: RESULTS

pH of column in treatment of contaminated

groundwater using reactive materials

The decrease of pH

for resin – result of

release of H+ ions

by resin in ion

exchange process

COLUMN TESTS: CONCLUSIONS

The ion exchange resin was the most effective material

of PRB. The percentage of metal ions removal was then

above 99 %.

The high efficiency of ion-exchange resin in PRB for

removal of heavy metals from groundwater was coupled

with its reactivity and long barrier lifetime. The sorption

capacity of the resin was significantly higher than other

materials. Therefore, the system using resin requires

smaller amount to treat a given volume of groundwater

as compared to other materials.

The presence of other ions did not impact on activity

and permeability of barrier filled with resin.

Types of liquid membranes:

Bulk Liquid Membrane - BLM

Supported Liquid Membrane – SLM

Emulsion Liquid Membrane - ELM

Polymer Inclusion Membrane - PIM

LIQUID MEMBRANES (I)

membrane BLM

ELM

SLM

source phasereceiving

phase

source phase

source phase

membrane

membrane

receiving

phase

receiving

phase

(external solution)(internal solution)

PIM

LIQUID MEMBRANES (II)

SUPPORTED LIQUID MEMBRANES

Supported liquid membranes are based on the use of a

porous solid membrane (polymeric or ceramic) which

supports or hold the organic phase and separates the feed

and the stripping aqueous solutions. The pores of the solid

membrane are completely filled, by capillarity, with the

organic or carrier phase and this impregnation process

makes relatively stable and heterogeneous solid-liquid

membranes. Often, the solid supports are hydrophobic in

nature, which facilitates wetting by the organic solution

and the reject of the aqueous phases. Membrane wetting

time by the organic phase ranges from a few minutes to

several hours.

SLM/PIM SEPARATION PROCESSES

Supported liquid membranes (SLMs) and,

recently, polymer inclusion membranes (PIMs)

separation processes can be an attractive

alternative for the removal of metal ions from

waste streams with very high efficiency. SLMs

achieve much higher fluxes than conventional

solid membranes, although the loss of the organic

reagent represents a serious drawback. In these

membrane systems the driving force are

extraction and reextraction processes which occur

simultaneously in both interface of membranes.

SLM, PIM

Species Concentration (g/l)

Species Concentration (mg/l)

TYPES OF TRANSPORT BY SLM,PIM (I)

Counter-transport. The transport of the metal contained in the feed

solution and the counter-ions, contained in the strip solution, is carried out

in opposite directions. The driving force for the metal transport is the

difference in the counter-ion concentrations between feed and stripping

phases. This type of transport is typical of cationic exchangers extractants

and quaternary ammonium salts.

nM

H

CH

nMC

H

nM

membranesource

phase

reveiving

phase

nMH

TYPES OF TRANSPORT BY SLM,PIM (II)

Co-transport. The transport of the metal and co-ions is

carried out in the same direction. In this case, the driving

force for metal transport is the difference of concentrations of

the co-ion between the feed and stripping solutions.

Cotransport mechanism is common for basic and solvation

extractants. nM

A

C

nMCA

A

nM

membranesource phasereceiving

phase

nMA

POLYMER INCLUSION MEMBRANES

PIMs can be used for:

treatment of landfill leachates to minimize the risk of groundwater

contamination

reduction of heavy metals concentrations in the groundwater flow

The PIMs appropriate for facilitated transport of ions (ion-exchange mechanism)

consist of a polymer, a plasticizer and an ion carrier. The resulting membrane is

used to separate source and receiving aqueous phases. PIMs combine the

advantages of higher selectivity with increased stability, because the ion carrier is

immobilized in the solid polymer matrix which is responsible for membrane

stability, while the addition of plasticizer significantly facilitates the permeation of

metal ions. Moreover, mechanical properties of PIMs are quite similar to those of

filtration membranes, thus enable PIM-based systems to exhibit many

advantages, such as: the ease of operation, minimum use of hazardous

chemicals and flexibility in membrane composition, to achieve the desired

selectivity and separation efficiency.

