US 5,510,032 AGrant
Process for Treating Aqueous Solutions Containing Industrial Wastes
Issue Date:1996-04-23
•35 Claims
•7 Drawing Sheets
Abstract
A treatment zone 10 in the form of a basin 12 having an inlet port 14 and an outlet port 16. The inlet port 14 allows water to flow into the basin 12. The outlet port 16 allows water to flow out of the basin 12. The inlet port 14 and the outlet port 16 are located at opposite ends of the basin 12 so as to allow water from a body of water having a concentration of water soluble metal ions contained therein to flow substantially through the entirety of the basin 12. A porous matrix 22 is disposed within the treatment zone 10. The porous matrix 22 is inoculated with a population of aerobic metal oxidizing bacteria. The population of aerobic metal oxidizing bacteria is capable of metabolizing water soluble metal ions in the water from the body of water into water insoluble metal oxides. Thus, there is an overall decrease in the concentration of the metal ions in the water flowing out of the treatment zone 10 as compared to water flowing into the treatment zone 10. The water flow out of the treatment zone also has a higher pH than the water flowing into the treatment zone.
Metadata
Inventors
- William J. Vail
- Robert K. Riley
Application Information
Application Number:US 3199835
Filing Date:1994-10-07
Priority Date:1992-07-13
Art Unit:138
Classifications
IPC:
C02F 334
Field of Search:
210435610;611;612;615;617;620;631;722;747;912262;264
Patent Drawings (7 sheets)
Description
Background of the Invention
1. Field of the Invention
The present invention relates to a process for reducing the concentration of water soluble metals in aqueous solutions, and, in particular, to a process for removing iron and/or manganese ions from aqueous solutions such as mine discharge waters or spent leaching waters prior to discharging such waters into surface or ground water systems.
2. Description of the Prior Art
The quality of water in the United States is important for the health and the quality of life of the people who live therein. For more than a hundred years the quality of water has been reduced by industrial pollution and deep mining, and, more recently, surface mining. Deep and surface mining pollution of water systems have been especially prevalent in the coal-producing regions of the Appalachian mountains. The pollutants resulting from these types of mining operations include iron, sulfate, manganese, aluminum, and acidity, to name a few. The toxicity of these pollutants impact both health and recreation in those regions.
A current method that is used to reduce the ionic and acidic pollution from the water systems around mining operations consists of raising the pH of the water above 8.5 with caustic soda. Ions then precipitate from the solution as hydroxides and a high pH supernatant is then discharged into streams. This process requires continuous maintenance and replenishment of caustic soda.
Recently, microorganisms have been used to reduce the concentration of pollutants from both industrial wastes and mine discharges. There have been many reports that bacteria can be used to remove metals as sulfides and sulfates from industrial and mining wastes.
It has been shown that sulfate can be removed using sulfate reducing bacteria in an anaerobic system (see U.S. Pat. No. 4,124,501 by Yen et at. and U.S. Pat. No. 4,200,523 by Balmat). Using similar methodology, sulfate reducing bacteria grown under anaerobic conditions has been shown to yield hydrogen sulfide gas which precipitates out metals as metal sulfides (see U.S. Pat. No. 4,354,937 by Hallberg). Also, in U.S. Pat. No. 4,789,478, Revis et at. used a mixed culture of Citrobacter freundii and sulfate reducing bacteria so as to precipitate heavy metal ions into sulfide form. Furthermore, in U.S. Pat. No. 4,522,723, Kauffman et at. were able to precipitate out metals into sulfide species using sulfate reducing bacteria of the genera Desulfovibro and Desulfotomaculum.
