Final Report

 

 

 

Submit to: United States Department of Interior

Bureau of Reclamation

P.O. Box 36900, Billings Montana 59107-6900

Contracting Officer, Gerri Voto

cc: Area Manager, Loveland (Littlepage)

 

Purchase Order No. 00PG600106

 

 

By:  Frank Burcik

Water Treatment and Decontamination International  (WTDI)

2010 Bell CT., Lakewood, CO 80215

 Phone: 303-202-9324    E-Mail: fburcik@attbi.com

 

This report summarizes a series of experiments performed at the Leadville Mine Drainage Tunnel (LMDT), in Leadville, Colorado, in order to determine the efficiency of WTDI’s phytoremediation technology in decontaminating water polluted by high concentrations of metals. The project was formally instigated on July 19, 1999 after WTDI received permission to begin preliminary test of our phytoremediation technology in the LMDT. On June 22, 2000 WTDI received a contract from the U.S. Government; Contract Number 00PG600106 from U.S. Bureau of Reclamation (BOR) and the Environmental Protection Agency (EPA).

During the course of this project, WTDI has collaborated closely with Drs. Duane Johnson (Department of Soil and Crop Science) and Dr. Elizabeth Pilon-Smits (Biology), of the Colorado State University at Fort Collins, Colorado.

 

Purpose of the project: 

To evaluate WTDI’s phytoremediation technology in decontaminating acid mine drainage water. Specifically, to determine if it is possible to meet NPDES regulations and successfully treat 600 GPM of discharge water at the LMDT using our phytoremediation technology.

 History:

 The Leadville Mine Drainage Tunnel (LMDT) was constructed for the purpose of draining water from the mining district located east of Leadville. The total length of the tunnel, which is located at altitude of 10,000 feet above sea level, is over 11,000 feet long. The tunnel is partially blocked in several places, making it accessible only along its initial length of 450 feet, (at approximately 450 feet into the tunnel, a pressure grouted portal previously installed to prevent further collapse denies access to the deeper, more upstream, parts of the tunnel). A portion of the water from beyond the portal is pumped into the treatment plant (approximately 1100 GPM). An additional 600 GPM, which flows through the tunnel, is also pumped into the treatment plant. Thus, the total amount of water treated in the treatment plant from this tunnel is approximately 1700 GPM.

The water coming from the tunnel has a mean TDS of around 8,000ug/l. The EPA has requested that the Bureau of Reclamation to conduct a treatability study for the surface water in the ponds at OU6, which is planed to divert into the existing tunnel system. The water has a TDS as high as 830,000ug/l; this could overload the treatment plant capability.

 Tunnel specifications of the tunnel are: length 450 feet, horseshoe design of 8x8 feet that is pressure grouted with two gutters on each side of the floor, 24x8 inches for water flow. The bulkhead constructed with treated 2x12 lumber; rock caving behind the bulkhead is restricting water flow to approximately 600 GPM; water temperature 43 F; pH = 7. The ambient air temperature is 52 F. Ventilation: negative pressure provided by electrical fan and duct system. 100-Watt bulbs spaced 20 feet apart originally provided lighting. The primary contaminants in the water are Iron, Manganese, Zinc and Cadmium, at about (~400 ppb) concentrations. 

Initially WTDI tested several plant species for efficiency of metal uptake from the LMDT water: houseplant; daisy; sagebrush; clover; yarrow; grass; marsh grass; mint; potentilla; mustard; moss. Many of the species where collected within the vicinity of the tunnel (See lab. Report #1 and # 1a).  Tobacco plants, provided by a local grower, were also tested (See Lab. report 2), as well as several edible species: onion, scallions, strawberries, garlic, carrots, kohlrabi, (See Lab. Report #3). For the first test, the water was preheated to 60F at a flow of 5GPM. These plants effected a 60 % reduction of metals in the water (Refer to report  # 1a), where the water exceeds EPA drinking water limits.

 

 In August 2000, we started the second test. The tunnel was prepared as follows: four (4), 40 feet sections of troughs were installed approximately 3 feet up off the ground. Each section consisted of (3) three 8 inch-wide and 4 inches deep troughs. A partition was installed at the bulkhead, which raised the water level up to the ceiling of the tunnel. This design allowed us to use gravity feed, via an 8-inch pipe with a flow control valve, for each test section. This eliminated need to pump water from the floor gutters up to the troughs.  At the beginning of the first section we installed a fertilizer injection system, as well as an acid injection system in order to modify the pH if needed.

