WO1991008176A1 - Cleaning halogenated contaminants from groundwater - Google Patents
Cleaning halogenated contaminants from groundwater Download PDFInfo
- Publication number
- WO1991008176A1 WO1991008176A1 PCT/GB1990/001848 GB9001848W WO9108176A1 WO 1991008176 A1 WO1991008176 A1 WO 1991008176A1 GB 9001848 W GB9001848 W GB 9001848W WO 9108176 A1 WO9108176 A1 WO 9108176A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- groundwater
- trench
- aquifer
- procedure
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/908—Organic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/908—Organic
- Y10S210/909—Aromatic compound, e.g. pcb, phenol
Definitions
- This invention relates to a procedure for cleaning groundwater, being groundwater which is permeating through an aquifer, that has been contaminated with chlorinated or halogenated organic compounds such as solvents, or pesticides.
- the invention is concerned with groundwater in its native aquifer, the term aquifer being used herein in its broad sense to signify any in-ground geological formation containing water, including sand and gravel, broken rock, etc, and is not intended to be limited only to those formations which yield a water supply.
- the contaminants are volatile, they may also be removed by air-stripping.
- the water is aerated, which cleans the water, but the problem again remains that the contaminants still exist. It is becoming increasingly unacceptable simply to discharge the contamin ⁇ ated air into the atmosphere, so that the contaminants once again have to be removed, for example by sorbtion onto activated carbon.
- the present invention is concerned, like Sweeny, with removing halogenated contaminants from water; unlike Sweeny, the invention is concerned with removing halogenated contaminants, particularly solvents, from groundwater that is permeating through its native aquifer. It is recognised, in the invention, that a key aspect of such groundwater is that, unlike a factory effluent, groundwater can be expected, as a general rule, to be substantially oxygen-free.
- the water containing the halogenated organic contaminants is placed under, and held for a subs ⁇ tantial period under, or remains under, highly reducing conditions, and the groundwater is brought into intimate contact, during the said period, with a metal. It is thought that under those conditions the chlorine (or it may be another halogen) ion in the organic material can be replaced by a hydroxide ion, whilst the released chloride ion remains in solution.
- the chloride remains in the water, or it may be precipitated out, at concentrations that usually are well below the permitted limits for inorganic chlorides.
- the organic molecule is rendered harmless by what is thought to be a hydrolysis reaction, and the chlorine passes into an inorganic compound that is harmless at these trace concentrations. It is recognized in the invention that this favourable reaction takes place because of the highly reducing conditions.
- the Eh voltage of the contaminated water ie the value as measured using an Eh probe and meter, must be brought below -100 mV, and preferably should be brought down to -200 mV.
- the metal should be in a very intimate contact with the groundwater, and the contact should be prolonged: thus the metal should be in the form of small particles or fibres, whereby each unit mass of the metal is utilized efficiently, in that it has a large interface area exposed to the groundwater. The larger the interface area, the shorter the residence period that the groundwater needs to spend in the body of metal before its Eh voltage drops.
- the metal is iron, and is in the form of iron filings or cuttings, or steel wool.
- the pH value of water is important in determining the rate at which the halogenated contaminants break down.
- Most groundwaters, while present in their native aquifers, are naturally at substantially neutral pH, and the invention provides that the contaminant breakdown occurs in such a naturally pH-neutral environment.
- Fig 1 is a plan view of a region of an aquifer, in which a body of an halogenated contaminant is being removed by means of a process which embodies the invention
- Fig 2 is a diagram showing the operation of another process which embodies the invention.
- Fig 3 is a graph showing how the contaminant concentration in the water, and the Eh value of the water, change with respect to time.
- Fig 1 shows a body of contaminated water 2, the contaminant being for example carbon tetrachloride or another industrial solvent, which has accidentally entered an aquifer 3 and is contaminating the groundwater 4.
- the contaminant being for example carbon tetrachloride or another industrial solvent
- the permeability of the aquifer 3 is such that the contaminant is able to move through the aquifer in a particular direction, thus forming a plume of the contaminant.