Another approach was taken by Lupton et at. in U.S. Pat. No. 5,062,956. Using anaerobic sulfate reducing bacteria, they were able to precipitate chromium as an insoluble hydroxide since the removal of sulfate causes a rise in pH. Similarly, in U.S. Pat. No. 4,519,912, Kauffman et al. were able to remove sulfate and heavy metals from aqueous solutions using mixed cultures of anaerobic bacteria of the genus Clostridium and at least one other bacteria from the genera Desulfovibrio and Desulfotomaculum. Kauffman et at. used a treatment zone to carry out the removal of water soluble species of heavy metals including selenium and sulfate ions. Analogously, in U.S. Pat. No. 4,519,913, Baldwin et al. disclosed the use of a porous matrix for retaining a population of bacterium of the genus Clostridium thereby reducing the concentration of water soluble ionic selenium species. The bacteria were grown under anaerobic conditions and definitive temperature and pH conditions.
In addition to the anaerobic methods discussed above, there have been several reports of using aerobic microorganisms to reduce the concentrations of ions in waste water. For example, in U.S. Pat. No. 3,923,597, Chakrabarty et al. used a genetically engineered species of Pseudomonas to remove mercury as a pollutant or an impurity. Also, in U.S. Pat. No. 4,468,461, Bopp was able to remove chromate from waste water using a strain of Pseudomonas fluorescens. Furthermore, in U.S. Pat. No. 4,728,427, Revis et at. were able to reduce the concentration of at least one heavy metal from an aqueous waste solution using a culture of Pseudomonas maltophilia. Moreover, in U.S. Pat. No. 4,898,827, Brierly et al. were able to remove ionic species of Ag, Cu, Pb, Cr, and Ni from waste waters using Bacillus subtilis and in the process recover these metals.
It has also been shown that metals can be recovered from aqueous solutions such as industrial waste water using several species of fungi (see U.S. Pat. No. 4,293,333 by Drobot).
In U.S. Pat. No. 4,530,763, Clyde et al. describe a method for treating waste fluids so as to remove selected chemicals with bacteria attached to porous fiber webbing. The waste fluids, containing nutrients, are drawn through the porous fiber webbing wherein ions of Cr, Ur, Fe, Ag, Pb, and V are removed from the solution.
Finally, it has been shown that manganese can be chemically removed from waste water by the addition of bisulfite to precipitate the manganese as manganese dioxide (see U.S. Pat. No. 3,349,031 by Hatch et al.).
Although all of the above-discussed methods are directed to treating waste water solutions and/or removing contaminants from waste water solutions, none are directed toward a process for removing iron and/or manganese ions from an aqueous solution by passing the aqueous solution through a porous matrix that is inoculated with metal oxidizing bacteria and is maintained under aerobic conditions. The present invention is directed to such a process.
Summary of the Invention
The present invention contemplates a process for removing iron and/or manganese ions from an aqueous solution by passing the aqueous solution through a porous matrix that is inoculated with metal oxidizing bacteria and is maintained under aerobic conditions. As a result of this process, the pH level of the aqueous solution is significantly increased. Also, as a result of this process, the acidity level of the aqueous solution is significantly decreased. Furthermore, as a result of this process, the alkalinity level of the aqueous solution is significantly increased.
From the foregoing descriptive summary it is apparent how the present process is distinguishable from the above-mentioned prior art. Accordingly, the primary objective of the present invention is to provide a process for removing iron and/or manganese ions from an aqueous solution by passing the aqueous solution through a porous matrix that is inoculated with metal oxidizing bacteria and is maintained under aerobic conditions, and which during said removal, reduces the acidity level of the aqueous solution.
Other objectives and advantages of the present invention will become apparent to those skilled in the art upon reading the following detailed description and claims, in conjunction with the accompanying drawings which are appended hereto.
Brief Description of the Drawings
In order to facilitate a fuller understanding of the present invention, reference is now be made to the appended drawings. The drawings should not be construed as limiting the present invention, but are intended to be exemplary only.
FIG. 1 is a graph showing the effect of wetland nutrients on bacterial removal of manganese from water.
FIG. 2 is a graph showing the manganese concentration taken at the inlet of the treatment zone compared with the manganese concentration taken at the outlet of the treatment zone over a seven month period.