Electrical lighting, fluorescent fixtures were installed over the full length of the test portion of the tunnel (200 feet).

In each of the individual troughs, a Styrofoam tray of 8inch by 26inches by 2 inch thick with ľ inch square openings for plant seeds was installed. Initially, plant seeds were germinated in a local nursery and transplanted into the test troughs. Later on, the ľ inch openings in each tray were filled with standard potting soil mix and test plant seeds. Water flowed at 5 GPM through each trough. In about 20 days contamination reduction in the water become apparent. At 30 days, a full root system had developed and water samples were taken weekly. Monthly samples of plant material including roots were also collected for laboratory analysis.

Plant species used in the second test were: Canola, Winter Canola, Winter mustard, Quinoa, Helios, Spring Barley, Sunflower. (See  Lab. Report # 4)

On December12, 2000, the third and last test was instigated. The primary plant species used in the final test was Indian mustard (Brassica juncea), which was selected on the basis on previous tests in the tunnel. In addition, several transgenic varieties of Indian mustard developed at CSU by Dr. Elizabeth Pilon-Smits to overproduce the metal binding peptides glutatione and phytochelatins were also tested.  The bioengineered species showed up to 2-fold higher metal concentrations compared to the non-transgenic mustard. Growth was similar for all varieties. We also determined that the plants could be readily germinated in the tunnel environment instead of in the greenhouse to reduce the cost of operation. The light was left on continuously 24 hours a day, 7 days a week, to prevent fluctuations of metal uptake by plants. The water flow in each individual trough was approximately 5 GPM, corresponding to 15 GPM for each section. In all four sections 60 GPM of water was treated.  

 

 

Overall conclusion

The main objective in this study was to determine the feasibility of meeting NPDES regulations using WTDI’s phytoremediation technology in treating the 600 GPM of metal-contaminated water discharged by the LMDT at Leadville, Colorado. Our results shows that the LMDT, which has usable length of 450 total feet, is not long enough to permit full decontamination of water using WTDI’s phytoremediation technology. Results indicate that in order to decontaminate the flow of water discharged by the LMDT (600 GPM) using our phytoremediation technology we would need to have at least 3000 feet of troughs. Therefore the tunnel would have to be at least 1500 feet long, with troughs on each side. Additional sections of 200 feet would be needed for germination of plants. An enlargement of the length of the tunnel for our phytoremediation system would exceed the cost of modification of the existing treatment facilities to deal with the projected goal.

  

Other objectives

 1. To determine which plant species work best for metal uptake in cold or warm water.

2. To determine how long plants effectively uptake metals (Cropping cycles).

3. To determine water temperature requirements for plant growth and cost of operation.

4.  To determine the best hydroponics system for the tunnel, that is low in maintenance.

5. To determine fertilizer requirements for plants and metal assays of effluent discharge.

6. To determine the effectiveness of the treatment by performing metal assays on influent and effluent water.

7. To determine where the metals are concentrated in the plant, by means of vegetational metal assays

8. To determine electrical lighting requirements for maximum plant growth and metal uptake.

9. To determine the best light conditions for optimal efficiency.

10. To determine if the plants are hazardous or not, by means of TCLPs.

11. To determine whether edible species grown in the tunnel would be safe for human or animal consumption.

 

Results

1a. The best species for this study was shown to be Indian mustard (Brassica juncea), due to its tolerance of the cold climate and its ability to hydroponically uptake large quantities of metals.

2a.  After the seeds germinated and developed a full root system (less than 30 days), and during the subsequent vegetative growth period which consisted of the next (4) months, the plants showed a constant uptake of metals. After four months, they developed seeds and became ready to harvest.

 3a.  Preheating of the 600 GPM of water could be cost prohibitive. For the selected Indian mustard, there was no necessity to preheat the water.

 4a.  The most efficient hydroponics system for decontamination would have square gutters that are 32 inch wide, 4 inch deep, and 100 feet in length, installed in series on both sides of the tunnel with each section having a 20 GPM flow rate. On the end of each 100 feet section a clean water discharge conduit would have to be installed. Each gutter would have two trays next to each other for a total of 96 trays, (trays are 16 inch wide by 26 inch long). The plants in trays would be exchanged every 18 to 20 weeks, or about three times in year.

