Method and system for remediation of groundwater contamination

• US 5,520,483 A
• Filed: 06/21/1995
• Issued: 05/28/1996
• Est. Priority Date: 02/12/1993
• Status: Expired due to Term

• Current Assignee: ManTech Environmental Corp. (Mantech International Corporation)
• Original Assignee: Cleanox Environmental Services Incorporated
• Inventors: Vigneri, Ronald J.
• Primary Examiner(s): Suchfield, George A.
• Application Number:
  US08/464,644
• Time in Patent Office: 342 Days
• Field of Search: 405/128, 405/129, 405/52, 405/263, 405/264, 166/250.01, 166/252.3, 166/245, 166/270, 166/300, 210/747, 210/759, 210/763, 588/205, 588/206, 588/207, 588/259, 588/260
• US Class Current: 210/747.8
• CPC Class Codes: B01F 2101/305 Treatment of water, waste water or sewage
• CPC Class Codes: B01F 23/451 by injecting one liquid into another
• CPC Class Codes: B01F 35/2132 Concentration, pH, pOH, p(ION) or oxygen-demand B01F35/2133 takes precedence
• CPC Class Codes: B01F 35/82 by adding a material to be mixed to a mixture in response to a detected feature, e.g. density, radioactivity, consumed power or colour
• CPC Class Codes: B09C 1/002 involving in-situ ground water treatment
• CPC Class Codes: B09C 1/08 chemically
• CPC Class Codes: B09C 2101/00 In situ
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 2103/06 Contaminated groundwater or leachate
• CPC Class Codes: E02D 31/00 Protective arrangements for foundations or foundation structures protective casings for piles E02D5/60; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution spillage retaining means for tanks B65D90/24
• CPC Class Codes: E21B 43/00 Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells applicable only to water E03B

Abstract

A method for remediating a hydrocarbon-contaminated region of a subterranean body of groundwater to destroy or reduce the initial concentration levels of hydrocarbon contaminants. A plurality of mutually spaced wells are provided which intersect the groundwater region. A treating flow of acetic acid is provided from one or more of the wells into the groundwater region, to establish acidic conditions. A turbulent flow of an aqueous solution of ferrous ion into the groundwater region is generated for mixing with the acidified groundwater, thereby providing a catalyst for disassociation of hydrogen peroxide. A treating flow of hydrogen peroxide solution from one or more of the wells into the groundwater region is then provided, so that the hydrogen peroxide may undergo a Fenton-like reaction in the presence of the acidic conditions and ferrous ion to generate hydroxyl free radicals for oxidizing the contaminants. An apparatus system for practicing the method is also disclosed.

Claims

1. A method for remediating a hydrocarbon-contaminated region of a subterranean body of groundwater to destroy or reduce the initial concentration levels of hydrocarbon contaminants, comprising the steps of:

(a) providing a plurality of mutually spaced wells intersecting said groundwater region;

(b) providing a treating flow of acetic acid from one or more of said wells into said groundwater region, to establish acidic conditions therein;

(c) introducing a turbulent flow of an aqueous solution of ferrous ion into said groundwater region, for mixing with said acidified groundwater, thereby providing a catalyst for disassociation of hydrogen peroxide; and

(d) providing a treating flow of hydrogen peroxide solution from one or more of said wells into said groundwater region, said hydrogen peroxide undergoing a Fenton-like reaction in the presence of said acidic conditions and said ferrous ion to generate hydroxyl free radicals for oxidizing said contaminants.

2. A method in accordance with claim 1, wherein in step (a) said groundwater region is brought to a pH of from 3.0 to 4.0.

3. A method in accordance with claim 1, wherein during step (b) the existence of acceptable continuity and well interflow paths for the said region are determined by monitoring pH changes at each other of said wells as a function of time to detect a pH drop of at least 0.2.

4. A method in accordance with claim 1, wherein between steps (b) and (c) and between steps (c) and (d) potable water is injected from the same said wells in place of acetic acid and ferrous ion solutions, to provide a transient buffer zone between the compositions introduced during steps (b), (c) and (d), thereby delaying the reaction of step (d) until the plume of injected miscible reactants has extended further into said groundwater region.

5. A method in accordance with claim 1, wherein said acetic acid is flowed as a solution at a rate of 5 to 10 gallons/min.

6. A method in accordance with claim 5, wherein said solution includes from 10% to 100% by weight of acetic acid.

7. A method in accordance with claim 1, wherein the total amount of acetic acid flowed into said region is from 1 to 3% by volume of the effective volume of contaminated water which is treated, based on a 100% acetic acid solution.

8. A method in accordance with claim 7, wherein the Fe²⁺ ion is provided as an aqueous solution of ferrous sulfate heptahydrate, the total volume of said solution flowed into said region being from 0.5 to 3% of the effective volume of the contaminated water which is treated, based on a 100% by weight solution of said heptahydrate.

