Groundwater Treatment

Clean up of contaminated sites
1 Bioremediation 2 Thermal Treatment 3 Groundwater Treatment/Purification 3.1 In-situ-Bioremediation (pump and treat) 3.2 Permeable Barriers (Sorption, Reaction), Funnel & Gate 4 Monitored Natural Attenuation
Otto-von-Guericke-University Magdeburg, Institute of Process Equipment and Environmental Technology Dr.-Ing. Hartmut Haida
Contaminants in the groundwater

Most of groundwater pollutions are caused by soil contaminations with organic substances. - Liquid organic contaminants get into the groundwater from the source through the soil and the unsaturated zone - Further spreading in the groundwater flow direction (migration) by different processes like advection, dispersion, diffusion, sorption, volatilization, degradation, which can produce contaminant plumes.
Groundwater pollution plume and degradation processes
Dr. Reinhard Wienberg

petrol tank (source)
Umwelttechnisches Labor
groundwater table
unsaturated zone pollution pool nitrate reducing zone iron sulfate reduction reduction methanogenic zone
aerobic zone
groundwater flow direction
Contaminants in the groundwater

The most frequent organic contaminants in the groundwater flow caused by hazardous waste sites or damages are:
Volatile halogenated hydrocarbons, e. g. Tetrachloroethene, Trichloroethene und 1,1,1-Trichloroethane Petroleum hydrocarbons as main constituents of fuel oil, Diesel oil, kerosene and gasoline Volatile aromatic hydrocarbons like benzene, toluene, ethylene benzene, xylenes (BTEX) as admixture in gasoline Methyltertir-butyl-ether (MTBE) as admixture in gasoline Polycyclic aromatic hydrocarbons (PAH), e. g. naphthalene and methylnaphthalenes
MTBE is very well soluble in water and is seen as nontoxic. But it is influencing the water quality by unpleasant odour and taste (>100 g/l). It is microbiologically hardly degradable. It is virtually not adsorbed at activated carbon. So it is not adhered to soil particles but washed out.
Soil contaminations with anorganic pollutants (heavy metals, cyanides) seldom result in greater groundwater contaminations because they are badly soluble and they have typically high affinity for adsorption at soil particles.
Groundwater contaminants: Comparison of presence in Germany and USA

Rank Germany, presence in % 1 42 2 39 3 24 4 5 6 7 8 9 10 11 12 13 14 15 16 14 8 6 5 4 4 3 3 2 2 2 * * * * * Contaminant USA, presence in % 35 62 28 11 10 27 20 not differentiated 12 * 20 * * * 25 20 15 14 13 Rank
Perchloroethylene (PCE) Trichloroethylene (TCE) Cis + trans Dichloroethylene Benzene Vinyl chlorid Trichloromethane 1,1,1-Trichloroethane Xylene trans-Dichloroethylen Toluene Ethylbenzen Dichloromethane Dichlorbenzene Monochlorobenzen Tetrachloromethane 1.2-Dichloroethylene 1.1-Dichloroethane 1.2-Dichlorethane Phenol Acetone
2 1 3 14 15 4 7
12 6
5 8 9 10 11
*) not called under 15 contaminants looked at

(from Teutsch u. Grathwohl 1997, zitiert nach Stottmeister, U.: Biotechnologie zur Umweltentlastung, Teubner 2003, S. 167)
Dispersion behaviour of organic contaminants in groundwater

These substances are liquid phases at the majority of sites which are contaminated by petroleum hydrocarbons or volatile halogenated hydrocarbons. They are not mixable with water and are so called NAPL (non-aqueous-phase liquid). The phase body can pass the unsaturated zone and reach the groundwater. Contaminant phases are a long time source for the release of soluble contaminants and for the beginning of contaminant plumes. NAPL with lower density than water (e. g. mineral oil products) are called as LNAPL (light non-aqueous-phase liquid). These liquids can spread over the groundwater table and concentrate in the capillary spaces (so called upswimming phase). LNAPL produce above all a plume in the upper region of the aquifer. The plume may spread in deeper aquifer regions depending on the hydrogeological situation and the distance to the source.