- the contaminant may be of unknown origin, and the reason for devoting resources to cleaning up the contaminant is to save the well water from being contaminated.
- a clean-up may be called for, not because of a danger to a particular water supply, but simply because an industrial undertaking has caused a spill to occur, and is obligated to clean it up.
- a trench 6 is excavated in the path of the plume, and a body 7 of mixed iron filings and sand is placed in the trench 6.
- the mixture may be placed in the lower part of the trench, while the upper portion of the trench, above the vertical extent of the plume, may be filled in with the excavated soil or gravel from the trench.
- the body 7 in the trench 6, as regards its horizontal extent and its vertical depth, is of such dimensions that substantially all of the plume must flow through the body 7.
- the body 7 should not constitute a barrier to the flow of water, and so the permeability of the iron-sand mixture should be no lower than that of the aquifer itself. There should be no liner present between the body 7 and the material of the aquifer 3, or at least none which would reduce the permeability of the trench; also, any shoring which was employed when excavating the trench, to support the walls, should be removed once the body 7 is in place.
- the dimensions of the trench, and the quantity of iron filings to be placed therein, should be such as will ensure an adequate residence time of the contaminated groundwater in contact with the metal.
- a residence period in the region of one or two days is preferred, in the invention, and the width of the trench should be set with this in mind.
- the iron should be so placed in the trench that no oxygen can reach the iron. Thus, the iron should be buried within the trench. Any portion of the iron which is accessible to oxygen will simply rust, and be ineffective to promote the breakdown of the contaminant. However, such exposed iron, once rusted, would act to seal off the rest of the iron below, which may be termed the anaerobic portion of the iron; but other less expensive materials, such as the soil excavated from the trench, are preferred to iron, to perform this sealing function.
- the anaerobic portion of the iron is so disposed in the trench that substantially all the contaminated water in the plume has to pass through the trench, and has to pass through the anaerobic portion of the iron, and in fact has to remain in the anaerobic portion for a considerable period.
- the trench should contain only the metal, and as mentioned sand or other bulk filler material may be included with the iron.
- sand or other bulk filler material may be included with the iron. The presence of the bulk material allows the groundwater moving through the trench to remain close to the iron for a long period, but the expense of providing a vast quantity of metal is avoided.
- the trench has to be wide enough that the trench can be excavated with conventional trench- cutting machinery.
- the trench may define a space of greater width than is strictly necessary to accommodate the quantity of metal needed to break down the contaminant: in such a case, sand may be used as a bulk filler material.
- the iron filings and the sand, if sand is provided, preferably are dispersed in an homogeneous mixture in the trench.
- the trench may be arranged so as to comprise an encirclement of the well.
- the trench may be created by conventional trench-cutting machinery.
- the body of metal can be injected into the ground using the drill-and-jet process. This process is used for forming walls in a geological formation, particularly in loose material such as gravel.
- a series of boreholes are drilled a suitable distance apart.
- a pipe is passed down to the bottom of the borehole, and the iron filings are injected under pressure through the pipe into the borehole, the pipe then being gradually withdrawn up the borehole.
- the filings penetrate into the gravel or other material. The engineer sets the spacing of the boreholes and the quantity of iron injected such that a continuous wall of filings of the required thickness is formed.
- Fig 2 shows another system.
- a tank or pond 8 is provided at the surface.
- the contaminated groundwater is drawn out of the soil by means of a pump 9, and is fed into the pond 8.
- Contained within the pond 8 is a body 10 of iron filings, or of mixed iron filings and sand, through which the water slowly percolates.
- the contaminated groundwater should remain in the pond for a residence time preferably again in the region of one or two days,' and the dimensions of the pond, and the quantity of iron, should be calculated accordingly.
- the pond should be about 10 metres square in extent, and about 3 metres deep.
- the contaminated groundwater should be fed straight into the bottom of the pond, and should not be exposed to the atmosphere prior to entering the pond.
- Groundwater from a deep region can be expected to be already substantially oxygen-free; it is recognised in the invention that the process of lowering the Eh value to -100 or -200 mV is much less demanding when the water remains oxygen-free than when the water has just been exposed to the atmosphere.
