EPA/600/R-01/077
June 2001
Selenium Treatment/Removal
Alternatives Demonstration
Project
Mine Waste Technology Program
Activity III, Project 20
by
MSE Technology Applications, Inc.
Butte, Montana 59702
IAGDW89938870-01-0
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
and
Federal Energy Technology Center
U.S. Department of Energy
Pittsburgh, Pennsylvania 15236
contract No. DE-AC22-96EW95405
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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Notice
The information in this document has been funded in part by the U.S. Environmental Protection
Agency under IAG DW89938870-01-0 and the Department of Energy Contract DE-AC22-96EW96405
to MSE Technology Applications, Inc., Butte, Montana 59702. EPA made comments and sugges-
tions on the document intended to improve the scientific analysis and technical accuracy of the
document. These comments are included in the report. However, the views expressed in this
document are those of MSE Technology Applications, Inc. and EPA does not endorse any
products or commercial services mentioned in this publication.
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Foreword
The mining and mineral processing industries are developing and modifying technologies that
will enable these industries to operate more efficiently. If improperly dealt with, the waste
generated by these industries can threaten public health and degrade the environment. The U.S.
Environmental Protection Agency (EPA) is charged by the Congress of the United States with
protecting the Nation's land, air, and water resources. Under a mandate of national environmental
laws, EPA strives to formulate and implement actions leading to a balance between human
activities and the ability of natural systems to support and nurture life. These laws direct EPA to
perform research to define and measure the impacts and search for solutions to environmental
problems.
The National Risk Management Research Laboratory (NRMRL) of EPA is responsible for
planning, implementing, and managing research, development, and demonstration programs to
provide an authoritative, defensible engineering basis to support the policies, programs, and
regulations of EPA with respect to drinking water, wastewater, pesticides, toxic substances, solid
and hazardous wastes, and Superfund-related activities. The National Energy Technology Labora-
tory (NETL) of the U.S. Department of Energy (DOE) has responsibilities similar to NRMRL in that
NETL is one of several DOE centers responsible for planning, implementing, and managing
research and development programs. This document is a product of the research conducted by
these two Federal organizations.
This document is the final report for EPA's Mine Waste Technology Program (MWTP) Activity
III, Project 20, Selenium Treatment/Removal Alternatives. MWTP is a program developed through
an Interagency Agreement between EPA and DOE. MSE Technology Applications, Inc., manages
MWTP and is responsible for the field demonstration and reporting activities. The information
generated under this program provides a vital communication link between the researcher and the
user community.
One of the objectives of MWTP is to identify the types of mining wastes impacting the nation
and the technical issues that need to be addressed. Other objectives of the program are: 1)
address these technical issues through application of treatment technologies; 2) determine the
candidate technologies that will be tested and evaluated; and 3) determine the candidate sites
where these evaluations will take place.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
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Acknowledgments
This document, Final Report—Selenium Treatment/Removal Alternatives Demonstration Project,
was prepared for the U.S. Environmental Protection Agency (EPA) National Risk Management
ResearchLaboratory (NRMRL) and the U.S. Department of Energy (DOE) National Energy Technol-
ogy Laboratory by MSE Technology Applications, Inc. (MSE) under contract DE-AC22-96EW96405.
The Selenium Treatment/Removal Demonstration Project was conducted under the Mine Waste
Technology Program (MWTP) and funded by EPA with in-kind support contributions from Kennecott
Utah Copper Corporation (KUCC). MWTP is jointly administered by EPA and DOE through an
Interagency Agreement. MSE manages MWTP and owns/operates the MSE Testing Facility in
Butte, Montana.
Roger Wilmoth from NRMRL served as EPA's MWTP Program Manager, and Melvin Shupe
from DOE served as DOE's Technical Program Officer. Mary Ann Harrington-Baker served as
MSE's Program Manager, Helen Joyce served as MSE's Project Manager, and Jon Cherry served
as the Project Manager for KUCC. KUCC was a major contributor to the project through in-kind
services including: permitting, laboratory analysis, influent tank rental, transfer of water from
Garfield Wetlands-Kessler Springs to the MSE Demonstration Site, site-specific safety training,
warehouse services, and miscellaneous supplies and chemicals. Dr. Larry Twidwell from Montana
Tech of the University of Montana was the technology provider of the catalyzed cementation
process and also served as technical consultant for the chemical processes demonstrated. Dr. D.
J. Adams and Tim Pickett of Applied Biosciences served as technology providers for the biological
selenium reduction technology and the enzymatic selenium reduction technology. The organization
and execution of this project was a collaborative effort between the participants mentioned above.
Without these contributions, this project could not have been completed.
In addition to the people listed above, the following agency and contractor personnel contrib-
uted their time and energy by participating in the Selenium Treatment/Removal Alternatives
Demonstration Project and preparing this document.
Alva Daniels, National Risk Management Research Laboratory
Lauren Drees, National Risk Management Research Laboratory
Gene Ashby, DOE
Jennifer Saran, KUCC
Dan Self, KUCC
Ray Ziolkowski, Montana Tech of the University of Montana
Jay McCloskey, MSE
DickHarned, MSE
June Pusich-Lester, MSE
Darcy Byrne-Kelly, MSE
Marietta Canty, MSE
Ken Reick, MSE
Michelle Gale, MSE
Ken Nelson, MSE
Jack Bugg, MSE
Diana Fawcett, MSE
Scott Nuthak, MSE
Bill Rees, MSE
Charlie Brown, MSE
Pam Mullaney, MSE
IV
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Contents
Foreword iii
Acknowledgments iv
Acronyms vii
1. INTRODUCTION 1
1.1 Project Overview 1
1.2 Project Purpose 1
1.3 Scope of the Problem 1
1.4 Site Description 1
1.5 Technology Descriptions 2
1.5.1 Ferrihydrite Adsorption of Selenium 2
1.5.2 Catalyzed Cementation of Selenium 3
1.5.3 Biological Reduction of Selenium 4
1.5.4 Enzymatic Reduction of Selenium 4
1.6 Project Objectives 4
2. DEMONSTRATION DESCRIPTION AND RESULTS 9
2.1 Ferrihydrite Adsorption Demonstration and Results 9
2.1.1 Low Iron Test Results 10
2.1.2 Medium Iron Test Results 10
2.1.3 High Iron Test Results 10
2.1.4 Ferrous/Ferric Test Results 10
2.1.5 Sludge Recycle Tests 10
2.1.6 TCLP Results 10
2.2 Catalyzed Cementation Process Demonstration 11
2.2.1 TCLP Results 12
2.3 Biological Selenium Reduction Process Demonstration 12
2.3.1 Series 1-Carbon/Biofilm and Biosolids Biofilm Reactors 12
2.3.2 Series 2 and 3 Carbon/Biofilm Reactors 13
2.4 Enzymatic Selenium Reduction Bench-Scale Evaluation 13
3. ECONOMIC ANALYSIS 17
3.1 Ferrihydrite Adsorption of Selenium 17
3.2 Catalyzed Cementation of Selenium 18
3.3 Biological Selenium Reduction (BSeR™) Process 18
3.3.1 Nutrient Costs 18
3.3.2 BSeR™ Process Biofilm Support Cost 19
3.3.3 BSeR™ Process Capital Costs 19
3.3.4 Comparative Economic Analysis 19
4. CONCLUSIONS/RECOMMENDATIONS 21
5. REFERENCES 22
Appendix A: Summary of Quality Assurance Activities
Appendix B: Test Data
Appendix C: Sampling Schedule and Analytical Protocols
Appendix D: Microbial Screening and Laboratory Testing
Appendix E. Enzymatic Selenium Reduction Laboratory Project
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Tables
1-1. Composition of Garfield Wetlands-Kessler Springs Water 2
2-1. Summary of Results for Wilcoxon Signed Rank Test 9
2-2. Summary Results for Ferrihydrite Adsorption Tests 10
2-3. TCLP/Total Selenium Results for Ferrihydrite Adsorption Filtercake Samples 11
2-4. Summary of Results for the Catalyzed Cementation process Demonstration 11
2-5. TCLP Results for Catalyzed Cementation Filtercake Samples 12
2-6. Summary of Results from BSeR™ process Field Tests 12
3-1. Capital Costs/Construction Schedule for Ferrihydrite Adsorption System Scale-Up 17
3-2. Capital Costs/Construction Schedule for Catalyzed Cementation System Scale-Up 18
3-3. Nutrient Usage and Cost Per 1,000 Gallons as a Function of Retention Time 19
3-4. Capital Costs for BSeR™ Process System Scale-Up 19
3-5. Comparative Economic Analysis of Demonstrated Technologies 20
Figures
1-1. MWTP Demonstration Trailer at the Field Site 5
1-2. Ferrihydrite Precipitation Process Flow Diagram 5
1-3. Ferrihydrite Adsorption Process in MWTP Demonstration Trailer 6
1-4. Catalyzed Cementation Process Flow Diagram 6
1-5. Catalyzed Cementation Process in MWTP Demonstration Trailer 7
1-6. BSeR™ Process Flow Diagram 7
1-7. Field-Scale BSeR™ Process Reactor 8
2-1. Summary of Results from Ferrihydrite Adsorption Tests 14
2-2. Summary of Results for Field Catalyzed Cementation Process Tests 14
2-3. Series 1 Pilot-Scale BSeR™ Process Operation at a 12-hr Retention Time Per Reactor 15
2-4. BSeR™ Process Pilot-Scale Reactor Summary Graph 15
2-5. A Red, Amorphous, Selenium Precipitate Observed in Process Piping After 8 hr of Operation 16
VI
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Acronyms
AA atomic absorption
AB Applied Biosciences Corporation
BASER baffled anaerobic solids bed reactors
BOAT best demonstrated available technology
BSeR™ biological selenium reduction
EPA U.S. Environmental Protection Agency
ICP inductively coupled plasma
KEL Kennecott Environmental Laboratory
KUCC Kennecott Utah Copper Corporation
MCL maximum contaminant level
MSE MSE Technology Applications, Inc.
MWTP Mine Waste Technology Program
ORP oxidation-reduction potential
std dev standard deviation
TCLP toxicity characteristic leaching procedure
TNPV total net present value
VII
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Executive Summary
This document is the final report forthe
U.S. Environmental Protection Agency's
(EPA) Mine Waste Technology Program
(MWTP) Activity III Project 20—Sele-
nium Treatment/Removal Alternatives
Demonstration Project. MWTP is a pro-
gram developed through an Interagency
Agreement (IAG) between EPA and the
U.S. Department of Energy. MSE Tech-
nology Applications, Inc. (MSE) man-
ages MWTP and owns/operates the
MSE Testing Facility in Butte, Montana.
MSE proposed and was granted fund-
ing forthe Selenium Treatment/Removal
Demonstration Project during the April
1999 IAG Management Committee
Meeting.
Selenium contamination originates from
many sources including mining opera-
tions, mineral processing, abandoned
mine sites, petroleum processing, and
agricultural run-off. Kennecott Utah Cop-
per Corporation's (KUCC) Garfield Wet-
lands-Kessler Springs site has a well
characterized selenium contaminated
artesian flow and was selected as the
site for demonstrating various selenium
treatment technologies. The contamina-
tion is of a low-level, high-volume na-
ture that makes most treatment options
expensive.
The objective of the Selenium Treatment/
Removal Alternatives Demonstration
Project was to test and evaluate tech-
nologies capable of removing selenium
from Garfield Wetlands-Kessler Springs
water to below 50 micrograms per liter
(ug/L), the National Primary Drinking
Water Regulation Maximum Contami-
nant Level for selenium established by
EPA. Several technologies with the po-
tential to treat this water were presented
in MWTP, Activity I, Volume VII, Issues
Identification and Technology
Prioritization Report-Selenium.
Three technologies were selected for
field demonstration during this project:
EPA's Best Demonstrated Avail-
able Technology (BOAT)—
ferrihydrite precipitation with
concurrent adsorption of selenium
onto the ferrihydrite surface
(ferrihydrite adsorption) optimized
by MSE;
a catalyzed cementation process
developed by Dr. Larry Twidwell of
Montana Tech of the University of
Montana with assistance from
MSE; and
a biological selenium reduction
(BSeR™) process developed by
Applied Biosciences Corporation
(AB) of Salt Lake City, Utah.
Because ferrihydrite adsorption is con-
sidered EPA's BOAT for selenium re-
moval from solution, it was considered
the baseline technology and was used
as a basis for comparison with the inno-
vative selenium removal processes. All
work was performed under an EPA-ap-
proved Quality Assurance Project Plan.
All three of the processes were able to
achieve the target level for selenium in
effluent samples under optimized con-
ditions. Table ES-1 summarizes the re-
sults from the field demonstration for
each technology and also includes re-
sults from additional testing of the cata-
lyzed cementation process that oc-
curred at MSE's testing facility follow-
ing the field demonstration.
The BSeR™ process performed most
consistently during the demonstration.
During the 187 days of evaluation, all
but four effluent samples from the
BSeR™ process were below 10 ug/L,
and greater than 70% of the effluent
samples were below detection (2 ug/L).
A secondary objective of the project was
to perform an economic analysis for
scale-up of the processes to treat 300
gallons per minute (gpm) flow at the
Kessler Springs site. The retrofit of a
vacant watertreatment plant/associated
equipment at the Kessler Springs site
was used as the basis for the capital
costs.
Table ES-2 is a summary of the outputs
of the economic analysis for the se-
lected technologies treating groundwa-
terwith 2 mg/L selenium operating at
viii
300 gpm. The figures are the total net
present value for each process that was
demonstrated in the field. The figures
used represent an order of magnitude
cost estimate. The BSeR™ process was
the most economically attractive tech-
nology demonstrated during this project.
A fourth technology—enzymatic sele-
nium reduction—was demonstrated on
a bench scale by AB. Enzymatic sys-
tems have the following advantages over
live microbial systems: 1) the potential
for greatly increasing kinetics; 2) nutri-
ents are not required; and 3) the effects
of toxic process solutions can be elimi-
nated. Methods to economically prepare
stable enzyme preparations and enzyme
preparations from different microorgan-
isms were investigated. Several immo-
bilization polymers were evaluated to
increase operational longevity. Calcium
alginate performed the best in regards
to ease of handling, toxicity, cost, and
performance. Problems with stability or
possibly the loss of an electron donor
system were problematicthroughout the
testing. The stability or electron donor
systems of the preparations tested was
not sufficiently reproducible to warrant
pilot-scale tests during this project.
These and other selenium treatment
technologies were also reviewed under
a Comprehensive Environmental Re-
sponse, Compensation, and Liability Act
feasibility study at the KUCC site. The
BSeR™ process technology has been
identified by KUCC as the preferred treat-
ment for Garfield Wetlands-Kessler
Springs water if KUCC is unable to re-
cycle the selenium-bearing water into
the existing process water circuit. Cur-
rently, KUCC is recycling 100% of the
Garfield Wetlands-Kessler Springs flow
back into various operations as make-
up water. If the process water circuit is
shut down, the BSeR™ process tech-
nology has been identified as the tech-
nology capable of treating the Garfield
Wetlands-Kessler Springs water.
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Table ES-1. Demonstration results summary.
Treatment Condition
Ferrihydrite Adsorption Results
Mean Selenium Effluent Concentration
iStandard Deviation (n = sample size)
Minimum Selenium
Concentration
Low iron (-1400 mg/L iron)
Medium iron (-3000 mg/L iron)
High iron (-4800 mg/L iron)
Ferrous/ferric (-1200 mg/L
ferrous/1200 mg/L ferric iron)
Recycle Sludge (-2340 to
13,290 mg/L iron)
Treatment Condition
304 ug/L ±69 (n = 27)
201 ug/L±103(n = 13)
90 ug/L ±28 (n = 5)
563 ug/L ±280 (n = 5)
387 ug/L ±58 (n = 12)
Catalyzed Cementation Results
Mean Selenium Effluent Concentration
(ug/L) ±Standard Deviation (n = sample size)
115 ug/L
42 ug/L (at midpoint of process)
35 ug/L (at midpoint of process)
409 ug/L
77 ug/L
Minimum Selenium Effluent
Concentration (ug/L)
Catalyzed Cementation
Catalyzed Cementation with
Increased Oxidation/Decreased
pH in the reactor tank
Additional Testing of Catalyzed
Cementation at MSE
834 ug/L ±204 (n = 42)
35 ug/L (n = 2)
3 ug/L1 ±4.4 (n = 5)
193 ug/L
26 ug/L
ug/L
Residence Time
BSeR™ Process Results
Mean Selenium Effluent Concentration
(ug/L)2± Standard Deviation
(n - sample size)
Minimum Selenium Effluent
Concentration (ug/L)
12 hrs (Series 1)
11 hr (Series 2)
8 hr (Series 3)
5.5 hr (Series 2)
1 Nondetects were substituted with 50% of detection limit (0.5 ug/L).
2 Nondetects were substituted with 50% of detection limit (1 ug/L).
8.8 ug/L ±10.2 (n = 17)
4.9 ug/L ±4.9 (n = 16)
< 2 ug/L ±2.6 (n = 12)
< 2 ugL ±2.1 (n = 26)
=2 ug/L
=2 ug/L
=2 ug/L
=2 ug/L
Table ES-2. Comparative economic analysis of demonstrated technologies.
Cost
Ferrihydrite Adsorption
Catalyzed Cementation
BSeR™ Process
Capital
Annual Operating and
Maintenance Cost
$1,026,835 (includes system
design, demolition, building
modifications, equipment purchase
and installation, construction,
system start-up, commissioning,
and project closeout)
$2,084,559 (includes reagent
costs, manpower, maintenance,
and power for equipment use)
Net Present Value of Annual $16,992,127
Operating and Maintenance Costs
Total Net Present Value $18,017,962
Net Present Value of $13.90
$/1,000 gallons treated
$1,083,285 (includes additional
research and development work,
system design, demolition,
building modifications, equipment
purchase and installation,
construction, system start-up,
commissioning, and project closeout)
$1,165,358 (includes
reagent costs, manpower,
maintenance, and power for
equipment use)
$9,499,323
$10,582,608
3.17
IX
$603,999 (includes biofim
support material, inoculum,
system design, building
modifications, equipment
purchase and installation,
construction, commissioning,
and project closeout)
$135,029 (includes nutrient
costs, manpower, maintenance,
and power for equipment use)
$1,100,682
$1,704,681
$1.32
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1. Introduction
1.1 Project Overview
This Final Report was prepared specifi-
cally forthe Mine Waste Technology Pro-
gram (MWTP), Activity III, Project 20—
Selenium Treatment/ Removal Alterna-
tives Demonstration Project, which ad-
dresses the U.S. Environmental Protec-
tion Agency's (EPA) technical issue of
Mobile Toxic Constituents—Water.
The Selenium Treatment/Removal Alter-
natives Demonstration Project con-
sisted of demonstrating one standard
process and three innovative processes
forselenium removal from Garfield Wet-
lands-Kessler Springs Water at
Kennecott Utah Copper Corporation
(KUCC) in Magna, Utah.
1.2 Project Purpose
The purpose of the Selenium Treatment/
Removal Alternatives Demonstration
Project was to test and evaluate tech-
nologies capable of removing selenium
from Garfield Wetlands-Kessler Springs
waterto below 50 ug/L, the National Pri-
mary Drinking Water Regulation maxi-
mum contaminant level (MCL) forsele-
nium. Garfield Wetlands-Kessler Springs
water has a selenium concentration of
approximately 2,000 ug/L. Several tech-
nologies with the potential to treat this
water were presented in MWTP, Activ-
ity I, Volume VII, Issues Identification
and Technology Prioritization Report-
Selenium (Ret 1).
Three technologies were selected for
field demonstration during Phase 1 of
this project:
EPA's Best Demonstrated Avail-
able Technology (BOAT) (Ref. 2)—
ferrihydrite precipitation with
concurrent adsorption of selenium
onto the ferrihydrite surface
(ferrihydrite adsorption) optimized
by MSE Technology Applications,
Inc. (MSE);
a catalyzed cementation process
developed by Dr. Larry Twidwell of
Montana Tech of the University of
Montana with assistance from
MSE; and
biological selenium reduction
(BSeR™) process developed by
Applied Biosciences (AB) of Salt
Lake City, Utah.
Because ferrihydrite adsorption is con-
sidered EPA's BOAT for selenium re-
moval from solution, it was considered
the baseline technology and was used
as a basis for comparison with the inno-
vative selenium removal processes.
The demonstrations of the ferrihydrite
and catalyzed cementation technologies
were conducted at KUCC during Octo-
ber and November 1999. These two tech-
nologies were demonstrated in the
MWTP demonstration trailer that was
constructed as part of MWTP Activity
III, Project 9-Arsenic Removal Demon-
stration Project. The BSeR™ process
was designed by AB and constructed
with assistance from KUCC.The
BSeR™ process demonstration was
conducted from October 1999 through
April 2000.
Phase 2 of this project included addi-
tional testing of the catalyzed cementa-
tion process under optimized conditions
identified during the field demonstration
and bench-scale testing of an enzymatic
selenium reduction process developed
byAB.The additional testing of the cata-
lyzed cementation process was con-
ducted at MSE's testing facility in Butte,
Montana, during March and April 2000.
The bench-scale testing of the enzy-
matic selenium reduction technology
was conducted at AB's testing facility
in Utah from March 2000 through Janu-
ary 2001.
1.3 Scope of the Problem
Selenium is a problem in many waste-
waters and is a common water contami-
nant throughout the world. Selenium con-
tamination represents a major environ-
mental problem in at least nine western
U.S. states. This contamination origi-
nates from many sources including min-
ing operations, mineral processing op-
erations, abandoned mine sites, petro-
leum processing, agricultural runoff and
natural groundwater. For mining waste,
the principal sources of selenium con-
tamination are copper- and uranium-
bearing ores and sulfur deposits. Sele-
nium is commonly found in mining
wastewaters in concentrations ranging
from 3 to >12,000 pg/L (Ref. 1). The
National Primary Drinking Water Stan-
dard MCL is 50 ug/L for selenium. The
National Fresh Water Quality Standard
is 5 ug/L for selenium. The U.S. Fish
and Wildlife Service has recommended
that the national fresh water quality stan-
dard be lowered to 2 ug/L to protect fish,
waterfowl, and endangered aquatic spe-
cies. Questioning of this standard has
arisen because some laboratory and
field studies indicate that water borne
selenium concentrations as low as 2.0
ug/L may bio-accumulate in aquatic food
chains to toxic levels.
1.4 Site Description
KUCC's Garfield Wetlands-Kessler
Springs site has a well defined selenium
contaminated artesian flow with the fol-
lowing characteristics:
• groundwater containing selenate
ranging from <50 to 10,000 ug/L;
• artesian flows 250-500 gpm, with
selenium concentrations from 200
to 2,000 ug/L; and
• varying site water quality with
some naturally occurring total dis-
solved solids concentrations greater
than 5,000 mg/L.
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Selenium, the primary contaminant of
concern at this site, is present as sel-
enate in the site's groundwater. Ground-
water formerly surfaced from two main
sources within the site into a large wet-
lands area on the boundary of the Great
Salt Lake. Selenium contaminated ar-
tesian flow is currently captured and
routed into KUCC's process water cir-
cuit. The contamination is of a low-level,
high-volume nature that makes most
treatment options expensive.
KUCC co-chairs a technical review com-
mittee with EPA, State organizations,
and public groups to evaluate
remediation/treatment strategies to sub-
stantially lowerthe release of selenium
into the Garfield Wetlands and the Great
Salt Lake.The Garfield Wetlands site is
well characterized with site water and
solids chemistry data available. A
Garfield Wetlands site assessment in-
dicated that natural selenium reduction
is occurring at limited locations in the
wetlands. Additionally, laboratory treat-
ability testing of site waters indicated
that these waters were at least some-
what difficult to treat, even though they
appear by chemical analysis to only
contain selenium as the major contami-
nant. A chemical profile of the Garfield
Wetlands-Kessler Springs water is pre-
sented in Table 1-1.
This site provided an excellent opportu-
nity to test the selected selenium re-
moval technologies under MWTR The
BSeR™ process was constructed near
Garfield Wetlands-Kessler Springs. The
portion of the water emanating from the
springs was fed directly to the biologi-
cal process. The MWTP demonstration
trailer was located near a vacant water
treatment facility at KUCC approximately
2 miles from the Garfield Wetlands-
Kessler Springs site. A photograph of
the MWTP demonstration trailer and
associated equipment at the demonstra-
tion site is shown in Figure 1-1. Feed
waterforthe catalyzed cementation and
the ferrihydrite precipitation processes
was transported from Garfield Wetlands-
Kessler Springs by a water truck and
placed in a large bulk storage tank at
that location.
Table 1-1. Composition of Garfield Wetlands-Kessler Springs Water
Analyte
Units
Sampled 5/5/99
Conductivity
PH
Temperature
Alkalinity
Hardness
Total Dissolved Solids
Total Suspended Solids
Calcium
Chloride
Potassium
Magnesium
Sodium
Sulfate
Silver
Aluminum
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Manganese
Molybdenum
Nickel
Lead
Selenium
Selenate
Selenite
Zinc
umho/cm
standard units
°C
mg/L as CaCO3
mg/L as CaCO3
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
2,720
7.08
13
315
601
1,520
<3
145
496
11.6
58
380
294
<1
<5
140
34
<1
<10
29
<300
<10
100
<40
<5
1,950
1,870
49
<10
All field testing of these processes was
conducted by MSE and AB with assis-
tance from KUCC personnel as neces-
sary. All sampling and field work was
performed according to procedures out-
lined in the project specific quality as-
surance project plan and existing stan-
dard operating procedures.
All chemical analyses for collected
samples were conducted at the
Kennecott Environmental Laboratory
(KEL) located at KUCC. KEL is certi-
fied by the State of Utah and audited
annually by EPA. Confirmatory analyses
were performed on 10% of samples at
the HKM Analytical Laboratory located
in Butte, Montana. A comparison of the
KEL analyses and the HKM confirma-
tory analyses is presented in
Appendix A—Summary of Quality As-
surance Activities.
1.5 Technology Descriptions
The following technologies were dem-
onstrated during Phase 1 of this project:
• BDAT-ferrihydrite adsorption of se-
lenium;
• catalyzed cementation of selenium;
and
BSeR™ process.
A brief description of each technology
is provided in the following sections.
During Phase 2 of the project, an enzy-
matic selenium reduction technology
was evaluated, and additional data was
collected forthe catalyzed cementation
technology.
1.5.1 Ferrihydrite Adsorption
of Selenium
Ferrihydrite precipitation with concurrent
adsorption of selenium onto the
ferrihydrite surface (ferrihydrite adsorp-
tion) is EPA's BOAT for treating selenium-
bearing waters. For adsorption of sele-
nium using ferrihydrite to occur, the fer-
ric ion (Fe+3) must be present in the
water. Selenate (Se+6) is most effectively
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removed from the water at pH levels
be low 4.
