Bench-Scale Testing of Virotec
TM
Media for the
Treatment of Acid Mine Drainage and Hydraulic
Fracturing Wastewaters
GAI Project Number: C111194.00
March 2012
Prepared for: Virotec Europe Ltd.
Spencer House, Market Lane
Swalwell, Tyne & Wear NE16 3DS
United Kingdom
Prepared by: GAI Consultants, Inc.
Pittsburgh Office
385 East Waterfront Drive
Homestead, Pennsylvania 15120-5005Use of Virotec
TM
Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
i
Table of Contents
Abstract...................................................................................................................................... 1
1.0 Introduction to Virotec...................................................................................................... 1
1.1 Potential Application for Virotec's Media - Acid Mine Drainage ........................... 1
1.2 Potential Application for Virotec's Media - Hydraulic Fracturing Wastewaters ..... 2
2.0 Statement of Purpose...................................................................................................... 2
3.0 Description of Test Protocol............................................................................................. 3
3.1 AMD Water ......................................................................................................... 3
3.2 Flowback Water and Produced Water................................................................. 4
4.0 Presentation of Findings.................................................................................................. 5
4.1 AMD Water - Treated Effluent............................................................................. 5
4.2 DI Water Control Samples .................................................................................. 8
4.3 AMD Water - Sludge........................................................................................... 8
4.4 Flowback and Produced Water ........................................................................... 9
5.0 Summary and Conclusions.............................................................................................11
6.0 Recommendations .........................................................................................................12
7.0 Acknowledgments ..........................................................................................................12
8.0 Limitations ......................................................................................................................12
9.0 References.....................................................................................................................12
Tables
Table 3.1 - Virotec media dosage and mixing time matrix for AMD water samples.
Table 3.2 - Control sample schedule for AMD water sample experiments.
Table 3.3 - Virotec media, hydrated lime and hydrogen peroxide dosage and mixing
time matrix for frac water samples.
Table 4.1 - Acidity, alkalinity and soluble heavy metals in the AMD water before and
after treatment with Virotec's treatment media. Results for treated
samples represent average values from triplicates.
Table 4.2 - Pennsylvania effluent limits for waters associated with an area disturbed
by coal mining activities - dry weather condition.
Table 4.3 - DI water control samples before and after "treatment" with
Virotec's media.Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
ii
Table 4.4 - Toxicity characteristics of the spent Virotec treatment media from treated
AMD water samples and DI water controls.
Table 4.5 - Soluble heavy metals in the Flowback water before and after treatment with
Virotec's media.
Table 4.6 - Soluble heavy metals in the Flowback water before and after treatment
with Virotec's media and Hydrated Lime.
Table 4.7 - Soluble heavy metals in the Produced water before and after treatment
with Virotec's media.
Table 4.8 - Soluble heavy metals in the Produced water before and after treatment with
Virotec's media and Hydrated Lime.
Figures
Figure 3.1 - Bench-scale set up of the AMD water treatment with Virotec's treatment
media.
Figure 4.1 - Dissolved iron, manganese and total suspended solids concentrations
and alkalinity and acidity levels for the raw, control and treated AMD
samples. Results for treated samples represent average values from
triplicates. Standard deviation from the mean is indicated where
applicable.
Appendices
Appendix A - Laboratory Bench-Scale Test Protocol
Appendix B - Parameters of Analysis for All Aqueous and Sludge Samples
Appendix C - Preliminary AMD Treatment Results
Appendix D - Initial Analytical Results for the Flowback and Produced Water Samples
Appendix E - Laboratory Results for Treated AMD Water Samples
Appendix F - Preliminary Flowback and Produced Water Treatment Results
11119400-bstr-rpt-mtk/tbv d-1Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
1
Abstract
A bench-scale treatment study was completed to assess and evaluate the performance and
potential applicability of Virotec Global Solutions’ proprietary media to the treatment of
mining-related discharges and wastewaters generated during the hydraulic fracturing (“fracking”)
gas extraction process. Acid mine drainage (AMD) and frac water samples (Flowback and
Produced water) were treated with Virotec’s proprietary treatment media. Aqueous and sludge
samples were analyzed for a list of key parameters to assess effectiveness of constituent
reduction and establish the waste characteristics of the spent media. Virotec's media effectively
reduced the concentrations of common AMD constituents, such as iron and manganese, in
many cases to below the detection limit of the laboratory analysis method. Initial testing of the
Virotec media as a treatment alternative for frac waters may indicate limited applicability but
potential use as a pretreatment or polishing step in conjunction with other treatment technology
should be investigated.
1.0 Introduction to Virotec
Virotec Global Solutions Pty Ltd., (Virotec) is an international environmental services company
that specializes in providing unique, high quality environmental remediation and waste treatment
services to a wide range of corporations across a variety of industries. Virotec, based in
Queensland, Australia, began operations in 2000. Prior to that time, Virotec was a mining
company, Tin Australia Ltd, with mining and lease interests in Queensland and New South
Wales.
Following the successful treatment of one of its tailings dams using newly trialled technology
derived from caustic alumina refinery residues (ARR) in 1999-2000, Virotec focused its efforts
on researching, developing and commercializing the technology, which initially centered on the
treatment of mining wastewater. Since then, Virotec has become a leader in delivering
effective, sustainable solutions to environmental remediation and waste treatment problems.
The proven, patented, state-of-the-art technologies developed by Virotec enable companies and
public utilities to meet government regulatory waste treatment standards, reduce future
liabilities, and help safeguard the environment.
Virotec’s technologies benefit many different industries, including mining and metals processing,
the oil and gas sector, metals finishing and other manufacturing industries, municipal sewage
treatment, property development and marine dredging, and timber preservation. Virotec’s
products and services have gained regulatory approval in the USA, Korea, UK, Italy, Portugal,
Laos, the Philippines, New Zealand and Australia.
Currently, Virotec is interested in expanding their sales market in the United States. In
particular, Virotec desires to identify potential applications for their treatment media to
mining-related discharges as well as in the treatment of wastes generated in the rapidly
developing shale oil and gas industry. Furthermore, Virotec is interested in pursuing regulatory
certification/approval for the use of their treatment media in the state of Pennsylvania (PA).
1.1 Potential Application for Virotec's Media - Acid Mine Drainage
In PA, AMD from abandoned underground mines, surface mines and coal refuse piles is the
greatest source of freshwater pollution, responsible for an estimated 2,400 miles of polluted
streams. A majority of these mines were abandoned prior to the 1964 amendment of the Clean
Streams Law that requires mine operators maintain the levels of key constituents in their
discharges within acceptable limits. Today, active mine operators are typically required to treat
their wastewaters prior to discharge in order to meet regulatory water quality limits, whereas the Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
2
PA Bureau of Abandoned Mine Reclamation (BAMR) is responsible for spearheading projects
related to treating AMD at abandoned mine sites. As such, the State presents a potentially
sizable market for Virotec's wastewater treatment products.