FIG. 3 is a graph showing the iron concentration taken at the inlet of the treatment zone compared with the iron concentration taken at the outlet of the treatment zone over a seven month period.
FIG. 4 is a graph showing the pH level of the water at the inlet of the treatment zone compared with the pH level of the water at the outlet of the treatment zone over a seven month period.
FIG. 5 is a graph showing the acidity and the alkalinity levels of the water at the inlet of the treatment zone compared with the acidity and the alkalinity levels of the water at the outlet of the treatment zone over a seven month period.
FIG. 6 is a top plan view of a typical treatment zone that is used to reduce the concentration of water soluble metal species in aqueous solutions according to the present invention taken along line 6--6 of FIG. 7.
FIG. 7 is a side plan view of a typical treatment zone that is used to reduce the concentration of water soluble metal species in aqueous solutions according to the present invention taken along line 7--7 of FIG. 6.
Preferred Embodiment of the Present Invention
A laboratory experiment was conducted so as to demonstrate how the concentration of water soluble metals may be reduced in aqueous solutions according to the present invention. In this laboratory experiment, six five-gallon buckets were filled with mine water containing 80 parts per million (ppm) manganese. Three of the five-gallon plastic buckets were filled with mine water that was taken directly from a mine seep and three of the five-gallon buckets were filled with mine water that was taken from a mine seep and then passed through a man-made cattail wetland. In four of these buckets, two containing seep water and two containing wetland water, a porous matrix of limestone shale was added. In two of these buckets, one containing seep water and limestone shale and one containing wetland water and limestone shale, an aerobic metal oxidizing bacteria, in this case the bacteria Metallogenium, was cultured on the porous matrix of limestone shale. The contents of all of the buckets were aerated by an aquarian pump and an airstone. Also, all of the buckets were held at a temperature within the range from about 32.degree. F. to about 90.degree. F., but it should be noted that is preferred that the buckets are held at a temperature within the range from about 50.degree. F. to about 85.degree. F.
The mine seep water was poor in nutrients for the bacteria while the wetland water was rich in nutrients for the bacteria. It should be noted that the nutrients in the wetland water may include biological breakdown products of plant material such as cellulose, hemicellulose, hydrocarbons, pectin and pectin substances, starches, fructans, levans, inulins, sugars, proteins, amino acids, chitin, lignin, organic acids, and derivatives of these materials. It should also be noted that the nutrients in the wetland water may include organic carbon sources such as yeast extract, malt extract, peptone, and biological and municipal waste water sludges. It should further be noted that the wetland water may also contain a trace nutrient such as the B-vitamins peridoxine and thiamine.
Referring to FIG. 1, the results of the laboratory experiment are shown indicating the effect that wetland nutrients have on bacterial removal of manganese from water containing the same. As can be clearly seen in FIG. 1, the most effective removal of manganese occurred in the bucket containing wetland water and limestone shale inoculated with the aerobic metal oxidizing bacteria. However, there was still a reduction of manganese in the bucket containing seep water and limestone shale inoculated with the aerobic metal oxidizing bacteria.
It should be noted that the aerobic metal oxidizing bacteria metabolizes the manganese on the porous matrix so that manganese may be recovered as a water insoluble oxide of manganese.
A field experiment was also conducted so as to demonstrate how the concentration of water soluble metals may be reduced in aqueous solutions according to the present invention. In this field experiment, a treatment zone was constructed comprising a pit having the dimensions of 100 feet long, 10 feet wide, and 3 feet deep. The pit was located next to a man-made cattail wetland containing water having a manganese ion concentration ranging from about 35 ppm to about 45 ppm, an iron ion concentration ranging from about 0.02 ppm to about 0.32 ppm, a pH level ranging from about 4.5 to about 4.8, an acidity level ranging from about 85 mg/l to about 125 mg/l, an alkalinity level ranging from about 4 mg/l to about 6 mg/l, and a rich supply of nutrients for the bacteria Metallogenium. The pit was filled with a porous matrix of limestone shale, comprising about two-thirds of the total volume of the pit. The porous matrix was then inoculated with twenty five-gallon plastic buckets of aerobic metal oxidizing bacteria, in this case the bacteria Metallogenium. It should be noted that the porous matrix may be comprised of other materials such as gravel, but an alkaline based material is preferred.