NAPL with higher density than water (e. g. volatile halogenated hydrocarbons) are called as DNAPL (dense non-aqueous-phase liquid). They can sink to the groundwater bottom and accumulate there. The dispersion of such phases in groundwater and in the unsaturated zone is influenced by inhomogeneities in soil and rock (e. g. layer borders, clay lenses, macropores, clefts) and by the morphology of the groundwater bottom. So DNAPL-phases can spread also in the opposite direction of grondwater flow.

Transport and distribution of dissolved contaminants in groundwater (migration) are above all determined by the groundwater flow direction and velocity. Sorption processes at solid aquifer particles can delay the contaminant spreading (retardation). Substances with unpolar characterization and high sorption affinity show a relative high retardation, i. e., the transport velocity of these substances is clear lower than the grounwater flow velocity. Contaminants are degraded/converted resp. removed from the plume by microbial degradation, hydrolysis and volatilization into the unsaturated zone. A dynamic balance is given in quasi-stationary contaminant plumes, i. e., the inflowing contaminant quantity is about equal to the contaminant quantity removed by degradation or volatilization.

The development of contaminant plumes with biodegradable contaminants versus time can be divided idealized in five phases:
1 2 3 4 5
Contamination takes place: Dissolution and spreading of contaminants Beginning of biological degradation: The plume is expanding slower Steady state: Balance between input and degradation Steady state over a long period: The contaminant mass in the source decreases but the emission remains on a high level Decrease of the contaminant emission

Statistical analyses of contaminant plumes show a relationship between the properties of the individual contaminant class and the length of the plumes. Destinct deviations are possible in particular case because of different hydrogeological and hydrochemical site conditions: Volatile relative good soluble in water, small retardation, slow degradation; halogenated plume length up to several kilometers hydrocarbons BTEX relative good soluble in water, small retardation, frequently quick degradation; plume length up to about 300 m petroleum little solubility in water, little up to medium retardation, frequently hydrocarbons quick degradation; plume length up to about 300 m PAH Naphthalene (2-ring-structure) and 3-ring-structures are little soluble in water, other PAH very little soluble. The retardation encloses several orders, an important degradation is as a rule only possible in case of naphthalene and 3-ring-structures. The plume length depends very strongly on the PAH-composition.
12
Technical processes for groundwater treatment

1 Active discharge remediation Pump and Treat, up to now broadest application, effective, but high costs 2 Passive discharge remediation sorption resp. reaction in permeable walls (even walls; funnel-and-gate-systems) 3 in-situ-treatment Stimulation of autochthonous degrading microorganisms by supply of oxygen and/or nutrients
13
Pump and treat

(treatment on the surface of the earth) The groundwater is pumped to the surface and treated there. The cleaned groundwater is either reinfiltrated or used in another way. Treatment: physical
- Adsorption at activated carbon - Stripping by means of air - activated sludge process Biological Contactor (where appropriate nutrient supply, addition of microorganism culture)
biological
14
Groundwater lowering and groundwater treatment

extraction well
treatment
receiving water
contamination extraction width groundwater flow pattern

ITVA-Arbeitshilfe Hydraulische Manahmen, Sept. 1999
15
Pump and Treat: Reinfiltration into the inflow
treatment
infiltration well
extraction well
contamination
16
water treatment discharge
unsaturated zone
groundwater
saturated zone
aquiclude Horizontal extraction well - schematic
17
drainage trench unsaturated zone
gravel filter saturated zone groundwater drainage pipe
aquiclude
Drainage trench as complete barrier
18
The pumped groundwater can be treated physically by means of different processes and corresponding plants:
Adsorption filter
Activated carbon filters are further on incomparable for the removal of a broad spectrum of organic substances in relative small concentrations because of their broad sorption range and high sorption capacity. The plants are wide maintenance free. Their effectivity is well controllable.
Degasing plants (Stripping plants)