a solution of CTA as a support, ONPPE as a plasticizer,

and Aliquat 336 as an ionic carrier in dichloromethane as

an organic solvent

a specified portion of this solution poured into a membrane

mold comprised of a 9.0 cm glass ring attached to a plate

glass with CTA-dichloromethane glue

dichloromethane evaporated overnight and the resulting

membrane separated from the glass plate by immersion in

cold water

PREPARATION OF POLYMER INCLUSION MEMBRANES

H2O

Polymer inclusion membrane view

TRANSPORT STUDIES

the permeation cell

the membrane film: 4.9 cm2 effective surface

the source phase: synthetic groundwater contaminated

with chromium(VI)

the receiving phase: 0.1M NaCl

temperature: 23÷25oC

samples removed periodically via a sampling port with

a syringe

chromium(VI) concentration analyzed with plasma

atomic emission spectroscopy (ICP-AES)

1 2

3

4

5

The transport cell: 1 - source phase, 2 -receiving phase,

3 - membrane, 4 -mechanical stirrers, 5 - pH electrode.

PERMEATION CELL

PRELIMINARY RESULTS

Chromium(VI) concentration in the source phase vs. transport

time through PIMs at different Aliquat 336 concentrations

RESULTS

At the source/receiving

phase volume ratio = 30:1 -

reduction of the Cr(VI)

concentration from 1.0 to

0.001 ppm in 3 h

Chromium(VI) removal from synthetic groundwater using PIM with Aliquat 336

CONCLUSIONS

The groundwater transport through PIM allows for reducing

chromium(VI) concentration in the source aqueous phase to

0.001 ppm - below the permissible limit for drinking water in

Poland

The tubular modules formed from immobilized membranes

provide rapid metal ions transport, easy setup and operation

The application of PIMs effective for heavy metals removal

from contaminated groundwater

Immobilization of specific ion carriers on the reactive material

within PRB a novel approach in groundwater remediation at

contaminated sites

NOVEL SORBENTS – IMPREGNATED RESINS (I)

Novel types of resins incorporating macrocyclic ligands, e.g. Amberlite

XAD-4 impregnated with calixarene derivatives, may be the best choice for

the removal of a variety of metal ions. Amberlite XAD-4 is a cross-linked

polymer which has excellent adsorptive properties for neutral small

molecules onto its macroreticular structure and a higher surface area.

These structures provide excellent chemical, physical and thermal stability.

The modification of Amberlite XAD-4 with calixarenes results in the high

capacity and selectivity of the impregnated resins. The extractant is

retained in the micropores of an inert polymer without any chemical bonds

onto the polymer matrix, and the properties of the impregnated extractant

are responsible for adsorption of a novel resin. The unique features of

impregnated resins, such as high capacity and selectivity, are associated

with metal ion properties including soft hardness, hydrated ionic radii,

hydration energies, electronegativity, stability constants of metal-ion

hydroxides and complexation constants.

NOVEL SORBENTS – IMPREGNATED RESINS (II)

Incorporation of calixarene based ionophores onto

synthetic resins offers promising solution to the

sorption technology. It is an emerging area of

research, which involves impregnation or

immobilization through physical adsorption or

covalent linkage of calixarene derivatives onto the

framework of resin. These polymeric materials act

as efficient adsorbents for toxic metals.

Calixarenes appended resins are highly selective,

thermally stable and have of regeneration ability.

Therefore, the resins impregnated with

calixarenes derivatives hold a tremendous

promise for processing of toxic metal ions bearing

effluents and cleansing of polluted streams.

„raw” resin

impregnated resin

IMPREGNATED RESIN – RESULTS OF THE NEWEST INVESTIGATION

Passing of pre-treated landfill leachate

through the column filled with the

impregnated resin reduced

concentrations of Pb(II), Cd(II) and Zn(II)

ions by 95, 75 and 40%, respectively. It

was found that resorcinarene is effective

in sorption of Pb(II) from landfill leachate.

This is due to the larger surface area

provided by the framework of Amberlite

resin to the ligand for interaction with

Pb(II) ions. Moreover, it is important that

impregnated resin is regenerable, thus

can be used several times. It was found

that after 15 repetitions no change in

sorption capacity of the resin occurred.

The alkyl(aliphatic) resorcinarene derivative

Succesive adsorption/desorption cycles for

removal/recovery of Pb(II) with impregnated

resin

Thank for your attention