The inoculum was prepared on limestone shale in the twenty five-gallon plastic buckets using water from the man-made cattail wetland site. This enrichment technique provided a steady state population of bacteria that were site specific.
After the treatment zone was inoculated with the aerobic metal oxidizing bacteria, water from the man-made cattail wetland was allowed to flow therethrough. The flow rate of the water through the treatment zone was about 2 gallons per minute thereby providing the water with a retention time in the treatment zone of about 2.5 days. Considering the dimensions of the treatment zone, the flow rate of the water through the treatment zone was about 2 gallons of water per cubic foot of the porous matrix per day. It should be noted that the flow rate of the water through the treatment zone may be controlled by gravity by properly positioning the treatment zone with respect to the manmade cattail wetland. It should also be noted that the treatment zone is left uncovered so as to allow the water to be sufficiently aerated.
Referring to FIG. 2, the manganese concentration taken at the inlet of the treatment zone compared with the manganese concentration taken at the outlet of the treatment zone is shown over a 7 month period. As can be clearly seen in FIG. 2, there was a significant removal of manganese from the water flowing through the treatment zone, even during the cold winter months. The aerobic metal oxidizing bacteria metabolized the manganese on the porous matrix so that manganese was recoverable as a water insoluble oxide of manganese. It should be noted that the manganese ions in the water were in the Mn (II) and Mn (IV) oxidation states.
Referring to FIG. 3, the iron concentration taken at the inlet of the treatment zone compared with the iron concentration taken at the outlet of the treatment zone is shown over a 7 month period. As can be clearly seen in FIG. 3, there was a nearly constant removal of iron from the water flowing through the treatment zone, even during the cold winter months. The aerobic metal oxidizing bacteria metabolized the iron on the porous matrix so that iron was recoverable as a water insoluble oxide of iron. It should be noted that the iron ions in the water were in the Fe (III) oxidation state.
Referring to FIG. 4, the pH level of the water at the inlet of the treatment zone compared with the pH level of the water at the outlet of the treatment zone is shown over a 7 month period. As can be clearly seen in FIG. 4, the pH level of the water at the outlet of the treatment zone was significantly increased from the pH level of the water at the inlet of the treatment zone, even during the cold winter months. The pH level change in the water was a result of the aerobic metal oxidizing bacteria interacting with the limestone shale. More specifically, the aerobic metal oxidizing bacteria interact with the limestone shale so as to release calcium carbonate into the water and thereby increase the pH level of the water.
Referring to FIG. 5, the acidity and the alkalinity levels of the water at the inlet of the treatment zone compared with the acidity and the alkalinity levels of the water at the outlet of the treatment zone are shown over a 7 month period. As can be clearly seen in FIG. 5, the acidity level of the water at the outlet of the treatment zone was significantly decreased from the acidity level of the water at the inlet of the treatment zone, even during the cold winter months. As can also be clearly seen in FIG. 5, the alkalinity level of the water at the outlet of the treatment zone was significantly increased from the alkalinity level of the water at the inlet of the treatment zone, even during the cold winter months. The acidity level change in the water was a result of the aerobic metal oxidizing bacteria interacting with the limestone shale. More specifically, the aerobic metal oxidizing bacteria interacts with the limestone shale so as to release calcium carbonate into the water and thereby decrease the acidity level of the water. The alkalinity level change in the water was a result of the aerobic metal oxidizing bacteria interacting with the limestone shale. More specifically, the aerobic metal oxidizing bacteria interacts with the limestone shale so as to release calcium carbonate into the water and thereby increase the alkalinity level of the water.