Stripping is performed as a rule with air. The degasing depends on the vapor pressure, the residence tim in the stripping column, the height of the column and the temperature. The exhaust gas can be treated catalytically, thermally or by condensation.
19
Schematic: Stripping plant for groundwater treatment
blower demister feed packings

waste air treatment
Air dryer treated air
air inflow
outflow
sewer system
well pump
VDI-Richtlinie 3897
20
Schematic: Trickle film apparatus (Corrugated sheet column) for Groundwater Stripping
VDI-Richtlinie 3897
21
Schlammbehlter
sludge tank
activated carbon air filter

Luftaktivkohlefilter Desorption Luftaktivkohle
Oxidator
activated
Filter 2
Aktivkohle carbon
Sandfilter 1 Sandfilter 2
Filter 1
activated carbon air filter

Luftaktivkohlefilter
Spllwasserbehlter
Splluftgeblse
flushing water tank
control tank
Kontrollbehlter
service water discharge

Brauchwasserablauf
extraction well
Frderbrunnen
flushing air blower
Grundwasser
groundwater
Grundwasseraufbereitungsanlage/ groundwater treatment plant Eidelstedt/Stellingen (Jtlnder Allee)
Infiltrationsbrunnen
infiltration well
Kollau
groundwater
Grundwasser
Bocian, B.-O.: Grundwassersanierung Industriegebiet Eidelstedt/Stellingen, altlasten spektrum, 05.2009, S. 238, Verfahrensschema der Grundwasseraufbereitungsanlage Jtlnder Allee
to Tierpark Hagenbeck
to the university
Zu Hagenbecks Tierpark
zur Universitt
22
Groundwater Treatment/Purification
Chosen Groundwater Purification Processes

Process Brief Description Pump & Treat feeding of nutrients and electron donors or acceptors, if necessary, specialized microorganisms to stimulate the microbial degradation of contaminants variation of pumping rate for better use of slow contaminant mobilization
In-situ-Bioremediation
Pulsed or variable pumping
23
Brief Description Thermally Enhanced Techniques Steam-enhanced extraction, mobilization and stripping of volatile contaminants Hot air injection by steam or hot air injection into the saturated or unsaturated zone In-situ thermal desorption + heating of soil or aquifer with several methods soil vapour extraction (Thermo Lance, electrical resistance heating, dielectric heating) for accelerated mobilization and evaporation of contaminants Thermally enhanced heating of soil or aquifer for chemical conversion of hydrolysis and oxidation contaminants Thermally enhanced moderate heating of soil or aquifer with the aim to biodegradation adjust optimal temperatures (30 ... 40 C, for thermophilic microorganisms 50 ... 70 C) for the microbial degradation of contaminants Oil flushing flushing of aquifer with tensides, microemulsions or cosolvents In-situ chemical treatment injection of chemical agents (e. g. oxidants like H2O2, KMnO4) for chemical conversion of contaminants
Process
24
Permeable Barriers (Sorption or Reactive Barriers)
Sorption or reactive barriers installed in the aquifer are the simplest in-situ remedial action. The decontamination is performed by sorption resp. by complex biological or other conversions. A wall is introduced in the aquifer across to the groundwater flow direction (e. g. by slit excavating) from material which has a small hydraulic resistance and reacts with the contaminants transferring them into harmless products.
25
Process Sorption barriers
Brief Description Permeable (Reactive) Barriers (PRB) retention of contaminants by sorption (e. g. at activated carbon, peat etc.) chem. reaction of contaminants during the passage through the barrier (e. g. dechlorination of chlorinated hydrocarbons at Fe0) or enrichment of groundwater with a reagent (e. g. O2 from an ORC) Funnel & Gate
Reactive barriers
like PRB but with unpermeable guiding walls (funnel) instead of permeable barriers and treatment of focused groundwater flow in a permeable reactive zone or in a reactor (gate)
ORC: Oxygen Releasing Compounds
26
Groundwater clean up by means of permeable barriers schematic representation