The chemical reactions for ferrihydrite
precipitation of selenium are:
3H20
Fe(OH)3(so|id)+ 3H+; and
Fe(OH)
Fe(OH)
3(so|id)
3(so|id)
SeCV(ad)
8H+.
The selenium-iron solid product must be
separated from the treated water before
the process of selenium removal is com-
plete. During the demonstration, solid-
liquid separation was accomplished us-
ing a settler and filter press.
The selenium process water was deliv-
ered to the test site by a small tank truck
and then transferred to a bulk storage
tank. From the storage tank, the process
water was pumped to the ferrihydrite
adsorption process and the catalyzed
cementation process. This arrangement
provided the capability for operating both
systems simultaneously.
Detailed in Figure 1-2 is the mechanical
configuration of the ferrihydrite precipi-
tation process system as tested during
the pilot scale demonstration at a flow
rate of approximately 5 gpm. Starting
from the bulk storage tank, Garfield
Wetlands-Kessler Springs water was
introduced to the front end of the sys-
tem. A digital programmable peristaltic
metering pump controlled the flow rate
of the process waterthrough the treat-
ment system. Following the pump, a
turbine flow meter recorded the flow rate
and the total volume of water processed.
The ferric chloride reagent was intro-
duced next just in front of a static mixer.
The static mixer ensured a homoge-
neous mix, thus, reducing reaction time.
From the static mixer, the process wa-
terwas fed directly into an 80-gallon tank
where a lime slurry was injected to in-
crease the pH of the process water. A
pH probe and controller monitored and
adjusted the pH to an operator-selected
set point. Additionally, the oxidation-re-
duction potential (ORP) of this tank was
monitored and recorded. The overflow
from the pH adjustment tank was col-
lected in the transfer tank. A flocculent
was added to the second 80-gallon tank
to assist with solid separation in the
1,000-gallon thickener. A level transmit-
ter and level controller regulated the pro-
cess water level in the transfer tank by
adjusting the pumping rate of the trans-
fer pump. At a flow rate of 5 gpm, the
residence time of the thickener was
about 200 minutes. This was adequate
time for the solids to settle in the cone
of the thickener tank.
The treated process water was removed
from the top of the thickener and grav-
ity fed to an 80-gallon-batch transfertank.
To bring the pH of the water to neutral, a
small amount of lime slurry was added
to the transfertank priorto final filtering
and discharge. A pH probe and control-
ler regulated the proper amount of lime
slurry injected.The discharge pump op-
eration was controlled by a level switch
system that forced the waterthrough a
three-stage bag filter system. The filter
system was a precaution against
carryover of thickener solids in the
event of an upset in the system.
Solids that accumulated in the bottom
of the thickener were periodically re-
moved by a diaphragm pump. This
sludge slurry was then dewatered using
a filter press.The liquid separated from
the solids was returned to the thickener.
The filter cake solids were removed from
the filter press and prepared for analy-
sis or disposal by placing them in ap-
propriate containers. A photograph of the
ferrihydrite adsorption process inside the
MWTP demonstration trailer is presented
in Figure 1-3.
1.5.2 Catalyzed Cementation
of Selenium
Catalyzed cementation is a process that
was developed to remove arsenic and
other heavy metals such as thallium and
selenium from water.The term catalyzed
cementation describes the process's
ability to remove heavy metals from
solution by cementation on the surface
of the iron particles. It was anticipated
that the catalyzed cementation process
would have the ability to treat and re-
move selenium from solution regardless
of its valence state (+6 or +4). To opti-
mize the cementation process, propri-
etary catalysts are added to the process
to increase the selenium removal effi-
ciency.
Detailed in Figure 1-4 is the configura-
tion of the catalyzed cementation pro-
cess system as tested during the pilot-
scale demonstration. Starting from the
bulk storage tank, Garfield Wetlands-
Kessler Springs water was introduced
to the front end of the system at ap-
proximately 1 gpm. A digital program-
mable peristaltic metering pump con-
trolled the flow rate of the process wa-
ter to the treatment system. Following
the pump, a turbine flow meter was used
to record the flow rate and the total vol-
ume of water processed. The catalyst
reagent was introduced next, just in front
of the first static mixer. The static mixer
ensured a homogeneous mix and re-
duced the reaction time. Next, sulfuric
acid was injected to lower the pH of the
process water to the desired level. A
second static mixer was used to speed-
up the pH adjustment before the pro-
cess water entered the elemental iron
reactor. This reactor was a specialized
tank designed to fluidize the iron par-
ticles. Additionally, pH and ORP were
both closely monitored and recorded
within this reactor. Iron particles that
carried over were trapped in a small,
cone-bottom tank and pumped back to
the reactor for reuse.
Under gravity flow, the process water
from the top of the small, cone-bottom
tank was routed to a second 80-gallon
reactor. Here, the pH of the water was
raised with a lime slurry and an oxidizer
was added to complete the required re-
action. Flocculent was also added to this
reactor to assist with solid separation.
A level transmitter and level controller
regulated the process water level in the
reactor tank by adjusting the pumping
rate of the transfer pump. At a flow rate
of 1 gpm, the residence time of the thick-
enerwas about 15 hr. This was adequate
time for the solids to settle in the cone
of the thickener tank.
The treated process water was removed
from the top of the thickener and grav-
ity fed to an 80-gallon batch transfertank.
The operation of the discharge pump was
controlled by a level switch system that
forced the waterthrough a three-stage
bag filter system. The filter system was
a precaution against carryover of thick-
-------
ener solids in the event of an upset in
the system.
Solids that accumulated in the bottom
of the thickener were periodically re-
moved by a diaphragm pump. This
sludge slurry was then processed by a
filter press. The sludge liquid separated
from the solids was returned to the thick-
ener. The filter cake solids removed from
the filter press were prepared for analy-
sis or disposal by placing them in ap-
propriate containers. A photograph of the
catalyzed cementation process in the
MWTP demonstration trailer is shown
in Figure 1-5. In addition to the
ferrihydrite adsorption and catalyzed
cementation processes, the BSeR™
process was also demonstrated.
1.5.3 Biological Reduction of
Selenium
To accomplish biological selenium re-
duction, researchers at AB of Salt Lake
City, Utah, have developed the BSeR™
process using anaerobic solids bed re-
actors (BASER). Selenium (selenate and
selenite) was reduced to elemental se-
lenium by specially developed biofilms
containing specific proprietary microor-
ganisms. This process produces a pre-
cipitate of elemental selenium. With the
aid of backflushing, 97% of the sele-
nium reduced in the system can be re-
moved from the bioreactors. This pro-
cess was designed by AB and con-
structed with assistance from KUCC.
The BSeR™ process was demonstrated
using a defined mixture of Pseudomo-
nas and other microbes for removing
selenium from Garfield Wetlands-Kessler
Springs water. A block flow diagram of
the BSeR™ process is shown in Fig-
ure 1-6. A photograph of the BSeR™
process at the Garfield Wetlands-Kessler
Springs site is shown in Figure 1-7.
Garfield Wetlands-Kessler Springs wa-
ter was pumped to the BSeR™ process
at a flow rate of approximately 1 gpm
using a solar pump. A flow meter/total-
izer recorded the actual flow rate and
the total volume of water processed by
the BSeR™ process.The Garfield Wet-
lands-Kessler Springs water then en-
tered a series of 500-gallon bioreactors
containing carbon/biosolids/biofilm com-
bination orcarbon/biofilm, depending on
the test series. Nutrients were supplied
to the reactors at three locations in the
process. When the water had flowed
through the appropriate number of
bioreactors, it was filtered by a slow sand
filter before discharge.
Testing done previous to the pilot-scale
demonstration produced the patent pend-
ing BSeR™ process that is demon-
strated to reduce selenate and selenite
in mining process solutions, petroleum
wastewaters, and agricultural run-off
using both single microbes and site-spe-
cific selenium-reducing bacteria. Initial
batch and continuous bioreactor tests
demonstrated selenium removal up to
97% in wastewaters containing up to
33.1 mg/L selenium in 4 to 6 hrwith high-
density microbial and microbial cocktail
biofilms. In additional laboratory tests
using a semi-fluidized bed reactor, live
microbial and microbial cocktail biofilms
have demonstrated selenium reduction
rates of approximately 40 mg/L per 6 hr
(Refs. 3 thro ugh 6).
The BSeR™ process implementation/
configuration approach was to charac-
terize and optimize naturally occurring
microbial and like proprietary laboratory
strains for each site-specific application.
Using known, tested microbial strains
and enhanced biofilm establishment
techniques prevented the nonintentional
incorporation of pathogens, undesirable
indigenous nonselenium reducing mi-
crobes, and helped to ensure optimum
selenium removal rates.
1.5.4 Enzymatic Reduction of
Selenium
AB has isolated an optimized mixture
of naturally occurring bacterial enzymes
from heterotrophic bacteria previously
isolated from selenium contaminated
mining waters and soils. The bacterial
enzymes reduce selenate and selenite
in mining wastewaters to elemental se-
lenium. Advantages of these cell-free
systems over live bacterial systems in-
clude: (1) the potential for greatly in-
creasing kinetics; (2) nutrients are not
required; and (3) the effects of toxic pro-
cess solutions can be eliminated. Bench-
scale testing was performed to evalu-
ate the enzymatic selenium reduction
process and to make a decision whether
to scale-up the process to pilot-scale
for field demonstration. The enzymatic
selenium reduction process was not rec-
ommended for scale-up due to the in-
stability of the enzyme system matrix;
therefore, a process flow diagram is not
included for this technology.
1.6 Project Objectives
The primary objective of the field dem-
onstration project was to assess the
effectiveness of the processes being
tested for removing selenium from
Garfield Wetlands-Kessler Springs Wa-
ter. More specifically, the objective that
was defined for the project was to re-
duce the concentration of dissolved se-
lenium in the effluent waters to a level
under the National Primary Drinking
Water Regulation MCL for selenium (50
ug/L) established by the EPA.
A secondary objective forthe products
from the catalyzed cementation and
ferrihydrite precipitation processes was
to render them environmentally stable
by demonstrating that selenium results
will be below the Maximum Concentra-
tion forToxicity Characteristic using tox-
icity characteristic leaching procedure
(TCLP)of1.0mg/L.
For AB's BSeR™ process, the product
was expected to be marketable, and the
secondary objective was to determine
the purity and marketability of the prod-
uct, and the impact the product had on
process economics.
Another secondary objective was to
perform an economic analysis for the
scale-up of the processes tested to treat
300 gpm flow at the Garfield Wetlands-
Kessler Springs site. The economic
analysis for this project is presented in
Section 3 of this report and represents
an order of magnitude cost estimate.
-------
Figure 1-1. MWTP demonstration trailer at the field site.
Reagent 1 ii Lime
PortFH4 15 Micron 10 Micron 1 Micron
T
Sample
Port FH5
Figure 1-2. Ferrihydrite precipitation process flow diagram.
-------
Figure 1-3. Ferrihydrite adsorption process in MWTP demonstration trailer.
Reagent 1 B Reagent 2
To Ferrihydrite
Precipetation
System
d -3
? pt q
Thickener
if
Sample
*l
Ljt'^
H M^f^^ ^3
x"^-^,r
80 gal i — fcf^
Sample T 5 Micron
Port CC4
Se^lceAr , Filter Pr6
n H
Return O— ^M-
U U 1
fT ^fl T
Sample
UJ UJ P°rtCC5
.0 Micron 0.5 Micron
s
:
Sludge
Figure 1-4. Catalyzed cementation process flow diagram.
-------
Figure 1-5. Catalyzed cementation process in MWTP demonstration trailer.
Sample
Port BROS
Figure 1-6. BSeR™ process flow diagram.
-------
Figure 1-7. Field-scale BSeR™ process reactor.
-------
2. Demonstration Description and Results
The following sections provide a descrip-
tion of the pilot-scale demonstration and
any additional work for each technology
as well as a brief discussion of the dem-
onstration results. Field and laboratory
data associated with each pilot-scale
and bench-scale technology demonstra-
tion are contained in Appendix B. The
sampling and analysis schedules for
each pilot-scale technology demonstra-
tion are contained in Appendix C.
The achievement of the primary project
objective for each process was deter-
mined by analyzing effluent samples for
dissolved selenium concentration. Ap-
propriate statistical tests were per-
formed to determine the effectiveness
of each process for selenium removal.
Procedures outlined in Guidance for
Data Quality Assessment (Ref. 6) were
used to determine whetherthe data from
each process was statistically below the
action level of 50 ug/L dissolved sele-
nium. During the demonstration of the
ferrihydrite precipitation and catalyzed
cementation processes, several differ-
ent testing conditions were necessary
before the processes removed selenium
below the action level. Eventually, all
three processes did remove selenium
to below the action level of 50 ug/L; how-
ever, the ferrihydite adsorption and the
catalyzed cementation processes did
not remove selenium to below 50 ug/L
on a consistent basis. To determine if
the primary project objective had been
met, a Wilcoxon Signed RankTestwas
performed on the effluent data set for
each process. The Wilcoxon Signed
RankTestwas selected because each
of the distributions were non-normal.
Data QUEST software was used to test
for normality. Filibens statistic (n>50) was
used for the BSeR™ process and the
ferrihydrite adsorption process, while the
Shapiro-Wilks test (n<50) was used for
the catalyzed cementation process. Non-
normality was detected for all three dis-
tributions at a 5% significance level.The
null hypothesis for the Wilcoxon Signed
RankTestwas Ho: mean >50 ppb, and
the alternative hypothesis was
Ha: mean <50 ppb.The calculated sum
of the Ranks for each process was com-
pared to the critical value (w) at <* =
0.05. Because the number of samples
was greaterthan 20, a large sample ap-
proximation to the Wilcoxon Signed
Rank Test was performed by calculat-
ing the z statistic for each process and
comparing it to the critical value of z1 _K
The results of the inferential analysis
for all three processes are presented in
Table 2-1. The BSeR™ process was
the only technology that could reject the
null hypothesis at a 5% significance
level; thus, the effluent data from the
BSeR™ process effluent suggests that
the alternative hypothesis is more likely.
The only process that was shown to sta-
tistically reduce selenium below the ac-
tion level of 50 ug/L was the BSeR™
process. In fact, all of the effluent data
from all BSeR™ process tests were less
than 50 ug/L with the exception of some
samples collected during start-up
phases as the biofilm was maturing.
2.1 Ferrihydrite Adsorption
Demonstration and Re-
sults
The ferrihydrite precipitation process was
optimized by MSE for the demonstra-
tion. During the demonstration, several
different tests were run to obtain the low-
est possible concentration of selenium
in the effluent water.
The effluent samples from the
ferrihydrite precipitation processes were
characterized to determine how effec-
tively each treatment condition removed
selenium from the Garfield Wetlands-
Kessler Springs water. The solid prod-
ucts from the ferrihydrite precipitation
process were analyzed forTCLP con-
stituents as well as total constituents
of interest.
Ferrihydrite precipitation is considered
ERA'S BOAT for selenium removal. Sev-
eral tests were performed to determine
the iron concentration necessary to re-
move selenium to below the target level
of 50 ug/L. The various tests included:
low iron condition (~1400 mg/L iron);
medium iron condition (~ 3000 mg/
L iron);
high iron condition (~4800 mg/L
iron);
ferrous/ferric condition (~1200 mg/
L ferrous/1200 mg/L ferric); and
sludge recycle conditions (~2340
to 13290 mg/L iron).
Table 2-1. Summary of Results for Wilcoxon Signed Rank Test
Process R calculated w, critical z calculated z1005critical
Result
Ferrihydrite Adsorption
Catalyzed Cementation
BSeR™ Process
0
3
2,256
1,211
636
1,565
-6.846
-21.85
5.603
1.645
1.645
1.645
Reject the null hypothesis at a 5%
significance level because
z calculated >z critical.
' There is not enough evidence to reject the null hypothesis at a 5% significance level because z calculated
-------
A graph of the results from the various
test conditions is presented in Figure 2-
1. The influent data represents Garfield
Wetlands-Kessler Springs water, FH3
results were from midpoint in the sys-
tem, and the effluent data are the dis-
charge from the process. FH3 data are
included because several times during
the testing, results from midpoint in the
process were less than the results at
the effluent location. This may have
been due to iron suppression of the se-
lenium signal during inductively coupled
plasma mass spectrometer analysis of
the samples. The only conditions that
removed selenium below 50 ug/L were
the medium and high iron conditions, and
this was only on a limited number of
samples at the midpoint (FH3) of the
process. Table 2-2 summarizes the re-
sults for each treatment condition.
2.1.1 Low Iron Test Results
The ferrihydrite demonstration was initi-
ated in the MWTP demonstration trailer.
The average pH during the low iron test-
ing period was 3.9.The initial target iron
concentration in the first 80-gallon tank
in the process was approximately 1,400
mg/L iron (Fe/Se ratio, 900:1). Garfield
Wetlands-Kessler Springs water was fed
to the system at approximately 5 gpm.
The mean selenium effluent concentra-
tion during the low iron tests was 303
ug/L [standard deviation (std dev), 69.4],
well above the target of 50 ug/L. The
minimum effluent selenium concentra-
tion during the low iron period was
115 ug/L.
2.1.2 Medium Iron Test Re-
sults
Because selenium removal was not at
target levels, the target iron concentra-
tion was increased to 3,000 mg/L iron
(Fe/Se ratio, 2000:1). The average pH
values recorded during this testing pe-
riod was 4.1 .The mean selenium efflu-
ent concentration during the medium iron
concentration tests was 201 ug/L (std
dev 103).The minimum effluent concen-
tration achieved during this testing pe-
riod was 42 ug/L selenium. Lower sele-
nium results were achieved in the efflu-
ent samples with an increase in iron
concentration from the low iron tests to
the medium iron tests, so the iron con-
centration was further increased during
the high iron concentration tests.
2.1.3 High Iron Test Results
The high iron test was initiated with iron
concentrations of 4,800 mg/L (Fe/Se
ratio, 3200:1).The mean selenium efflu-
ent concentration for this testing period
was 90 ug/L (std dev28), and the aver-
age pH value was 3.8. The minimum
selenium effluent concentration
achieved was 35 ug/L. Because reagent
consumption (ferric chloride) was exces-
sive during this period, high iron testing
was suspended, and the system was
set up to run a mixture of ferrous/ferric
iron.
2.1.4 Ferrous/Ferric Test Re-
sults
To determine if the presence of ferrous
iron in the system would positively im-
pact selenium removal, a treatment con-
dition using both ferrous and ferric iron
was established.The amount of ferrous
iron was increased in the system using
ferrous sulfate. For this testing period,
ferrous iron was approximately 1,200
mg/L, and ferric iron was approximately
1,200 mg/L. This process modification
was not successful. The mean effluent
selenium concentration during this test
period was 563 ug/L (std dev280). Once
Table 2-2. Summary Results for Ferrihydrite Adsorption Tests
Treatment Condition
Mean Se Effluent Concentration
iStandard Deviation
(n = sample size)
Minimum Selenium Concentration
Low iron
Medium
iron
High iron
Ferrous/ferric
Recycle
Sludge
304
201
90
563
387
ug/L
ug/L
ug/L
ug/L
ug/L
+69
+ 103
+28
(n =
(n =
(n =
+280 (n
+58
(n =
27)
= 13)
5)
= 5)
12)
42 ug/L
35 ug/L
(at
(at
1
115 ug/L
midpoint of
midpoint of
409 ug/L
77 ug/L
0
process)
process)
these high selenium results were re-
ceived from the laboratory, testing of this
configuration was suspended.
2.1.5 Sludge Recycle Tests
The sludge generated from previous pro-
cess tests was recycled during this test
period. The iron used to attain the me-
dium and high iron concentration condi-
tions was in excess stoiciometrically so
the sludge was recycled to take advan-
tage of additional, available adsorption
sites.To attain the desired iron concen-
tration while minimizing reagent con-
sumption, the sludge was recycled to
the initial 80-gallon tank in the process.
The mean selenium effluent concentra-
tion during this testing period was 387
ug/L (std dev 58). The minimum con-
centration of selenium in the effluent
achieved during this testing period was
77 ug/L.
2.1.6 TCLP Results
To determine if the secondary objective
had been achieved, filter cakes produced
by the ferrihydrite adsorption process
were subjected to TCLP analysis. The
results are summarized in Table 2-3.
While both filter cake samples failed
TCLP for selenium (i.e., >1 mg/L), the
total metal results presented in the last
column of the table should be at least
20 times greater than the TCLP results
but are instead less than detection.
Therefore, TCLP results are question-
able for the ferrihydrite adsorption pro-
cess because the TCLP results for se-
lenium do not correlate with the total
selenium values. In the presence of ex-
cess iron, selenium is very difficult to
detect in small concentrations.
Approximately 19,090 gallons of Garfield
Wetlands-Kessler Springs water were
processed during the ferrihydrite precipi-
tation portion of the demonstration. The
processed waterwas routed into KUCC's
process water circuit and any wastes
generated from the project were placed
in KUCC's on site Comprehensive En-
vironmental Response, Compensation,
and Liability Act repository. Three days
afterthe ferrihydrite tests were initiated,
the catalyzed cementation process test-
ing was initiated.
-------
Table 2-3. TCLP/Total Selenium Results for Ferrihydrite Adsorption Filtercake Samples
AG-TCLP AS-TCLP BA-TCLP CD-TCLP CR-TCLP HG-TCLP PB-TCLP SE-TCLP SE-Total
Sample Col. 0.1 0.1 0.1 0.01 0.1 0.001 0.1 0.1 0.5
Description Date mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/kg
FH 10/31/1999 0.1 <0.1 0.1
Filtercake-221
FH 11/18/1999 <0.1 <0.1 0.1
Filtercake-225
0.01
0.001
<0.001
1.6
1.1
<0.5
<0.5
2.2 Catalyzed Cementation
Process Demonstration
MSE tested several physical/chemical
selenium removal technologies on a
bench-scale to determine which tech-
nology would be tested on a pilot scale.
Catalyzed cementation was the best
selenium removal technology to emerge
as a result of the bench-scale testing.
Previous tests performed by Dr.Twidwell
along with thermodynamic data strongly
indicated that catalyzed cementation
would be effective. Bench-scale results
indicated that this process could remove
selenium to below 50 ug/L. Scale-up to
the pilot-scale did not immediately yield
the same results.
Garfield Wetlands-Kessler Springs wa-
ter was fed to the catalyzed cementa-
tion process at approximately 1 gpm.
Chemistry conditions that were suc-
cessful on a bench-scale were dupli-
cated to maximize selenium removal.
Despite attaining the proper conditions,
selenium removal was not very success-
ful for the majority of the tests. During
the first 16 days of the test, the mean
effluent selenium concentration was 834
ug/L (std dev 204). The minimum sele-
nium concentration attained in the efflu-
ent water was 193 ug/L.
Near the end of the testing period, the
pH in the cementation reactor was re-
duced to 3 and an increased oxidation
condition was generated following the
cementation step in an effort to improve
the results. The mean effluent selenium
concentration during this testing period
was 35 ug/L, and the minimum effluent
selenium concentration was 26 ug/L.
These results were more promising than
the initial portion of the testing, and the
testing would have been continued; how-
ever, results were not received from the
laboratory until the operation of the cata-
lyzed cementation process had been
suspended. A summary of results from
the field testing and additional testing
of the catalyzed cementation process
are summarized in Table 2-4. A graph of
the influent and effluent selenium con-
centrations for the catalyzed cementa-
tion process is presented in Figure 2-2.
Influent values represent the selenium
concentration in Garfield Wetlands-
Kessler Springs water, CCS values rep-
resent midpoint of the process, and ef-
fluent values represent the discharge
stream from the process. Approximately
10,000 gallons of Garfield Wetlands-
Kessler Springs water were processed
during the catalyzed cementation por-
tion of the demonstration.
Additional testing to duplicate these
optimum conditions for selenium re-
moval was performed at MSE's testing
facility. Preliminary results indicated that
the process consistently removed sele-
nium to below 40 ug/L, the inductively
coupled plasma (ICP) detection limit at
the HKM Laboratory. All samples below
100 ug/L were reanalyzed by furnace
atomic absorption spectroscopy (AA)
(detection limit 1 ug/L) to better quan-
tify the selenium removal.The AA analy-
sis yielded sample concentrations rang-
ing from <1 to 28 ug/L with a mean ef-
fluent concentration of 3 ug/L.
A process similar to catalyzed cemen-
tation is currently being investigated by
Dr.Twidwell at Montana Tech of the Uni-
versity of Montana as part of MWTP,
Activity IV, Project 19-Removing
Oxyanions of Arsenic and Selenium
from Mine Waste Waters Using Galvani-
cally Enhanced Cementation Technol-
ogy.The results of the research thus far
have been very promising. If this modi-
fied cementation technology proves to
be effective, it should be considered for
pilot-scale testing.
Investigations utilizing agitated iron slur-
ries and columns packed with iron have
been performed by Eric Dahlgren (MSc
graduate student at Montana Tech of the
University of Montana and Dr.Twidwell
(thesis advisor). These studies have
demonstrated and optimized the cemen-
tation process applied to selenium re-
moval from synthetic and actual plant
process waters. Their results (Ref. 7)
show that detection limit concentrations
of selenium (<1 ppb) can be obtained
utilizing the iron cementation technol-
ogy.
Table 2-4. Summary of Results for the Catalyzed Cementation Process Demonstration
Treatment Condition
Mean Selenium Concentration
(ug/L)±standard deviation
(n = sample size)
Minimum Effluent
Selenium
Concentration (ug/L)
Catalyzed Cementation
Catalyzed Cementation with Increased
Oxidation/Decreased pH in the Reactor
834 ug/L ±204 (n = 42)
35 ug/L (n = 2)
Tank
193 ug/L
26 ug/L
Additional Testing of Catalyzed
Cementation Under Optimized Conditions
3 ug/L1 ±4.4 (n = 5)
ug/L
1 Nondetects were substituted with 50% of the detection limit (0.5 ug/L) to determine the mean
selenium concentration.
11
-------
Table 2-5. TCLP Results for Catalyzed Cementation Filtercake Samples
Sample Description
CC Filtercake-221
CC Filtercake-225
Col.