1.2 Potential Application for Virotec's Media - Hydraulic Fracturing
Wastewaters
Recent advancements in hydraulic fracturing ("fracking"), a method employed to extract oil and
natural gas from within deep shale formations, have caused an economic boom in the Marcellus
Shale gas extraction market. The fracking process involves the injection of a highly-pressurized
fluid, consisting primarily of sand and water (98 percent to 99.5 percent) and a small percentage
of chemical additives, into the rock formation to create new fissures and liberate the trapped
natural gas. In a typical fracking process, approximately 10-40 percent of the fluid is recovered
as a highly saline/brine solution with total dissolved solids (TDS) concentration of up to ten
times that of sea water. An estimated total of 4.5 to five million gallons of water are required per
well to complete the gas extraction, resulting in the need for treatment/disposal of roughly one
half to two million of gallons of brine water per well.
The treatment and/or disposal of this waste stream presents a unique challenge to the well
operator, since current long-term alternatives are either energy intensive (evaporationcrystallization) or geographically limited (deep-well injection). Furthermore, future regulatory
guidelines for the shale gas industry are expected to intensify. As a result, novel methods of
wastewater treatment are continually sought out. The Marcellus Shale formation extends
throughout much of the Appalachian Basin, spanning New York, Ohio, PA and West Virginia. In
PA alone, over 3,500 Marcellus Shale Drilling Permits were issued by the Department of
Environmental Protection in 2011 and over 400 in the first month of 2012. With hundreds of
new wells being developed in the region and millions of gallons of wastewater generated each
day, the shale oil and gas industry presents a potentially substantial market for Virotec's
wastewater treatment products.
2.0 Statement of Purpose
The purpose of this study was to generate results and allow an independent, third party
representative to evaluate the performance and applicability of Virotec's proprietary treatment
media to the treatment of wastewaters generated in the emerging oil and shale gas market as
well as mining-related discharges throughout the 'Appalachian Region'. In addition, the study
attempted to determine the waste characterization properties of the spent media and evaluate
the potential recycle/ reuse of the material as an aggregate substance for roadbed construction
or other beneficial use.
GAI Consultants, Inc. (GAI) of Pittsburgh, PA was contracted by Virotec Europe Ltd, to: develop
a bench-scale laboratory test protocol for the evaluation of Virotec's treatment media and its
effectiveness at reducing constituents of concern from wastewaters; to compare the cost of
Virotec's treatment media to current chemical and/or physical treatment methods utilized for
similar wastewaters; and to present the findings in a summary report. GAI was not a proponent
of the treatment media during the development of the test procedure and regards application of
the procedure to Virotec's treatment media to be with full and due respect of process and the
scientific method. GAI's test protocol could be applied to other available treatment products
intended to be employed in the same manner as Virotec's proprietary media. Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
3
3.0 Description of Test Protocol
The bench-scale test protocol was developed by GAI in cooperation with Virotec and
implemented by Pace Analytical Services, Inc. (Pace) of Greensburg, PA which is a state
certified laboratory. AMD water samples were provided from a discharge at a facility located in
Greene County, PA by a regional mining company. Two 'frac water' samples were supplied by
an independent oil and gas exploration and production company from a Marcellus Shale drilling
operation located in the southwestern PA region. Flowback Water represented typical water
produced as a result of hydraulic fracturing (fracking) during the development of a natural gas
well in shale plays, where as Produced Water consisted of brine water that returns to the
surface during gas production. All samples in the study were processed at ambient
temperatures present in a controlled laboratory environment and experiments involving different
waters and varying treatment conditions were carried out at different times to minimize the
potential for cross-contamination of spent media and water samples. The complete test
protocol is included as Appendix A.
3.1 AMD Water
AMD water samples were delivered to Pace and analyzed for a list of parameters provided in
Appendix B. The results of the analysis, (Appendix C) were reviewed by Virotec, who in turn
provided input regarding the recommended treatment media dosage and contact time to be
implemented in the bench-scale study. Once the treatment media requirements were
established, 1,500 milliliter (mL) of AMD water sample was transferred into a 2,000 mL beaker,
set on a stir plate and stirred using a magnetic stir bar. The treatment media was weighed
using a digital scale and added to the AMD sample at a dose of five grams of media per liter of
AMD water (5 g/L). The slurry was stirred for 120 minutes and the pH was monitored
periodically throughout the duration of the mixing process. The bench-scale set up of the
process is shown in Figure 3.1. After the elapsed time, the slurry was allowed to settle until the
solid and aqueous phases separated, approximately 30 minutes.
Figure 3.1. Bench-scale set up of the AMD water treatment with Virotec's treatment
media.
Following the settling period, the supernatant was decanted and aqueous samples were
collected, filtered and analyzed for parameters listed in Appendix B. Spent treatment media
was rinsed with deionized (DI) water, dewatered using a vacuum filter apparatus, collected and
analyzed using the Total Characteristic Leaching Procedure (TCLP) for constituents outlined in Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
4
Appendix B. The above procedure was repeated varying the mixing (contact) time and the dose
of the treatment media according to the matrix shown in Table 3.1.
Table 3.1 Virotec media dosage and mixing time matrix for AMD water samples.
Sample ID Virotec Media Dose (g/L) Mixing Time (min)
AMD+5+120 5 120
AMD+10+90 10 90
AMD+10+120 10 120
All AMD water tests were conducted in triplicate. In addition, four control samples were carried
out during the AMD bench scale study; a blank sample consisting of DI water only, two treated
blank samples containing DI water and varying amounts of the treatment media and a sample
containing only raw AMD water. These are summarized in the Table 3.2, below.
Table 3.2 Control sample schedule for AMD water sample experiments.
Control Sample ID Matrix Virotec Media Dose (g/L) Mixing Time (min)
DI DI water None 120
DI+5 DI water 5 120
DI+10 DI water 10 120
AMD Control AMD water None 120
3.2 Flowback Water and Produced Water
Flowback and Produced water samples were delivered to Pace and analzyed for a list of
parameters provided in Appendix B. The results of the analysis, (Appendix D) were reviewed by
Virotec and upon review, Virotec conducted preliminary tests on the two frac waters to identify
the most promising blend composition of their confidential media, the dosage and contact time
that could be used in the full-scale bench study.
Virotec's media was added to Flowback and Produced water samples per the procedure
outlined in Section 3.1. Following Virotec's media addition, lime [Ca(OH)2] was added to some
samples in order to quickly raise the effluent pH. Previous AMD work conducted by Virotec has
shown that more caustic media blends improved the removal efficiencies of the strontium metal
(Sr). Hydrogen peroxide (H2O2) was added as a pre-treatment stage to four water samples in
order to break any potential complexed/chelated metal bonds and make them available for
reaction with Virotec's media. The water samples were dosed and mixed as shown in Table 3.3.Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
5
Table 3.3 Virotec media, hydrated lime and hydrogen peroxide dosage and mixing time
matrix for frac water samples.
Sample ID
Virotec Media
Dose (g/L)
Lime
Dose?