Tests with blending of the OU6 water and tunnel water was not done since at the time of these tests the OU6 water had yet to be introduced into the tunnel.

5a.   No significant improvement in plant performance was seen after addition of fertilizers, or after making pH adjustment.

6a.   Metal assays showed satisfactory reduction of metal concentrations such that with proper setup, the NPDES permit levels can be achieved.

7a.  Most of the metals were concentrated in the root system (>25% of the root dry weight was metals). Plant stems and leaves also showed significant metal concentrations which were about  ~1000 fold higher than in the water (~400 ppm Fe, Mn and Zn in shoot tissue). Marginal concentrations of metals were also incorporated in the flowers and seeds.

8a.  It was determined that standard High Output fluorescent fixtures were sufficient to promote plant growth and metal uptake.

Note: WTDI has under development a Solar Transfer System that would reduce the electrical energy consumption for the hydroponics water treatment system. Due to lack of additional funding WTDI’s Solar Transfer System has not been tested in the tunnel.  

9a.  It was determined that it is not necessary to switch the lights on and off. By living the lights on all the time, plants showed steady growth and metal uptake.

10a.  TCLP tests showed that the plants were not saturated by hazardous metals to the point to be hazardous for disposition in a landfill. In case of additional hazardous metals or higher concentrations, WTDI has developed a technology to separate the hazardous metals from the harvested plant materials; the decontaminated biomass can then be used as a fertilizer or disposed in a landfill.

11a. Some edible species were tested in this system. As an example, strawberry showed  no significant metal concentration in the fruit, therefore they appear to be edible. Carrot, Garlic, and Onions show higher concentrations of metals, including Zinc and Cadmium, therefore they may not be recommended for human consumption with out further study.

Laboratory tests of water and plants material were performed at: (originals on file)

 Rinehart Laboratories, Inc

5810 Lamar Street, PO Box 564, Arvada, CO 80001  

 

Barringer Laboratories, Inc.

15000 W 6th Avenue Suite 300, Golden, CO 80401 

 

Evergreen Analytical Laboratory

4036 Youngfield Street

Wheat Ridge, CO 80033

 

ENVIRO-CHEM Analytical, Inc.

685 W. Gunnison, Suite # 108 

Grand Junction, CO 81505

 

Colorado State University

Department of Soil and Crop Science / Biology

Ft. Collins, CO 80523

Laboratory report #1

By: Rinehart Laboratory, Inc, Reference No 990244, Date: January 18,  2000     

A:  Houseplant           Zn                  Cd               Mn               Fe            All in mg/kg of dry solids

Root                         1051.0               4.71            82.4          360.0

Stem                         1039.0              12.8             60.8          740.0

Seed                          434.0                1.8            108.0          473.0

B:  Daisy

Root                          288.0               1.95           142.0          292.0

Stem                            25.3               2.1               60.8          280.0

Seed                           161.0               3.38             55.0            22.6

C:  Sagebrush

Root                           229.0               0.92             32.3          172.0

Stem                           112.0               0.8              22.2          206.0

Seed                           165.0                1.03            33.2          727.0

D:  Clover

Root                           293.0               0.54            274.0       2064.0

Stem                           240.0               0.67              83.6         460.0

Seed                             45.3                0.45           114.0         460.0

E:  Yarrow

Root                          7969.0               3.27         2002.0       8220.0

Stem                           240.0                1.64             12.8         288.0

Seed                         1620.0                 0.35           132.0        387.0

F:  Grass

Root                           157.0                 0.36           118.0            7.3

Stem                            17.6                 0.08               1.9            4.3

Seed                            15.4                 0.13                8.1            7.0

G:  Marsh Grass   

Root                              <.1                 0.08                0.1           0.86

Stem                             <.1                  0.05                0.1           0.43

Seed                             <.1                  0.04                                 1.43

H:  Mint

Root                             <.1                  0.05                0.6            0.43

Stem                            <.1                   0.02               10.1           0.43

Seed                             <.1                  0.07                 3.57          0.6

I:  Potentilla

Root                             <.1                 0.05                  1.0           0.43

Stem                             <.1                 0.02                 0.28          0.88

Seed                             0.18                0.07                  <.1           2.41