Sorption/Reactive Barrier pollution input (source)
groundwater withdrawal
pollution plume
sorption/degradation
dissolved pollution
small permeable zone
Advection
aquifer basis
pollution emission dissolution, desorption
Teutsch, G., Grathwohl, P., Schad, H., Werner, P. (1996): In-situ-Reaktionswnde Ein neuer Ansatz zur passiven Sanierung von Bodenund Grundwasserverunreinigungen; Grundwasser Zeitschrift der Fachsektion Hydrogeologie, Heft 1, S. 13 - 20
passive outflow decontamination
Sorption resp. reactive wall

(The flow passes the entire surface)
Contaminated ground water stream
ground water flow direction Contaminated zones
wall kf,Wall kf,Aqifer
Cleaned ground water
Sorption resp. reactive wall

The adsorption is supported by microbiological processes after longer operation periods. A biofilm is growing up at the activated carbon. It can essentially contribute to the decontamination by degradation of organic matter. It can also cause negative effects: - methane generation under anaerobic conditions -> troublesome gas bubbles - strong biofilm development may close pores (clogging) -> increase of flow resistance/pressure loss
Permeable reactive barriers

Metallic iron (chips, small particles) is particularly suitable for low molecular halogenated hydrocarbons. A rosty wall is today (since 1994) a standard process. Reduction of chlorinated hydrocarbons by iron Fe + 2 H2O Fe
o o 2+
+ 2 OH + H2
2+ structural
Fe + H2O + R-Cl Fe 2Fe

2+ structural +
+ OH + R-H + Cl
+ R-Cl +H 2Fe
3+ dissolved
+ R-H + Cl
The reduction of chlorinated hydrocarbons seems to be directly connected to the metal oxidation at the surface. The reaction causes a pH-increase., Fe-hydroxides or Fe-carbonates can precipitate depending on the buffer capacity in the whole system. A reaction rate decrease because of this precipitation could experimentally not be observed. The H2-production has to take into consideration.
passive outflow decontamination kf,Gate >> kf,Aqifer kf,Funnel << kf,Aqifer
Funnel and Gate-system

Contaminated zones
Cleaned ground water
contaminated ground water outflow
Funnel
Gate
Conceptions of different PRB

Schad, H.: Vor- und Nachteile verschiedener Reinigungswandtypen und mgliche Bauverfahren zu ihrer Herstellung, RUBIN-Seminar Reinigungswnde, Dresden, 03.07.2007
receiving water
32
Funnel and Gate Plant Karlsruhe

Gas-works Karlsruhe Ost, up to 1965 production, contaminant plume over the whole aquifer depth, up to 200 m wide, PAH up to 500 600 g/l, Benzene up to 22 g/l Aquifer: gravel-sand-mixture, broad particle size distribution 15 17 m thickness -3 5*10 m/s average permeability depth of the groundwater table 2 4 m flow velocity about 2 m/d Funnel and Gate-Plant 250 m long sheet piling (funnel) 8 quidistant passage ways (gates) with activated carbon Gates are steel tubes (di = 1,8 m) up to 18 m length, slotted holes for horizontal cross flow 3 chambers (volume ratio 10 : 80 : 10) activated carbon in the main chamber The total costs amounted up to 2 million euro, for an operational term of 50 years. Operation started in 2001!
groundwater output drilled temporary casing filter gravel 2 measuring point
pass partition plate adjusting plank funnel activated carbon
gate, perforated
groundwater input
Gates der Funnel and Gate Plant Karlsruhe

Funnel and GatePlant Karlsruhe

Schad, H.: Vor- und Nachteile verschiedener Reinigungswandtypen und mgliche Bauverfahren zu ihrer Herstellung, RUBIN-Seminar Reinigungswnde, Dresden, 03.07.2007
Funnel and GatePlant Karlsruhe: Results

In the year 2005 the monitoring results were very pleasing. 99.5 % of the total contaminant load are catched and cleaned by the funnel-and-gatesystem. The PAH-contents of all measuring points behind the gates are now less than the remedial action objective 0.2 g/l. At the beginning of the remedial action in the year 2001 the effectivity was below 70 %, about 30 % of the contaminants floiwed past the funnel (bypass) in the north or they were not adsorbed in the gates. One of the reasons for the unsufficient function in the beginning was a bad sealing of the gates against bypass flows. Since August 2004 the part of contaminants which is flowing past the system can be neglected. Water level measurements prove a very low hydraulic resistance of the funnel-and-gate-system. A banked-up water level cannot be seen. Altogether the desired effect could be achieved.
from: http://www.imes-gmbh.net/frames/news_d.htm (20.01.2011)
Continuous reactive barrier system in Rheine