Date
11/06/1999
11/15/1999
AG-TCLP
0.1
mg/L
<0.1
<0.1
AS-TCLP
0.1
mg/L
<0.1
<0.1
BA-TCLP
0.1
mg/L
0.1
0.1
CD-TCLP
0.01
mg/L
<0.1
0.02
CR-TCLP
0.1
mg/L
<0.1
<0.1
HG-TCLP
0.001
mg/L
0.001
0.002
PB-TCLP
0.1
mg/L
<0.1
<0.1
SE-TCLP
0.1
mg/L
0.3
<0.1
2.2.1 TCLP Results
To determine if the secondary objective
was achieved, filter cake produced by
the catalyzed cementation process was
subjected to TCLP analysis. The results
are summarized in Table 2-5. Both filter
cake samples were below the TCLP
threshold value forselenium of 1 mg/L.
These results indicate that the catalyzed
cementation process produced an envi-
ronmentally stable precipitate, and there-
fore achieved the secondary project
objective. In addition to the catalyzed
cementation and ferrihydrite adsorption
technologies, the BSeR™ process was
also demonstrated.
2.3 Biological Selenium Re-
duction Process Demon-
stration
The BSeR™ process was demonstrated
at the Garfield \Afetlands-Kessler Springs
site with a feed flow rate of approxi-
mately 1 gpm. Tests with residence times
of approximately 12, 11, 8, and 5.5 hr
(per reactor) were conducted. The
BSeR™ process was demonstrated
longer than the other processes to de-
termine the reliability/longevity of the
system. The BSeR™ process treatment
unit was designed and built by AB with
assistance from KUCC. Selenium val-
ues for all effluent samples were main-
tained below the 50 ug/L target for the
entire test period.The pH in the individual
reactor effluents ranged from 6.3 to 7.5,
and the final discharge had an average
pH of 7.26 over the entire pilot test pe-
riod; anaerobic conditions were main-
tained in the reactors. Three different
reactorseries were operated in the field,
treating a combined total of over 100,000
gallons of Garfield Wetlands-Kessler
Springs water:
Series 1 used 5 reactors in series
(carbon/biosolids/biofilm) with a
sixth reactor for inoculum and mix-
ing nutrients to feed the reactors;
Series 2 used 3 anaerobic reac-
tors (carbon/biofilm) in series; and
Series 3 used 3 anaerobic reac-
tors (carbon/biofilm) in series.
Series 2 and 3 allowed for side-by-side
comparison of two identical systems.
Laboratory-scale reactors, started in
advance of the field demonstration
project, were used to help predict and
optimize the BSeR™ process field re-
actors. Laboratory testing results are in
Appendix D. An agricultural grade mo-
lasses was used as a base for a propri-
etary nutrient supplement that was
mixed with the reactor feed waters to
maintain the biofilm and provide energy
for selenium reduction. A summary of
the results from the BSeR™ process
field testing is presented in Table 2-6.
The mean selenium concentrations in
the effluent for each residence time test
were well below the 50 ug/L target con-
centration. Over 70% of the samples
collected during the approximately 6
months of operation were below detec-
tion.
2.3.1 Series 1-Carbon/Bio-
film and Biosolids
Biofilm Reactors
The initial test configuration utilized both
carbon/biofilm and biosolids/biofilm re-
actors in series. This test series was at
a fixed retention time of 12-hr per reac-
tor. After approximately 1 month of con-
tinuous operation, the reactors were
decommissioned, and the matrix mate-
rial was disposed. The five-reactor
BSeR™ process system was terminated
when the entire system was inadvert-
ently heated to over 55 °C.The system
was cleaned up, replumbed for opera-
tion as two, three-reactor systems; filled
with new activated carbon; and reinocu-
lated. Based on an evaluation of the
biosolids matrix material, a decision was
made to remove this matrix from future
testing.The mean effluent concentration
during this test series was 8.8 ug/L, and
minimum effluent concentration was <2
ug/L. Figure 2-3 shows the results of
these tests. The selenium removal was
very good within the initial reactors; there-
fore, a decision was made that fewer
reactors (three rather than five) could
be used during subsequent test series.
Table 2-6. Summary of Results from BSeR™ Process Field Tests
BSeR™ Process Results
Residence Time
Mean Selenium Concentration
(ug/L)1 istandard deviation
(n = sample size)
Minimum Effluent Selenium
Concentration (ug/L)
12 hr (Series 1)
1 1 hr (Series 2)
8 hr (Series 3)
5.5 hr (Series 2)
8.8 ug/L ±10.2 (n = 17)
4.9 ug/L ±4.9 (n = 16)
<2 ug/L ±2.6 (n = 12)
<2 ug/L ±2.1 (n = 26)
<2 ug/L
<2 ug/L
<2 ug/L
<2 ug/L
Nondetects were substituted with 50% of detection limit (1 ug/L) to determine the mean selenium
concentrations.
12
-------
2.3.2 Series 2 and 3 Carbon/
Biofilm Reactors
Two new series of reactors (three car-
bon/biofilm reactors each) were
reconfigured for operation at the site.
This new configuration allowed forside-
by-side performance comparisons of two
identical systems. In three different runs,
systems were operated at retention
times of 11, 8, and 5.5 hr (per reactor).
Selenium removal, as a function of re-
actor retention time, is shown in Figure
2-4 combining data from the three reac-
tor retention times (11,8, and 5.5 hr).
The average reactor temperature was
about the same as the influent spring
water ~16 °C and the pH of the influent
and effluent waters ranged from ~7.0 to
7.7 with a general slight lowering of pH
through the reactor systems. The het-
erotrophic facultative anaerobic nature
of the selected microbial biofilm allowed
effective selenium removal to below
MCL levels at ORP values ranging from
>200 to <-50 millivolts.
Biofilms capable of reducing both sel-
enate and selenite produced an elemen-
tal selenium precipitate that was readily
evident in the reactors and connecting
tubes after ~48 hr of operation (see Fig-
ure 2-5). All but four effluent samples
were below 10 ug/L, and greater than
70% of the effluent samples were be-
low detection.
An ICP metals scan was performed on
the system effluents to determine the
removal efficiencies of other metals
present in the Garfield Wetlands-Kessler
Springs water. The BSeR™ process
system also effectively removed trace
levels of arsenic and copper from the
system. Arsenic in the Garfield Wet-
lands-Kessler Springs water was re-
moved from 70 ug/L to below detection,
and copper was removed from 26 ug/L
to below detection.
Laboratory tests demonstrated that agi-
tation and/or back flushing freed much
of the biologically reduced selenium
from the biofilm support materials
(granular carbon) and that filtration
through a filter press would remove ap-
proximately 97% of the selenium. The
collected elemental selenium/microbial
product has a potential market niche as
an animal feed supplement. Marketabil-
ity analysis conducted in collaboration
with in international feed supplement
distributor indicates that the elemental
selenium from the BSeR™ process can
be used in various feed supplements.
According to the distributor, the micro-
bial biomass associated with the
BSeR™ process will contribute an ad-
ditional value.
2.4 Enzymatic Selenium Re-
duction Bench-scale
Evaluation
Applied Biosciences has isolated an
optimized mixture of naturally occurring
bacterial enzymes from heterotropic
bacteria previously isolated from sele-
nium contaminated waters and soils.The
bacterial enzymes, which reduce sel-
enate and selenite to elemental selenium
were used to develop the enzymatic
selenium reduction process. The enzy-
matic selenium reduction process was
demonstrated at bench-scale by AB.
The testing included the following tasks:
test enzyme extracts from mi-
crobes with best demonstrated se-
lenium reduction capabilities;
optimize selenium enzyme extrac-
tion/purification protocols;
examine immobilization/encapsula-
tion formulations to increase the
stability and extend the functional
longevity of the enzyme prepara-
tions;
evaluate the immobilized/encapsu-
lated enzyme preparations for du-
rability and enzyme function (ki-
netics and stability); and
determine initial bench-scale pro-
cess operational parameters and
any pretreatment recommenda-
tions.
Top performing microbial cultures previ-
ously isolated from selenium contain-
ing mining wasters and soils were used
as the source material for enzyme prepa-
rations. The prepared extracts were
evaluated and screened over a 2-month
period and compared to live cell prepa-
rations and appropriate controls. While
the enzyme preparations initially ex-
ceeded the activity of the live cell prepa-
rations, a loss of stability was observed
in the enzyme preparations that was not
observed in the live cell preparations.
Due to the instability of the enzyme sys-
tems tested, the technology was not
recommended for pilot-scale testing.The
following conclusions were drawn based
on the enzymatic selenium reduction
bench-scale testing.
Microorganisms are an alternative
source for inorganic contaminant
reducing enzymes.
Selenium reduction in the pres-
ence of cyanide is possible using
select enzyme preparations.
Calcium alginate outperformed
other encapsulation polymers in re-
gards to ease of handling, toxicity,
cost, and performance. AB's re-
port summarizing the enzymatic
bench-scale testing is contained
in Appendix E.
Further research is recommended to
further develop the electron donor sys-
tem and enhance the operational lon-
gevity of the enzymatic selenium reduc-
tion technology. This research and de-
velopment work is necessary to com-
plete prototype development for this
technology.
13
-------
Selenium Removal Demonstration Project
Ferrihydrite Adsorption Process
0
100
200 300 400
Hours of Test
500
600
700
• Influent
• Effluent
FH3 Selenium
Figure 2-1. Summary of results from ferrihydrite adsorption tests.
Selenium Removal Demonstration Project
Catalyzed Cementation Process Increased
Oxidation/Decreased
pH in reactor tank
1600
1400 -
"ex 1200
"^ 1000 -
c
0
U 800 -
E
- 600
—
grj ^tUU
200
^•^
"" "* *""""--*— ^__«/\
; \
^MtfU^H t^J-
: ^^ \ *v m^9 v
"^A^'^ ^B*M , ^r \ H
• \
\
: \
— *
^
m
"•.
_» , » ,
0 100 200 300 400 50
Hours of Test
• Ffflnpnt A PP^ ^plpniiir
1 Influent
n
Figure 2-2. Summary of results for field catalyzed cementation process
tests.
14
-------
Biological Selenium Removal (12 Hour RT)
• Influent
d Reactor 1
d Reactor 2
d Reactor 3
• Reactor 4
d Reactor 5
Figure 2-3. Series 1 Pilot-scale BSeR™ process operation at a 12-hr retention time
per reactor.
Biological Selenium Removal
2500
O)
Dlnfluent
D Reactor 1
D Reactor 2
D Reactor 3
Day
Figure 2-4. BSeR™ process pilot-scale reactor summary graph.
15
-------
Figure 2-5. A red, amorphous, selenium precipitate observed in process piping
after 8 hr of operation.
16
-------
3. Economic Analysis
A secondary objective of this study was
to perform an economic analysis of the
processes demonstrated.The costs pre-
sented are an order of magnitude cost
estimate based on each of the treatment
flow sheets. Definitions and cost esti-
mation factors are taken primarily from
similar work performed under MWTR
Itemized equipment lists were used
where available.
Major cost items have been included.
Capital costs include minor equipment,
instrumentation, process piping, auxil-
iary engineering, and plant size factors
forthe ferrihydrite adsorption and cata-
lyzed cementation processes. Capital
costs provided by AB for the BSeR™
process included only biofilm support
materials and $40,000 to perform retro-
fits to the existing watertreatment plant.
The following assumptions were made
for completing the cost estimates:
- the processes would be installed
at KUCC utilizing an existing wa-
ter treatment facility;
- regulatory permits are in place;
- the Garfield Wetlands-Kessler
Springs flow rate is 300 gpm, con-
taining 2 mg/L selenium; and
- depreciation, leases, salvage and
taxes were not considered.
A scale-up of each process to treat the
entire 300 gpm of Garfield Wetlands-
Kessler Springs flow was used as the
basis of the economic analysis. Retrofit
of equipment located at the existing
water treatment facility was used as the
basis forthe scale-up. Because the field
testing of the BSeR™ process and the
catalyzed cementation process were
only performed at 1 gpm, scaling up of
these processes may not be as accu-
rate as scaling up the ferrihydrite ad-
sorption process that was demonstrated
at 5 gpm.
3.1 Ferrihydrite Adsorption
of Selenium
The cost estimates presented for the
scale-up of the ferrihydrite adsorption
system are conceptual in nature and
would be adjusted when an actual sys-
tem design was implemented. Initial in-
dications are that the reagent consump-
tion of this technology when effective
(high iron condition) makes it cost pro-
hibitive.The reagent consumption of this
technology alone is estimated to be
$15.17/1,000 gallons treated when re-
agents are purchased in bulk. The esti-
mates are based on information con-
tained in the Chemical Market Reporter
(Ref. 8). The majority of this cost was
due to the high cost of the ferric chlo-
ride reagent, which accounts for$14.31/
1,000 gallons treated of the reagent
costs. In a full-scale system, these
costs would probably be lower if sludge
generated was recycled to the reaction
tank, thus, minimizing the fresh reagent
usage.
Table 3-1 summarizes the capital costs
and construction times necessary to
retrofit the existing KUCC Waste Water
Treatment Plant for ferrihydrite adsorp-
tion of selenium (high iron condition).
The costs are associated with a sys-
tem designed to handle a 300-gpm peak
flow rate. Due to the difference in flow
rate capability between the existing sys-
tem and that of the scaled-up systems,
most pumps and piping will require re-
placement.
Table 3-1. Capital Costs/Construction Schedule for Ferrihydrite Adsorption System Scale-Up
Task
MSE System Design
MSE Subcontract Construction Oversight
MSE System Startup, Commissioning, and
Project Closeout
Demolition, Building Modifications,
Construction
Time Materials
1 1 .3 weeks
8 weeks
5 weeks
12 weeks $612,107
Labor
$145,450
$51,530
$44,190
$36,079
Travel
Nonlabor
$1 1 ,538
$21 ,568
$10,266
Total
$156,988
$73,274
$54,375
$648,850
Equipment Purchase, and Installation by Subcontract
Total
Schedule/Cost Contingency @ 10%
TOTAL
27.3 weeks
2.7 weeks
30 weeks
$933,487
$93,348
$1,026,835
17
-------
The cost of a filter press (approximately
$89,000) was also included in this esti-
mate and may not be necessary depend-
ing on how the wastestreams from the
system would be handled atKUCC. If a
filter press was not necessary, the as-
sociated savings including shipping, fil-
ter press stand, sludge handling equip-
ment, labor for installation, and design
labor would be estimated at $113,000.
3.2 Catalyzed Cementation of
Selenium
The cost estimates presented for the
scale-up of the catalyzed cementation
system are conceptual in nature and
would be adjusted when an actual sys-
tem design was implemented. Initial in-
dications are that the reagent consump-
tion of this technology is still high, al-
though approximately half of the reagent
costs forthe ferrihydrite adsorption sys-
tem. The reagent consumption of this
technology is estimated to be $8.11/
1,000 gallons treated. The majority of
this cost is due to the cost of the oxi-
dizing reagent, which accounts for
$5.81/1,000 gallons treated of the re-
agent costs. One way to reduce this cost
would be to substitute the reagent used
with a more cost effective alternative.
Table 3-2 summarizes the capital costs
and construction times necessary to
retrofit the existing KUCC Waste Water
Treatment Plant. The costs are associ-
ated with a system designed to handle
a 300-gpm peak flow rate. Due to the
difference in flow rate capability between
the existing system and that of the
scaled-up systems, most pumps and
piping will require replacement.
The cost of a filter press (approximately
$89,000) was included in this estimate
and may not be necessary depending
on how the wastestreams from the sys-
tem would be handled at KUCC. If a fil-
ter press was not necessary, the asso-
ciated savings including shipping, filter
press stand, sludge handling equipment,
labor for installation, and design labor
would be estimated at $113,000.
Also included in this cost estimate is
approximately $75,000 in the system
design task to perform additional re-
search and development work on this
process. Additional work is necessary
to optimize reactordesign, optimize el-
emental iron selection, optimize the con-
ditions to maximize selenium removal,
and optimize reagent additions.
The work of Dahlgren (Ref. 7) has shown
that if a reactor is constructed so that
very little air infiltration occurs, then the
second-stage oxidation of the ferrous
iron to ferric iron (with the subsequent
ferric hydroxide, ferrihydrite, precipita-
tion ) is unnecessary. This is because
the cementation process is very effec-
tive at removing selenium (<5 ppb) at
pH 7-8. When the system is operated
at pH 7-8, very little ferrous iron is pro-
duced (i.e., only a few ppm of iron dis-
solves). The ferrihydrite precipitation
second stage of the present process is
the most cost intensive step in the en-
tire treatment sequence. Therefore, the
cost of the catalyzed cementation tech-
nology will likely be a cost competitive
bioprocess or less than $1.32 per 1,000
gallons (Ref. 9).
3.3 Biological Selenium Re-
duction (BSeR™) Pro-
cess
Nutrient costs can be a primary contribu-
torto the long-term operating cost of any
biological process. Biotreatability results
indicated that efficient short-term sele-
nium reduction could be obtained with
several media types; however, long-term
selenium removal is dependent on a
balanced nutrient mixture formulated to
match process, microbial, and site wa-
ter characteristics. The BSeR™ process
has worked effectively in all waters
tested with an inexpensive molasses-
based nutrient. Nutrient costs can be
reduced through careful microorganism
selection and managed bioreactor mi-
crobial density. As determined in labo-
ratory and pilot-scale tests, operating
costs forthe BSeR™ process are esti-
mated to be less than $0.50/1,000 gal-
lons of treated waterwhen nutrients are
purchased in bulk quantities.
3.3.1 Nutrient Costs
Nutrient costs for reactor operation at
the selected flow rates are shown in
Table 3-3. Nutrient costs ranged from
$0.51/1,000 gallons at a reactor reten-
tion time of 11 hrto $0.58/1,000 gallons
with a reactor retention time of 5.5 hr
and averaged $0.54/1,000 gallons.
Table 3-2. Capital Costs/Construction Schedule for Catalyzed Cementation System Scale-Up
Task
MSE System Design
MSE Subcontract Construction Oversight
MSE System Startup, Commissioning, and
Project Closeout
Demolition, Building Modifications, Equipment
Purchase and Installation by Subcontract
Total
Schedule/Cost Contingency @ 10%
TOTAL
Construction
Time Materials
13.5 weeks $74,580
7 weeks
5 weeks
12 weeks $588,342
26.5 weeks
2.7 weeks
29.2 weeks
Labor
$156,670
$44,730
$44,190
$35,587
Travel
Nonlabor
$1 1 ,487
$18,952
$10,266
Total
$242,737
$63,683
$54,456
$623,929
$984,805
$98,480
$1,083,285
18
-------
Table 3-3. Nutrient Usage and Cost Per 1,000 Gallons as a Function of Retention Time
Retention
Time
11
8
5.5
Flow
(gal/min)
0.3
0.4
0.6
Time
(days)
14
14
7
Water
Treated (L)
22982.4
30643.2
22982.4
Nutrient
(9)
1 1 ,000
15,000
12,500
Nutrient
Use (g/L)
0.48
0.49
0.54
Nutrient
(g/1000gal)
1818.8
1860.1
2066. 8
Nutrient
($/ton)
250
250
250
Nutrient
($71000 gal)
0.51
0.52
0.58
3.3.2 BSeR™ Process
Biofilm Support Cost
In a pump-and-treat bioreactorsystem,
it is advantageous to use an optimized
support material for biofilm establish-
ment. The BSeR™ process allows for
establishing high-density biofilms that
result in faster kinetics. The results of
this and previous tests, including full-
scale bioprocess implementation, con-
tinue to validate the use of carbon as a
bioreactor support material for the
BSeR™ process. Laboratory and field-
tests have proven the durability of car-
bon as a stable biolfim support for long-
term BSeR™ process operation. In fact,
testing indicates that the biofilm sup-
port materials should have a life expect-
ancy of 15+years. Pilot tests completed
at the Garfield \Afetlands-Kessler Springs
site indicate that the current selenium
levels (2.0 mg/L) can be reduced to near
or below detection with a retention time
of<5.5hr.
The BSeR™ process normally uses
granular carbon as a biofilm support to
establish specific biofilms that will en-
dure long-term exposure to contami-
nated waters containing indigenous
nonselenium reducing microorganisms.
This testing allowed additional compari-
sons and evaluations of other biofilm
support materials. Granular carbon (8 x
30, l#900), evaluated in the laboratory
along with the granular carbon from the
field reactors, in bulk at a cost of $0.48
per delivered pound, is the best biofilm
support material tested to date for the
BSeR™ process.
3.3.3 BSeR™ Process Capi-
tal Costs
Capital costs for the BSeR™ process
are dependent on a great variety of fac-
tors including tank construction materi-
als, use of available on-site tanks, pump
and piping material specifications, and
biofilm support materials.These factors
all vary and can be adjusted to accom-
modate various site requirements of re-
actor materials, varying selenium con-
tamination levels, and short or extended
operating times. For example, the flow
rates and projected extended operation
times at the KUCC Garfield Wetlands-
Kessler Springs site dictate a require-
ment for a durable biofilm support and
shorter retention times; this was accom-
modated by using a biofilm support of
granular carbon.
The cost of producing a bulk inoculum
is estimated at $0.75/1,000 gallons
(cost dependent on BSeR™ process
reactor size) and should only be required
at start up. Two, 850,000-gallon clarifi-
ers at the KUCC site would be used for
this process. Granular carbon (8 x 30,
l#900) costs $0.48 per delivered pound.
Conservatively, an estimated 360,000
Ib of carbon support material is required
fora 300 gpm BSeR™ process system
at a cost of $172,800. Laboratory and
field tests suggest that the carbon can
be used for a minimum of 25 reactor
back flushing cycles for selenium re-
moval and recovery, or an estimated 15
years at the Garfield Wetlands-Kessler
Springs site.
Table 3-4 summarizes the capital costs
estimated by MSE for the BSeR™ pro-
cess system scale-up.
3.3.4 Comparative Economic
Analysis
The three technologies demonstrated in
the field were economically evaluated
for a system operating at 300 gpm for
10 years @ 3.9% interest, 300 days per
Table 3-4. Capital Costs for BSeR™ Process System Scale-Up
Task Construction
Materials
Labor
Total
Schedule/Cost Contingency @ 10%
TOTAL
20 weeks
2 weeks
22 weeks
Total
AB System Design
AB Project Management
AB System Startup, Commissioning, and
Project Closeout
Demolition, Building Modifications,
Equipment Purchase and Installation by Subcontract
4 weeks
20 weeks
5 weeks
1 1 weeks
$53,807
$9699
$113,875
$342,270 $24,000
$53807
$9699
$113,875
$366,270
$549,090
$54,909
$603,999
19
-------
year, to treat ground water containing 2
ppm selenium. The technologies were
compared using the total net present
value (TNPV) for each. The TNPV was
determined by the following relationship:
TNPV = (CapitalCost + NPVO &
MCost)
Where:
- TNPV is the total net present
value;
- Capital Cost is the estimated capi-
tal cost to install each technolog
in the KUCC Wastewater Treat-
ment Plant; and
- NPVO & MCost is the net present
value of the estimated annual op-
erating and maintenance costs.
The NPV function in Excel was used to
calculate the NPV Operating Cost for
each technology. A summary of the eco-
nomic analysis of the three technolo-
gies is presented in Table 3-5.
Among the three technologies, the
BSeR™ process technology dominates
both technical and economical perfor-
mance. Catalyzed cementation was the
next most cost effective treatment. The
baseline technology, ferrihydrite adsorp-
tion, was the least attractive alternative
from an economic standpoint. The oper-
ating and maintenance costs for the
ferrihydrite adsorption and catalyzed
cementation technology are much
higherthan the BSeR™ process due to
high reagent usage. Optimization of re-
agent usage coupled with reagent sub-
stitution with lower cost reagents would
make ferrihydrite adsorption and cata-
lyzed cementation more economically
attractive.
Table 3-5. Comparative Economic Analysis of Demonstrated Technologies
Cost
Ferrihydrite
Adsorption
Catalyzed
Cementation
BSeR™
Process
Capital
Annual Operating and
Maintenance Cost
$1,026,835 (includes system design,
demolition, building modifications,
equipment purchase and installation
construction, system start-up,
commissioning, and project closeout)
$2,084,559 (includes reagent costs,
manpower, maintenance, and power
for equipment use)
$16,992,127
Net Present Value of Annual
Operating and Maintenance Costs
Total Net Present Value $18,017,962
Net Present Value of $/1 OOP gallons treated $13.90
$1,083,285 (includes additional
research and development work
system design, demolition, building
modifications, equipment purchase
and installation, construction,
system start-up, comissioning, and
$1,165,358 (includes reagent costs,
manpower, maintenance, and power
for equipment use)
$9,499,323
$10,582,608
$8.17
$603,999(includes biofilm support
material, inoculum, system design,
building modifications, equipment
purchase and installation,
construction, comissioning, and
project closeout)
$135,029 (includes nutrient costs,
manpower, maintenance, and
power for equipment use)
$1,100,682
$1,704,681
$1.32
20
-------
4. Conclusions/Recommendations
Of the three technologies demonstrated,
the BSeR™ process produced the most
consistent results. A site-specific opti-
mization is an essential component of
any selenium removal process imple-
mentation, including the BSeR™ pro-
cess. This optimization allowed the
BSeR™ process to achieve economi-
cal removal efficiencies using realistic
retention times while minimizing oper-
ating costs. Optimization of the BSeR™
process for the KUCC site produced a
microbial cocktail that was later con-
firmed to efficiently remove selenium to
near or below detection from Garfield
Wetlands-Kessler Springs water using
an inexpensive molasses-based nutri-
ent blend and 5.5-hr retention times. The
optimized microbial cocktail consisted
of site-endemic and other naturally oc-
curring, nonpathogenic microbes, includ-
ing Pseudomonasstutzeriand RC-large.
The BSeR™ process consistently re-
moved selenium to below the target con-
centration (50 ug/L) and the majority of
the time to below the detection limit of
2 ug/L.
The ferrihydrite adsorption process can
also be optimized to achieve the desired
level of selenium removal; however, re-
agent usage is excessive and cost pro-
hibitive. Although this technology is con-
sidered the BOAT by EPA, it would not
be feasible to utilize this technology to
treat Garfield Wetlands-Kessler Springs
water on a large scale. Another remain-
ing question about this technology is the
stability of the filter cake produced dur-
ing this demonstration. Filter-cake
samples did not pass TCLP for selenium
but results were questionable because
total metal analyses on the same
samples did not correlate with the TCLP
results.
The catalyzed cementation technology
has also produced promising, albeit, er-
ratic results. Additional testing of this
process is necessary to provide more
information about this innovative sele-
nium removal technology. Further test-
ing and optimization such as perform-
ing a solubility product or kinetic study
to determine the optimum parameters
for selenium and iron would make sele-
nium removal using catalyzed cemen-
tation even more consistent and cost
effective. The cementation reactor de-
sign may hold the key to the success-
ful implementation of this technology. It
is known that cementation of selenium
can be accomplished in simple columns
and stir tanks (Ref. 10). However, long
residence times are required to achieve
selenium removal to acceptable levels
(Ref. 11). The recent work of Dahlgren
(Ref. 7) and the continuation work by Dr.