- the decision between the two systems is one of economics: the expense of pumping has to be offset against the expense of making a deep trench.
- a trench will not generally be economical for depths below about 20 or 30 metres.
- the upper levels of the pond may be expected to contain some oxygen, and indeed the iron in the upper levels may be expected to oxidize.
- the volume of the pond should obtain therefore preferably in its depth rather than in its extent.
- the pond should be lined with impermeable material, eg concrete or clay, to prevent oxygen-containing water from seeping in.
- the pond also should be roofed over with impermeable material: Insofar as the pond is open to the atmosphere the upper levels of the pond, and of the iron, will be ineffective in lowering the Eh voltage of the water, and if the pond is exposed it therefore should be correspondingly deeper, and be large enough to retain the water at depth for a good residence period.
- the graph CS shows the level of concentration of a halogenated contaminant in water, over a period of time.
- Graph ES shows the Eh voltage of the same water over the same period. (The graphs are shown diagrammatically, and merely illustrate the trends.) It may be seen that once the Eh veflue has fallen, the breakdown of the contaminant quickly occurs.
- the graphs CS and ES arose from the use of soft iron.
- Graphs CG and EG are the corresponding graphs when galvanized iron is used
- graphs CA and EA are the corresponding graphs when aluminum is used.
- a delay occurs before the Eh voltage falls, and before the contaminant breaks down. This delay is thought to be attributable to the time required for the final depletion of oxygen in the groundwater and the onset of the low Eh values. Also, the delay varies in accordance with the type of metal used. It may be surmised that the variation in the delay is due to the variation in the extent to which metals are reactive. Thus, zinc is more reactive than iron which is more reactive than aluminum, and this corresponds to the series shown in Fig 3.
- stainless steel may be the metal used to cause the Eh value to fall although the delay then is quite considerable. It is preferred to use a metal which has a small delay time, so that the required residence time is at a minimum, with the proviso that the metal itself should be obtainable, in bulk and in particulate or filings form, without undue cost. Iron would be the first choice in most cases.
- the purpose of providing the metal in the form of filings is to ensure that the metal has a high surface-area-to-volume ratio: other forms of the metal with a correspondingly high ratio may be used, depending on the kind of metal selected, such as metal dust, or fibres as in metal wool.
- the iron filings need not be specially prepared for use in the invention: one of the parameters of the economics of the invention is the fact that the filings may be the kind of filings that are scrapped from metal treatment processes. A particular example is the filings that are produced from the fettling of iron castings.
- Such filings are inherently very clean.
- Other kinds of metal filings or cuttings may contain traces of cutting oils, etc, which might have to be cleaned off. On the one hand, these substances might interfere with the breakdown reaction of the halogenated contaminant: on the other hand, such substances can be sufficiently toxic in themselves as to warrant being kept from entering the aquifer.
- the invention has been described as it relates to the cleaning of contaminated groundwater in an aquifer, ie water from deep underground.
- groundwater can be expected, usually, to be naturally almost completely oxygen-free.
- groundwater does contain some dissolved oxygen: the invention is much less advantageous with such groundwaters, because of the large quantities of iron or other metal, and the very long residence times, that are needed to bring about the required fall in the Eh voltage.
- M Eh voltage as used herein is an art-term refering to the measure of the presence of oxidizable material.