The primary contaminants Perchloroethylene (20,000 g/l) and cisDichloroethylene (500 g/l) is generated from a former dry cleaning facility located in the town Rheine, about 30 km in the west of Osnabrck. To remove the contaminants a pilot scale continuous reactive barrier was built (22.5 m long, 6 m deep, 0.6 0.9 m thick, overlapping boreholes) filled with two types of zero valent iron (granular iron mixed with gravel and iron sponge). It was the first continuous reactive barrier in Germany. Since 1998, the barrier system shows significant degradation of primary contaminants with efficiency of 80 - 90 % in the granular iron section and > 98 % in the sponge iron section. The concentration of chlorinated VOCs in the downgradient reduces to < 10 g/l which successfully meets the remediation goal. The total cost for the barrier system was about 170,000 Euro.
Sketch of continuous reactive barrier system in Rheine
Funnel-and-gate-system Edenkoben
Compounds treated: chlorinated VOCs (20 % Trichloroethylene, 50 % cisDichloroethene, 30 % 1,1,1-Trichloroethane) In 1994, a massive soil and groundwater contamination by cVOCs were detected on the premises of a supplier for car manufacturer in Edenkoben. The contamination was attributed to a former use of chlorinated hydrocarbon solvents for production processes. For remediation of cVOCs, in 1998, a pilot scale funnel and gate system was built for field test with zero valent iron (ZVI) as reactive material. Promising destruction rate of 99 % were observed during that term. Hence in 2001, the full scale funnel and gate were installed (length 440 m, depth 15 m and 6 gates). The total cost for pilot scale installation was 350,000 Euro and the full scale was 1,750,000 Euro.
Peschla and Rochmes GmbH (www.gpr.de)
Scheme of the funnel-and-gate-system Edenkoben

Drain and gate system in Denkendorf

At the trading estate of the town Denkendorf, located near Stuttgart, six different sources of VOC-contamination were detected along with VC. The overall concentration was detected at around 200 mg/l. Due to low hydraulic gradient of 2 %, a drain and gate barrier system was built. This system provides collecting of groundwater passively by means of 90 m long and 6 m deep gravel drainage system directing the flow right towards the reactor. The reactor was loaded with GAC and constructed as a shaft structure. The system meets the remediation goal of 10 g/l VOC effectively.
Sketch of the drain and gate system in Denkendorf

Informations and data collected from: RUBIN (www.rubinonline.de) SAFIRA (www.safira.ufz.de) PEREBAR (www.perebar.bam.de)
see also: Rahaman, Md. Mahfujur: Permeable Barriers in Groundwater Purication, Master-Thesis, OvGU, FVST, 2011
Sorptive/Reactive Barriers
Advantages: The contaminant source must not be exactly known with respect to position and dimension. There are as a rule no utilization limits for the site during the construction because the construction actions are carried out in the outflow zone and not in the reach of production plants or buildings. There are no utilization limits for the site surface after the construction because installations above ground are hardly necessary. Only the monitoring must be carried out during the lifetime of the adsorptive/reactive material. Lower costs can be expected in many cases with several years operation period compared to conventional processes (pump and treat).
43
Sorptive/Reactive Barriers
Disadvantages and risks: Design and positioning of the wall is of decisive importance for the hydraulic function of the whole system. Inadequate information on local flow patterns can lead to bypass or underflow of the wall. At present there are no sufficient experiences on the long time behaviour of the wall. The contamination source remains in the underground and has to be considered later in underground engineering. The single investment is high in comparison to conventional pump-andtreat-processes. This technology will be a technical and economical interesting alternative to conventional processes if the site specific conditions for the installation of a sorptive resp. reactive barrier are fulfilled.
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Process Physical or chemical containment Soil Vapor Extraction (SVE), Airsparging, Bioventing
Brief Description Another In-situ-Techniques inclusion of contaminants by walls or chemical in-situimmobilization
stripping of volatile contaminants by air flushing; flushing of the saturated or the unsaturated zone by air in order to stimulate the aerobic microbial degradation of contaminants
Intrinsic Bioremedation microbial degradation of contaminants without or with small (Monitored influence by engineered measures Natural Attenuation)
from: Kopinke et al., CIT (75) 4/2003, S. 329 ... 339
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Specific total costs of groundwater treatment