Twidwell (Ref. 9) has shown that iron
packed columns are very effective for
selenium removal (<1 ppb at pH 7) and
require only a relatively short residence
time (30 minutes). Current research in-
dicates that novel agitation methods
may provide the key to efficient sele-
nium removal from solution.Testing of a
system with a unique reactor design to
accomplish the correct agitation method
is necessary to furtherdevelopthe cata-
lyzed cementation technology.
The enzymatic selenium reduction tech-
nology was tested on a bench-scale
during this project. The technology was
not demonstrated in the field due to the
instability of the enzyme reactor matrix.
Plant enzyme preparations are commer-
cially available; however, these plant-
based preparations are much too expen-
sive forwatertreatment applications. The
use of microbial enzyme preparations
are expected to eventually reduce these
costs. More research is necessary to
gain a better understanding of what is
occurring in the immobilization of the
enzymes and the linking of electron do-
nors within the various immobilization
techniques. If the enzyme matrix can
be demonstrated to be stable for 6 to 9
months, the process may be an eco-
nomical treatment alternative. At the
current operational longevity of 3 weeks
to several months, the treatment costs
become prohibitive. It is recommended
that additional research be performed on
the enzymatic selenium reduction tech-
nology because enzyme systems have
the potential to outperform live micro-
bial systems in many ways. Enzymatic
technologies are still in the prototype
development stage but have the poten-
tial to revolutionize drinking water and
wastewater treatment.
In addition to furthertesting of the cata-
lyzed cementation technology and en-
zymatic selenium reduction technology,
other newly developed selenium treat-
ment/removal technologies that may be
ready for small-scale demonstration
have been identified during this project.
It is important to demonstrate these new
technologies,
in addition to the technologies tested
during this project, to determine which
technologies are effective at treating
Garfield Wetlands-Kessler Springs wa-
ter and also other waters with differing
selenium concentrations and more com-
plicated matrices. Further testing of
these additional technologies could iden-
tify promising/economical technologies
that could address the environmental
problem of selenium contamination
faced by the mining/mineral processing
industries as well as the agricultural
sector and the petroleum industry.
21
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5. References
1. MWTP. Issues Identification and Tech-
nology Prioritization Report-Sele-
nium, Mine Waste Technology
Program, Activity I, Volume VII,
MWTP-106, January 1999.
2. Rosengrant, L. and L. Fargo. Final
Best Demonstrated Available Tech-
nology (BOAT) Background Docu-
ment for K031, K084, K101, K102,
Characteristic Arsenic Wastes
(D004), Characteristic Selenium
Wastes (D010), and P and U Wastes
Containing Arsenic and Selenium
Listing Constituents, Volume 1, Versar
Inc., Springfield, Virginia, EPA/530/
SW-90/059A, NTIS PB90-23014,
1990.
3. Adams, D. J. and K. R. Gardner. "Im-
mobilized Bacteria and Enzymes for
Bioremediation of Cyanide and Se-
lenium Containing Wastewaters." / &
EC Special Symposium: American
Chemical Society, Atlanta, Georgia,
1994.
4. Adams, D. J., R. A. Davidson, and K.
R. Gardner. "Enzymatic Bio-
remediation of Cyanide and Sele-
nium Containing Wastewaters."
Emerging Technologies In Hazard-
ous Waste Management VII, Atlanta,
Georgia, 1995.
5. Adams, D. J. and T. M. Pickett. "Mi-
crobial and Cell-Free Selenium
Bioreduction in Mining Waters." En-
vironmental Chemistry of Selenium,
Marcel Dekker, Inc ., New York, 1998,
479-499.
6. U.S. Environmental Protection
Agency, Guidance for Data Quality
Assessment: Practical Methods for
Data Analysis, EPAQA/G-9, EPA/600/
R-96/084, July 1996.
7. Dahlgren, E. "Parameters Affecting
the Cementation Removal of Sele-
nium," MSc Thesis, Montana Tech of
the University of Montana, Butte,
Montana, May 2001.
8. Schnell Publishing Company. Chemi-
cal Market Reporter, May 8, 2000.
9. Twidwell, L. G. Personal communi-
cation between H. Joyce (MSE Tech-
nology Applications, Inc., Butte,
Montana) and L. Twidwell (Montana
Tech of the University of Montana,
Butte, Montana), April 2001.
10. Ogoshi, T., Y. Tsurumara, H. Tsuboya,
T. Watanbe, and M. Enami. Process
for Treating Waste Water of Flue Gas
Desulfurization, U.S. Patent
5,853,598, December 1998.
11. Koyama, K., M. Kobayashi, and A.
Tsunashima. "Removal of Selenate
in Effluents of Metal Refineries by
Chemical Reduction Using Solid Iron,
Minor Elements 2000," Proceedings
SME, Salt Lake City, Utah, February
2000, 363-69.
22
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APPENDIX A
Summary of Quality Assurance Activities
Kennecott Environmental Laboratory/HKM Laboratory Data Evaluation
Mine Waste Technology Program
Activity III, Project 20
Selenium Treatment/Removal Alternatives
Al
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ACRONYMS
AB Applied Biosciences Corporation
BDAT best demonstrated available technology
CCV continuing calibration verification
COC chain-of-custody
EPA U.S. Environmental Protection Agency
IDL instrument detection limit
KEL Kennecott Environmental Laboratory
KUCC Kennecott Utah Copper Corporation
LCS laboratory control sample
MDL method detection limit
mg/L milligrams per liter
MSB MSB Technology Applications, Inc.
MWTP Mine Waste Technology Program
ORP oxidation-reduction potential
QA quality assurance
QAPP quality assurance project plan
QC quality control
RPD relative percent differences
SOP standard operating procedures
TCLP toxicity characteristic leachate procedure
• g/L micrograms per liter
A2
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1. BACKGROUND
On October 23, 1999, sampling officially began for the Mine Waste Technology Program (MWTP)
Activity III, Project 20—Selenium Treatment/Removal Alternatives at the Kennecott Utah Copper
Corporation (KUCC) in Magna, Utah. The intent of the project was to obtain performance data on
two chemical removal processes and one biological technology capable of selenium treatment/removal.
The demonstration was conducted using Garfield Wetlands-Kessler Springs Water that has an
approximate selenium concentration of 2 milligrams per liter (mg/L). The technologies demonstrated
included:
• ferrihydrite precipitation with concurrent adsorption of selenium onto the ferrihydrite surface
[U.S. Environmental Protection Agency's (EPA) Best Demonstrated Available Technology
(BOAT)] as optimized by MSB Technology Applications, Inc. (MSB);
•• catalyzed cementation process developed by MSB; and
• biological selenium reduction technology developed by Applied Biosciences Corporation (AB)
and implemented by AB with assistance from KUCC.
Because ferrihydrite precipitation is considered EPA's BDAT for selenium removal, it was the baseline
technology used as a basis for comparison with the innovative selenium removal technologies.
The stated objective of the project was to reduce the concentration of dissolved selenium in the effluent
waters to a level under the National Primary Drinking Water Regulation Maximum Contaminant Level
for selenium [50 micrograms per liter (• g/L)] established by the EPA.
Samples were collected according to the schedule outlined in the approved project-specific quality
assurance project plan (QAPP) document. The ferrihydrite precipitation and catalyzed cementation
technologies were demonstrated for 3 weeks. The biological process was demonstrated for over 5
months. All field and laboratory data available has been evaluated to determine the usability of the
data. Dissolved selenium analysis has been classified as a critical analysis for this project. A critical
analysis is an analysis that must be performed to determine if project objectives were achieved. Data
from noncritical analyses were also evaluated.
A3
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2. PROJECT REVIEWS
During the project, two evaluations were performed: 1) preproject evaluation of the Kennecott
Environmental Laboratory (KEL); and 2) field systems review at KUCC demonstration site and KEL.
2.1 PREPROJECT EVALUATION OF KEL
Before the project began, a determination was made as to whether KEL was prepared/qualified to
perform selenium analysis for this project. KEL holds accreditation from the following organizations
that perform routine external audits:
• Certified by the State of Utah for Environmental Testing performed under the Safe Drinking
Water Act, the Clean Water Act, and the Resource Conservation and Recovery Act. The State
of Utah audits KEL twice a year.
• Accredited by the American Industrial Hygiene Association for all aspects of industrial hygiene
analysis including heavy metals, free silica, and asbestos.
• Participant regularly in Interlaboratory Performance Evaluation Testing for EPA, Proficiency
Analytical Testing (four times a year), College of American Pathology, Discharge Monitoring
Resource Quality Association, and Environmental Lead Proficiency Analytical Testing.
•• Audited by EPA for the National Pollution Discharge Elimination System once a year.
In addition to the external audits, KEL's quality assurance (QA) department performs internal audits
twice a year. A review of the facilities indicated that KEL was prepared and qualified to perform
analyses for the project. The unique matrix of the samples due to the high salinity in ground water
samples near the Great Salt Lake made KEL a good choice because they routinely analyze these
samples.
2.2 FIELD SYSTEMS REVIEW AT KUCC
A field systems review was performed on November 3, 1999, at the KUCC demonstration site and
KEL. The field systems review included a review of the following items:
- personnel, facilities, and equipment;
- documentation (chain-of-custody and logbooks);
- calibration of equipment; and
- sampling procedures.
No concerns were identified during the audit. Some observations were made for areas not conforming
exactly to the project specific QAPP.
A4
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2.2.1 Personnel, Facilities, and Equipment
Personnel present during the audit included: Michelle Lee, MSB Project Engineer, and Ken Reick,
MSB Project QA Officer. Some equipment for the demonstration was housed in the MWTP process
demonstration trailer, while the influent feed tank and other associated equipment was located outside
the confines of the trailer. Analysis and preparation of the samples (filtering and preserving) were
performed in the sampling area provided inside a water treatment plant. The Project Engineer was
knowledgeable about the demonstration and their duties and responsibilities at the demonstration site.
All equipment was calibrated prior to measurements in the MWTP process demonstration trailer or the
designated sampling area. All calibration information was available and recorded in the project
logbooks.
2.2.2 Documentation
Chain-of-custody forms (COC) were reviewed at the demonstration site, and all COC procedures were
being followed. The project logbooks were also reviewed. The sampling logbook was very thorough,
and included spaces where specific information was required. Sampling personnel were familiar with
the logbook format and COC procedures. The sampling logbook did not conform to the standard
operating procedure (SOP) because the pages of the logbook were not numbered consecutively, and the
unused portions of the logbook pages were not lined out and dated as stated in the SOP that was
attached to the project-specific QAPP.
2.2.3 Calibration of Equipment
Field equipment was used to manually measure pH and oxidation-reduction potential (ORP). This
information was recorded in the project logbooks. All meters were properly calibrated prior to
performing measurements. Standard operating procedures were available at the demonstration site for
reference on how to calibrate/operate the meters. Sampling personnel were familiar with the SOPs and
requirements for routine calibration of the various meters.
2.2.4 Sampling Procedures
A review of sampling activities was also performed during the systems review. All sample collection
procedures and equipment decontamination procedures were followed by sampling personnel with one
exception. The QAPP required that the sample container that is shipped to the laboratory be rinsed
three times with the solution to be analyzed. In this case, some of the filtered solution should have
been used to rinse the 500-mL sample containers. None of the sample containers for samples collected
during the audit were rinsed in this manner. The unfiltered sample containers were triple rinsed.
As a corrective action, the sampler was notified of this deficiency to ensure that compliance with the
QAPP would occur at future sampling events. Michelle Lee indicated that the QAPP she had used to
prepare for the audit did not indicate a separate rinsing procedure for the filtered sample bottle. This
was a draft version of the QAPP. The official, approved version of the QAPP was available in the
A5
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trailer, as well as SOPs which indicated the proper rinsing procedure. In addition, other samplers
were notified of the problem, and they indicated that they had been following the proper rinsing
procedure since project initiation.
As a follow-up corrective action, this lesson learned was reiterated in annual sample collection
refresher training for all MWTP personnel to avoid this problem in the future.
2.2.5 Analytical Facility Evaluation
Project personnel delivered samples to KEL in sealed coolers containing blue ice with a COC. The
COC was properly filled out, and samples were logged into KEL upon receipt. When samples from
the project were delivered, an evaluation of KEL was also performed. No deficiencies with KEL were
identified. The auditor described the facility as one of the best equipped inorganic analytical
laboratories in the western United States.
A6
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3. DATA EVALUATION
The data quality indicator objectives for dissolved selenium analysis were outlined in the QAPP and
were compatible with project objectives and the methods of determination being used. The data
quality indicator objectives are method detection limits (MDL) for accuracy, precision, and
completeness. Control limits for each of these objectives are summarized in Table 3-1.
Table 3-1. Data quality indicator objectives.
Parameter
Dissolved Se
Matrix
Aqueous
Unit
Mg/L
MDL"
5
Precision1"
•20%
Accuracy1
75-125%
Completeness11
90%
'Minium detection limits are based on what is achievable by the methods, what is necessary to achieve project objectives,
and account for anticipated dilutions to eliminate matrix interferences. MDLs will be adjusted as necessary when dilutions
of concentrated samples are required.
'Relative percent difference of analytical sample duplicates.
Percent recovery of matrix spike, unless otherwise indicated.
'Based on number of valid measurements, compared to the total number of samples.
In addition to the data quality indicators listed in Table 3-1, KEL also analyzes internal quality control
(QC) checks, including calibration, calibration verification checks, calibration blanks, matrix spike
duplicates, blank spikes, method blanks, and laboratory control samples. These QC checks have also
been evaluated for the purposes of this data review.
A7
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4. VALIDATION PROCEDURES
Data that was generated to date for all analyses was validated. The purpose of data validation is to
determine the usability of data that was generated during a project. Data validation consists of two
separate evaluations: an analytical evaluation and a program evaluation.
4.1 ANALYTICAL EVALUATION
An analytical evaluation is performed to determine that:
- all analyses were performed within specified holding times;
- calibration procedures were followed correctly by field and laboratory personnel;
- laboratory analytical blanks contain no significant contamination;
- all necessary independent check standards were prepared and analyzed at the proper frequency
and remained within control limits;
- duplicate sample analysis was performed at the proper frequency and all relative percent
differences (RPDs) were within specified control limits; and
- matrix spike sample analysis was performed at the proper frequency and all spike percent
recoveries were within specified control limits;
Measurements that fall outside of the control limits specified in the QAPP, or for other reasons, were
judged to be outlier and were flagged appropriately to indicate that the data is judged to be estimated
or unusable.
An analytical evaluation was performed to determine the usability data that was generated by the KEL
and the HKM Laboratory for the project. Laboratory data validation was performed using USEPA
Contract Laboratory Program National Functional Guidelines for Inorganics Data Review (USEPA,
1994) (Ref. 1) as a guide. The QC criteria outlined in the QAPP were also used to identify outlier
data and to determine the usability of the data for each analysis. A summary of QC check results for
the critical selenium analysis and the noncritical total and TCLP selenium analyses is presented in
Table 4-1. All data requiring flags is summarized in Table 4-2. In addition to the analytical
evaluation, a program evaluation was performed.
4.2 PROGRAM EVALUATION
Program evaluations include an examination of data generated during the project to determine that:
- all samples, including field QC samples, were collected, sent to the appropriate laboratory for
analysis, and were analyzed and reported by the laboratory for the appropriate analyses;
- all field blanks contain no significant contamination; and
- all field duplicate samples demonstrate precision of field as well as laboratory procedures by
remaining within control limits established for RPD.
A8
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Table 4-1. Summary of QC checks for critical selenium analysis and noncritical total selenium
and TCLP analysis.
Analysis
Dissolved Selenium
Selenium Hydride
Dissolved Selenium
Selenium Hydride
Total Selenium (solid)
TCLP Selenium
Dissolved Selenium
Selenium Hydride
Dissolved Selenium
Selenium Hydride
Mean RPD for Sample Duplicates
-0.38%
0.8
Mean Matrix Spike Recovery
100
98.4%
103%
100%
Mean Matrix Spike Duplicate Recovery
98.6%
101.5%
Mean Matrix Spike/Matrix Spike Duplicate RPD
-0.07%
-1.8%
Range of RPDs for Sample Duplicates
-5.4% to 2.9%
-1.6% to 4.3%
Range of Matrix Spike Recoveries
80% to 120%
76% to 124%
100% to 110%
90% to 120%
Range of Matrix Spike Duplicate Recoveries
80% to 108%
76% to 120%
Range of Matrix Spike/Matrix Spike Duplicate RPDs
-5.1% to 3.4%
-11.1% to -4.9%
Table 4-2. Summary of qualified data for MWTP Activity III, Project 20.
Date1
10/23/99
10/31/99
11/12/99
11/14/99
11/14/99
11/14/99
11/14/99
11/15/99
11/16/99
Sample
ID
FH1-201
CC5-137
FH2-309
CC1-215
FH1-315
FH5-319
FH4-318
FH3-317
FH2-316
FH1-315
FH5-319
FH4-318
FH3-317
FH2-316
FH1-315
FH3-321
FH5-322
FH3-323
FH5-324
FH3-325
FH5-326
FH3-327
FH5-328
Analysis
Iron
Speciation
Barium
Copper
Barium
Cadmium
Lead
Zinc
QC
Criteria
Holding
Time
Field Blank
Field Blank
Field
Duplicate
Continuing
Calibration
Verification
Control
Limit
Analyze
Immediately
< 10 • g/L
< 10 • g/L
+ 20 -g/L
90-110%
Recovery
Result
48 hr
78 • g/L
538 • g/L
68 • g/L
Out of control on
chart
Flag2
R
U
U
J
J
Comment
The data is considered unusable because
samples were not brought to the laboratory
for immediate analysis. A study was
performed by KEL to determine the effect oi
the holding time on these samples; and as
expected, the ferrous iron was significantly
impacted. This data should be removed
from consideration.
Samples with less than 10 times the
contamination concentration in the blank,
but above the MDL, should be flagged "U".
Because samples were • 5 times the
instrument detection limit (IDL) for barium,
the normal precision control limit of • 20%
RPD does not apply . An alternative control
limit of +2 times the IDL was applied and
resulted in the arsenic data being flagged
"J", as estimated.
Flag samples "J" for out-of-control
continuing calibration verification (CC V) .
A9
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Table 4-2. Summary of qualified data for MWTP Activity III, Project 20.
Date1
11/13/99
11/14/99
11/14/99
11/18/99
10/27/99
10/26/99
11/11/99
11/16/99
10/31/99
11/18/99
1/10/00
Sample
ID
CC3-217
CC8-219
CC5-219
CC5-348
CC2-102
FH2-233
CC2-190
CC1-215
FH Filter
Cake-221
FH Filter
Cake-225
BX-001
BX-002
BX-003
BX-004
Analysis
All analytes
All analytes
Selenium
Speciation
Selenium
Speciation
Selenium
Iron
Iron
Selenium
Selenium
Selenium
QC
Criteria
All
Field Blank
Field Blank
Field
Duplicate
T=870
D = 990
T= 1340000
0 = 1800000
T= 409000
0 = 955000
T=974
0 = 1030
TCLP=1.6
ppm
Total =< 0.5
ppm
TCLP=1.1
ppm
Total =< 0.5
ppm
CCV
LCS
Control
Limit
N/A
No significant
contamination
<2timeIDL
(4 ppb)
<35% RPD
Total should
be greater than
dissolved
TCLP results
should be less
than total
metals results
90-110%
recovery
80-120%
recovery
Result
Dissolved greater
than total for all
analytes
Contamination for
barium, copper, and
molybdenum
15 ppb (selenium)
12ppb (selenite)
50% RPD
(selenium)
93% RPD (selenite)
Total results less
than dissolved
TCLP results 2 to 4
times higher than
total metals results
Out-of-control on
chart
Out-of-control on
chart
Flag2
X
X
U
J
J
J
J
Comment
The dissolved portion of this sample was
considerably darker than the total metal
sample. This sample should be removed
from consideration.
This field blank was obviously contaminated
and was removed from consideration.
Samples with less than 10 times the
contamination concentration in the blank,
but above the MDL, should be flagged "U".
Flag results "J" as estimated due to suspect
field duplicate.
Flag results "J" as estimated for suspect
dissolved versus total results.
Flag results "J" as estimated for suspect
TCLP versus total metals results.
Flag samples "J", as estimated for out of
control CCV and laboratory control sample
(LCS).
1 Date the samples were collected.
2 Data-qualifier definitions.
U- The material was analyzed for, but was not detected above the level of the associated value (quantitation or detection limit) .
J- The sample results are estimated.
R- The sample results are unusable.
UJ- The material was analyzed for, but was not detected. The associated value is estimated.
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Program data that was inconsistent or incomplete and did not meet the QC objectives outlined in the
QAPP were viewed as program outliers and were flagged appropriately to indicate the usability of the
data. Both the analytical and program evaluations consisted of evaluating the data available as of
June 1, 2000, from KEL and HKM Laboratory, which performed confirmatory analysis on 10% of the
project samples.
4.2.1 Field QC Samples
In addition to internal laboratory checks, field QC samples were collected to determine overall
program performance.
4.2.2 Field Blanks
None of the field blanks collected for the project showed significant contamination for dissolved
selenium analysis, with two exceptions. The field blank (FH9-319) collected on November 14, 1999,
did show significant contamination for barium and copper, which resulted in five samples-FH5-319,
FH4-318, FH3-317, FH2-316, and FHl-315-receiving a "U" flag for these analytes. A "U" flag
indicates the data is undetected below the associated value. Another field blank, CC8-219, collected
on November 14, 1999, showed significant contamination for selenium speciation analysis, which
resulted in the selenium and selenite values for sample CC5-219 receiving a "U" flag. The fact that
both of these contaminated field blanks were collected on the same day may indicate a problem with
sampling and/or laboratory procedures on that date.
4.2.3 Field Duplicates
All field duplicates collected were within control limits for all analyses, with the two exceptions. A
field duplicate, FH8-319, was out of control for barium analysis. While EPA does not specify control
limits for field duplicates, the data reviewer is allowed discretion when evaluating field duplicates.
For this project, precision control limits of • 35% RPD were used for field duplicates. As a result, the
following samples were flagged "J", as estimated: FH5-319; FH4-318; FH3-317; FH2-316; and
FH1-315. A field duplicate collected on November 18, 1999 (CC8-348) was out of control for
selenium speciation analyses, resulting in sample CC5-348 being flagged "J" for selenium and selenite
values.
In addition to the collection of field duplicates, HKM Laboratory performed confirmatory selenium
analysis on 10 % of the samples collected for the project. A comparison of the results from KEL and
HKM Laboratory are presented in Table 4-3.
Basically, samples analyzed by the two laboratories were comparable. The results in Table 4-2
summarize all of the data that was flagged for various reasons throughout the project.
All
-------
Table 4-3. Comparison of results from KEL and HKM Laboratory.
Sample ID
FH 1-201
CC1-101
CC5-118
FH5-257
CC5-157
FH5-304
CC1-215
CCS -2 19
CC8-219
CC9-219 (blank)
FH8-319
FH9-319 (blank)
FH5-319
FH1-315
Date of Collection
10/23/99
10/27/99
10/28/99
10/31/99
11/04/99
11/10/99
11/14/99
11/14/99
11/14/99
11/14/99
11/14/99
11/14/99
11/14/99
11/14/99
KEL Result (• g/L)
1570
1530
977
115
44
64
1030
105
29
<10
825
<10
800
1500
HKM Laboratory
Result (• g/L)
1590
1390
827
88
90
58
1370
119
60
<0.75
642
<1.4
603
1340
Relative Percent
Difference
1.3%
9.6%
16.6%
26.6%
68.7%
10.5%
28.3%
12.5%
69.2%
N/A
24.9%
N/A
28.1
11.3
4.3 IRON SUPPRESSION ON SELENIUM
The samples submitted for the ferrihydrite process had high iron interference, which suppressed the
selenium spectra significantly. KEL's analyst talked to the manufacturer about inter-element
correction calculations that could be made through the software. Suggested corrections were made;
however, the suppression of the selenium spectra continued. The majority of the problems were
encountered on samples from sample ports FH2 and FH3 (midpoints of the ferrihydrite system).
Effluent samples did not have enough iron to cause problems with the laboratory analysis or data
analysis.
4.4 DISSOLVED METALS VERSUS TOTAL METALS
On several occasions, the dissolved metal results were higher than the totals. KEL reanalyzed the
samples a second time for verification, and the dissolved results were still higher than the totals.
Dissolved results should be less than or equal to the total metal results. These results may indicate a
problem with sampling techniques such as contaminated filter paper/apparatus, insufficient
decontamination procedures, or mislabeling of containers.
4.5 TCLP VERSUS TOTAL METALS
There were also inconsistencies in TCLP versus total metal results on the filter-cake samples collected
from the ferrihydrite adsorption process. Total metal results should be greater than or equal to the
total metal results because the TCLP represents at least a 20 times dilution of the total metals.
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5. SUMMARY
All data from KEL and HKM Laboratory has been validated according to EPA guidelines and the
project specific QAPP. Some of the data was flagged for various reasons and is summarized in
Table 4-2.
Two major findings are listed below.
• When a difficult matrix water must be analyzed for a project, it is recommended that the
laboratory receive samples to perform analysis on and determine the presence of interferents so
that interferent can be dealt with before it results in qualification of data.
• Miscommunication between MSB and KEL personnel resulted in data for iron speciation
flagged "R" as unusable. KEL had requested that the samplers notify the laboratory the day
before ferrous samples would arrive so KEL could be prepared to analyze them promptly.
MSB agreed to do this but did not follow through. There were eleven sampling events for iron
speciation, and only four of the eleven times the holding time was met. KEL's analyst did a
mini experiment to see the effect of the holding time on the sample. On sample CC5-193,
ferrous iron was 37 mg/L on the day the sample was delivered and only 10 mg/L two days
later, illustrating the importance of the holding time on iron speciation analysis. Holding time
requirements should be communicated better to the sampling team to avoid this problem on
future projects.
MWTP, Activity III, Project 20 presented unique challenges for the sampling and analytical team.
While several of the data points were flagged for various reasons, none of the critical data was
discarded during the data evaluation/validation process.
A13
-------
6. REFERENCES
1. U.S. Environmental Protection Agency, "USEPA Contract Laboratory Program National
Functional Guidelines for Inorganic Data Review," EPA-540/94-013, February 1994.
A14
-------
APPENDIX B
Test Data
B1
-------
CONTENTS
Table B-l.
Table B-2.
Table B-3.
Table B-4.
Table B-5.
Table B-6.
Table B-7.
Table B-8.
Table B-9.
Table B-10.
Table B-l 1.
Table B-12.
Table B-13.
Table B-l4.
Table B-15.