H2O2
Pre-treatment?
Mixing
Time (min)
Flowback Water
FBW+10+60 10 N/A No 60
FBW+10+120 10 N/A No 120
FBW+50+60 50 N/A No 60
FBW+50+120 50 N/A No 120
FBW-50+240 50 N/A No 240
FBW+LIME+60 50 Yes No 60
FBW+ H2O2 50 N/A Yes N/A
Produced Water
PW+50+60 50 N/A No 60
PW+50+120 50 N/A No 120
PW+50+240 50 N/A No 240
PW+LIME+60 50 Yes No 60
PW+LIME+60+H2O2 50 Yes Yes 60
PW+LIME+165+H2O2 50 Yes Yes 165
PW+LIME+240+H2O2 50 Yes Yes 240
After the elapsed time, the slurry was allowed to settle until the solid and aqueous phases
separated, at which point aqueous samples were collected and analyzed for dissolved metals
concentrations shown in Appendix B. No sludge analysis was conducted on the solid samples.
4.0 Presentation of Findings
4.1 AMD Water - Treated Effluent
Full results from the AMD water treatment trials are available as Appendix E; a summarized
version of the data for key aqueous parameters of interest is shown in Table 4.1. As can be seen
from the results, Virotec's media was effective at reducing the concentrations of key heavy metals
and total acidity, in many cases below the detection limit. At the same time, the alkalinity and pH
of the water was increased. Effective treatment was achieved even at the lowest Virotec media
dose of only five grams of media per one liter of AMD sample.
It is interesting to note, that the aluminum, lead and zinc concentrations as well as the alkalinity
level were each over 30 percent lower in the AMD Control sample than in the AMD Raw
sample. Similar result was also observed for sample turbidity (see Appendix E). It is possible Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
6
that sample stirring provided aeration and caused metal precipitation. The difference in the data
could also result from laboratory equipment/sensor tolerance, in particular for the low
concentration metals.
Table 4.1. Acidity, alkalinity and soluble heavy metals in the AMD water before and after
treatment with Virotec's treatment media. Results for treated samples represent average
values from triplicates.
Parameter
Raw
AMD
AMD
Control
AMD+5+120 AMD+10+90 AMD+10+120
pH 6.5 6.7 8.75 8.63 8.86
Total Acidity (mg/L as
CaCO3)
250 230 < 10 < 10 < 10
Total Alkalinity (mg/L as
CaCO3)
630 386 529 697 600
Aluminum (µg/L) 268 < 50.0 88.2 71.5 79.9
Arsenic (µg/L) 12.5 11.2 < 5.0 < 5.0 < 5.0
Iron (µg/L) 470,000 360,000 < 70 < 70 < 70
Lead (µg/L) 20.2 5.4 < 5.0 < 5.0 < 5.0
Manganese (µg/L) 4,200 4,290 746 777 39.9
Nickel (µg/L) 26 22.6 < 10.0 < 10.0 < 10.0
Zinc (µg/L) 20.7 12.7 < 10.0 < 10.0 <10.0
Under Title 25, Chapter 87 of The PA Code, Section 87.102 sets effluent criteria and limitations for
waters associated with an area disturbed by coal mining activities. Effluent limits during dry
weather conditions, as per Section 87.102(a) and (b)(1), are shown in Table 4.2
Table 4.2 PA effluent limits for waters associated with an area disturbed by coal mining
activities - dry weather condition.
Parameter
30-Day Average
(mg/L)
Daily Maximum
(mg/L)
Instantaneous
Maximum (mg/L)
Total Iron 3.0 6.0 7.0
Total Manganese 2.0 4.0 5.0
Suspended Solids 35 70 90
pH Greater than 6.0; less than 9.0 - applicable at all times
Alkalinity greater than acidity (Alk > Acy) - applicable at all timesUse of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
7
Graphical representation of the dissolved metal concentration for iron, manganese and
suspended solids, as well as the alkalinity and acidity for the raw, control and treated AMD
samples is shown in Figure 4.1. For the treated samples, the result represents the average
concentration from triplicates and the error bars represent the standard deviation from the
mean. In the instances where the average concentration was below the limit of detection, half
of the detection limit was used to represent the concentration of the constituent in the sample.
The detection limit for each constituent is indicated on the figure.
Figure 4.1 also compares the concentrations of metals and suspended solids to the strictest
regulatory limit as presented in Table 4.2. The regulations stipulate a limit for total iron and
manganese concentrations; treated AMD samples were filtered prior to analysis in order to
exclude any suspended treatment media from the analysis and to simulate anticipated large
scale application of this technology. All treated samples exhibited dissolved iron, manganese
and total suspended solids concentrations below the regulatory limits. Manganese removal
effectiveness appears to improve with increased sample mixing time. The pH of the treated
samples increased but remained within the acceptable range of 6.0 to 9.0. Overall, Virotec's
treatment media appears to be a promising treatment technology for effectively reducing the
concentrations of common AMD pollutants and improving the water quality.
Figure 4.1 Dissolved iron, manganese and total suspended solids concentrations and
alkalinity and acidity levels for the raw, control and treated AMD samples. Results for
treated samples represent average values from triplicates. Standard deviation from the
mean is indicated where applicable.
1
10
100
1,000
10,000
100,000
1,000,000
AMD RAW AMD CONTROL AMD+5+120 AMD+10+90 AMD+10+120
Dissolved Iron Concentration (µg/L)
Iron Concentration
PA Regulatory Limit
Detection Limit
1
10
100
1,000
10,000
AMD RAW AMD CONTROL AMD+5+120 AMD+10+90 AMD+10+120
Dissolved Manganese Concentration (µg/L)
Manganese Concentration Detection Limit PA Regulatory Limit
1
10
100
1,000
AMD RAW AMD CONTROL AMD+5+120 AMD+10+90 AMD+10+120
Total Suspended Solids Concentration (mg/L)
TSS Concentration Detection Limit PA Regulatory Limit
1
10
100
1,000
AMD RAW AMD CONTROL AMD+5+120 AMD+10+90 AMD+10+120
Acidity and Alkalinity Concentration as CaCO3 (mg/L)
Total Acidity Total Alkalinity Detection Limit Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
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4.2 DI Water Control Samples
Complete results for the DI water control samples are presented in Appendix E; a summary of
the data for parameters that exhibited changes between the "blank control" (DI water only) and
"treated controls" (DI water + media) is shown in Table 4.3.
Table 4.3 DI water control samples before and after "treatment" with Virotec's media.