Referring to FIGS. 6 and 7, there is shown a treatment zone 10 similar to the one just described. The treatment zone 10 is in the form of a basin 12 having an inlet port 14 and an outlet port 16. The inlet port 14 allows water to flow into the basin 12. The outlet port 16 allows water to flow out of the basin 12. The inlet port 14 and the outlet port 16 are located at opposite ends of the basin 12 so as to allow water from a body of water having a concentration of water soluble metal ions contained therein to flow substantially through the entirety of the basin 12. The flow rate of the water from the body of water through the basin 12 may be controlled by gravity by properly positioning the treatment zone 10 with respect to the body of water.
The basin 12 also has a plurality of upper flow barriers 18 and a plurality of lower flow barriers 20. These upper and lower flow barriers 18, 20 are provided so as to prevent a direct flow path and thereby insure that the water from the body of water flows substantially through the entirety of the basin 12. It should also be noted that the treatment zone 10 is left uncovered so as to allow the water flowing therethrough to be sufficiently aerated.
A porous matrix 22 is disposed within the treatment zone 10. The porous matrix 22 is inoculated with a population of aerobic metal oxidizing bacteria. The population of aerobic metal oxidizing bacteria is capable of metabolizing water soluble metal ions in the water from the body of water into water insoluble metal oxides. The water insoluble metal oxides are deposited on the porous matrix 22, thereby allowing for their recovery. Thus, there is an overall decrease in the concentration of the metal ions in the water flowing out of the treatment zone 10 as compared to water flowing into the treatment zone 10. It is important to note that the porous matrix 22 never needs to be regenerated through the use of conditioned water or any other means.
With the present invention treatment zone 10 and corresponding process now fully described, it can thus be seen that the primary objective set forth above is efficiently attained and, since certain changes may be made in the above-described treatment zone 10 and corresponding process without departing from the scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
Claims
What is claimed is:
1. A process for reducing the concentration of water soluble metal ions in an aqueous solution containing the same, said process comprising the steps of: providing an aqueous solution having contained therein a concentration of water soluble metal ions; providing a porous matrix containing cultured populations of aerobic metal oxidizing bacteria from the genus Metallogenium, said bacteria being capable of metabolizing said water soluble metal ions in said aqueous solution into water insoluble metal oxides, said porous matrix being provided under aerobic conditions; and passing said aqueous solution through said porous matrix in a continuous fashion so as to allow said bacteria to metabolize said metal ions in said aqueous solution into water insoluble metal oxides, which are substantially retained on said porous matrix, thereby resulting in a reduction in the concentration of said water soluble metal ions in said aqueous solution.
2. The process as defined in claim 1, wherein said water soluble metal ions in said aqueous solution are manganese ions in the Mn (II) and Mn (IV) oxidation states and iron ions in the Fe (III) oxidation state.
3. The process as defined in claim 1, wherein said aqueous solution is mine discharge water.
4. The process as defined in claim 1, wherein said porous matrix is a porous matrix of alkaline based material.
5. The process as defined in claim 1, further comprising separating and recovering said water insoluble metal oxides from said porous matrix.
6. The process as defined in claim 1, wherein said aqueous solution is continuously passed through said porous matrix at a rate of up to about 2 gallons of aqueous solution per cubic foot of porous matrix per day.
7. The process as defined in claim 6, wherein the passing of said aqueous solution through said porous matrix containing said bacteria results in an increase in the pH level of said aqueous solution.
8. The process as defined in claim 6, wherein the passing of said aqueous solution through said porous matrix containing said bacteria results in a decrease in the acidity level of said aqueous solution.
9. The process as defined in claim 6, wherein the passing of said aqueous solution through said porous matrix containing said bacteria results in an increase in the alkalinity level of said aqueous solution.
10. The process as defined in claim 6, wherein the passing of said aqueous solution through said porous matrix is carried out in the presence of at least one nutrient and in the presence of at least one trace nutrient.