Table B-l6.
Table B-17.
Table B-18.
Table B-19.
Table B-20.
Table B-21.
Table B-22.
Table B-23.
Table B-24.
BSeR™ Series 1
BSeR™ Series 1
PILOT TEST DATA
Ferrihydrite adsorption process demonstration field data record.
Selenium demonstration test—ferrihydrite process analytical data summary
Summary total metals data.
Summary toxicity characteristic leachate procedure data.
Catalyzed cementation process demonstration field data record.
Selenium demonstration project—summary data for catalyzed cementation process.
BSeR™ Series 1, 12-hr retention time, total selenium.
12-hr retention time, dissolved oxygen.
12-hr retention time, oxidation-reduction potential.
BSeR™ Series 1, 12-hr retention time, temperature.
BSeR™ Series 1, 12-hr retention time, pH.
BSeR™ Series 2, 11- and 5.5-hr retention time, total selenium.
BSeR™ Series 2, 11- and 5.5-hr retention time, dissolved oxygen.
BSeR™ Series 2, 11- and 5.5-hr retention time, oxidation-reduction potential.
BSeR™ Series 2, 11- and 5.5-hr retention time, temperature.
BSeR™ Series 2, 11- and 5.5-hr retention time, pH.
BSeR™ Series 3, 8-hr retention time, total selenium.
BSeR™ Series 3, 8-hr retention time, dissolved oxygen.
BSeR™ Series 3, 8-hr retention time, oxidation-reduction potential.
BSeR™ Series 3, 8-hr retention time, temperature.
BSeR™ Series 3, 8-hr retention time, pH.
Catalyzed cementation process demonstration test data record follow on testing.
Summary data for additional testing of catalyzed cementation test (aqueous).
Summary data for additional catalyzed cementation tests (solid).
B2
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
BACKGROUND DAYS
WEEK1
Sample
Time
HOUR-
Sample
Number
Sample
Port
Sample
Analysis
pH, ORP
Totalizer
Flow
PH
Value
7.1
ORP
Value
185
Iron
Field Analy
Sampled
Time
Initials
Comments
WEEK 1 (CONTINUOUS)
DAY 1 INITIAL 10/23/99 Time Zero= 13:00 hours
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 0
HOUR - 0
Sample
Number
Sample
Port
101
102
103
FIT
Sample
Analysis
pH
pH, ORP
pH
Total Flow
Totalizer
Flow
115
PH
Value
3.7
3.92
7.5
ORP
Value
605
Iron
Field Analy
Sampled
Time
14:00
Initials
JM
Comments
WEEK 1 (CONTINUOUS)
DAY 1 INITIAL
Sample
Time
HOUR - 4
HOUR - 4
HOUR - 4
HOUR - 4
HOUR- 8
HOUR- 8
HOUR - 8
HOUR- 8
HOUR- 12
HOUR -12
HOUR -12
HOUR -12
HOUR -16
HOUR -16
HOUR -16
HOUR -16
HOUR -20
HOUR -20
HOUR -20
HOUR -20
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
221.32
-
494.2
670
4.3
117.38
^m
PH
Value
3.85
4.01
3.85
4
3.88
4.05
-
3.9
4.1
-
4.04
4.16
4.98
4.18
4.29
5.93
6.6
ORP
Value
420
565
425
451
422
409
405
Iron
Field Analy
1370
1450
1280
1290
1290
1420
Sampled
Time
17:00
21:00
1:00
5:00
9:00
13:00
Initials
JB
JB
RZ
RZ
KN
KN
Comments
B3
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
WEEK 1 (CONTINUOUS)
DAY 2
Sample
Time
HOUR - 4
HOUR - 4
HOUR - 4
HOUR - 4
HOUR- 8
HOUR- 8
HOUR - 8
HOUR- 8
HOUR- 12
HOUR- 12
HOUR -12
HOUR -12
HOUR -16
HOUR -16
HOUR -16
HOUR -16
HOUR -20
HOUR -20
HOUR -20
HOUR -20
Sample
Number
Sample
Port
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
Totalizer
Flow
254.8
390.09
559.34
662.95
808.83
PH
Value
3.97
4.16
6.15
3.87
4
6.09
3.78
4.11
6
3.84
4.17
6.04
3.91
4.14
3.06
ORP
Value
555
430
435
432
426
Iron
Field Analy
1310
1370
1260
1240
Sampled
Time
17:00
21:00
1:45
5:00
9:00
Initials
JB
JB
RZ
RZ
MGL
Comments
Sampling delayed due to pump problems
WEEK 1 (CONTINUOUS)
DAY 2
Sample
Time
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
991
PH
Value
4.1
4.2
6.08
6.6
ORP
Value
400
430
Iron
Field Analy
Sampled
Time
13:00
Initials
KN
Comments
WEEK 1 (CONTINUOUS)
DAYS
Sample
Time
HOUR- 8
HOUR- 8
HOUR - 8
HOUR- 8
HOUR -16
HOUR -16
HOUR -16
Sample
Number
Sample
Port
101
102
103
FIT
101
102
103
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Totalizer
Flow
1213.6
PH
Value
3.88
4.1
596
3.82
4.1
6.27
ORP
Value
473
455
Iron
Field Analy
1290
1210
Sampled
Time
21:00
5:00
Initials
JB
RZ
Comments
B4
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
HOUR -16
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
FIT
101
102
103
FIT
FH5
Total Flow
pH
pH, ORP
pH
Total Flow
pH
1492.2
1777.95
4.04
4.12
6.39
6.55
-
1250
13:00
MGL
WEEK 1 (CONTINUOUS)
DAY 4
Sample
Time
HOUR- 8
HOUR- 8
HOUR - 8
HOUR- 8
HOUR -16
HOUR -16
HOUR -16
HOUR -16
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
2039.2
2340.56
2557
PH
Value
3.77
4
6.18
3.85
4.08
6.07
3.96
3.96
5.97
-
ORP
Value
471
492
675
462
535
-
Iron
Field Analy
1310
1240
Sampled
Time
21:00
5:00
12:00
Initials
JB
RZ
KN
Comments
WEEK 1 (CONTINUOUS)
DAYS
Sample
Time
HOUR- 8
HOUR- 8
HOUR - 8
HOUR- 8
HOUR -16
HOUR -16
HOUR -16
HOUR -16
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
101
102
103
FIT
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
2840
3091.24
3233
^m
PH
Value
3.87
4.1
6.14
3.94
4.1
6.02
4
4.11
6.13
ORP
Value
515
514
399
-
Iron
Field Analy
1250
1140
1550
Sampled
Time
21:00
5:00
13:00
Initials
JB
RZ
MGL
Comments
FH2 Sample Port
FH2 Sample Port
FH2 Sample Port
B5
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
WEEK 1 (CONTINUOUS)
DAY 6
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
Sample
Number
Sample
Port
101
102
103
FIT
Sample
Analysis
pH
pH, ORP
pH
Total Flow
Totalizer
Flow
3380
PH
Value
3.87
4.1
6.1
ORP
Value
403
Iron
Field Analy
1160
Sampled
Time
19:00
Initials
JB
Comments
FH2 Sample Port
WEEK 1 (CONTINUOUS)
DAY?
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
4243
PH
Value
3.83
4.22
7.12
5.92
ORP
Value
-
505
Iron
Field Analy
Sampled
Time
Initials
Comments
pump 106 is stopped/probe
uncovered/caused excess lime
WEEK 2 (CONTINUOUS)
DAY1
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
5030
PH
Value
3.84
4
6.33
6.06
ORP
Value
419
495
Iron
Field Analy
Sampled
Time
19:00
Initials
JB
Comments
WEEK 2 (CONTINUOUS)
DAY 2
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
Sample
Number
Sample
Port
101
102
103
FIT
Sample
Analysis
pH
pH, ORP
pH
Total Flow
Totalizer
Flow
5889
PH
Value
3.43
4.3
6.41
ORP
Value
493
Iron
Field Analy
Sampled
Time
20:00
Initials
JB
Comments
18:00 samples taken 20:00 (plugged
filters/problems w/ filter cake
WEEK 2 (CONTINUOUS)
DAYS
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
6614
PH
Value
4.04
4.01
6.21
ORP
Value
396
-
Iron
Field Analy
Sampled
Time
18:00
Initials
JB
Comments
B6
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
WEEK 2 (CONTINUOUS)
DAY 4
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
7403
PH
Value
3.93
3.9
6.59
6.82
ORP
Value
464
200
Iron
Field Analy
2290
Sampled
Time
18:00
Initials
JB
Comments
WEEK 2 (CONTINUOUS)
DAYS
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
8183
PH
Value
3.89
3.8
608
ORP
Value
-
Iron
Field Analy
Sampled
Time
18:00
Initials
JB
Comments
Acid Leak
WEEK 2 (CONTINUOUS)
DAY 6
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
9040
PH
Value
4.25
-
6.14
5.89
ORP
Value
537
480
Iron
Field Analy
3310
2.68
Sampled
Time
20:30
Initials
JB
Comments
Data collected at 20:30 due to error
FH2 Sample Port
FH4 Sample Port
WEEK 2 (CONTINUOUS)
DAY?
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
9608
PH
Value
4.42
-
651
6.29
ORP
Value
537
290
Iron
Field Analy
2750
Sampled
Time
18:00
Initials
JB
Comments
FH2 Sample Port
WEEK 3 (CONTINUOUS)
DAY1
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
310
^m
PH
Value
4.11
3.9
5.62
6.1
ORP
Value
526
355
Iron
Field Analy
2510
Sampled
Time
18:10
Initials
JB
Comments
FH2 Sample Port
B7
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
WEEK 3 (CONTINUOUS)
DAY 2
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
1050
PH
Value
4.13
4.2
568
6.7
ORP
Value
522
510
Iron
Field Analy
2400
Sampled
Time
18:00
Initials
JB
Comments
WEEK 3 (CONTINUOUS)
DAYS
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
1816
PH
Value
3.98
-
6.07
6.06
ORP
Value
549
295
Iron
Field Analy
2210
Sampled
Time
16:30
no time
Initials
JB
JM
Comments
WEEK 3 (CONTINUOUS)
DAY 4
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
2577
PH
Value
3.61
-
5.95
6.25
ORP
Value
455
290
Iron
Field Analy
4020
Sampled
Time
18:10
Initials
JB
Comments
FH2 Sample Port
WEEK 3 (CONTINUOUS)
DAYS
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
11/12/99
Sample
Number
Sample
Port
101
102
103
FIT
FH5
101
102
103
FIT
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH
pH, ORP
pH
Total Flow
Totalizer
Flow
3394
PH
Value
3.68
621
7.3
7.56
2
4.13
ORP
Value
455
300
640
Iron
Field Analy
3280
Sampled
Time
19:30
18:00
Initials
JB
JM
Comments
FH2 Sample Port
No sample taken because no water to
sample
WEEK 3 (CONTINUOUS)
DAY 6
Sample
Time
HOUR - 6
HOUR - 6
Sample
Number
Sample
Port
101
102
Sample
Analysis
pH
pH, ORP
Totalizer
Flow
•
PH
Value
IE
ORP
Value
456
Iron
Field Analy
Sampled
Time
16:00
Initials
JM
Comments
B8
-------
Table B-l. Ferrihydrite adsorption process demonstration field data record
HOUR - 6
HOUR - 6
HOUR -24
103
FIT
FH5
pH
Total Flow
pH
4059.2
7.3
-
-
WEEK 3 (CONTINUOUS)
DAY 7 FINAL
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
101
102
103
FIT
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
pH, ORP
pH
Total Flow
Totalizer
Flow
-
PH
Value
-
ORP
Value
-
Iron
Field Analy
Sampled
Time
12:00
Initials
MGL
Comments
Hour 6 samples not collected
WEEK 3 (CONTINUOUS)
DAY 7 FINAL
Sample
Time
HOUR -24
Sample
Number
Sample
Port
FH5
Sample
Analysis
pH
Totalizer
Flow
-
PH
Value
ORP
Value
Iron
Field Analy
Sampled
Time
12:00
Initials
MGL
Comments
WEEK 4 (CONTINUOUS)
DAY 1 - 11/14/99
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -6
HOUR -24
Sample
Number
Sample
Port
101
102
103
FIT
FH5
Sample
Analysis
pH
pH, ORP
pH
Total Flow
pH
Totalizer
Flow
6432
PH
Value
-
4.05
5.87
ORP
Value
455
Iron
Field Analy
Sampled
Time
18:00
Initials
KN
Comments
B9
-------
Table B-2. Selenium demonstration test—ferrihydrite process analytical data summary
Sample Collection Collection Submission .^p™
Description Date Time Date
Low Iron Test; Fe:Se mole ratio = 921:1
AH26360 MSE\FH1-001 10/21/99 8:55 10/21/99
AH26361 MSE\FH1-001 10/21/99 8:55 10/21/99
AH26583 MSE\FH1-201 10/23/99 14:00 10/25/99
AH26584 MSA\FH1-201 10/23/99 14:00 10/25/99
AH26585 MSA\FH2-202 10/23/99 14:00 10/25/99
AH26586 MSA\FH2-202 10/23/99 14:00 10/25/99
AH26587 MSA\FH3-203 10/23/99 14:00 10/25/99
AH26588 MSA\FH3-203 10/23/99 14:00 10/25/99
AH26589 MSA\FH3-206 10/23/99 17:00 10/25/99
AH26590 MSA\FH3-207 10/23/99 21:00 10/25/99
AH26591 MSA\FH3-208 10/24/99 1:00 10/25/99
AH26592 MSA\FH3-209 10/24/99 5:00 10/25/99
AH26593 MSA\FH5-210 10/24/99 9:00 10/25/99
AH26594 MSA\FH3-2 1 1 10/24/99 13:00 10/25/99
AH26595 MSA\FH5-212 10/24/99 13:00 10/25/99
AH26596 MSA\FH5-213 10/24/99 17:00 10/25/99
AH26597 MSA\FH5-214 10/24/99 19:00 10/25/99
AH26598 MSA\FH5-215 10/24/99 21:00 10/25/99
AH26599 MSA\FH5-216 10/25/99 1:00 10/25/99
AH26600 MSA\FH5-217 10/25/99 5:00 10/25/99
AH26656 MSE\FH5-218 10/25/99 9:00 10/26/99
AH26657 MSE\FH1-219 10/25/99 13:00 10/26/99
AH26658 MSE\FH1-219 10/25/99 13:00 10/26/99
AH26659 MSE\FH2-220 10/25/99 13:00 10/26/99
AH26660 MSE\FH2-220 10/25/99 13:00 10/26/99
AH26661 MSE\FH3-221 10/25/99 13:00 10/26/99
AH26662 MSE\FH3-221 10/25/99 13:00 10/26/99
AH26663 MSE\FH4-222 10/25/99 13:00 10/26/99
AH26664 MSE\FH4-222 10/25/99 13:00 10/26/99
AH26665 MSE\FH5-223 10/25/99 13:00 10/26/99
AH26666 MSE\FH5-223 10/25/99 13:00 10/26/99
AH26667 MSE\FH4-224 10/25/99 19:00 10/26/99
AH26668 MSE\FH5-225 10/25/99 19:00 10/26/99
AH26669 MSE\FH5-226 10/25/99 21:00 10/26/99
AH26670 MSE\FH5-227 10/26/99 5:00 10/26/99
AH26721 MSE\FH3-228 10/26/99 13:00 10/27/99
AH26722 MSE\FH5-229 10/26/99 13:00 10/27/99
AH26723 MSE\FH8-229 10/26/99 13:00 10/27/99
AH26724 MSE\FH9-229 10/26/99 13:00 10/27/99
AH26725 MSE\FH5-230 10/26/99 21:00 10/27/99
AH26726 MSE\FH5-231 10/27/99 5:00 10/27/99
AH26727 MSE\FH5-005 10/26/99 19:00 10/27/99
AH26837 MSE\FHl-232 10/27/99 13:00 10/28/99
AH26838 MSE\FHl-232 10/27/99 13:00 10/28/99
AH26839 MSE\FH2-233 10/27/99 13:00 10/28/99
AH26840 MSE\FH2-233 10/27/99 13:00 10/28/99
AH26841 MSE\FH3-234 10/27/99 13:00 10/28/99
AH26842 MSE\FH3-234 10/27/99 13:00 10/28/99
IDS
20
mg/L
6140
6040
TSS
3
mg/L
11
13
Iron
0.3
mg/L
5.9
0.9
0.4
< 0.3
Ferrous
0.5
mg/L
0.7
< 0.5
Ferric
0.5
mg/L
< 0.5
< 0.5
Calcium
1
mg/L
111
109
120
120
117
115
1310
1310
122
122
120
120
730
730
834
834
840
840
116
115
115
115
1190
1190
Magnesium
1
mg/L
46.7
46.7
48
48
47
47
51
51
49.1
48.7
48
48
340
340
296
292
296
294
48.6
48.4
46.8
46.5
110
110
Sodium
1
mg/L
360
360
342
338
336
334
356
356
355
355
350
350
340
340
340
339
340
340
365
365
355
355
370
370
Nitrate
0.2
mg/L
4.1
4.2
4.1
5.8
4.2
Sultate
5
mg/L
267
263
266
31
261
Arsenic
10
ug/L
16
13
22
17
< 10
< 10
< 10
< 10
13
13
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
18
12
11
< 10
15
15
< 10
< 10
< 10
< 10
Barium
10
ug/L
44
44
52
50
89
85
135
129
52
51
150
145
98
74
80
80
80
80
35
32
94
88
87
61
Copper
10
ug/L
15
< 10
14
< 10
210
189
233
208
18
< 10
233
180
185
77
113
47
25
25
16
< 10
210
159
159
103
Iron
300
ug/L
180000
0
180000
0
200000
655
513
< 300
139000
0
139000
0
129000
0
< 300
4110
< 300
347
< 300
< 300
< 300
< 300
< 300
< 300
< 300
134000
0
180000
0
841000
< 300
Molybdenum
10
ug/L
130
130
144
122
68
61
20
< 10
135
118
75
75
60
< 10
< 10
< 10
< 10
< 10
82
77
45
44
38
< 10
Selenium
10
ug/L
1550
1550
1570
1570
1510
1510
350
186
247
266
254
262
402
278
194
265
267
297
336
330
1500
1500
959
885
1150
458
300
300
300
300
347
363
358
347
358
< 10
342
345
1060
1023
980
949
833
400
Hydride
2
ug/L
1633
1840
243
333
340
Selenate
2
ug/L
586
473
133
179
223
Seleniti
2
ug/L
509
172
30
28
24
-------
Table B-2. Selenium demonstration test—ferrihydrite process analytical data summary
Sample Collection Collection Submission .^p™
Description Date Time Date
AH26843 MSE\FH4-235 10/27/99 13:00 10/28/99
AH26844 MSE\FH4-235 10/27/99 13:00 10/28/99
AH26845 MSE\FH5-236 10/27/99 13:00 10/28/99
AH26846 MSE\FH5-236 10/27/99 13:00 10/28/99
AH26847 MSE\FH5-237 10/27/99 19:00 10/28/99
AH26848 MSE\FH5-238 10/27/99 21:00 10/28/99
AH26849 MSE\FH5-239 10/28/99 5:00 10/28/99
AH26961 MSE\FH3-240 10/28/99 13:00 10/29/99
AH26962 MSE\FH5-241 10/28/99 13:00 10/29/99
AH26963 MSE\FH5-242 10/28/99 19:00 10/29/99
AH27037 MSE\FHl-243 10/29/99 13:00 11/1/99
AH27038 MSE\FHl-243 10/29/99 13:00 11/1/99
AH27039 MSE\FH2-244 10/29/99 13:00 11/1/99
AH27040 MSE\FH3-245 10/29/99 13:00 11/1/99
AH27041 MSE\FH3-245 10/29/99 13:00 11/1/99
AH27042 MSE\FH4-246 10/29/99 13:00 11/1/99
AH27043 MSE\FH4-246 10/29/99 13:00 11/1/99
AH27044 MSE\FH5-247 10/29/99 13:00 11/1/99
AH27045 MSE\FH5-247 10/29/99 13:00 11/1/99
AH27046 MSE\FH5-248 10/29/99 19:00 11/1/99
AH27047 MSE\FH3-249 10/30/99 13:00 11/1/99
AH27048 MSE\FH5-250 10/30/99 13:00 11/1/99
AH27049 MSE\FH5-251 10/30/99 19:00 11/1/99
AH27050 MSE\FHl-252 10/31/99 12:00 11/1/99
AH27051 MSE\FHl-252 10/31/99 12:00 11/1/99
AH27052 MSE\FH2-253 10/31/99 12:00 11/1/99
AH27053 MSE\FH3-254 10/31/99 12:00 11/1/99
AH27054 MSE\FH3-254 10/31/99 12:00 11/1/99
AH27055 MSE\FH5-256 10/31/99 12:00 11/1/99
AH27056 MSE\FH5-256 10/31/99 12:00 11/1/99
AH27057 MSE\FH4-255 10/31/99 12:00 11/1/99
AH27058 MSE\FH4-255 10/31/99 12:00 11/1/99
AH27059 MSE\FH5-257 10/31/99 20:15 11/1/99
AH27062 MSE\FH FILTRATE-221 10/31/99 17:45 11/1/99
AH27063 MSE\FH FILTRATE-221 10/31/99 17:45 11/1/99
AH27151 MSE\FH3-258 11/1/99 12:00 11/2/99
AH27152 MSE\FH5-259 11/1/99 12:00 11/2/99
Medium Iron Test; Fe/Se mole ratio = 1945:1
AH27153 MSE\FH4-260 11/1/99 18:00 11/2/99
AH27154 MSE\FH5-261 11/1/99 18:00 11/2/99
AH27155 MSE\FH5-261 11/1/99 18:00 11/2/99
AH27418 MSE\FHl-262 11/2/99 12:00 11/3/99
AH27419 MSE\FHl-262 11/2/99 12:00 11/3/99
AH27420 MSE\FH2-263 11/2/99 12:00 11/3/99
AH27421 MSE\FH3-264 11/2/99 12:00 11/3/99
AH27422 MSE\FH3-264 11/2/99 12:00 11/3/99
AH27423 MSE\FH4-265 11/2/99 12:00 11/3/99
AH27424 MSE\FH4-265 11/2/99 12:00 11/3/99
AH27425 MSE\FH5-266 11/2/99 12:00 11/3/99
AH27426 MSE\FH5-266 11/2/99 12:00 11/3/99
AH27427 MSE\FH8-266 11/2/99 12:00 11/3/99
IDS
20
mg/L
TSS
3
mg/L
Iron
0.3
mg/L
Ferrous
0.5
mg/L
Ferric
0.5
mg/L
Calcium
1
mg/L
1140
1140
1140
1120
1230
117
117
115
1700
1700
1800
1760
1790
1790
119
118
115
1200
1200
1800
1800
1750
1750
1500
1500
Magnesium
1
mg/L
149
148
150
148
115
48
48
46.1
60
60
68.7
68.1
69
68.9
49.2
48.7
46.3
230
230
72.5
72.4
74
74
244
244
Sodium
1
mg/L
381
376
381
379
335
342
342
327
335
335
342
340
344
344
347
347
331
340
340
353
353
350
350
350
350
Nitrate
0.2
mg/L
4.2
4.2
4.1
4.5
4
5.6
Sultate
5
mg/L
31
267
10
248
13
273
Arsenic
10
ug/L
< 10
< 10
< 10
< 10
< 10
< 10
< 10
17
17
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
99
< 10
< 10
< 10
Barium
10
ug/L
74
58
80
80
69
68
56
92
97
60
62
61
64
60
51
47
85
86
61
62
61
61
59
96
69
Copper
10
ug/L
182
49
65
40
27
14
14
130
155
102
103
41
69
31
16
< 10
139
135
97
50
15
86
20
105
38
Iron
300
ug/L
1630
< 300
1080
< 300
459
52
40
< 300
< 300
166000
0
138000
0
582
2470
< 300
1480
< 300
583
< 300
< 300
< 300
165000
0
985000
654
2800
< 300
4990
< 300
213000
< 300
455
< 300
Molybdenum
10
ug/L
< 10
< 10
< 10
< 10
11
145
145
74
64
< 10
< 10
< 10
< 10
< 10
118
114
66
46
< 10
< 10
< 10
< 10
< 10
< 10
< 10
Selenium
10
ug/L
300
300
300
300
264
334
261
325
350
1440
1440
1200
1030
232
227
239
230
230
240
222
256
245
1450
1450
1200
817
239
240
240
240
240
115
1250
1190
386
377
Hydride
2
ug/L
329
278
1480
Selenate
2
ug/L
266
156
911
Seleniti
2
ug/L
21
22
40
7200
6900
19
< 3
118
118
113
830
830
982
965
976
964
966
48.7
48.6
46.9
395
395
346
343
347
342
340
350
350
343
350
350
354
348
353
343
346
4
4
278
52
13
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
57
50
72
78
63
65
65
52
49
64
15
< 10
107
105
50
27
< 10
< 10
< 10
< 10
< 300
< 300
161000
0
140000
0
828
1790
< 300
1210
< 300
< 300
128
115
52
38
< 10
< 10
< 10
< 10
< 10
< 10
452
1550
1550
1020
886
380
400
400
343
339
439
380
197
31
-------
Table B-2. Selenium demonstration test—ferrihydrite process analytical data summary
Sample Collection Collection Submission .^p™
Description Date Time Date
AH27428 MSE\FH9-266 11/2/99 12:00 11/3/99
AH27429 MSE\FH5-267 11/2/99 18:00 11/3/99
AH27525 MSE\FH3-268 11/3/99 12:00 11/4/99
AH27526 MSE\FH5-269 11/3/99 12:00 11/4/99
AH27527 MSE\FH5-270 11/3/99 20:00 11/4/99
AH27650 MSE\FH1-271 11/4/99 12:00 11/5/99
AH27651 MSE\FH1-271 11/4/99 12:00 11/5/99
AH27652 MSE\FH2-272 11/4/99 12:00 11/5/99