Parameter DI DI+5 DI+10 Mixing Time (min)
pH 9.2 10.4 10.4 120
Total Acidity (mg/L as CaCO3) < 10.0 60 58 120
Total Hardness (mg/L) < 2.1 49 24.4 120
Aluminum (µg/L) < 50.0 < 50.0 105 120
Bromide (mg/L) < 0.062 < 0.062 0.11 120
Calcium (µg/L) < 500 6,140 5,690 120
Chloride (mg/L) < 3.0 < 3.0 7 120
Iron (µg/L) 231 < 70.0 < 70.0 120
Parameter DI DI+5 DI+10 Mixing Time (min)
Magnesium (µg/L) < 200 8,180 2,470 120
Sodium (µg/L) 3,160 9,070 22,600 120
Vanadium (µg/L) < 5.0 36.8 68.8 120
Of the parameters listed above, the greatest increases were observed in calcium, magnesium,
sodium and vanadium concentrations in both of the treated controls. Despite relatively large
increases when compared to the DI only sample, typically the concentrations of these metals
are expected to be significantly greater in wastewaters that would benefit from treatment with
Virotec's media. As such, the contribution of these ions from the media to the bulk-solution
concentration would likely be negligible. Where removal of these constituents is of particular
interest or importance, Virotec's media could be used in conjunction with other chemical
treatment methods.
4.3 AMD Water - Sludge
The analytical TCLP results for sludge generated during the AMD water treatment trial for the
three AMD samples, as well as the DI water controls are summarized in Table 4.4. The results
for spent media generated during AMD water sample treatment represent an average from
triplicates. The TCLP analysis was performed to establish the waste characteristics of the spent
media. The results are compared to the toxicity characteristics for the Characterization of
Hazardous Waste as specified in 40 CFR 261.24. Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
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Table 4.4 Toxicity characteristics of the spent Virotec treatment media from treated AMD
water samples and DI water controls. Results for treated samples represent average
values from triplicates.
Parameter
RAW
AMD
(LIQUID)
DI+5
(SOLID)
DI+10
(SOLID)
AMD+5+120
(SOLID)
AMD+10+90
(SOLID)
AMD+10+120
(SOLID)
Regulatory
Level
(mg/L)
1
Arsenic (mg/L) 0.0125 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 5.0
Barium (mg/L) 0.0101 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 100.0
Cadmium (mg/L) < 0.003 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 1.0
Chromium
(mg/L)
< 0.005 < 0.050 < 0.050 0.12 0.11 < 0.073 5.0
Lead (mg/L) 0.0202 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 5.0
Mercury (mg/L) < 0.0002 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 0.2
Selenium (mg/L) < 0.008 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 1.0
Silver (mg/L) < 0.006 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 5.0
From the TCLP results, it appears that the sludge generated in the treatment process is capable
of effectively immobilizing the metals into an insoluble, non-reactive precipitate. It should be
noted, however, that the concentration of these metals in the raw AMD sample was relatively
low and, in many instances, below the detection limit. As such, it is difficult to assess the
toxicity characteristics of the spent media based on the eight metals listed above, as many of
them do not appear to have been present in the initial water sample, and thus would not be
present in the spent media. Additional experiments conducted with a highly acidic and heavy
metal-laden AMD discharge are required, in order to assess the toxicity characteristics of the
spent media as per the above criteria.
4.4 Flowback and Produced Water
The results of the analysis on the raw frac waters are provided in Appendix F. Initial testing of
the Virotec media as a treatment alternative for frac water produced marginal results. Overall,
the Virotec media performed similarly when used alone or in conjunction with lime and/or
hydrogen peroxide for all tested mixing times. Lime addition, however, did improve the removal
of magnesium (Mg) which most likely precipitated as magnesium hydroxide (Mg(OH)2). An
example of some of the results of the laboratory testing is provided in the Table 4.5 and Table
4.6 for Flowback water and Table 4.7 and Table 4.8 for Produced water, below.
1
Code of Federal Regulations - Title 40: Protection of Environment, Part 261: Identification and Listing of Hazardous Waste.Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
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Table 4.5 Soluble heavy metals in the Flowback water before and after treatment with
Virotec's media.
Table 4.6 Soluble heavy metals in the Flowback water before and after treatment with
Virotec's media and Hydrated Lime.
Table 4.7 Soluble heavy metals in the Produced water before and after treatment with
Virotec'smedia.
Parameter
Raw
Produced
PW+50+60 PW+50+120 PW+50+240
pH 5.39 8.7 8.75 8.75
Iron (mg/L) 90 0.2 0 0
Magnesium (mg/L) 2395 2512 2534 2580
Manganese (mg/L) 16 0.2 0 0.05
Silica (mg/L) 9 0.9 0.4 0.3
Parameter
Raw
Flowback
FBW+10+60 FBW+10+120 FBW+50+60 FBW+50+120 FBW+50+240
pH 4.90 8.40 8.40 8.91 9.00 8.9
Iron (mg/L) 100 4 4 1 1 0.4
Magnesium
(mg/L)
1,975 2,114 2,082 2,054 2,096 2,109
Manganese
(mg/L)
22 11 1 0.06 0.01 0.03
Silica (mg/L) 10 3 2 1 1 0.9
Parameter Raw Flowback Water FBW+Lime+60
pH 4.85 10.4
Iron (mg/L) 65 0.3
Magnesium (mg/L) 1891 111.5
Manganese (mg/L) 22 0.3
Silica (mg/L) 2 0Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
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Table 4.8 Soluble heavy metals in the Produced water before and after treatment with
Virotec's media and Hydrated Lime.
Parameter Raw Produced PW+Lime+60
pH 5.36 10.4
Iron (mg/L) 72 0.3
Magnesium (mg/L) 2,346 48
Manganese (mg/L) 16 0.03
Silica (mg/L) 2 0
The application of Virotec media may be beneficial to the natural gas industry. Development of
a natural gas well requires a significant volume of water. The cost of conveying water to the
well site and environmental concerns regarding water withdrawal and usage has caused gas
producers to look for innovative ways to reduce their water demand. One common practice is to
reuse flowback and produced water to develop new wells. There are limits to the water quality
that can be reused due to negative effects of certain contaminants on the production and yield
of a well.
Virotec media reduces metal concentrations that are typically present in flowback and produced
waters. These metals reduce productivity if injected back into a well. Reduction in these
metals could potentially increase the number of times that water could be recycled by the user.
Additionally, Virotec media could be utilized to complement another treatment technology as a
pretreatment or polishing step. If cost effective, AMD waters treated with Virotec’s media could
also be used as source water for fracking operations if fresh water supplies are limited or
unavailable near the well site.
5.0 Summary and Conclusions
Mining-related discharges and wastewaters generated by hydraulic fracturing during natural gas
extraction present a potential sales market for Virotec and its novel treatment technologies. In
order to evaluate the performance and applicability of Virotec’s proprietary treatment media to
these industries, a bench-scale treatment study was carried out. An AMD water sample and
two frac water samples (Flowback and Produced water) were treated with Virotec’s proprietary
treatment media. Aqueous and sludge samples were analyzed for a list of key constituents to
assess effectiveness of pollutant reduction and establish the waste characteristics of the spent
media.
Based on the observed results, the following conclusions can be drawn:
1. Virotec's media appears to be a promising treatment technology for effectively
reducing the concentrations of common AMD pollutants and improving the water
quality. Virotec's media was effective at reducing the concentrations of key metals,
such as iron and manganese as well as total acidity, in many cases below the detection
limit.