11. The process as defined in claim 10, wherein said at least one nutrient comprises at least one material selected from the group consisting of yeast extract, malt extract, peptone, cellulose, hemicellulose, hydrocarbons, pectin and pectin substances, starches, fructans, levans, inulins, sugars, proteins, amino acids, chitin, lignin, organic acids, derivatives of said materials, and biological and municipal waste water sludges.
12. The process as defined in claim 11, wherein the passing of said aqueous solution through said porous matrix in the presence of said nutrients is carried out at a temperature ranging from about 32.degree. F. to about 90.degree. F.
13. A process for reducing the concentration of water soluble metal ions in an aqueous solution containing the same, said process comprising the steps of: providing an aqueous solution having contained therein a concentration of water soluble metal ions; providing a porous matrix suitable for maintaining a population of aerobic metal oxidizing bacteria, said porous matrix being provided under aerobic conditions; inoculating said porous matrix with a population of aerobic metal oxidizing bacteria from the genus Metallogenium, wherein said bacteria is capable of metabolizing said water soluble metal ions in said aqueous solution into water insoluble metal oxides; and passing said aqueous solution through said porous matrix in a continuous fashion so as to allow said bacteria to metabolize said metal ions in said aqueous solution into water insoluble metal oxides which are substantially retained on said porous matrix, thereby resulting in a reduction in the concentration of said water soluble metal ions in said aqueous solution.
14. The process as defined in claim 13, wherein said water soluble metal ions in said aqueous solution are manganese ions in the Mn (II) and Mn (IV) oxidation states and iron ions in the Fe (III) oxidation state.
15. The process as defined in claim 13, wherein said aqueous solution is mine discharge water.
16. The process as defined in claim 13, wherein said porous matrix is a porous matrix of alkaline based material.
17. The process as defined in claim 13, further comprising separating and recovering said water insoluble metal oxides from said porous matrix.
18. The process as defined in claim 13, wherein said step of passing said aqueous solution in a continuous fashion comprises allowing said aqueous solution to continuously flow through said porous matrix at a controlled rate of up to about 2 gallons of aqueous solution per cubic foot of porous matrix per day.
19. The process as defined in claim 18, wherein said controlled rate is determined by gravity.
20. The process as defined in claim 18, wherein said step of continuously passing said aqueous solution through said porous matrix results in an increase in the pH level of said aqueous solution.
21. The process as defined in claim 18, wherein said step of continuously passing said aqueous solution through said porous matrix results in a decrease in the acidity level of said aqueous solution.
22. The process as defined in claim 18, wherein said step of continuously passing said aqueous solution through said porous matrix results in an increase in the alkalinity level of said aqueous solution.
23. The process as defined in claim 18, wherein said step of continuously passing said aqueous solution through said porous matrix is carded out in the presence of at least one nutrient and in the presence of at least one trace nutrient.
24. The process as defined in claim 23, wherein said at least one nutrient comprises at least one material selected from the group consisting of yeast extract, malt extract, peptone, cellulose, hemicellulose, hydrocarbons, pectin and pectin substances, starches, fructans, levans, inulins, sugars, proteins, amino acids, chitin, lignin, organic acids, derivatives of said materials, and biological and municipal waste water sludges.
25. The process as defined in claim 24, wherein said step of continuously passing said aqueous solution through said porous matrix in the presence of said nutrients is carried out at a temperature ranging from about 32.degree. F. to about 90.degree. F.
26. A process for reducing the concentration of water soluble metal ions in a body of water containing the same, said process comprising the steps of: constructing a treatment zone in the form of a basin having an inlet port through which water from said body of water may flow into said basin and an outlet port through which water contained in said basin may flow out of said basin, said inlet port and said outlet port being located and configured so as to allow said water to flow substantially throughout the entirety of said basin at a controlled rate; filling said treatment zone with a porous matrix suitable for maintaining a population of aerobic metal oxidizing bacteria thereon; inoculating said porous matrix with a population of aerobic metal oxidizing bacteria from the genus Metallogenium, wherein said bacteria is capable of metabolizing said water soluble metal ions in said body of water into water insoluble metal oxides; and allowing water from said body of water to flow through said treatment zone, and hence through said porous matrix inoculated with said aerobic metal oxidizing bacteria from the genus Metallogenium, in a continuous fashion at said controlled rate so as to allow said bacteria to metabolize said water soluble metal ions in said flowing water into water insoluble metal oxides, thereby resulting in an overall decrease in the concentration of said water soluble metal ions in water flowing out of said treatment zone as compared to water flowing into said treatment zone.