J:  Mustard

Root                             0.13                0.06                   <.1           <.1

Stem                             0.2                 0.05                   <.1           2.76

Seed                             0.12                0.2                    <.1            <.1

K:  Houseplant

Root                             0.12               0.08                   <.1           1.28

Stem                             0.27               0.05                   0.2        < 0.43

Seed                             <.1                 0.28                   <.5           0.43

L:  Moss

Root                             <.1                 0.05                   <.1           <.1

Stem                             <.1                <.03                   <.1           <.1

Seed                             0.9                 0.08                   <.1           <.1

 

Laboratory report # 1a          

By: Rienhart Laboratory, Inc., Reference No.990244-C   Date: January 26, 2000

Water samples in respect to the test used plant species identified in the Lab report #1

(All in mg/l)     Influent          Effluent             Metal loading        EPA drinking

                                               from troughs     reduction (%)         water limits          

Cd (213.1)       0.012              0.0066                45 %                       0.01

Fe (236.1)        0.678              0.082                  87.91 %                  0.3

Mn (243.1)      0.281              0.0019                 99.32 %                 0.05

Zn (289.1)       1.79                1.68                     6.15 %                   5.0

5 GPM flow, water temp. 60 F, no fertilizer added, total metal reduction of 59.59 %

 

Laboratory report #2

Laboratory test on tobacco plant performed by graduate student Eric August at Colorado University in Boulder, Colorado. Date: 7/24/2000

Results from Atomic Adsorption Spec. run on H2O and Tobacco

                          Zn (mg/l)             Mn (mg/l)                 Fe (mg/l)

Inflow               1.640                    0.385                         0.495

Outflow             1.589 (3.11 %)    0.372 (3.37 %)          0.447 (9.69 %)  (% reduction)     

                          Zn (mg/kg)          Mn (mg/kg)              Fe (mg/kg)

Roots                 9883 +/- 13         7559 +/- 40              11121 +/- 1030

Stems                  726 +/- 12           282 +/- 14                1213 +/- 185

Leaves                 568 +/- 2             318 +/- 3                    780 +/- 31

Note: Cadmium has not been tested due to problem with the AA unit.

 

Laboratory report #3

By: Rinehart Laboratory, Inc., Reference No. 000059-A Date: April 26, 2000

Sample             Cd  (mg/kg)         Fe (mg/kg)             Mn (mg/kg)        Zn (mg/kg)

Onions             1.02                      3,222                      .295                    162

Scallions          25.6                      2,251                      2,248                  357

Strawberries    0.64                       436                        73                        46

Garlic              19.2                       4,335                     2,654                   266

Carrots            51.3                       34,444                   2,808                   1,616

Kohlrabi          6.79                      3,127                      427                      121

  Note: Metals calculated on dry weight basis

 

 

Laboratory report # 4

By: Rinehart Laboratory, Inc., Reference No. 990244-D  Date: February 29, 2000

Sample                 Fe (mg/kg)          Mn (mg/kg)             Cd (mg/kg)        Zn (mg/kg)

Canola                 4,588                   416                           1.6                    203

Winter Canola     4,954                   808                           16.3                   450

Winter Mustard   4,588                   286                           17.4                   1,104

Quinoa                14,450                 110                            12.5                   170

Helios                  3,863                   283                           1.74                    529

Spring Barley      3,670                   130                           3.48                    407

Sunflower            8,258                  596                            6.45                    1,138

Note: Metals calculated on dry weight basis

 

Last and final phase of the Phytoremediation study in the LMDT started on December 12, 2000, by seeding a Mustard plant species in section #4, #3 and #2 (A,B,C respectively),with help from Mr. Chad Molear and later Aubrey Cain a students from CMC in Leadville. On 12/20/00 we finished installation and testing of the acid injection system. On 12/28/00 we installed and tested the fertilizer injection system.

On January 4, 2001 the fertilizer was adjusted as follow; 5 gallons (18.92 Liter) of water was mixed with (950ml) of Ionic fertilizer and 10 teaspoon (0.056 ml) of Alaska Fish fertilizer. Injection was set for 3.33 ml/minute for total of 15 GPM (56.78 liter) of water for the # 4 section consisting of three troughs, 5 gallons (18.92 L) per trough. At the time, the plants where 3 1/2 to 4 inches tall. Plants samples was taken before the fertilizer injection system was turned on.