2. Low concentrations of eight metals (As, Ba, Cd, Cr, Pb, Hg, Se, Ag) in the raw
AMD water sample did not allow for an adequate evaluation of toxicity
characteristics of the spent media. Sludge generated during AMD water sample
treatment exhibited low toxicity characteristics for the eight metals analyzed. This, Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
12
however, is due to the fact that many of the metals were not detected in the initial AMD
water sample, and thus were potentially only present in the spent media at extremely low
levels.
3. Initial testing of the Virotec media as a treatment alternative for frac waters
appears to suggest limited applicability. Virotec’s media reduces concentrations of
metals that are typically present in flowback and produced waters and could be used in
conjunction with another treatment technology as a pretreatment or polishing step.
6.0 Recommendations
In order to further evaluate the applicability of Virotec’s media for the treatment of AMD and frac
wastewaters, the following recommendations are proposed:
1. Repeat the treatability study using a highly acidic and heavy metal-laden AMD
discharge in order to assess the toxicity characteristics of the spent media as per the
criteria set forth is this test protocol.
2. Carry out a pilot-scale study for the treatment of AMD wastewaters to confirm the results
observed in the bench-scale experiments and identify optimal mixing times and dosages
of the Virotec media, as well as explore the potential of spent media recycling/reuse for
additional AMD treatment.
3. Investigate the potential for use of the Virotec media in conjunction with another
chemical and/or physical treatment application for the treatment of frac waters.
7.0 Acknowledgments
GAI would like to acknowledge Pace Analytical Services, Inc. of Greensburg, PA for their
assistance during the test protocol development.
8.0 Limitations
The findings of this study are based on GAI’s professional judgment of the treatment study
results as discernible from the limited, and often indirect, information provided by others and
obtained or observed by GAI using the methods specified. GAI does not warrant the accuracy
or completeness of information provided or developed by others and assumes no responsibility
for documenting conditions detectable with methods or techniques not specified in the scope of
work. If additional data concerning this study becomes available, such information should be
provided to GAI so that our interpretation of the results can be reviewed and modified as
necessary.
9.0 References
Chesapeake Energy, "Hydraulic Fracturing Facts - Water Usage",
http://www.hydraulicfracturing.com/Water-Usage/Pages/Information, Date Accessed:
February 15, 2012.
Fergusson, Lee, "Virotec - A Ten-Year Story of Success in Environmental Remediation", Prana
World Publishing, Oxenford, Australia, 2010.
PA Department of Environmental Protection Office of Mineral Resources Management, Bureau
of District Mining Operations. " Evaluation of Mining Permits Resulting In Acid Mine
Drainage1987-1996: A Post Mortem Study",
http://www.dep.state.pa.us/dep/deputate/minres/districts/amdpostmortem.htm, Date
Accessed: February 9, 2012.Use of VirotecTM Treatment Media for the Treatment of Acid Mine Drainage and Hydraulic Fracturing
Wastewaters- Bench Scale Testing Results
13
PA Department of Environmental Protection, "Marcellus Shale - Permits Issued-Wells Drilled
Maps", http://www.portal.state.pa.us/portal/server.pt/community/marcellus_shale/20296,
Date Accessed: February 14, 2012.
Skousen, J.G., et. al., "Acid Mine Drainage Control and Treatment", West Virginia University,
Morgantown, WV, http://www.wvu.edu/~agexten/landrec/Chap6.pdf, Date Accessed:
February 16, 2012.
Skousen, J.G., et. al., "Overview of Acid Mine Drainage Treatment with Chemicals", West
Virginia University, Morgantown, WV, http://www.wvu.edu/~agexten/landrec/chemtrt.htm,
Date Accessed: February 16, 2012.
U.S. Department of Energy, "Modern Shale Gas Development in the United States - Hydraulic
Fracturing Fluids Composition and Additives", http://geology.com/energy/hydraulicfracturing-fluids, Date Accessed: February 14, 2012.
US Inflation Calculator, http://www.usinflationcalculator.com/, Date Accessed: February 13,
2012.APPENDIX A
LABORATORY BENCH-SCALE TEST PROTOCOL Proposed Bench-Scale Procedure
This procedure was developed in cooperation with Virotec International (Virotec), GAI Consultants, Inc.
(GAI), and Pace Analytical Services, Inc. (Pace). The procedure is intended to provide results to allow an
independent, 3
rd
party representative to determine the performance and suitability of an emerging
treatment media for application to a selected water treatment need of interest by others. The author of
this procedure, GAI Consultants, Inc., was not an advocate or proponent of the treatment media during
development of the procedure and regards application of the procedure to the confidential Virotec media
to be with full and due respect of process and scientific principles. The procedure below would be applied
to other available media intended to be employed in the same manner as Virotec’s confidential treatment
media. In addition, the procedure will attempt to determine the waste characterization properties of used
treatment media.
Background
Virotec desires to identify applications for use of their confidential treatment media to the emerging oil and
gas industry and mining-related discharges throughout the ‘Appalachian Region’. In particular, the use of
abundant volumes of water for exploration and production purposes as well as incidentally produced water
during the extraction of natural gas and oil resources may be suitable options for application of Virotec’s
treatment media. As such, GAI has been provided ‘frac water’ samples from Range Resources, Inc. that
represent typical water produced as a result of hydraulic fracturing during the development of a natural gas
well in shale plays (Flowback Water) and for commonly produced brine water that returns to the surface
during production (Produced Water). For the mine discharge sample, Rosebud Mining, Inc. has supplied a
sample of acid mine drainage (AMD) water from a discharge at one of their facilities.
Performance Protocol
The protocol will involve the analysis of ‘frac water’ samples (one flowback water sample and one produced
water sample) and an AMD water sample before and after treatment. In addition, each sample analysis will
be processed in triplicate to provide statistical ranges and deviations from a mean. Therefore, forty-five
(45) water samples are anticipated for analysis. Samples will be processed at ambient temperatures in a
controlled laboratory at the time of processing and will occur at separate times to minimize the potential
for cross-contamination of water samples and spent media. The following equipment is considered
necessary for the bench-scale procedure:
1) Bench top pH Meter
2) 2 liter glass beakers (6)
3) Magnetic stirrers and stirring bars
4) Electronic balance (accurate to 1/100 of a gram)
5) Buchner vacuum flasks
6) GF/A filter papers
7) Deionized Water The general procedure for sample processing will be as follows:
1. A 1,500 mL sample of water from each source will be analyzed for the list of constituents provided
in Appendix A. The results of the analysis will be provided to Virotec for input regarding the
recommended volume of media and duration of testing to be used in the bench-scale study.
2. The quantity of Virotec media specified by Virotec in Step #1 above will be weighed using
laboratory equipment, added to the water sample, stirred in a two (2) liter beaker using a magnetic
stirring bar.
3. The pH of the treated water sample will be periodically checked with a pH meter supplied by the
laboratory.