9. A method in accordance with claim 8, wherein the treating flow of said hydrogen peroxide is at the rate of 0.1 to 10 gallons of hydrogen peroxide per minute per well, expressed on the basis of a 35% by weight solution of hydrogen peroxide.

10. A method in accordance with claim 1, wherein the total said treating flow of hydrogen peroxide solution is 1 to 5% by weight of the effective volume of contaminated water which is treated, expressed on the basis of a 100% solution of hydrogen peroxide.

11. A method is accordance with claim 1, wherein the treating flows of steps (a), (b) and (c) are provided under a pressure not more than the hydrostatic head relative to surface at the point of treating flow discharge from said well.

12. A method in accordance with claim 11, wherein the treating flow is provided under a pressure of from 6 to 40 psig.

13. A method in accordance with claim 11, wherein the total said treating flow of hydrogen peroxide solution is 0.1 to 10% by weight of the effective volume of contaminated water which is treated, expressed on the basis of a 35% solution of hydrogen peroxide.

14. A method in accordance with claim 1, further including determining the existence of acceptable continuity and well interflow paths for the said region by generating a test flow of a solution of hydrogen peroxide or acetic acid from one of said wells and monitoring pH changes at each other of said wells as a function of time to detect a pH drop of at least 0.2.

15. A method in accordance with claim 14, wherein the total volume in the test flow is 0.05 to 0.1% by weight of the effective volume of contaminated water, expressed on the basis of a 35% solution of hydrogen peroxide, and is injected at the rate of 0.3 to 10 gallons/minute and at a pressure which is not more than the hydrostatic head relative to surface at the point of treating flow discharge from said well.

16. A method in accordance with claim 1, including at least 3 said wells, which are spaced about the periphery of said groundwater region.

17. A method in accordance with claim 14, wherein said test flow is injected at one said well and the said pH change monitored at said other wells.

18. A method in accordance with claim 14, further including in step (b), monitoring temperature changes at one or more other of said wells to detect a temperature rise of at least 2°

F. as a confirmatory indicator of said acceptable continuity and well interflow paths.

19. A method in accordance with claim 1, wherein at least one of said treating solutions further includes a reaction surface enhancing reagent.

20. A method in accordance with claim 1, wherein the treating flow is periodically stopped and the hydrocarbon contaminant levels measured at each said well, until the said initial contaminant concentration levels drop below predetermined acceptable values.

21. A method of remediating a hydrocarbon-contaminated subterranean static plume of groundwater to destroy or reduce the initial concentration levels of hydrocarbon contaminants, comprising the steps of:

(a) providing a plurality of mutually spaced wells intersecting said static plume groundwater;

(b) measuring the change in water depth at each of said wells following atmospheric precipitation, to determine by common depth changes the likelihood of said plume;

(c) confirming the existence of the static plume by generating a test flow of a solution of hydrogen peroxide or acetic acid from one of said wells and monitoring the absence of pH changes at each other of said wells as a function of time; and

(d) providing a treating flow of solutions of acetic acid, of ferrous ion, and of hydrogen peroxide from each of said wells to establish a radial sweep about each said well, the total volumes and respective concentrations of treating solutions being effective to bring about a Fenton-like reaction generating hydroxyl free radicals for oxidizing said contaminants.

22. A method for remediating a hydrocarbon-contaminated region of a subterranean body of groundwater to destroy or reduce the initial concentration levels of hydrocarbon contaminants, comprising:

establishing acidic conditions at said groundwater region; and

introducing flows of aqueous solutions of ferrous ion and of hydrogen peroxide into said groundwater region, for mixing with said acidified groundwater;

said hydrogen peroxide undergoing a Fenton-like reaction in the presence of said acidic conditions and said ferrous ion to generate hydroxyl free radicals for oxidizing said contaminants.

23. A method in accordance with claim 22, wherein said groundwater region is acidified to a pH of from 3.0 to 4.0.

24. A method in accordance with claim 23, wherein said acidic conditions are brought about by introducing a flow of an acetic acid solution;

the total amount of acetic acid flowed into said region being from 1 to 3% by volume of the effective volume of contaminated water which is treated, based on a 100% acetic acid solution.

25. A method in accordance with claim 24, wherein the Fe²⁺ ion is provided as an aqueous solution of ferrous sulfate heptahydrate, the total volume of said solution flowed into said region being from 0.5 to 3% of the effective volume of the contaminated water which is treated, based on a 100% by weight solution of said heptahydrate.

26. A method in accordance with claim 25, wherein the total amount of treating solution of hydrogen peroxide solution is 1 to 5% by weight of the effective volume of contaminated water which is treated, expressed on the basis of a 100% solution of hydrogen peroxide.