AH27653 MSE\FH3-273 11/4/99 12:00 11/5/99
AH27654 MSE\FH3-273 11/4/99 12:00 11/5/99
AH27655 MSE\FH4-274 11/4/99 12:00 11/5/99
AH27656 MSE\FH4-274 11/4/99 12:00 11/5/99
AH27657 MSE\FH5-275 11/4/99 12:00 11/5/99
AH27658 MSE\FH5-275 11/4/99 12:00 11/5/99
AH27659 MSE\FH5-276 11/4/99 18:00 11/5/99
AH27735 MSE\FH3-277 11/5/99 12:00 11/8/99
AH27736 MSE\FH5-278 11/5/99 12:00 11/8/99
AH27737 MSE\FH5-279 11/5/99 18:00 11/8/99
AH27738 MSE\FH1-280 11/6/99 12:00 11/8/99
AH27739 MSE\FH1-280 11/6/99 12:00 11/8/99
AH27740 MSE\FH2-281 11/6/99 12:00 11/8/99
AH27741 MSE\FH2-281 11/6/99 12:00 11/8/99
AH27742 MSE\FH3-282 11/6/99 12:00 11/8/99
AH27743 MSE\FH3-282 11/6/99 12:00 11/8/99
AH27744 MSE\FH4-283 11/6/99 12:00 11/8/99
AH27745 MSE\FH4-283 11/6/99 12:00 11/8/99
AH27746 MSE\FH5-284 11/6/99 12:00 11/8/99
AH27747 MSE\FH5-284 11/6/99 12:00 11/8/99
AH27748 MSE\FH5-285 11/6/99 18:00 11/8/99
AH27749 MSE\FH3-286 11/7/99 12:00 11/8/99
AH27750 MSE\FH5-287 11/7/99 12:00 11/8/99
AH27751 MSE\FH5-288 11/7/99 18:00 11/8/99
AH27863 MSE\FHl-289 11/8/99 12:00 11/9/99
AH27864 MSE\FHl-289 11/8/99 12:00 11/9/99
AH27865 MSE\FH2-290 11/8/99 12:00 11/9/99
AH27866 MSE\FH2-290 11/8/99 12:00 11/9/99
AH27867 MSE\FH3-291 11/8/99 12:00 11/9/99
AH27868 MSE\FH3-291 11/8/99 12:00 11/9/99
AH27869 MSE\FH4-292 11/8/99 12:00 11/9/99
AH27870 MSE\FH4-292 11/8/99 12:00 11/9/99
AH27871 MSE\FH5-293 11/8/99 12:00 11/9/99
AH27872 MSE\FH5-293 11/8/99 12:00 11/9/99
AH27873 MSE\FH4-294 11/8/99 18:00 11/9/99
AH27874 MSE\FH5-295 11/8/99 18:00 11/9/99
AH27875 MSE\FH5-295 11/8/99 18:00 11/9/99
Highlron Test; Fe/Se mole ratio = 3186:1
AH27940 MSE\FH3-296 11/9/99 12:00 11/10/99
AH27941 MSE\FH5-297 11/9/99 12:00 11/10/99
AH27942 MSE\FH8-297 11/9/99 12:00 11/10/99
IDS
20
mg/L
9400
10200
TSS
3
mg/L
6
6
Iron
0.3
mg/L
Ferrous
0.5
mg/L
Ferric
0.5
mg/L
Calcium
1
mg/L
< 1
120
120
114
1600
1600
1710
1710
1680
1640
120
111
106
106
2760
2760
2760
2680
2680
2680
122
113
107
107
2500
2500
2500
2500
2500
2500
Magnesium
1
mg/L
< 1
50
50
46.9
750
750
786
777
750
736
48.4
45.8
42
42
170
170
451
441
453
452
48.5
46.5
43
43
59.3
58.2
82
82
85
85
Sodium
1
mg/L
< 1
370
370
351
360
360
362
362
343
340
400
392
368
368
380
380
387
335
338
337
348
341
330
330
348
344
350
350
348
348
Nitrate
0.2
mg/L
3.5
3.6
3.8
3.7
4.2
3.8
Sultate
5
mg/L
512
18
268
27
256
15
Arsenic
10
ug/L
< 10
< 10
< 10
15
10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
13
11
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
Barium
10
ug/L
< 10
61
51
121
112
61
74
71
77
69
50
38
85
85
160
150
73
69
74
62
52
40
115
115
140
67
76
66
76
65
Copper
10
ug/L
< 10
18
12
276
191
14
56
< 10
61
< 10
30
< 10
222
220
255
65
103
46
101
45
39
11
296
279
330
150
145
110
171
108
Iron
300
ug/L
< 300
2560
< 300
< 300
< 300
227000
0
141000
0
310
6010
< 300
9270
< 300
345
< 300
< 300
< 300
330000
0
330000
0
198000
0
1630
8730
311
2510
< 300
950
< 300
< 300
< 300
296000
0
2100
296000
0
2290
< 300
< 300
3770
303
Molybdenum
10
ug/L
14
125
125
< 10
< 10
< 10
< 10
< 10
< 10
< 10
120
91
118
15
64
< 10
< 10
< 10
< 10
< 10
121
100
118
118
119
< 10
< 10
< 10
< 10
< 10
Selenium
10
ug/L
< 10
438
42
415
179
1580
1450
75
650
369
140
140
144
142
154
150
174
217
1440
1240
69
27
652
160
188
157
189
163
138
48
133
130
1520
1430
77
73
1100
1050
158
152
159
154
173
Hydride
2
ug/L
128
Selenate
2
ug/L
30
Seleniti
2
ug/L
18
< 10
< 10
< 10
973
313
338
54
124
125
-------
Table B-2. Selenium demonstration test—ferrihydrite process analytical data summary
Sample Collection Collection Submission .^p™
Description Date Time Date
AH27943 MSE\FH9-297 11/9/99 12:00 11/10/99
AH27944 MSE\FH5-298 11/9/99 18:00 11/10/99
AH28108 MSE\FHl-299 11/10/99 12:00 11/11/99
AH28109 MSE\FHl-299 11/10/99 12:00 11/11/99
AH28110 MSE\FH2-300 11/10/99 12:00 11/11/99
AH28111 MSE\FH2-300 11/10/99 12:00 11/11/99
AH28112 MSE\FH3-301 11/10/99 12:00 11/11/99
AH28113 MSE\FH3-301 11/10/99 12:00 11/11/99
AH28114 MSE\FH4-302 11/10/99 12:00 11/11/99
AH28115 MSE\FH4-302 11/10/99 12:00 11/11/99
AH28116 MSE\FH5-303 11/10/99 12:00 11/11/99
AH28117 MSE\FH5-303 11/10/99 12:00 11/11/99
AH28118 MSE\FH5-304 11/10/99 18:00 11/11/99
AH28241 MSE\FH3-305 11/11/99 12:00 11/12/99
AH28242 MSE\FH5-306 11/11/99 12:00 11/12/99
AH28243 MSE\FH5-307 11/11/99 12:00 11/12/99
Ferrous/Ferric Test
AH28304 MSE\FH1-308 11/12/99 11:00 11/15/99
AH28305 MSE\FH1-308 11/12/99 11:00 11/15/99
AH28306 MSE\FH2-309 11/12/99 11:00 11/15/99
AH28307 MSE\FH2-309 11/12/99 11:00 11/15/99
AH28308 MSE\FH3-310 11/12/99 11:00 11/15/99
AH28309 MSE\FH3-310 11/12/99 11:00 11/15/99
AH28310 MSE\FH4-311 11/12/99 11:00 11/15/99
AH28311 MSE\FH4-311 11/12/99 11:00 11/15/99
AH28312 MSE\FH5-312 11/12/99 11:00 11/15/99
AH28313 MSE\FH5-312 11/12/99 11:00 11/15/99
AH28314 MSE\FH3-360 11/13/99 12:00 11/15/99
AH28315 MSE\FH5-361 11/13/99 12:00 11/15/99
AH28316 MSE\FH5-362 11/13/99 18:00 11/15/99
AH28317 MSE\FH5-314 11/14/99 12:00 11/15/99
AH28318 MSE\FH1-315 11/14/99 12:00 11/15/99
AH28319 MSE\FH1-315 11/14/99 12:00 11/15/99
AH28320 MSE\FH2-316 11/14/99 12:00 11/15/99
AH28321 MSE\FH2-316 11/14/99 12:00 11/15/99
AH28322 MSE\FH3-317 11/14/99 12:00 11/15/99
AH28323 MSE\FH3-317 11/14/99 12:00 11/15/99
AH28324 MSE\FH4-318 11/14/99 12:00 11/15/99
AH28325 MSE\FH4-318 11/14/99 12:00 11/15/99
AH28326 MSE\FH8-319 11/14/99 12:00 11/15/99
AH28327 MSE\FH9-319 11/14/99 12:00 11/15/99
AH28328 MSE\FH5-319 11/14/99 12:00 11/15/99
AH28329 MSE\FH5-319 11/14/99 12:00 11/15/99
AH28330 MSE\FH3-320 11/14/99 18:00 11/15/99
Recycle Fe Sludge Test
AH28425 MSE\FH3-321 11/15/99 12:00 11/16/99
AH28426 MSE\FH5-322 11/15/99 12:00 11/16/99
AH28427 MSE\FH3-323 11/15/99 18:00 11/16/99
AH28428 MSE\FH5-324 11/15/99 18:00 11/16/99
AH28429 MSE\FH3-325 11/15/99 0:00 11/16/99
IDS
20
mg/L
TSS
3
mg/L
Iron
0.3
mg/L
Ferrous
0.5
mg/L
Ferric
0.5
mg/L
Calcium
1
mg/L
120
120
109
109
2920
2920
2920
2920
2920
2920
Magnesium
1
mg/L
49.3
47.9
42.9
42.6
62.6
62.1
66
66
66
66
Sodium
1
mg/L
379
340
313
311
335
335
335
335
340
340
Nitrate
0.2
mg/L
4
3.5
Sultate
5
mg/L
254
< 5
Arsenic
10
ug/L
< 10
12
12
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
Barium
10
ug/L
50
50
129
98
137
86
66
59
94
72
Copper
10
ug/L
< 10
< 10
378
197
398
191
198
187
219
185
Iron
300
ug/L
< 300
< 300
< 300
480000
0
480000
0
423000
4030
19800
632
20000
472
4880
333
Molybdenum
10
ug/L
88
88
193
119
120
< 10
< 10
< 10
< 10
< 10
Selenium
10
ug/L
< 10
111
1100
1100
49
43
563
79
50
30
60
60
64
35
93
147
Hydride
2
ug/L
43
Selenate
2
ug/L
Seleniti
2
ug/L
5920
5840
128
122
412
364
< 0.3
< 0.3
116
< 0.5
248
< 0.5
114
114
116
740
740
2780
2780
2780
2780
118
117
115
115
1220
1220
1340
1330
1380
< 1
1360
1360
48.1
48.1
46.9
50
50
56.4
56.2
58
58
48
48
45
45
51
51
52.2
51.8
52.7
< 1
53
53
346
345
350
350
350
356
353
355
355
355
355
337
335
346
346
350
347
351
< 1
347
347
4
3.5
4
2.6
237
126
245
1230
15
15
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
12
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
50
50
63
88
68
72
72
73
72
49
49
110
110
97
84
73
73
< 10
78
92
78
< 10
< 10
43
110
100
182
181
222
191
< 10
< 10
15
14
< 10
< 10
17
< 10
< 10
538
634
145
< 300
< 300
135000
0
500000
52600
47100
36900
18700
29900
15800
295000
0
295000
0
189000
0
754000
814000
711000
537000
< 300
746000
593000
80
78
127
124
< 10
< 10
< 10
< 10
< 10
122
115
60
< 10
74
< 10
< 10
< 10
< 10
< 10
< 10
< 10
994
990
1460
1330
652
451
432
409
403
664
706
758
852
1500
1500
79
77
1170
918
800
800
825
< 10
800
800
822
1440
961
13
935
1210
265
< 2
364
142
202
13
126
515
879
190
747
222
-------
Table B-2. Selenium demonstration test—ferrihydrite process analytical data summary
Sample Collection Collection Submission .^p™
Description Date Time Date
AH28430 MSE\FH5-326 11/15/99 0:00 11/16/99
AH28431 MSE\FH3-327 11/16/99 6:00 11/16/99
AH28432 MSE\FH5-328 11/16/99 6:00 11/16/99
AH28503 MSE\FH3-329 11/16/99 12:00 11/17/99
AH28504 MSE\FH5-330 11/16/99 12:00 11/17/99
AH28505 MSE\FH3-331 11/16/99 18:00 11/17/99
AH28506 MSE\FH5-332 11/16/99 18:00 11/17/99
AH28507 MSE\FH3-333 11/16/99 0:00 11/17/99
AH28508 MSE\FH5-334 11/16/99 0:00 11/17/99
AH28509 MSE\FH3-335 11/17/99 6:00 11/17/99
AH28510 MSE\FH5-336 11/17/99 6:00 11/17/99
AH28677 MSE\FH3-337 11/17/99 12:00 11/18/99
AH28678 MSE\FH5-338 11/17/99 12:00 11/18/99
AH28679 MSE\FH3-339 11/17/99 18:00 11/18/99
AH28680 MSE\FH5-340 11/17/99 18:00 11/18/99
AH28681 MSE\FH3-341 11/17/99 0:00 11/18/99
AH28682 MSE\FH5-342 11/17/99 0:00 11/18/99
AH28683 MSE\FH5-343 11/18/99 6:00 11/18/99
AH28684 MSE\FHl-344 11/18/99 6:00 11/18/99
AH28685 MSE\FHl-344 11/18/99 6:00 11/18/99
AH28686 MSE\FH2-345 11/18/99 6:00 11/18/99
AH28687 MSE\FH2-345 11/18/99 6:00 11/18/99
AH28688 MSE\FH3-346 11/18/99 6:00 11/18/99
AH28689 MSE\FH3-346 11/18/99 6:00 11/18/99
AH28690 MSE\FH4-347 11/18/99 6:00 11/18/99
AH28691 MSE\FH4-347 11/18/99 6:00 11/18/99
AH28692 MSE\FH5-348 11/18/99 6:00 11/18/99
AH28693 MSE\FH5-348 11/18/99 6:00 11/18/99
AH28694 MSE\FH8-349 11/18/99 6:00 11/18/99
AH28695 MSE\FH9-350 11/18/99 6:00 11/18/99
AH29009 MSE\FH3-341 11/18/99 11/22/99
AH29010 MSE\FH2-345 11/18/99 11/22/99
AH29011 MSE\FH3-346 11/18/99 11/22/99
AH29012 MSE\FH9-350 11/18/99 11/22/99
IDS
20
mg/L
5770
5650
TSS
3
mg/L
16
21
Iron
0.3
mg/L
< 0.3
< 0.3
Ferrous
0.5
mg/L
< 0.5
Ferric
0.5
mg/L
< 0.5
Calcium
1
mg/L
127
122
541
540
2940
2900
1740
1730
1710
1710
1670
3.8
Magnesium
1
mg/L
50.2
49.9
45
45
55
55
54.7
54.3
55
55
54.5
< 1
Sodium
1
mg/L
350
350
320
320
335
335
350
350
350
350
344
2
Nitrate
0.2
mg/L
3.9
3.6
Sultate
5
mg/L
248
62
Arsenic
10
ug/L
12
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
Barium
10
ug/L
53
43
201
90
125
65
50
50
50
50
54
< 10
Copper
10
ug/L
< 10
< 10
686
581
301
213
97
97
90
82
95
< 10
Iron
300
ug/L
824000
0
613000
564000
0
773
6730
3450
6380
1670
1840
< 300
Molybdenum
10
ug/L
136
103
< 10
< 10
253
< 10
< 10
< 10
< 10
< 10
< 10
< 10
Selenium
10
ug/L
695
195
200
231
369
214
288
220
275
225
266
283
230
185
239
103
231
231
1570
1280
89
< 10
1770
77
200
200
200
200
244
< 10
Hydride
2
ug/L
1600
272
163
< 2
100
61
79
< 7.
Selenate
2
ug/L
1400
137
128
< 2
Seleniti
2
ug/L
134
22
8
< 2
-------
Table B-3. Summary total metals data
, , „ , „ . ^. Collection Submission „,
Lab ft Sample Description RL
r r Date Date TT .
Units
AH27060 MSE\FH FILTER CAKE -221 10/31/99 11/1/99
AH27767 MSE\CC FILTER CAKE 221 11/6/99 11/8/99
AH28433 MSE\CCFILTERCAKE 11/15/99 11/16/99
AH28671 FH Filter Cake-225 11/18/99 11/18/99
Arsenic
0.5
mg/kg
21
22
13
22.7
Barium
5
mg/kg
< 0.5
< 0.5
< 0.5
80
Calcium
1
mg/kg
1600
2500
1130
Cadmium
0.2
mg/kg
0.8
1
4.7
< 0.2
Chromium
1
mg/kg
72.6
31.4
15.1
10.5
Copper
1
mg/kg
23.6
638
3300
63.1
Iron
1
mg/kg
76400
11600
29200
Mercury
0.01
mg/kg
0.7
0.6
0.46
0.48
Lead
0.5
mg/kg
< 0.5
< 0.5
< 0.5
6.4
Selenium
0.5
mg/kg
< 0.5
< 0.5
40
< 0.5
Silver
1
mg/kg
< 1
< 1
< 1
< 1
Total Solid
1
%
29
24
26
51
Table B-4. Summary toxicity characteristic leachate procedure data
„ „ .. „ , . . Analyte
, , „ „ , „ . .. Collection Submission /
Lab # Sample Description „ ^ „ ^ RL
F F Date Date TT
Units
AH27061 MSE\FH FILTER CAKE -221 10/31/99 11/1/99
AH27768 MSE\CC FILTER CAKE 221 11/6/99 11/8/99
AH28434 MSE\CC FILTER CAKE 11/15/99 11/16/99
AH28670 FH Filter Cake-225 11/18/99 11/18/99
AG-TCLP
0.1
mg/L
0.1
< 0.1
< 0.1
< 0.1
AS-TCLP
0.1
mg/L
< 0.1
< 0.1
< 0.1
< 0.1
BA-TCLP
0.1
mg/L
0.1
0.1
0.1
0.1
CD-1CLP
0.01
mg/L
< 0.1
< 0.1
0.02
0.01
CK-1CLP
0.1
mg/L
< 0.1
< 0.1
< 0.1
< 0.1
HG-TCLP
0.001
mg/L
0.001
0.001
0.002
< 0.001
PB-TCLP
0.1
mg/L
< 0.1
< 0.1
< 0.1
< 0.1
SE-1CLP
0.1
mg/L
1.6
0.3
< 0.1
1.1
-------
Table B-5. Catalyzed cementation process demonstration field data record
BACKGROUND DAYS
WEEK 1 10/26/99
Sample
Time
HOUR-
HOUR-
Sample
Port
CCS
CCS
Sample
Analysis
Totalizer
Flow
0
0
pH
Value
6.01
N/A
ORP
Value
OR
N/A
Iron
Field Analy
66
N/A
Copper
Field Analys
1.1
N/A
Sampled
Time
20:10
N/A
Initials
JB
MGL
Comments
ORP Over Range
WEEK 1 (CONTINUOUS)
BAY 1 INITIAL 10/27/99 Selenium Speciation
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 0
Sample
Port
108
109
FIT
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
Totalizer
Flow
145
pH
Value
3.59
6.12
ORP
Value
-366
OR
Iron
Field Analy
1400
Copper
Field Analys
2
Sampled
Time
0:00
0:00
0:00
Initials
JB
Comments
ORP Over Range
Flow Meter not functioning properly
WEEK 1 (CONTINUOUS)
BAY 1 INITIAL
Sample
Time
HOUR - 4
HOUR - 4
HOUR - 4
HOUR- 8
HOUR- 8
HOUR- 8
HOUR- 12
HOUR- 12
HOUR -12
HOUR -16
HOUR -16
HOUR -16
HOUR -20
HOUR -20
HOUR -20
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
108
109
FIT
108
109
FIT
108
109
FIT
108
109
FIT
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
346.81
423.38
451.9
456.9
457.61
pH
Value
5.37
6.16
5.26
6.03
5.38
6.01
5.67
6.1
5.01
6
3.63
6.16
6.31
ORP
Value
-423
OR
-396
-435
-403
-343
-353
OR
-396
OR
OR
OR
OR
Iron
Field Analy
3300
330
280
320
0.62
Copper
Field Analys
58
2.4
5.9
1.7
0.03
Sampled
Time
5:35
8:30
12:00
16:00
20:00
0:00
Initials
RZ
KN
MGL
JB
JB
RZ
Comments
Cu = 3.0ppminCC2
Cu=5.9ppminCCs
All on PCS
WEEK 1 (CONTINUOUS)
OAY2
Sample
Time
HOUR - 4
HOUR - 4
HOUR - 4
HOUR- 8
HOUR- 8
HOUR- 8
HOUR- 12
HOUR- 12
HOUR -12
HOUR -16
HOUR -16
HOUR -16
Sample
Port
108
109
FIT
108
109
FIT
108
109
FIT
108
109
FIT
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
Totalizer
Flow
55.65
-
-
-
pH
Value
5.34
6.05
4.72
6.2
5.34
6.04
4.98
6.06
ORP
Value
-406
OR
-509
-390
-512
-405
-377
OR
Iron
Field Analy
230
234
157
180
Copper
Field Analys
1.2
4
7.2
6.5
0.91
Sampled
Time
4:00
8:00
13:45
16:00
Initials
RZ
MGL
MGL
JB
Comments
CCS Sample Port
CC2 Sample Port
CCS Sample Port
CC2 Sample Port
CC2 Sample Port
CCS Sample Port
CC2 Sample Port
CCS Sample Port
-------
Table B-5. Catalyzed cementation process demonstration field data record
HOUR -20
HOUR -20
HOUR -20
108
109
FIT
pH, ORP
pH, ORP
Total Flow
-
4.49
6.18
-370
OR
110
360
1
CC2 Sample Port
CCS Sample Port
CCS Sample Port
WEEK 1 (CONTINUOUS)
BAY 2
Sample
Time
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
4.45
6.19
-
ORP
Value
-344
OR
-
Iron
Field Analy
220
140
Copper
Field Analys
1.4
Sampled
Time
0:00
Initials
RZ
Comments
CCS Sample Port
CCS Sample Port
WEEK 1 (CONTINUOUS)
BAY 3
Sample
Time
HOUR- 8
HOUR- 8
HOUR- 8
HOUR -16
HOUR -16
HOUR -16
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
108
109
FIT
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
-
-
pH
Value
5.33
6.06
3.53
6.08
5.04
6.2
ORP
Value
-527
-
-324
-368
-298
Iron
Field Analy
194
Copper
Field Analys
3.84
1.19
1.16
6.1
0.09
1
Sampled
Time
8:00
16:00
0:00
Initials
MGL
JB
RZ
Comments
CC2 Sample Port
CCS Sample Port
CC2 Unfiltered
CCS Filtered
CC2 Sample Port
CCS Sample Port
CCS Sample Port
WEEK 1 (CONTINUOUS)
BAY 4
Sample
Time
HOUR- 8
HOUR- 8
HOUR- 8
HOUR -16
HOUR -16
HOUR -16
Sample
Port
108
109
FIT
108
109
FIT
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
Totalizer
Flow
-
-
pH
Value
3.3
6.07
5.17
6.13
ORP
Value
-319
-290
-330
Iron
Field Analy
Copper
Field Analys
8
1.7
1.34
Sampled
Time
8:00
16:00
Initials
MGL
JB
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
18:30 Added 5 pounds of powdered Iron to reactor tank and increased copper sulfate flow to 90? As per Larry Twi dwell
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
108
109
FIT
PCS
PCS
pH, ORP
pH, ORP
Total Flow
ORP
pH
-
4.54
6.18
5.66
-425
-210
-89
3.0/5.9
1.2/1.5
0.2/1.5
0:00
RZ
CC2 filtered/unfiltered
CCS filtered/unfiltered
CCS filtered/unfiltered
-------
Table B-5. Catalyzed cementation process demonstration field data record
WEEK 1 (CONTINUOUS)
BAYS
Sample
Time
HOUR- 8
HOUR- 8
HOUR- 8
HOUR -16
HOUR -16
HOUR -16
HOUR -24
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
108
109
FIT
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
-
-
pH
Value
-
-
3.93
6.08
4.31
6.06
5.88
ORP
Value
-
-
-475
-336
-280
-280
-78
Iron
Field Analy
Copper
Field Analys
0.6
13
4.9
2.6
Sampled
Time
7:00
15:00
23:00
Initials
RZ
MGL
RZ
Comments
CCS Sample Port
CC2 Sample Port
CCS Sample Port
CCS Sample Port
WEEK 1 (CONTINUOUS)
BAY 6
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
5.16
5.98
5.5
ORP
Value
-543
-280
-217
Iron
Field Analy
Copper
Field Analys
18.2
3.2
1.3
Sampled
Time
5:00
23:00
23:00
Initials
RZ
JB
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
WEEK 1 (CONTINUOUS)
OAY7
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
5.29
6.18
5.82
ORP
Value
-526
-254
OR
Iron
Field Analy
Copper
Field Analys
23.7
3.8
2.9
2.8
Sampled
Time
5:00
23:00
Initials
RZ
JB
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
CCS Sample Port
WEEK 2 (CONTINUOUS)
OAY1
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.68
6.04
6.03
ORP
Value
-486
-505
-264
Iron
Field Analy
Copper
Field Analys
24.1
2.5
Sampled
Time
5:00
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
WEEK 2 (CONTINUOUS)
OAY2
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
5.15
6.3
5.65
ORP
Value
-331
-345
Iron
Field Analy
Copper
Field Analys
27.7
8.4
24.5
Sampled
Time
5:00
23:00
Initials
RZ
RZ
Comments
CC2 Sample Port
CCS Sample Port
CC2 Sample Port
WEEK 2 (CONTINUOUS)
BAY 3
-------
Table B-5. Catalyzed cementation process demonstration field data record
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
0.264
pH
Value
5.13
6.01
5.62
ORP
Value
-530
-284
-367
Iron
Field Analy
360
Copper
Field Analys
23.1
13.7
7.6
Sampled
Time
5:00
Initials
RZ
Comments
CCS Sample Port
WEEK 2 (CONTINUOUS)
BAY 4
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.77
6.04
5.55
ORP
Value
-254
235
89
Iron
Field Analy
650
520
500
Copper
Field Analys
20.2
8.1
8.2
26.5
7.8
Sampled
Time
5:00
23:00
Initials
RZ
RZ
Comments
CC2 Sample Port
CCS Sample Port
CC4 Sample Port
CC2 Sample Port
CCS Sample Port
WEEK 2 (CONTINUOUS)
BAYS
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
4.54
5.61
ORP
Value
-329
Iron
Field Analy
range -30 to +48
-415
Copper
Field Analys
23.2
6.3
4.7
Sampled
Time
5:00
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
WEEK 2 (CONTINUOUS)
BAY 6
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
4.74
6.07
5.67
ORP
Value
-515
Iron
Field Analy
120 to 280
-350
70
Copper
Field Analys
17.6
7.3
1.5
24.2
1.5
Sampled
Time
5:00
23:00
Initials
RZ
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
CC2 Sample Port
CCS Sample Port
WEEK 2 (CONTINUOUS)
BAY?