27. The process as defined in claim 26, wherein said water soluble metal ions in said flowing water are manganese ions in the Mn (II) and Mn (IV) oxidation states and iron ions in the Fe (III) oxidation state.
28. The process as defined in claim 26, wherein said body of water is mine discharge water.
29. The process as defined in claim 26, wherein said porous matrix is a porous matrix of alkaline based material.
30. The process as defined in claim 26, further comprising separating and recovering said water insoluble metal oxides from said porous matrix.
31. The process as defined in claim 26, wherein said step of allowing water from said body of water to flow through said treatment zone in a continuous fashion at said controlled rate comprises allowing water from said body of water to continuously flow through said treatment zone at a rate of up to about 2 gallons of water per cubic foot of porous matrix per day.
32. The process as defined in claim 31, wherein said controlled rate is determined by gravity.
33. The process as defined in claim 31, wherein said step of allowing water from said body of water to flow through said treatment zone in a continuous fashion at said controlled rate results in an increase in the pH level of said water.
34. The process as defined in claim 31 , wherein said step of allowing water from said body of water to flow through said treatment zone in a continuous fashion at said controlled rate results in a decrease in the acidity level of said water.
35. The process as defined in claim 31 wherein said step of allowing water from said body of water to flow through said treatment zone in a continuous fashion at said controlled rate results in an increase in the alkalinity level of said water.
Patent Citations (24)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3349031 | 1967-10-01 | Hatch et al. | |
| US3846296 | 1974-11-01 | Raymond | |
| US3923597 | 1975-12-01 | Chakrabarty et al. | |
| US4124501 | 1978-11-01 | Yen et al. | |
| US4200523 | 1980-04-01 | Balmat | |
| US4218318 | 1980-08-01 | Niimi et al. | |
| US4293333 | 1981-10-01 | Drobot | |
| US4354937 | 1982-10-01 | Hallberg | |
| US4401569 | 1983-08-01 | Jhaveri et al. | |
| US4468461 | 1984-08-01 | Bopp | |
| US4519912 | 1985-05-01 | Kauffman et al. | |
| US4519913 | 1985-05-01 | Baldwin et al. | |
| US4522723 | 1985-06-01 | Kauffman et al. | |
| US4530763 | 1985-07-01 | Clyde et al. | |
| US4576717 | 1986-03-01 | Collin et al. | |
| US4728427 | 1988-03-01 | Revis et al. | |
| US4755304 | 1988-07-01 | Hallberg et al. | |
| US4765902 | 1923-08-01 | Ely et al. | |
| US4789478 | 1988-12-01 | Revis et al. | |
| US4793929 | 1988-12-01 | Kickuth et al. | |
| US4898827 | 1990-02-01 | Brierley et al. | |
| US5062956 | 1991-11-01 | Lupton et al. | |
| US5062958 | 1991-11-01 | Bateson et al. | |
| US5080793 | 1992-01-01 | Urlings |
Non-Patent Literature (4)
- Coal Chronicle; Briefs Section Feb. 1993 Stream Cleaning Experiment.
- Bureau of Mines Information Circular/1988 vol. 1: Minewater and Mine Waste.
- Isolation and Culture of Manganese-Oxidizing Bacterium from a Man-Made Cattailwetcand; Vail, Wilson, Riley Charleston Daily Mail; Business Section Jan. 26, 1993.
- Pair Touts Mine Stream Cleaning System.