4. The water sample will be mixed, per the guidance of Virotec, and then solid particles will be
allowed to settle until a separated, identifiable supernatant can be acquired for analysis of the
constituents provided in Appendix A.
5. The procedure will be repeated two additional times (for a total of three runs per water source)
with alternative doses of Virotec media (as recommended by Virotec).
Waste Management Protocol
The protocol will involve the analysis of the treatment Media before and after treatment in triplicate, for a
total of thirty (30) samples given the three (3) types of samples provided. A single sample of the media
before application will be analyzed and a sample of the media after the application of the performance
protocol provided above for each sample source will be processed for the parameters provided in Appendix
A that have an applicable Toxicity Characteristic Leaching Procedure.
Procedure Controls
The following “controls” will be applied during the bench-scale study:
1. A “Blank Sample” consisting of de-ionized water will be processed according to the Performance
Protocol to determine changes to water quality caused by environmental conditions in the
laboratory.
2. A “Treated Blank Sample” consisting of a representative blend of deionized water and the Virotec
media will be prepared and processed in the same manner as the test samples to determine
changes to water quality caused by the media.
3. A “Control Sample” will be prepared consisting of the wastewater only and processed in the same
manner as the test samples to determine changes to water quality caused by the process alone.
APPENDIX A
Acidity (as CaCO3) 50 mL
Alkalinity (as CaCO3) Same aliquot as Acidity
Bromide 25 mL
Chloride 30 mL
Conductivity 25 mL
Dissolved Metals: 50 mL (ICP)
Aluminum (Al)
Antimony (Sb)
Arsenic (As) TCLP RCRA 8
Barium (Ba) TCLP RCRA 8
Beryllium (Be)
Cadmium (Cd) TCLP RCRA 8
Calcium (Ca)
Chromium (Cr) TCLP RCRA 8
Cobalt (Co)
Copper (Cu)
Iron (Fe)
Lead (Pb) TCLP RCRA 8
Magnesium (Mg)
Manganese (Mn)
Mercury (Hg) 50 mL TCLP RCRA 8
Nickel (Ni)
Potassium (K)
Selenium (Se) TCLP RCRA 8
Silver (Ag) TCLP RCRA 8 Sodium (Na)
Strontium (Sr)
Thallium (Tl)
Vanadium (V)
Zinc (Zn)
Gross Alpha 200 mL (could be much less
depending on TDS)
Could be used as screen for
Ra-226/228 and U
Gross Beta Same aliquot as Gross Alpha
Hardness Calculated from results of
other parameters
pH Same aliquot as Conductivity
Phosphates 150 mL
Phosphorus Same aliquot as Phosphates
Sulfate 10 mL
Surfactants (i.e. MBAs) 100 mL
Total Dissolved Solids 100 mL (could be much less
depending on conductivity)
Total Organic Carbon 40 mL
Total Suspended Solids 100 mL
Turbidity 50 mL APPENDIX B
PARAMETERS OF ANALYSIS FOR ALL AQUEOUS
AND SLUDGE SAMPLES Parameters of Analysis for Aqueous Samples
Parameter Volume Required (mL)
Acidity (as CaCO3) 50 mL
Alkalinity (as CaCO3) Same aliquot as Acidity
Bromide 25 mL
Chloride 30 mL
Conductivity 25 mL
Aluminum (Al)dissolved 50 mL
Antimony (Sb) dissolved 50 mL
Arsenic (As) dissolved 50 mL
Barium (Ba) dissolved 50 mL
Beryllium (Be) dissolved 50 mL
Cadmium (Cd) dissolved 50 mL
Calcium (Ca) dissolved 50 mL
Chromium (Cr) dissolved 50 mL
Cobalt (Co) dissolved 50 mL
Copper (Cu) dissolved 50 mL
Iron (Fe) dissolved 50 mL
Lead (Pb) dissolved 50 mL
Magnesium (Mg) dissolved 50 mL
Manganese (Mn) dissolved 50 mL
Mercury (Hg) dissolved 50 mL
Nickel (Ni) dissolved 50 mL
Potassium (K) dissolved 50 mL
Selenium (Se) dissolved 50 mL
Silver (Ag) dissolved 50 mL
Sodium (Na) dissolved 50 mL
Strontium (Sr) dissolved 50 mL
Thallium (Tl) dissolved 50 mL
Vanadium (V) dissolved 50 mL
Vanadium (V) dissolved 50 mL
Hardness Calculated from results of other parameters
pH Same aliquot as Conductivity
Phosphates 150 mL
Phosphorus Same aliquot as Phosphates
Sulfate 10 mL
Total Dissolved Solids (TDS) 100 mL (could be much less depending on conductivity)
Total Organic Carbon (TOC) 40 mL
Total Suspended Solids (TSS) 100 mL
Turbidity 50 mL
Gross Alpha* 200 mL (could be much less depending on TDS)
Gross Beta* Same aliquot as Gross Alpha
Surfactants (i.e. MBAs)* 100 mL
_________
* To be analyzed in frac water samples, only. Constituents of Analysis for All Solid Samples
Parameter Analysis
Arsenic (As) TCLP
Barium (Ba) TCLP
Cadmium (Cd) TCLP
Chromium (Cr) TCLP
Lead (Pb) TCLP
Mercury (Hg) TCLP
Selenium (Se) TCLP
Silver (Ag) TCLPAPPENDIX C
PRELIMINARY AMD TREATMENT RESULTSFe Mn Si Sr
17th Jan
Inlet NA NA NA 6.28 504 4 7 8
Treated T10 10 60 7.15 77 4 5 8
Treated T10 10 90 8.53 0.04 2 3 7
18th Jan
Inlet NA NA NA 6.29 432 4 7 8
Treated T10 10 60 6.93 14 3 4 7
Treated T10 10 90 8.56 0.08 1 2 6
Treated T10 10 120 8.85 0.01 0.19 1.6 5
Treated T20 5 60 6.81 69 4 5 7
Treated T20 5 90 7.10 5 4 5 8
Treated T20 5 120 8.43 0.52 1.8 3 7
Inlet NA NA NA 6.25 460 4 7 8
19th Jan
Inlet NA NA NA 6.46 431 4 6 8
Treated T10 10 60 6.88 6 4 4 7
Treated T10 10 90 8.54 0.008 <1 2 6
Treated T10 10 120 8.96 0.001 0.1 1 5