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.31
5.96
6.25
ORP
Value
-221
78
220
Iron
Field Analy
510
30
Copper
Field Analys
24.1
8.7
1.2
Sampled
Time
5:00
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
-------
Table B-5. Catalyzed cementation process demonstration field data record
WEEK 3 (CONTINUOUS)
OAY1
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.15
-
-
ORP
Value
-440
-
-387
Iron
Field Analy
Copper
Field Analys
38.6
21.8
1.8
-
-
Sampled
Time
5:00
23:00
Initials
RZ
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
WEEK 3 (CONTINUOUS)
BAY 2
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.37
6.27
-
ORP
Value
-330
-
-360
Iron
Field Analy
Copper
Field Analys
20.7
2.1
Sampled
Time
5:00
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
WEEK 3 (CONTINUOUS)
BAY 3
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.26
6.49
5.46
ORP
Value
-344
-
-293
Iron
Field Analy
570
Copper
Field Analys
16.6
43.4
9.2
17.7
17.3
Sampled
Time
23:00
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
CC2 Sample Port
CCS Sample Port
WEEK 3 (CONTINUOUS)
BAY 4
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
2.85
6.38
4.52
ORP
Value
-326
130
121
Iron
Field Analy
Copper
Field Analys
22.5
28
21.6
27.9
Sampled
Time
6:15
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
CCS Sample Port
WEEK 3 (CONTINUOUS)
BAYS
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
3.1
6.2
ORP
Value
-349
118
Iron
Field Analy
Copper
Field Analys
21.2
27.2
23.2
Not Collected
Not Collected
Sampled
Time
5:00
Initials
RZ
Comments
CC2 Sample Port
CCS Sample Port
CCS Sample Port
-------
Table B-5. Catalyzed cementation process demonstration field data record
WEEK 3 (CONTINUOUS)
BAY 6
Sample
Time
HOUR - 6
HOUR - 6
HOUR - 6
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
PCS
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
ORP
pH
Totalizer
Flow
-
pH
Value
ORP
Value
Iron
Field Analy
Copper
Field Analys
Not Collected
Not Collected
Not Collected
Not Collected
Not Collected
Sampled
Time
Initials
Comments
WEEK 3 (CONTINUOUS)
BAY 7 FINAL
Sample
Time
HOUR -6
HOUR -6
HOUR -6
HOUR -24
HOUR -24
HOUR -24
HOUR -24
Sample
Port
108
109
FIT
108
109
FIT
PCS
Sample
Analysis
pH, ORP
pH, ORP
Total Flow
pH, ORP
pH, ORP
Total Flow
ORP
Totalizer
Flow
-
-
pH
Value
3.15
6.2
ORP
Value
-288
-
121
Iron
Field Analy
Copper
Field Analys
Not Collected
Not Collected
Not Collected
Sampled
Time
7:30
Initials
RZ
Comments
WEEK 3 (CONTINUOUS)
BAY 7 FINAL
Sample
Time
HOUR -24
Sample
Port
PCS
Sample
Analysis
pH
Totalizer
Flow
-
pH
Value
ORP
Value
Iron
Field Analy
Copper
Field Analys
Sampled
Time
7:30
Initials
RZ
Comments
-------
Table B-6. Selenium demonstration project—summary data for catalyzed cementation process
„ , ^ .... ^ .... Submissio Analyte
Sample Collection Collection ^™™
Lab# „ ".. „ . „. n CRDL
Description Date lime ^ .
p Date Units
AH26728 MSE\CC3-001 10/26/99 20:00 10/27/99
AH26729 MSE\CC1-101 10/27/99 0:00 10/27/99
AH26730 MSE\CC1-101 10/27/99 0:00 10/27/99
AH26731 MSE\CC2-102 10/27/99 0:00 10/27/99
AH26732 MSE\CC2-102 10/27/99 0:00 10/27/99
AH26733 MSE\CC3-103 10/27/99 0:00 10/27/99
AH26734 MSE\CC3-103 10/27/99 0:00 10/27/99
AH26735 MSE\CC4-106 10/27/99 5:35 10/27/99
AH26736 MSE\CC4-107 10/27/99 8:00 10/27/99
AH26850 MSE\CC4-108 10/27/99 12:00 10/28/99
AH26851 MSE\CC4-109 10/27/99 16:00 10/28/99
AH26852 MSE\CC5-110 10/27/99 20:00 10/28/99
AH26853 MSE\CC3-111 10/28/99 0:00 10/28/99
AH26854 MSE\CC5-112 10/28/99 0:00 10/28/99
AH26855 MSE\CC5-113 10/28/99 4:00 10/28/99
AH26856 MSE\CC5-114 10/28/99 6:00 10/28/99
AH26857 MSE\CC5-115 10/28/99 8:00 10/28/99
AH26964 MSE\CC5-125 10/29/99 6:00 10/29/99
AH26965 MSE\CC5-125 10/29/99 6:00 10/29/99
AH26966 MSE\CC5-126 10/29/99 8:00 10/29/99
AH26967 MSE\CC5-116 10/28/99 12:00 10/29/99
AH26968 MSE\CC5-117 10/28/99 16:00 10/29/99
AH26969 MSE\CC5-118 10/28/99 20:00 10/29/99
AH26970 MSE\CC1-119 10/29/99 0:00 10/29/99
AH26971 MSE\CC1-119 10/29/99 0:00 10/29/99
AH26972 MSE\CC2-120 10/29/99 0:00 10/29/99
AH26973 MSE\CC2-120 10/29/99 0:00 10/29/99
AH26974 MSE\CC3-121 10/29/99 0:00 10/29/99
AH26975 MSE\CC3-121 10/29/99 0:00 10/29/99
AH26976 MSE\CC4-122 10/29/99 0:00 10/29/99
AH26977 MSE\CC4-122 10/29/99 0:00 10/29/99
AH26978 MSE\CC5-123 10/29/99 0:00 10/29/99
AH26979 MSE\CC5-123 10/29/99 0:00 10/29/99
AH26980 MSE\CC4-124 10/29/99 6:00 10/29/99
AH27064 MSE\CC5-127 10/29/99 16:00 11/1/99
AH27065 MSE\CC3-128 10/30/99 0:00 11/1/99
AH27066 MSE\CC5-129 10/30/99 0:00 11/1/99
AH27067 MSE\CC8-129 10/30/99 0:00 11/1/99
AH27068 MSE\CC9-129 10/30/99 0:00 11/1/99
AH27069 MSE\CC5-002 10/30/99 6:00 11/1/99
AH27070 MSE\CC5-130 10/30/99 8:00 11/1/99
AH27071 MSE\CC5-131 10/30/99 16:00 11/1/99
AH27072 MSE\CC1-132 10/31/99 0:00 11/1/99
AH27073 MSE\CC1-132 10/31/99 0:00 11/1/99
AH27074 MSE\CC2-133 10/31/99 0:00 11/1/99
AH27075 MSE\CC2-133 10/31/99 0:00 11/1/99
AH27076 MSE\CC3-134 10/31/99 0:00 11/1/99
AH27077 MSE\CC3-134 10/31/99 0:00 11/1/99
AH27078 MSE\CC4-135 10/31/99 0:00 11/1/99
AH27079 MSE\CC4-135 10/31/99 0:00 11/1/99
AH27080 MSE\CC5-136 10/31/99 0:00 11/1/99
TDS
20
mg/L
2020
1940
TSS
3
mg/L
52
147
Iron
0.3
mg/L
< 0.3
< 0.3
112
Ferrous
0.5
mg/L
< 0.5
96
Ferric
0.5
mg/L
< 0.5
16
Calcium
1
mg/L
120
120
119
117
120
119
119
116
118
111
114
114
203
195
197
184
119
119
119
119
118
118
189
189
190
Magnesium
1
mg/L
50
50
48
47
48
48
46.8
46.8
46.4
45.4
47
47
52.2
48.4
52.1
50.1
49.4
49.1
48.2
47.8
47.6
47.6
49.4
49.4
49
Sodium
1
mg/L
350
350
342
342
360
360
336
335
331
327
340
340
365
343
356
338
355
355
355
351
350
350
359
359
354
Nitrate
0.2
mg/L
4.1
4.2
2.5
4.2
3.5
Sulfate
5
mg/L
256
255
992
258
826
Arsenic
10
ug/L
93
13
12
< 10
< 10
< 10
< 10
< 10
< 10
11
15
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
14
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
Barium
10
ug/L
54
45
32
30
58
43
47
56
56
49
58
59
55
51
47
95
139
50
52
49
60
58
48
47
45
Copper
10
ug/L
13
< 10
6080
1250
1700
298
15
10
4020
733
365
106
592
38
25
14
38
10
10000
3290
982
157
94
43
53
Iron
300
ug/L
6340
6700
6700
52400
10200
247000
13250
830
208
54100
16200
184000
176000
172000
113000
125000
129000
213000
134000
131000
< 300
534
< 300
78700
23700
244000
232000
93300
77200
81900
Molybdenum
10
ug/L
124
110
59
54
79
< 10
111
123
85
48
< 10
< 10
< 10
< 10
< 10
< 10
137
116
73
17
< 10
< 10
< 10
< 10
< 10
Selenium
10
ug/L
3700
1550
1530
870
990
1470
672
482
536
680
828
193
785
493
490
624
1060
948
1030
977
1340
1690
1240
1400
996
1190
1150
1060
1010
890
1040
1120
1050
1020
< 10
1030
1060
1540
1530
1200
1200
832
830
1000
1000
1000
Selenium
Hydride
2
ug/L
1510
755
1090
1240
Selenate
2
ug/L
917
446
452
586
Selenite
2
ug/L
147
34
81
32
-------
Table B-6. Selenium demonstration project—summary data for catalyzed cementation process
AH27081 MSE\CC5-136 10/31/99 0:00 11/1/99
AH27082 MSE\CC5-137 10/31/99 5:00 11/1/99
AH27083 MSE\CC5-138 10/31/99 7:00 11/1/99
AH27084 MSE\CC5-139 10/31/99 15:00 11/1/99
AH27085 MSE\CC3-140 10/31/99 23:00 11/1/99
AH27086 MSE\CC5-141 10/31/99 23:00 11/1/99
AH27087 MSE\CC5-142 11/1/99 5:00 11/1/99
AH27156 MSE\CC1-143 11/1/99 23:00 11/2/99
AH27157 MSE\CC1-143 11/1/99 23:00 11/2/99
AH27158 MSE\CC2-144 11/1/99 23:00 11/2/99
AH27159 MSE\CC2-144 11/1/99 23:00 11/2/99
AH27160 MSE\CC3-145 11/1/99 23:00 11/2/99
AH27161 MSE\CC3-145 11/1/99 23:00 11/2/99
AH27162 MSE\CC4-146 11/1/99 23:00 11/2/99
AH27163 MSE\CC4-146 11/1/99 23:00 11/2/99
AH27164 MSE\CC5-147 11/1/99 23:00 11/2/99
AH27165 MSE\CC5-147 11/1/99 23:00 11/2/99
AH27166 MSE\CC5-148 11/2/99 5:00 11/2/99
AH27415 MSE\CC3-149 11/2/99 23:00 11/3/99
AH27416 MSE\CC5-150 11/2/99 23:00 11/3/99
AH27417 MSE\CC5-151 11/3/99 5:00 11/3/99
AH27514 MSE\CC1-152 11/3/99 23:00 11/4/99
AH27515 MSE\CC1-152 11/3/99 23:00 11/4/99
AH27516 MSE\CC2-153 11/3/99 23:00 11/4/99
AH27517 MSE\CC2-153 11/3/99 23:00 11/4/99
AH27518 MSE\CC3-154 11/3/99 23:00 11/4/99
AH27519 MSE\CC3-154 11/3/99 23:00 11/4/99
AH27520 MSE\CC4-155 11/3/99 23:00 11/4/99
AH27521 MSE\CC4-155 11/3/99 23:00 11/4/99
AH27522 MSE\CC5-156 11/3/99 23:00 11/4/99
AH27523 MSE\CC5-156 11/3/99 23:00 11/4/99
AH27524 MSE\CC5-157 11/4/99 5:00 11/4/99
AH27660 MSE\CC3-158 11/4/99 23:00 11/5/99
AH27661 MSE\CC5-159 11/4/99 23:00 11/5/99
AH27662 MSE\CC4-160 11/5/99 5:00 11/5/99
AH27663 MSE\CC5-161 11/5/99 5:00 11/5/99
AH27664 MSE\CC5-161 11/5/99 5:00 11/5/99
AH27752 MSE\CC1-162 11/5/99 23:00 11/8/99
AH27753 MSE\CC1-162 11/5/99 23:00 11/8/99
AH27754 MSE\CC2-163 11/5/99 23:00 11/8/99
AH27755 MSE\CC2-163 11/5/99 23:00 11/8/99
AH27756 MSE\CC3-164 11/5/99 23:00 11/8/99
AH27757 MSE\CC3-164 11/5/99 23:00 11/8/99
AH27758 MSE\CC4-165 11/5/99 23:00 11/8/99
AH27759 MSE\CC4-165 11/5/99 23:00 11/8/99
AH27760 MSE\CC5-166 11/5/99 23:00 11/8/99
AH27761 MSE\CC5-166 11/5/99 23:00 11/8/99
AH27762 MSE\CC8-166 11/5/99 23:00 11/8/99
AH27763 MSE\CC9-166 11/5/99 23:00 11/8/99
AH27764 MSE\CC5-167 11/6/99 5:00 11/8/99
AH27765 MSE\CC3-168 11/6/99 23:00 11/8/99
AH27766 MSE\CC5-169 11/6/99 23:00 11/8/99
AH27769 MSE\CC FILTRATE 221 11/6/99 16:00 11/8/99
AH27770 MSE\CC FILTRATE 221 11/6/99 16:00 11/8/99
AH27771 MSE\CC5-170 11/7/99 5:00 11/8/99
AH27772 MSE\CC1-171 11/7/99 23:00 11/8/99
2400
2540
76
38
87
93
245
74
87
234
13
6
11
190
119
117
114
114
114
114
175
175
175
175
118
118
115
115
115
114
166
166
162
162
115
114
115
115
110
110
163
163
163
162
164
< 1
415
415
116
49
48.5
48.3
46
46
47
46.9
56
56
56
56
49
48.4
45
45
47.3
47.1
69
69
70
70
46.4
46.4
46
46
44
44
70
70
69.9
69.8
69.5
< 1
98
98
46.7
354
337
331
330
330
330
330
335
335
335
334
358
351
340
340
346
343
346
340
346
346
344
344
350
350
340
340
348
342
346
346
345
< 1
876
876
347
4.2
2.3
3.7
1.2
3.8
1.3
2.1
3.8
265
1050
509
1200
259
1260
1520
265
< 10
< 10
< 10
14
10
14
14
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
14
14
55
21
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
13
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
124
< 10
11
45
60
60
68
56
198
64
128
51
58
51
54
50
56
53
76
69
61
52
59
53
51
39
51
39
72
55
57
43
57
46
46
< 10
36
30
90
26
12
12
25400
19100
1480
47
27
20
28
20
18
12
74400
71600
2200
182
49
31
20
< 10
31
< 10
75
33
5400
614
13
< 10
< 10
< 10
< 10
< 10
941
276
37
73200
489000
81100
85000
< 300
< 300
67000
67000
480000
477000
248000
238000
240000
234000
377000
324000
< 300
< 300
2420
1240
830000
830000
350000
325000
330000
312000
965000
301000
< 300
< 300
< 300
< 300
1100000
1100000
385000
347000
335000
328000
329000
< 300
717000
551000
140000
57300
< 300
< 10
132
114
94
83
< 10
< 10
< 10
< 10
< 10
< 10
130
130
120
116
< 10
< 10
< 10
< 10
< 10
< 10
118
89
120
92
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
118
1000
1050
1030
592
1050
1050
1570
1530
1320
1220
681
668
886
855
874
845
747
967
752
789
1500
1500
1500
1400
760
760
856
825
850
850
861
745
867
817
1440
1220
1460
1270
824
735
810
694
821
732
739
< 10
676
783
645
1260
1100
600
1430
1290
1120
733
901
671
705
86
679
15
137
254
51
-------
Table B-6. Selenium demonstration project—summary data for catalyzed cementation process
AH27773 MSE\CC1-171 11/7/99 23:00 11/8/99
AH27774 MSE\CC2-172 11/7/99 23:00 11/8/99
AH27775 MSE\CC2-172 11/7/99 23:00 11/8/99
AH27776 MSE\CC3-173 11/7/99 23:00 11/8/99
AH27777 MSE\CC3-173 11/7/99 23:00 11/8/99
AH27778 MSE\CC4-174 11/7/99 23:00 11/8/99
AH27779 MSE\CC4-174 11/7/99 23:00 11/8/99
AH27780 MSE\CC5-175 11/7/99 23:00 11/8/99
AH27781 MSE\CC5-175 11/7/99 23:00 11/8/99
AH27782 MSE\CC5-176 11/8/99 5:00 11/8/99
AH27860 MSE\CC3-177 11/8/99 23:00 11/9/99
AH27861 MSE\CC5-178 11/8/99 23:00 11/9/99
AH27862 MSE\CC5-179 11/9/99 5:00 11/9/99
AH27929 MSE\CC1-180 11/9/99 23:00 11/10/99
AH27930 MSE\CC1-180 11/9/99 23:00 11/10/99
AH27931 MSE\CC2-181 11/9/99 23:00 11/10/99
AH27932 MSE\CC2-181 11/9/99 23:00 11/10/99
AH27933 MSE\CC3-182 11/9/99 23:00 11/10/99
AH27934 MSE\CC3-182 11/9/99 23:00 11/10/99
AH27935 MSE\CC4-183 11/9/99 23:00 11/10/99
AH27936 MSE\CC4-183 11/9/99 23:00 11/10/99
AH27937 MSE\CC5-184 11/9/99 23:00 11/10/99
AH27938 MSE\CC5-184 11/9/99 23:00 11/10/99
AH27939 MSE\CC5-185 11/10/99 5:00 11/10/99
AH28119 MSE\CC3-186 11/10/99 23:00 11/11/99
AH28120 MSE\CC5-187 11/10/99 23:00 11/11/99
AH28121 MSE\CC5-188 11/11/99 5:00 11/11/99
AH28228 MSE\CC1-189 11/11/99 20:00 11/12/99
AH28229 MSE\CC1-189 11/11/99 20:00 11/12/99
AH28230 MSE\CC2-190 11/11/99 20:00 11/12/99
AH28231 MSE\CC2-190 11/11/99 20:00 11/12/99
AH28232 MSE\CC3-191 11/11/99 20:00 11/12/99
AH28233 MSE\CC3-191 11/11/99 20:00 11/12/99
AH28234 MSE\CC4-192 11/11/99 20:00 11/12/99
AH28235 MSE\CC4-192 11/11/99 20:00 11/12/99
AH28236 MSE\CC5-193 11/11/99 20:00 11/12/99
AH28237 MSE\CC5-193 11/11/99 20:00 11/12/99
AH28238 MSE\CC4-194 11/12/99 5:00 11/12/99
AH28239 MSE\CC5-195 11/12/99 5:00 11/12/99
AH28240 MSE\CC5-195 11/12/99 5:00 11/12/99
AH28331 MSE\CC3-196 11/12/99 23:00 11/15/99
AH28332 MSE\CC5-197 11/12/99 23:00 11/15/99
AH28333 MSE\CC8-197 11/12/99 23:00 11/15/99
AH28334 MSE\CC9-197 11/12/99 23:00 11/15/99
AH28335 MSE\CC5-198 11/13/99 5:00 11/15/99
AH28336 MSE\CC5-204 11/14/99 5:00 11/15/99
AH28337 MSE\CC5-214 11/14/99 7:30 11/15/99
AH28338 MSE\CC1-215 11/14/99 7:30 11/15/99
AH28339 MSE\CC1-215 11/14/99 7:30 11/15/99
AH28340 MSE\CC2-216 11/14/99 7:30 11/15/99
AH28341 MSE\CC2-216 11/14/99 7:30 11/15/99
AH28342 MSE\CC3-217 11/14/99 7:30 11/15/99
AH28343 MSE\CC3-217 11/14/99 7:30 11/15/99
AH28344 MSE\CC4-218 11/14/99 7:30 11/15/99
AH28345 MSE\CC4-218 11/14/99 7:30 11/15/99
AH28346 MSE\CC8-219 11/14/99 7:30 11/15/99
4260
4330
7200
45
90
38
72
60
1.1
4.8
37
< 0.5
23
4.8
116
111
107
108
108
380
380
345
345
116
116
110
110
387
384
460
460
460
460
116
112
111
110
108
108
452
451
450
444
116
116
110
110
112
112
616
615
46.7
45.2
42.2
44.5
44.4
67.6
67.6
69
69
47.8
47.7
46
46
47.1
47
55
55
55
55
47.8
45.9
46.1
45.5
44
44
53
53
54
54
47
47
45
45
46
46
47.8
47.8
347
342
325
337
334
780
780
720
720
352
348
345
343
657
642
900
900
940
940
337
325
336
333
325
325
830
830
850
850
344
336
340
340
345
345
1000
1000
1.9
4
2.5
3.9
2.3
4.3
1620
257
1430
260
1490
36
< 10
30
30
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
16
15
32
23
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
13
11
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
< 10
32
< 10
24
< 10
< 10
< 10
47
54
39
70
55
40
29
46
34
102
85
92
57
78
45
183
30
30
29
60
60
181
74
137
113
107
35
34
34
50
50
39
35
39
57
76
71
< 10
21200
17000
5900
850
182
74
83
18
12
10
22000
21100
7480
430
320
227
195
116
14
14
86300
1700
9217
1780
311
207
240
179
< 10
< 10
25000
1610
25200
1570
1128
1012
< 300
< 300
< 300
730000
730000
190000
142000
245000
234000
667000
10200
< 300
< 300
5600
5600
889000
433000
83400
2470
103000
2100
2660000
14500
< 300
< 300
409000
955000
2760000
2140000
75100
62600
2040000
495000
482000
< 300
359000
1740
3130
1140000
1030000
1030000
96
111
81
< 10
< 10
< 10
< 10
< 10
< 10
141
121
110
111
18
< 10
< 10
< 10
< 10
< 10
115
115
246
37
< 10
< 10
< 10
< 10
< 10
< 10
117
106
120
< 10
139
< 10
< 10
< 10
1310
1320
1150
898
743
879
729
845
687
747
853
886
900
1630
1630
1450
1240
920
920
1060
940
1090
930
1060
< 10
1000
994
1050
1050
1430
830
< 10
< 10
1020
869
693
719
815
< 10
642
642
< 10
443
44
26
974
1030
1460
1430
1500
< 10
78
70
867
1370
84
448
1089
24
176
198
25
-------
Table B-6. Selenium demonstration project—summary data for catalyzed cementation process
AH28347 MSE\CC9-219
AH28348 MSE\CC5-219
AH28349 MSE\CC5-219
AH28350 MSE\CC8-219
AH28351 MSE\CC9-219
11/14/99
11/14/99
11/14/99
11/14/99
11/14/99
7:30
7:30
7:30
7:30
7:30
11/15/99
11/15/99
11/15/99
11/15/99
11/15/99
6970
54
596
574
703
< 1
47.8
47.8
47.8
< 1
965
915
1220
< 1
0.6
3190
< 10
< 10
< 10
< 10
78
72
< 10
147.
715
466
< 10
47.0
1100000
1090000
775000
< 300
< 10
< 10
< 10
177.