(Different processes for more than 10,000 m3 water volume
Adsorption by activated carbon Stripping (with post treatment) Biological clean up Advanced oxidation De-ironing
0.30 0.65 /m3 0.25 1.10 /m3 0.25 0.75 /m3 0.40 1.50 /m3 0.20 0.40 /m3
(source: Altlasten Fachinformation, Ministerium fr Umwelt und Verkehr Baden-Wrttemberg) from: Grundwasser-kologie, Griebler, Msslacher, Facultas Universittsverlag (2003), Seite 394
Groundwater Treatment
Thermal Treatment floating matter (org. phases) contaminated GW mech. sep. Adsorption (act. carbon) waste air (VOC) Stripping waste air (CO2) bioprocess precipitation treated waste air
treated GW
solids
air
biomass (sludge)
sludge aeration
GW - Groundwater
Adsorption (act. carbon) membrane process
treated GW

Groundwater Treatment

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Groundwater Treatment

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Clean up of contaminated sites

Contaminants in the groundwater

Groundwater pollution plume and degradation processes

Dr. Reinhard Wienberg

groundwater flow direction

Contaminants in the groundwater

Groundwater contaminants: Comparison of presence in Germany and USA

*) not called under 15 contaminants looked at

Dispersion behaviour of organic contaminants in groundwater

Dispersion behaviour of organic contaminants in groundwater

Dispersion behaviour of organic contaminants in groundwater

Dispersion behaviour of organic contaminants in groundwater

Dispersion behaviour of organic contaminants in groundwater

Technical processes for groundwater treatment

Pump and treat

Groundwater lowering and groundwater treatment

contamination extraction width groundwater flow pattern

Pump and Treat: Reinfiltration into the inflow

ITVA-Arbeitshilfe Hydraulische Manahmen, Sept. 1999

water treatment discharge

aquiclude Horizontal extraction well - schematic

ITVA-Arbeitshilfe Hydraulische Manahmen, Sept. 1999

drainage trench unsaturated zone

gravel filter saturated zone groundwater drainage pipe

Drainage trench as complete barrier

ITVA-Arbeitshilfe Hydraulische Manahmen, Sept. 1999

Degasing plants (Stripping plants)

Schematic: Stripping plant for groundwater treatment

blower demister feed packings

Air dryer treated air

activated carbon air filter

activated carbon air filter

flushing water tank

service water discharge

flushing air blower

Grundwasseraufbereitungsanlage/ groundwater treatment plant Eidelstedt/Stellingen (Jtlnder Allee)

Chosen Groundwater Purification Processes

Pulsed or variable pumping

Permeable Barriers (Sorption or Reactive Barriers)

Process Sorption barriers

Groundwater clean up by means of permeable barriers schematic representation

small permeable zone

pollution emission dissolution, desorption

passive outflow decontamination

Sorption resp. reactive wall

Contaminated ground water stream

ground water flow direction Contaminated zones

wall kf,Wall kf,Aqifer

Cleaned ground water

passive outflow decontamination

Sorption resp. reactive wall

passive outflow decontamination

Permeable reactive barriers

Fe + H2O + R-Cl Fe 2Fe

passive outflow decontamination kf,Gate >> kf,Aqifer kf,Funnel << kf,Aqifer

Funnel and Gate-system

Cleaned ground water

contaminated ground water outflow

Conceptions of different PRB

Funnel and Gate Plant Karlsruhe

groundwater output drilled temporary casing filter gravel 2 measuring point

pass partition plate adjusting plank funnel activated carbon

Gates der Funnel and Gate Plant Karlsruhe