Treated T10 10 240 9.58 0 0.004 1 3
24th Jan
Inlet NA NA NA 6.21 477 5 6 7
Treated T10 10 60 6.90 0.2 2 2 6
Treated T10 10 90 8.95 0.03 0.5 1 6
Treated T10 10 120 9.21 0.07 0.2 0.7 5
Treated T15 10 60 8.11 0.03 0.5 2 6
Treated T15 10 90 9.11 0.4 0.06 2 3
Treated T15 10 120 9.43 0 0.006 1 3
Treated T20 10 30 6.98 32 4 4 7
Treated T20 10 60 9.00 0.02 0.06 2 4
Treated T20 10 90 9.54 0.01 0.007 2 2
Treated T20 10 120 9.70 0.15 0.002 2 1
Treated T25 10 30 8.74 0.005 0.3 3 6
Treated T25 10 60 9.20 0.14 0.04 2 3
Treated T25 10 90 9.69 0.0006 0.005 2 1
Treated T25 10 120 9.90 0 0.001 2 0.9
Inlet NA NA NA 6.19 447 5 5 7
Preliminary AMD Water Treatment Results
Virotec Treatment Media Study
February 2012
GAI Project No. C111194.00
Sample
Blend
type
Dose rate
(g/litre)
Reaction period
(mins)
pH
Sol metals (mg/litre)APPENDIX D
INITIAL ANALYTICAL RESULTS
FOR THE FLOWBACK AND PRODUCED WATER SAMPLES Sample ID FLOWBACK WATER PRODUCED WATER
Date 01/17/2012 01/17/2012
Acidity, Total (mg/L) 324 320
Alkalinity, Total as CaCO3 (mg/L) <10.0 16
Aluminum, Dissolved (ug/L) 2,080 2,010
Antimony, Dissolved (ug/L) <60.0 <60.0
Arsenic, Dissolved (ug/L) 65.2 <50.0
Barium, Dissolved (ug/L) 168,000 173,000
Beryllium, Dissolved (ug/L) <10.0 <10.0
Bromide (mg/L) 1100 1170
Cadmium, Dissolved (ug/L) <30.0 <30.0
Calcium (ug/L) 20,600,000 25,400,000
Calcium, Dissolved (ug/L) 20,600,000 25,400,000
Chloride (mg/L) 138,000 124,000
Chromium, Dissolved (ug/L) <50.0 <50.0
Cobalt, Dissolved (ug/L) <50.0 <50.0
Copper, Dissolved (ug/L) <50.0 <50.0
Gross Beta (pCi/L) 1.56E+10 3.64E+11
Iron, Dissolved (ug/L) 110,000 64,700
Lead, Dissolved (ug/L) <50.0 <50.0
Magnesium (ug/L) 2,000,000 2,500,000
Magnesium, Dissolved (ug/L) 2,000,000 2,500,000
Manganese, Dissolved (ug/L) 18,500 14,000
Mercury, Dissolved (ug/L) <5.0 <5.0
Molybdenum, Dissolved (ug/L) <200 <200
Nickel, Dissolved (ug/L) <100 <100
Orthophosphate as P (mg/L) <250 <250
pH (Std_ Units) 4.8 5.6
Phosphorus (mg/L) 0.035 0.9
Potassium, Dissolved (ug/L) 900,000 406,000
Selenium, Dissolved (ug/L) <80.0 <80.0
Silver, Dissolved (ug/L) <60.0 <60.0
Sodium, Dissolved (ug/L) 28,400,000 25,100,000
Specific Conductance (umhos/cm) 186,000 200,000
Strontium, Dissolved (ug/L) 1,820,000 3,330,000
Sulfate (mg/L) 62.7 14.2
Surfactants (mg/L) 144 0.37
Thallium, Dissolved (ug/L) <100 <100
Total Dissolved Solids (mg/L) 186,000 212,000
Total Hardness (mg/L) 59,800 73,600
Total Organic Carbon (mg/L) 298 234
Total Suspended Solids (mg/L) 164 71
Turbidity (NTU) 377 26.5
Vanadium, Dissolved (ug/L) <50.0 <50.0
Zinc, Dissolved (ug/L) 282 <100
Virotec Treatment Media Study
February 2012
GAI Project No. C111194.00
Flowback and Produced Water Pre-treatment Constituent Levels APPENDIX E
LABORATORY RESULTS
FOR TREATED AMD WATER SAMPLES R1 R2 R3 R1 R2 R3 R1 R2 R3
Acidity, Total mg/L SM 2310B <10.0 <10.0 <10.0 250 230 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0
Alkalinity, Total as CaCO3 mg/L SM 2320B <10.0 58 60 630 386 642 602 556 704 726 662 470 546 570
Aluminum, Dissolved ug/L EPA 6010 <50.0 105 <50.0 268 <50.0 75.8 81.9 82.1 68.5 74.8 71.3 83.6 62.9 118
Antimony, Dissolved ug/L EPA 6010 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0
Arsenic, Dissolved ug/L EPA 6010 <5.0 <5.0 <5.0 12.5 11.2 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0
Barium, Dissolved ug/L EPA 6010 <10.0 <10.0 <10.0 10.1 13.4 13.3 11.8 10.9 19.8 25.5 22.3 15.8 <10.0 <10.0
Beryllium, Dissolved ug/L EPA 6010 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0
Bromide mg/L EPA 300.0 <0.062 0.11 <0.062 18 18.2 18.4 17.2 18 18.4 18.2 17.6 20.4 18.4 18.4
Cadmium, Dissolved ug/L EPA 6010 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0 <3.0
Calcium ug/L SM 2340B <500 5,690 6,140 424,000 432,000 177,000 127,000 120,000 335,000 376,000 367,000 412,000 84,400 124,000
Calcium, Dissolved ug/L EPA 6010 <1,000 5,690 6,140 424,000 432,000 177,000 127,000 120,000 335,000 376,000 367,000 412,000 84,400 124,000
Chloride mg/L SM 4500-Cl-E <3.0 7 <3.0 900 781 923 849 959 868 874 832 851 825 792
Chromium, Dissolved ug/L EPA 6010 <5.0 6.3 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0
Cobalt, Dissolved ug/L EPA 6010 <5.0 <5.0 <5.0 6.1 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0
Copper, Dissolved ug/L EPA 6010 <5.0 <5.0 <5.0 <50.0 <50.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0
Iron, Dissolved ug/L EPA 6010 231 <70.0 <70.0 470,000 360,000 <70.0 <70.0 <70.0 <70.0 <70.0 <70.0 <70.0 <70.0 <70.0
Lead, Dissolved ug/L EPA 6010 <5.0 <5.0 <5.0 20.2 5.4 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0
Magnesium ug/L SM 2340B <200 2470 8,180 303,000 312,000 636,000 673,000 683,000 567,000 533,000 539,000 455,000 667,000 659,000
Magnesium, Dissolved ug/L EPA 6010 <200 2470 8,180 303,000 312,000 636,000 673,000 683,000 567,000 533,000 539,000 455,000 667,000 659,000
Manganese, Dissolved ug/L EPA 6010 <5.0 <5.0 <5.0 4200 4290 50.9 32.2 36.5 503 1130 698 2160 35.4 42.6