- the voltage as measured by an Eh probe is the electrical potential with respect to the hydrogen reference electrode.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002069621A CA2069621C (en) | 1989-11-28 | 1990-11-28 | Cleaning halogenated contaminants from groundwater |
DE69025479T DE69025479T2 (en) | 1989-11-28 | 1990-11-28 | REMOVAL OF HALOGENED POLLUTION FROM GROUNDWATER |
EP90917655A EP0506684B1 (en) | 1989-11-28 | 1990-11-28 | Cleaning halogenated contaminants from groundwater |
JP03500237A JP3079109B2 (en) | 1989-11-28 | 1990-11-28 | How to remove halogenated pollutants in groundwater |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8926853.6 | 1989-11-28 | ||
GB898926853A GB8926853D0 (en) | 1989-11-28 | 1989-11-28 | Cleaning halogenated contaminants from water |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991008176A1 true WO1991008176A1 (en) | 1991-06-13 |
Family
ID=10667030
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1990/001848 WO1991008176A1 (en) | 1989-11-28 | 1990-11-28 | Cleaning halogenated contaminants from groundwater |
Country Status (10)
Country | Link |
---|---|
US (1) | US5266213A (en) |
EP (1) | EP0506684B1 (en) |
JP (1) | JP3079109B2 (en) |
AU (1) | AU645048B2 (en) |
CA (1) | CA2069621C (en) |
DE (1) | DE69025479T2 (en) |
DK (1) | DK0506684T3 (en) |
ES (1) | ES2088437T3 (en) |
GB (2) | GB8926853D0 (en) |
WO (1) | WO1991008176A1 (en) |
Cited By (14)
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EP0502460A2 (en) * | 1991-03-04 | 1992-09-09 | University Of Waterloo | System for treating contaminated groundwater |
WO1992019545A1 (en) * | 1991-04-25 | 1992-11-12 | University Of Waterloo | Removal of contaminants from water |
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EP0502460A2 (en) * | 1991-03-04 | 1992-09-09 | University Of Waterloo | System for treating contaminated groundwater |
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US5534154A (en) * | 1991-04-25 | 1996-07-09 | University Of Waterloo | System for cleaning contaminated soil |
US5487622A (en) * | 1992-04-23 | 1996-01-30 | University Of Waterloo | System for treating polluted groundwater |
AU666203B2 (en) * | 1992-04-23 | 1996-02-01 | University Of Waterloo | System for treating polluted groundwater |
WO1993022241A1 (en) * | 1992-04-23 | 1993-11-11 | University Of Waterloo | System for treating polluted groundwater |
US5398756A (en) * | 1992-12-14 | 1995-03-21 | Monsanto Company | In-situ remediation of contaminated soils |
US5476992A (en) * | 1993-07-02 | 1995-12-19 | Monsanto Company | In-situ remediation of contaminated heterogeneous soils |
WO1995029129A1 (en) * | 1994-04-23 | 1995-11-02 | University Of Waterloo | Water treatment system |
US5800096A (en) * | 1995-04-27 | 1998-09-01 | Barrow; Jeffrey | Subsurface barrier wall and method of installation |
WO1998042457A1 (en) * | 1997-03-24 | 1998-10-01 | Enpar Technologies Inc. | Removal of oxygen from water |
US6758979B1 (en) | 1998-12-17 | 2004-07-06 | Ufz-Umweltforschungzentrum Leipzig-Halle Gmbh | Method and reactor for decontaminating ground water |
US6596190B1 (en) | 1999-07-29 | 2003-07-22 | Hazama Corp. | Remediation agent for contaminated soil and method for the remediation of soil |
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RU2536496C1 (en) * | 2013-05-08 | 2014-12-27 | Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Профессионального Образования "Новочеркасская Государственная Мелиоративная Академия (Фгбоу Впо Нгма) | Method of creation of curtain grouting with filter windows and beam water intake |
Also Published As
Publication number | Publication date |
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CA2069621C (en) | 1999-08-03 |
JPH05501520A (en) | 1993-03-25 |
JP3079109B2 (en) | 2000-08-21 |
EP0506684B1 (en) | 1996-02-21 |
AU6873691A (en) | 1991-06-26 |
CA2069621A1 (en) | 1991-05-29 |
DK0506684T3 (en) | 1996-06-24 |
DE69025479D1 (en) | 1996-03-28 |
EP0506684A1 (en) | 1992-10-07 |
DE69025479T2 (en) | 1996-09-19 |
GB9025878D0 (en) | 1991-01-09 |
GB2238533B (en) | 1993-01-06 |
ES2088437T3 (en) | 1996-08-16 |
GB8926853D0 (en) | 1990-01-17 |
GB2238533A (en) | 1991-06-05 |
AU645048B2 (en) | 1994-01-06 |
US5266213A (en) | 1993-11-30 |
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