Acid injection system was turned on February 10, 2001;  Sulfuric acid H2SO4 diluted with water to pH 1.2 in the supply container equipped with metering pump. The metering pump was set to 50 strokes per minute for 15 GPM (56.78liter) of feed water mixing container and pH was adjusted from pH 7.3 to pH 5.77 at water temperature of  44 F (6.66 C). On February 12, 2001 adjustment of pH was made running at 5.75.

Process control was set up on September 11, 2000 upon agreement between, Frank Burcik (WTDI), Brad Littlepage and Janelle Stefanic (BOR).

Process control consisted of monitoring the Influent and Effluent water for pH, UMHOs, temperature (H2O^C), ambient temperature (^C), flow rate in (GPM) and plant condition. Plant condition as: Height (inches), Root (inches), condition scaled from 1 to 5 (5 being great), color of the plants, G,Y,GY,F, (G-green, Y-yellow, GY- greenish-yellow, F-flowering) include periodical test for Manganese performed in the treatment plant laboratory for effluent water.                 

 

Influent water, metal loadings on average in mg/l:

Cadmium                0.0061  to  0.0067

Iron                             0.96  to  1.05

Manganese                 0.63  to  0.70

Zinc                              2.1  to  2.2                                                                                                                          

Laboratory report # 5

By: Barringer Laboratories, Inc., Work Order No. 0102094, Date: February 12, 2001 This is the part of final test run in this study. All water run through the test sections contained Indian mustard plant species, in three repetitions each. The pH of influent water has been modified, fertilizer applied.

All in (mg/l)

Sample I.D. # 1a Aqueous  (Influent) to the system  (pH=6.09) 

Cd, total          0.0061                                

Fe, total           0.96                                     

Mn, total          0.63                                    

0.Zn, total        2.1                                      

Sample # 2a, Aqueous  (Effluent), trough system A  (pH=6.08)         Metal loadings in (%)

Cd                  0.011                                                                                Increased 80.32 %    

Fe                   0.18                                                                                  Removed 81.25 %   

Mn                  0.68                                                                                 Increased 7.93 %     

Zn                    3.0                                                                                  Increased 42.85 %  

Sample # 3a, Aqueous (Effluent), trough system B  (pH=6.37)

Cd                0.0                                                                                      Removed 100 %

Fe                 ND  (Not detected at the reporting limits)                                         Removed 100 %  

Mn                0.71                                                                                   Increased 12.69 %

Zn                 3.4                                                                                     Increased 61.90 %

Sample # 4a, Aqueous (Effluent), through system C  (pH=6.73)

Cd                0.0072                                                                                Increased 18.03 %

Fe                 ND                                                                                     Removed 100 %

Mn                0.65                                                                                   Increased 3.17 %

Zn                 2.8                                                                                     Increased 33.33 %

Note: Do to poor performance of the system at the beginning of the final test, we have decided to cascade the effluent water into next set of troughs to see if any changes will be seen. Water which run through first section was channeled into to second and third section (in series). Results show that some metal loadings being higher at the effluent than influent.  This problem we did not have on previous two tests, which we run for more than a year, possibly, because we did not changed the pH of influent water. It has been determined that by modifying the influent water (pH) a transformation of the dissolved metals into suspended metals, in the influent water has acured. Therefore the root system could not uptake the suspended metals which then passed through, affecting the laboratory results.

(Note: Laboratory report # 5). 

Conclusion: 

Phytoremediation technology is a potential solution for many application, not only for the decontamination of polluted streams and soil from mining sides or industrial sides, but it may also prove to be efficient method for production of quality food for human or animal consumption.

Decontamination of large areas of soil contaminated by heavy metals and or radioactive elements, with traditional chemical treatment or vitrification or removal and shipment of soil to hazardous waste sites, may be very costly. Phytoremediation technology can provide an economically feasible solution. Underground greenhouses can be used for food production in areas otherwise not suitable such as desert or artic. This technology could also be used to provide shelter and food production in space exploration.

 

 

 Frank Burcik

 

President, 

(WTDI)

 

Supporting Document:

Letters from;

Elizabeth Pilon-Smits PhD, CSU professor. Department of Biology

Duane Johnson PhD, Former CSU professor, Presently Montana State University professor. Department of Soil and Crop science.

Brooks Kelly PhD, Molecular Biologist.