Mercury, Dissolved ug/L EPA 7470 <0.20 <0.20 <0.20 <0.20 <0.20 <1.0 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20
Nickel, Dissolved ug/L EPA 6010 <10.0 <10.0 <10.0 26 22.6 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0
Orthophosphate as P mg/L EPA 300.0 <0.12 <0.12 <0.12 <25.0 <25.0 <25.0 <25.0 <25.0 <25.0 <25.0 <25.0 <25.0 <25.0 <25.0
pH Std. Units SM 4500-H+B 9.2 10.4 10.4 6.5 6.7 8.8 8.9 8.9 8.7 8.6 8.6 8.6 8.9 8.8
Phosphorus mg/L SM 4500-P E <0.030 <0.030 <0.030 0.032 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 0.032
Potassium, Dissolved ug/L EPA 6010 <500 <500 <500 15,000 15,200 16,200 16,500 16,400 16,100 16,100 16,400 15,300 15,000 15,200
Selenium, Dissolved ug/L EPA 6010 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0 <8.0
Silver, Dissolved ug/L EPA 6010 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0 <6.0
Sodium, Dissolved ug/L EPA 6010 3,160 22,600 9,070 3,510,000 3,600,000 3,480,000 3,500,000 3,550,000 3,610,000 3,510,000 3,560,000 3,470,000 3,400,000 3,540,000
Specific Conductance umhos/cm EPA 9050 8.4 181 162 15,000 15,000 15,100 15,100 15,100 15,200 15,200 15,100 15,200 15,100 15,000
Strontium, Dissolved ug/L EPA 6010 <5.0 6.1 6.2 8,280 8,200 4,760 3,550 3,100 6,500 7,190 6,950 7,450 1,640 2,920
Sulfate mg/L ASTM D516-90,02 <10.0 <10.0 <10.0 7,930 8,670 7,670 7,840 6,240 8,760 7,840 9,310 8,540 8,940 8,420
Thallium, Dissolved ug/L EPA 6010 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0
Total Dissolved Solids mg/L SM 2540C <10.0 25 <10.0 14,100 13,800 13,900 13,900 13,900 13,500 14,100 13,700 13,500 13,800 13,700
Total Hardness mg/L SM 2340B <2.1 24.4 49 2,310 2,370 3,060 3,090 3,110 3,170 3,130 3,130 2,900 2,960 3,020
Total Organic Carbon mg/L SM 5310C <1.0 <1.0 <1.0 1.6 1.1 2.5 2.8 2.7 2.2 3 2.4 1.5 1.4 1.5
Total Suspended Solids mg/L SM 2540D <4.0 <4.0 <4.0 190 184 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0
Turbidity NTU EPA 180.1 <10.0 0.21 0.16 101 48.3 0.24 0.34 0.12 0.21 0.2 0.64 0.38 0.26 0.26
Vanadium, Dissolved ug/L EPA 6010 <5.0 68.8 36.8 <5.0 <5.0 8.3 8.1 8.6 5.2 <5.0 <5.0 <5.0 8.7 6.2
Zinc, Dissolved ug/L EPA 6010 <10.0 <10.0 <10.0 20.7 12.7 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0 <10.0
DI
Virotec Treatment Media Study
February 2012
GAI Project No. C111194.00
AMD Water Constituent Levels Before and After Treatment
Parameter Units Method of Analysis
AMD+10+120 AMD+10+90 AMD+5+120
DI+10 DI+5 AMD RAW AMD CONTROLAPPENDIX F
PRELIMINARY FLOWBACK AND PRODUCED
WATER TREATMENT RESULTS Al B Ba Ca Fe K Li Mg Mn Na Si Sr
Produced 1
RAW Produced Inlet NA NA NA 5.39 2 17 185 22420 90 387 113 2395 16 52720 9 3080
PW+50+60 Treated T10 50 60 8.70 4 15 176 24660 0.2 313 101 2512 0.02 48620 0.9 3160
PW+60+120 Treated T10 50 120 8.75 3 13 179 24720 0 319 102 2534 0 49140 0.4 3179
PW+50+240 Treated T10 50 240 8.75 3 11 178 25160 0 324 103 2580 0.05 49910 0.3 3274
23rd Jan
Inlet NA NA NA 5.36 3 17 182 23480 72 319 103 2346 16 49750 2 2851
Treated Lime(pH) 50 60 10 4 11 178 27040 0.6 320 100 93 0.04 49620 0 2863 Note Mg
Treated Lime(pH) 50 60 10.8 4 14 183 26870 0 308 98 3 0.01 49750 0 2880 Note Mg
AVG 10.4 4 12.5 180.5 26955 0.3 314 99 48 0.025 49685 0 2871.5
Inlet H2O2 treated NA NA NA 2.5 3 17 183 21720 28 288 98 2193 16 47620 2 2766
PW+LIME+60+H2O2 Treated Lime (pH) 50 60 10 4 11 181 25810 0.6 304 98 5 0.02 48920 0 2776 Note Mg
PW+LIME+165+H2O2 Treated Lime (pH) 50 165 10.3 4 12 186 26650 0.06 310 99 3 0.01 50050 0 2832 Note Mg
PW+LIME+240+H2O2 Treated Lime (pH) 50 240 10.48 4 11 166 29020 0 316 96 3 0.02 47330 0.09 2909
RAW Flowback Flow back 1
Inlet NA NA NA 4.90 2 15 170 19460 100 820 80 1975 22 45480 10 1794
FBW+10+60 Treated T10 10 60 8.40 2 15 170 19450 4 829 80 2114 11 45290 3 1824
FBW+10+120 Treated T10 10 120 8.40 2 15 180 20810 4 829 74 2082 1 42910 2 1829
FBW+50+60 Treated T10 50 60 8.91 3 14 162 20740 1 711 74 2054 0.06 42410 1 1866
FBW+50+120 Treated T10 50 120 9.00 4 13 164 21050 1 720 75 2096 0.01 42890 1 1885
FBW+50+240 Treated T10 50 240 8.90 4 11 163 21110 0.4 722 75 2109 0.03 43240 0.9 1895
23rd Jan
Inlet NA NA NA 4.85 3 15 167 19900 65 702 73 1891 22 42170 2 1800
Treated Lime (pH) 50 60 10 3 7 170 22210 0.6 700 73 219 0.04 43770 0 1803 Note Mg
Treated Lime (pH) 50 60 10.8 3 13 165 23430 0 724 74 4 0.02 43610 0 1828 Note Mg
AVG 10.4 3 10 167.5 22820 0.3 712 73.5 111.5 0.03 43690 0 1815.5
FBW+H2O2
Inlet H2O2
treated NA NA NA NT 3 16 173 18610 17 665 73 1798 21 41760 0.2 1733 severe rxn with lime
Notes:
1) pH meter affected by high ionic strength and other additives (such as surfactants) - probe not allowed to stand for extended periods in media/effluent mix.
2) Only metals levels at >1mg/litre are shown shown.
Flowback and Produced Water Constituent Levels after Treatment
Virotec Treatment Media Study
February 2012
GAI Project No. C111194.00
FBW+LIME+60
Sample
Blend
type
Dose
rate
Reaction
period pH
Soluble metals by ICP (mg/litre)
Sample ID Notes
PW+LIME+60