105
105
29
< 10
15
81
< 2
25
12
20
-------
Table B-7. BSeR™ Series 1, 12-hr retention time, total selenium
Biological Selenium
Removal, Series 1
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Date
9/27/99
9/28/99
9/29/99
9/30/99
10/1/99
10/2/99
10/3/99
10/4/99
10/5/99
10/6/99
10/7/99
10/8/99
10/9/99
10/10/99
10/11/99
10/12/99
10/13/99
10/14/99
10/15/99
10/16/99
10/17/99
10/18/99
10/19/99
10/20/99
10/21/99
10/22/99
10/25/99
10/26/99
10/28/99
Total Selenium, ug/L
Influent
1470.00
1600.00
1470.00
1680.00
860.00
1580.00
1440.00
1010.00
1120.00
1520.00
1470.00
1410.00
1540.00
1580.00
1440.00
1480.00
1520.00
1120.00
1580.00
1880.00
1540.00
1610.00
1650.00
1920.00
1780.00
1950.00
1570.00
1680.00
Reactor 1
(Carbon)
624.00
749.00
817.00
276.00
227.00
711.00
792.00
736.00
1100.00
693.00
910.00
524.00
581.00
261.00
276.00
22.00
15.00
0.00
0.00
0.00
22.00
47.00
73.00
81.00
99.00
17.00
16.00
Reactor 2
(Carbon)
620.00
230.00
336.00
323.00
260.00
339.00
300.00
321.00
270.00
220.00
236.00
148.00
321.00
66.00
68.00
160.00
18.00
0.00
0.00
0.00
3.00
2.00
2.00
18.00
19.00
47.00
0.00
12.00
Reactor 3
(Biosolids)
69.50
7.00
9.00
6.00
0.00
0.00
8.00
12.00
13.00
36.00
29.00
0.00
0.00
0.00
24.00
16.00
16.00
0.00
0.00
0.00
3.00
2.00
2.00
28.00
22.00
19.00
15.00
Reactor 4
(Biosolids)
139.00
8.00
8.00
3.00
0.00
0.00
5.00
9.00
11.00
37.00
30.00
0.00
0.00
0.00
13.00
11.00
12.00
5.00
0.00
0.00
0.00
0.00
2.00
22.00
22.00
44.00
18.00
15.00
Reactor 5
(Biosolids)
5.00
5.00
5.00
0.00
0.00
0.00
0.00
5.00
6.00
25.00
22.00
0.00
0.00
0.00
9.00
6.00
2.00
3.00
0.00
0.00
0.00
0.00
21.00
19.00
45.00
0.00
15.00
Final
Effluent
6.00
6.00
7.00
0.00
0.00
0.00
3.00
6.00
8.00
26.00
20.00
0.00
0.00
0.00
8.00
6.00
4.00
0.00
0.00
0.00
0.00
35.00
14.00
16.00
-------
Table B-8. BSeR ™ Series 1, 12-hr retention time, dissolved oxygen
Biological Selenium
Removal, Series 1
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Date
9/27/99
9/28/99
9/29/99
9/30/99
10/1/99
10/2/99
10/3/99
10/4/99
10/5/99
10/6/99
10/7/99
10/8/99
10/9/99
10/10/99
Dissolved Oxygen, Percent Saturation
Influent
77.00
61.00
57.00
77.00
70.00
73.00
76.00
63.00
70.00
62.00
69.00
72.00
70.00
72.00
Reactor 1
(Carbon)
60.00
53.00
45.00
67.00
62.00
64.00
73.00
61.00
65.00
49.00
76.00
66.00
59.00
68.00
Reactor 2
(Carbon)
49.00
51.00
82.00
55.00
64.00
60.00
49.00
48.00
61.00
49.00
51.00
57.00
51.00
62.00
Reactor 3
(Biosolids)
48.00
39.00
38.00
46.00
61.00
58.00
45.00
40.00
55.00
37.00
48.00
57.00
48.00
51.00
Reactor 4
(Biosolids)
45.00
35.00
49.00
52.00
55.00
60.00
43.00
44.00
55.00
36.00
45.00
52.00
48.00
43.00
Reactor 5
(Biosolids)
54.00
48.00
52.00
63.00
62.00
61.00
43.00
49.00
54.00
43.00
47.00
61.00
52.00
48.00
Final
Effluent
65.00
63.00
60.00
80.00
61.00
63.00
59.00
84.00
74.00
55.00
57.00
63.00
58.00
69.00
-------
Table B-9. BSeR™ Series 1, 12-hr retention time, oxidation-reduction potential
Biological Selenium
Removal, Series 1
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Date
9/27/99
9/28/99
9/29/99
9/30/99
10/1/99
10/2/99
10/3/99
10/4/99
10/5/99
10/6/99
10/7/99
10/8/99
10/9/99
10/10/99
10/11/99
10/12/99
10/13/99
10/14/99
10/15/99
10/16/99
10/17/99
10/18/99
10/19/99
10/20/99
10/21/99
10/22/99
10/25/99
10/26/99
10/28/99
Oxidation/Reduction Potential, mV
Influent
248.00
172.00
281.00
193.00
155.30
147.10
100.00
136.00
146.50
97.00
248.00
178.00
94.30
142.30
172.30
146.70
95.70
98.50
120.00
121.30
131.70
210.00
248.00
208.00
226.00
136.00
323.00
314.00
325.00
Reactor 1
(Carbon)
215.00
129.00
209.00
134.00
147.50
140.00
151.70
112.00
159.30
125.30
152.00
116.00
145.00
116.00
153.00
125.30
166.50
65.00
93.30
100.70
115.70
116.30
116.30
115.60
126.50
102.50
67.00
113.00
Reactor 2
(Carbon)
210.00
135.00
167.00
138.70
149.50
137.20
159.20
132.00
163.50
140.00
154.00
81.30
176.00
93.20
198.70
150.00
91.50
89.30
107.50
85.50
116.50
100.50
131.30
104.50
96.30
112.30
(0.30)
90.30
72.30
Reactor 3
(Biosolids)
23.30
(3.00)
44.70
17.30
49.00
48.00
26.00
14.50
83.00
23.00
37.30
(2.70)
27.00
46.80
205.00
(17.50)
(42.70)
(21.70)
(30.70)
(5.70)
(30.10)
59.00
(3.30)
(10.50)
(15.70)
24.70
(14.00)
42.00
Reactor 4
(Biosolids)
(3.00)
(40.00)
(27.00)
(33.00)
(29.50)
(31.00)
(13.30)
11.30
56.50
(3.00)
(3.00)
(15.00)
(32.50)
(36.30)
182.00
(47.30)
(29.50)
(10.30)
(22.50)
(52.30)
(51.00)
7.50
(19.70)
(16.70)
(33.00)
11.30
81.30
69.70
9.70
Reactor 5
(Biosolids)
205.00
125.00
122.00
126.30
74.50
84.10
64.90
110.00
125.30
98.00
128.50
153.00
140.70
116.00
201.00
105.30
100.90
93.00
123.50
95.70
90.20
126.00
60.30
68.00
105.50
82.50
143.00
27.50
Final
Effluent
226.00
152.00
144.00
167.70
120.00
136.10
128.30
165.30
154.30
135.00
174.00
194.00
149.70
144.20
198.00
196.30
130.30
164.00
157.00
135.50
118.00
152.70
99.30
108.00
139.00
-------
Table B-10. BSeR™ Series 1, 12-hr retention time, temperature
Biological Selenium
Removal, Series 1
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Date
9/27/99
9/28/99
9/29/99
9/30/99
10/1/99
10/2/99
10/3/99
10/4/99
10/5/99
10/6/99
10/7/99
10/8/99
10/9/99
10/10/99
10/11/99
10/12/99
10/13/99
10/14/99
10/15/99
10/16/99
10/17/99
10/18/99
10/19/99
10/20/99
10/21/99
10/22/99
10/25/99
10/26/99
10/28/99
Temperature, °C
Influent
17.00
16.50
16.20
16.20
16.20
18.10
18.20
17.10
16.60
17.10
16.40
16.20
17.20
17.60
15.50
16.50
16.00
17.10
16.20
15.70
15.50
15.20
15.70
15.80
16.50
16.30
16.10
17.10
16.80
Reactor 1
(Carbon)
14.40
13.10
13.30
16.30
14.20
18.00
19.00
17.10
16.50
19.40
14.10
14.30
18.00
20.10
14.20
18.30
16.00
16.50
15.60
14.10
14.20
14.00
12.40
12.60
14.00
13.00
19.20
19.10
Reactor 2
(Carbon)
16.60
14.20
14.10
17.30
17.10
18.00
18.00
17.60
19.00
21.00
16.90
16.90
18.40
20.10
18.40
19.50
18.20
18.00
16.90
13.80
13.90
13.80
13.20
13.20
14.50
14.10
14.60
19.40
16.80
Reactor 3
(Biosolids)
15.10
12.20
13.80
15.50
14.50
18.40
18.00
15.00
17.00
20.50
16.30
15.10
18.10
21.10
15.90
20.20
18.40
18.00
17.10
13.60
13.90
13.80
13.10
13.20
13.00
13.00
21.60
19.80
Reactor 4
(Biosolids)
16.80
14.10
14.10
16.70
16.40
18.30
18.50
16.00
18.60
20.30
17.20
16.70
17.80
19.60
18.20
20.10
19.60
19.20
19.20
13.80
13.70
13.60
12.70
12.90
14.50
14.50
15.30
19.70
16.70
Reactor 5
(Biosolids)
16.80
13.10
14.10
15.40
14.30
19.00
19.50
15.00
18.00
20.20
16.60
15.80
19.40
21.40
16.30
21.40
19.90
19.00
17.50
14.30
14.00
11.90
12.00
12.00
13.20
15.00
20.90
19.10
Final
Effluent
15.20
13.10
13.70
14.10
13.80
16.40
18.70
16.40
15.60
16.70
14.90
14.40
16.30
17.90
14.30
16.00
15.10
15.30
14.90
12.70
12.90
11.30
11.50
12.00
14.80
-------
Table B-ll. BSeR™ Series 1, 12-hr retention time, pH
Biological Selenium
Removal, Series 1
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
12 hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Date
9/27/99
9/28/99
9/29/99
9/30/99
10/1/99
10/2/99
10/3/99
10/4/99
10/5/99
10/6/99
10/7/99
10/8/99
10/9/99
10/10/99
10/11/99
10/12/99
10/13/99
10/14/99
10/15/99
10/16/99
10/17/99
10/18/99
10/19/99
10/20/99
10/21/99
10/22/99
10/25/99
10/26/99
10/28/99
Influent
7.22
7.20
7.40
7.12
7.02
7.66
7.33
7.49
7.27
7.22
7.36
7.40
7.48
7.20
7.38
7.64
7.31
7.68
7.55
7.40
7.42
7.56
7.32
7.53
7.56
7.23
7.43
7.37
7.45
pH
Reactor 1
(Carbon)
7.55
7.60
7.86
8.01
7.75
7.85
7.90
8.02
7.86
8.12
7.70
7.80
8.08
8.10
7.98
8.06
7.78
7.35
7.24
7.31
7.35
6.85
6.94
7.10
7.08
7.04
7.17
7.10
Reactor 2
(Carbon)
7.53
7.50
7.74
7.88
7.57
7.80
7.82
7.82
7.75
7.98
7.69
7.86
7.90
7.95
7.76
7.93
7.86
7.80
7.85
7.64
7.60
7.62
7.51
7.31
7.20
7.00
7.09
6.99
7.03
Reactor 3
(Biosolids)
7.54
7.52
7.43
7.66
7.53
7.53
7.87
7.65
7.55
7.77
7.43
7.63
7.68
7.69
7.49
7.66
7.60
7.64
7.68
7.48
7.51
7.52
7.56
7.52
7.60
7.26
7.30
7.25
Reactor 4
(Biosolids)
7.25
7.10
7.34
7.56
7.40
7.44
7.34
7.50
7.42
7.64
7.33
7.55
7.63
7.54
7.37
7.61
7.55
7.56
7.59
7.40
7.42
7.48
7.59
7.50
7.56
7.35
7.32
7.34
7.30
Reactor 5
(Biosolids)
7.00
7.12
7.03
7.15
7.09
7.18
7.09
7.17
7.12
7.37
7.12
7.26
7.31
7.20
7.03
7.29
7.29
7.30
7.40
7.14
7.23
7.45
7.45
7.58
7.38
7.98
8.06
7.96
Final
Effluent
7.10
7.06
7.31
7.66
7.49
7.48
7.25
7.40
7.39
7.52
7.39
7.57
7.60
7.26
7.35
7.55
7.47
7.44
7.82
7.52
7.52
7.72
7.60
7.72
7.47
-------
Table B-12. BSeR ™ Series 2, 11- and 5.5-hr retention time,
total selenium
Biological Selenium
Removal, Series 2
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
11 lu-
ll lu-
ll hr
11 lu-
ll lu-
ll hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
Day
1
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
1
2
3
4
5
6
7
8
9
10
11
12
Date
1/10/99
1/11/00
1/13/00
1/14/00
1/15/00
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/13/00
2/14/00
2/16/00
2/17/00
2/18/00
Total Selenium, • g/L
Influent
1700
1520
1500
1750
1650
1600
1570
1880
1670
1540
1810
1670
1800
1640
1590
1740
2230
1830
1860
1400
1650
1210
1590
1626
1510
1480
1451
1585
1590
1540
1530
1560
1580
1780
1400
Reactor 1
1350
1150
1110
1260
690
1140
940
328
184
139
92
77
42
15
44
9
12
12
5
11
36
16
40
24
26
22
30
15
15
9
21
8
10
14
Reactor 2
139
881
551
324
213
199
235
317
347
154
7
9
10
9
8
13
5
8
8
2
3
3
2
3
3
0
2
3
0
0
0
0
0
0
0
Reactor 3
241
187
113
65
34
16
9
8
19
8
5
11
0
4
0
7
2
3
2
0
0
3
2
2
2
0
10
0
0
0
0
0
0
0
0
-------
Table B-13. BSeR ™ Series 2, 11- and 5.5-hr retention time,
dissolved oxygen
Biological Selenium
Removal, Series 2
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
11 lu-
ll lu-
ll hr
11 lu-
ll lu-
ll hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
Day
1
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
1
2
3
4
5
6
7
8
9
10
11
12
Date
1/10/99
1/11/00
1/13/00
1/14/00
1/15/00
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/13/00
2/14/00
2/16/00
2/17/00
2/18/00
Dissolved Oxygen, Percent Saturation
Influent
53
58.3
57.4
47.4
47.6
55.4
55.7
51.6
51.6
49.3
52.1
51.2
54.6
44.1
49.8
53.8
44
52.4
55.9
52.6
52.9
47.6
50.2
56.6
52
47.4
48.3
48.2
46.9
47.7
44.1
44.5
46.1
Reactor 1
40.2
48.7
45.4
41.2
42
38
46
34.1
34.1
40.1
35.6
39.8
42.7
39.9
36.1
39.8
24.8
37.7
44.6
24.2
42.5
39.5
35.7
37.7
28.5
33.2
30.5
24.5
25.2
23.1
26.4
30
23.7
Reactor 2
66.7
12.7
12.3
11.7
16.6
12.4
12.2
12.3
12.3
19.1
11.6
17
20.2
14.5
13.2
17.2
27.6
17.1
18.4
17.3
21
20.1
17.2
20
15.9
14.8
15.6
10.8
16
11.6
12
15.7
17
Reactor 3
68
46.9
33
36
39.2
47.6
44.7
42.2
42.2
39.2
40.5
38.7
39.7
43.1
35.1
37.9
39.2
40
41.5
43.7
46.6
41.2
46.5
39.9
30
31.4
30.3
24.6
30.1
26.7
27.6
29.5
33.5
-------
Table B-14. BSeR ™ Series 2, 11- and 5.5-hr retention time,
oxidation-reduction potential
Biological Selenium
Removal, Series 2
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
11 lu-
ll lu-
ll hr
1 1 lu-
ll lu-
ll hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
Day
1
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
1
2
3
4
5
6
7
8
9
10
11
12
Date
1/10/99
1/11/00
1/13/00
1/14/00
1/15/00
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/13/00
2/14/00
2/16/00
2/17/00
2/18/00
Oxidation/Reduction Potential, mV
Influent
272
147
290
251
282
313
336
332
333
335
332
328
145.7
304
334
342
327
330
223
272
312
311
318
315
308
306
293
313
310
309
319
308
Reactor 1
226
310
361
265
303
296
312
315
224
155
141
136
143.7
114
98
91
75
67
3
13.5
5
-2.5
19.5
-72
-105.7
-129
-130.5
-102
-124.7
-83.5
-60.7
-41.7
Reactor 2
182
314
347
248
327
286
313
313
234
217
198
187
206
207
159
144
133
117
4.5
92.7
99.7
110.3
132
98.7
62
44.5
44.5
75.7
40.5
65.5
73
112.7
Reactor 3
150
355
394
266
311
289
283
148
108
8037
65
62
71
52
33
37
42
24
-14.3
-49
-41.5
-51.3
-23
-43.7
-40.6
-11.3
2
12.7
18.3
37.3
45.5
56
-------
Table B-15. BSeR ™ Series 2, 11- and 5.5-hr retention time,
temperature
Biological Selenium
Removal, Series 2
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
11 lu-
ll lu-
ll hr
11 lu-
ll lu-
ll hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
Day
1
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
1
2
3
4
5
6
7
8
9
10
11
12
Date
1/10/99
1/11/00
1/13/00
1/14/00
1/15/00
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/13/00
2/14/00
2/16/00
2/17/00
2/18/00
Temperature, °C
Influent
14.5
14.7
14.8
14
15.3
14.8
15
14.9
14.8
15
15.3
15.5
15
14.9
16.1
14.5
16.3
16.6
14.7
15.2
14.7
15.6
16.3
16.1
14.4
15.1
14.2
15.3
15.4
14.6
14.8
14.9
Reactor 1
14.7
14.2
14
13.5
14.7
14
14.2
14.1
14.3
15.1
15.1
16.1
14.7
16
15.8
14.2
16.3
17.4
19.2
17.7
14.3
17.8
16.8
18.5
14.7
15.3
14.3
15
14.9
15.5
15.4
17.9
Reactor 2
13
14
13.8
13.1
14.5
14
13.2
14.4
13.5
14.6
14.1
14.3
14.2
14.5
14.8
13.1
16.8
18.6
20
20.3
14.6
19.2
16.6
19.7
13.9
14.6
14
14.3
14.1
14.1
14.2
16.1
Reactor 3
12.2
11.3
10.9
11.3
13
12.9
12.7
12.2
12.6
12.7
12.6
12.7
12.5
12.9
14
11.3
14.7
16.4
15.9
16.8
15.8
16.3
18.2
17.4
14.9
14
14
13.9
14.1
14.6
13.3
16
-------
Table B-16. BSeR™ Series 2, 11- and 5.5-hr retention time, pH
Biological Selenium Removal,
Series 2
RT
Startup
Startup
Startup
Startup
Startup
Startup
Startup
11 lu-
ll lu-
ll hr
1 1 lu-
ll lu-
ll hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
11 hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
5.5hr
Day
1
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
1
2
3
4
5
6
7
8
9
10
11
12
Date
1/10/99
1/11/00
1/13/00
1/14/00
1/15/00
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/13/00
2/14/00
2/16/00
2/17/00
2/18/00
pH
Influent
7.7
7.46
7.29
7.39
7.39
7.37
7.42
7.45
7.42
7.39
7.45
7.38
7.37
7.35
7.37
7.37
7.4
7.38
7.4
7.33
7.44
7.41
7.4
7.43
7.42
7.38
7.4
7.43
7.48
7.43
7.42
7.43
7.45
Reactor 1
8.48
7.6
7.41
7.43
7.48
7.51
7.62
7.6
7.57
7.22
6.9
6.64
6.55
6.46
6.42
6.36
6.31
6.36
6.45
6.59
6.65
6.8
6.84
6.86
6.72
6.86
6.97
7.02
7.09
7.18
7.41
7.54
7.48
Reactor 2
7.67
8.27
8.07
7.89
7377
7.61
7.58
7.54
7.45
7.44
7.35
7.38
7.42
7.16
7.11
7.02
7.05
6.74
6.65
6.58
6.65
6.8
6.7
6.78
6.66
6.73
6.58
6.6
6.75
6.82
7.09
7.12
7.15
Reactor 3
7.38
7.94
7.22
7.19
7.24
7.2
7.22
7.24
7.3
7.21
7.31
7.23
7.31
7.36
7.45
7.43
7.51
7.44
7.46
7.35
7.21
7.18
7.1
7.05
6.95
6.94
6.86
6.91
6.8
6.81
6.99
7.1
7.15
-------
Table B-17. BSeR™ Series 3, 8-hr retention time, total selenium
Biological Selenium Removal,
Series 3
RT
Startup
Startup
Startup
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
16
18
19
20
21
22
23
24
25
26
27
28
29
31
32
33
Date
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/13/00
2/14/00
2/16/00
2/17/00
2/18/00
Total Selenium, ug/L
Influent
1600
1570
1880
1670
1540
1810
1670
1800
1640
1590
1740
2230
1830
1860
1400
1650
1210
1590
1626
1510
1480
1451
1585
1590
1540
1530
1560
1580
1780
1400
Reactor 1
152
294
80
0
0
3
40
30
4
4
10
7
12
11
16
16
9
5
8
5
5
2
3
3
4
5
2
2
Reactor 2
67
0
0
0
0
11
0
4
2
7
4
8
8
7
7
8
9
9
7
5
5
4
3
4
4
2
2
Reactor 3
0
0
0
0
0
0
11
0
3
0
4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
0
0
-------
Table B-18. BSeR™Series 3, 8-hr retention time, dissolved oxygen
Biological Selenium Removal,
Series 3
RT
Startup
Startup
Startup
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
16
18
19
20
21
22
23
24
25
26
27
31
32
33
Date
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/16/00
2/17/00
2/18/00
Dissolved Oxygen
Influent
55.4
55.7
51.6
51.6
49.3
52.1
51.2
54.6
44.1
49.8
53.8
55.9
52.6
52.9
47.6
50.2
56.6
52
47.4
48.3
48.2
46.9
47.7
44.1
44.5
46.1
Reactor 1
12.2
17.9
12.6
12.6
10.4
18.3
14.7
21.4
18.2
15.7
17.8
17.5
18.6
21.4
18.7
17.7
20.1
18.4
20.6
21.2
18.7
20
18.5
18.9
14.1
18.9
Reactor 2
17.6
17.6
18.4
17.7
22.1
22.1
16.9
21.7
16.5
23
26.1
19
16.9
22.2
20
21.3
18.2
16.4
17
17.5
13.4
15.9
13.6
18
Reactor 3
26.2
39.7
30.6
30.6
29.8
23.6
27.3
38.1
36.8
26.7
35.5
32
28.2
31.8
32.7
32.2
47
37
15.9
29.2
29.3
35.5
31
35.7
39.3
34.1
-------
Table B-19. BSeR™Series 3, 8-hr retention time, oxidation-
reduction potential
Biological Selenium
Removal, Series 3
RT
Startup
Startup
Startup
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
16
18
19
20
21
22
23
24
25
26
27
31
32
33
Date
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/16/00
2/17/00
2/18/00
Oxidation/Reduction Potential, mV
Influent
282
313
336
332
333
335
332
328
145.7
304
334
342
327
330
223
272
312
311
318
315
308
306
293
313
310
309
319
308
Reactor 1
28.3
287
1.5
-29.7
-20
-15.3
-1.5
-5
-25.5
-39
-29
-41
-49.3
-51.7
-51
-59.5
-55.3
-84.5
-74
-78.3
-76.5
-50.5
-82.3
-105.7
-93.7
-74.5
Reactor 2
119
60.7
8.3
30.7
33.5
26
6.7
-16
-27
-38
-96.3
-98.5
-99.5
-100.7
-91.7
-90.3
-117.3
-117.5
-103
-90.5
-65.5
-51
-49.3
-27
Reactor 3
220
272
188
150
115
18.5
-24.3
-16
17.3
20
23
14
36
-39.5
-26
-46.3
-39.5
-42
-50
-67.3
-58.7
-51.5
-45
-43.3
-47.3
-45.7
-------
Table B-20. BSeR™ Series 3, 8-hr retention time, temperature
Biological Selenium
Removal, Series 3
RT
Startup
Startup
Startup
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
16
18
19
20
21
22
23
24
25
26
27
31
32
33
Date
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/16/00
2/17/00
2/18/00
Temperature, °C
Influent
15.3
14.8
15
14.9
14.8
15
15.3
15.5
15
14.9
16.1
14.5
16.3
16.6
14.7
15.2
14.7
15.6
16.3
16.1
14.4
15.1
14.2
15.3
15.4
14.6
14.8
14.9
Reactor 1
14.5
14.2
14.5
13.8
14.5
14
14.4
14.1
14.7
14.8
15.4
16.4
16
16.4
15.9
15.7
16.7
16.3
14.8
14.8
14.5
15.1
15.2
15.4
15
15.9
Reactor 2
13.8
13.6
12.9
13.9
13.6
13.9
13.6
14.8
14.2
16.7
16.7
17.1
16
15
16.8
15.9
13.6
14.4
14.8
15.9
15.7
14.6
14.1
15.2
Reactor 3
10.1
13.6
13
12.7
12.5
13
12.6
12.6
12.9
13.3
13.7
16.6
15.7
17.3
16.4
14.6
16.5
15.3
13.3
13.7
13.9
15.6
15.2
15.6
13.6
14.6
-------
Table B-21. BSeR™Series 3, 8-hr retention time, pH
Biological Selenium
Removal, Series 3
RT
Startup
Startup
Startup
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
8hr
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
16
18
19
20
21
22
23
24
25
26
27
31
32
33
Date
1/16/00
1/17/00
1/18/00
1/19/00
1/20/00
1/21/00
1/22/00
1/23/00
1/25/00
1/26/00
1/27/00
1/28/00
1/29/00
1/30/00
2/1/00
2/3/00
2/4/00
2/5/00
2/6/00
2/7/00
2/8/00
2/9/00
2/10/00
2/11/00
2/12/00
2/16/00
2/17/00
2/18/00
pH
Influent
7.37
7.42
7.45
7.42
7.39
7.45
7.38
7.37
7.35
7.37
7.37
7.4
7.38
7.4
7.33
7.44
7.41
7.4
7.43
7.42
7.38
7.4
7.43
7.48
7.43
7.42
7.43
7.45
Reactor 1
7.15
7.24
6.95
6.78
6.64
6.67
6.68
6.8
6.72
6.64
6.66
6.72
6.83
7.01
7.08
7.15
7.22
7.1
7.06
6.98
6.97
6.96
6.96
7.05
7.12
7.15
Reactor 2
6.93
6.94
6.85
6.63
6.47
6.57
6.63
6.55
6.53
6.57
6.71
6.83
6.9
6.94
6.97
7
6.98
7.05
7.08
7.08
7.09
7.11
7.11
7.13
Reactor 3
8.2
7.82
7.49
7.49
7.33
7.15
6.98
6.89
6.83
6.8
6.91
6.84
6.73
6.74
6.88
6.97
7.1
7.04
7.09
7.05
6.95
6.86
6.9
7.14
7.26
7.31
-------
Table B-22. Catalyzed Cementation Process Demonstration Test Data Record Follow on Testing
BACKGROUND DAYS 3/28/00
WEEK1
Sample
Time
HOUR-
HOUR-
HOUR-
HOUR-
HOUR-
HOUR-
Sample
Number
CC 1 -050
CC 1-051
CC2-052
CC 2-053
Sample
Port
CC1
Metal Reactor
Floe Tank
CC1
CC2
CC2
WEEK 1 (CONTINUOUS)
DAY 1 INITIAL 3/30/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 0
HOUR - 0
HOUR - 0
HOUR - 0
HOUR - 0
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Sample
Analysis
pH, ORP
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH
Value
7.89
3.02
6.78
8.26
3.48
3.52
ORP
Value
284.9
337
416
372
Sample
Analysis
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
Value
3.8
6.3
8.3
3.5
2.93
6.48
3.93
ORP
Value
267
389
277
-108
2.34
Sampled
Time
11:50
10:40
10:45
10:35
10:30
15:30
Initials
RS
RS
RS
RS
RS
RS
Comments
Sampled
Time
7:20
7:20
7:35
7:50
8:25
8:50
9:10
Initials
RS
RS
RS
RS
RS
RS
RS
Comments
Comments
Time Zero Begins when system has been filled, and residual tap water has been flushed out
WEEK 1 (CONTINUOUS)
DAY 1 3/30/00
Sample
Time
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
HOUR - 8
Comment
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Floe Tank
Sample
Analysis
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
pH
Value
2.7
7
8.27
3.5
3.22
7.01
NR
3.3
6.9
ORP
Value
275
390
278
-218
269
Sampled
Time
11:45
11:45
13:20
13:35
1350
14:20
14:45
15:30
15:30
Initials
RS
RS
RS
RS
RS
RS
RS
RS
RS
Comments
WEEK1
DAY 2 3/31/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
Value
2.8
7
2.5
6.4
7.49
3.35
3.22
6.87
4.06
ORP
Value
241.9
459
310
-157
312
Sampled
Time
7:45
7:45
11:25
11:25
14:16
14:00
13:39
13:20
13:11
Initials
DL
DL
DL
DL
DL
Comments
-------
Table B-22. Catalyzed Cementation Process Demonstration Test Data Record Follow on Testing
HOUR - 8
HOUR - 8
Metal Reactor 2
Floe Tank
pH
pH
2.2
6.9
15:40
15:40
DL
DL
Comments
WEEK1
DAY 3 (WEEKLY) 4/3/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
HOUR - 8
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
oxidation tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Floe Tank
Sample
Analysis
pH
pH
pH, ORP
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
pH
Value
2.6
11.1
5.9
2.7
7
7.64
3.3
2.5
6.62
3.83
3.1
7
ORP
Value
-5.1
136
300
300
-202
320
Sampled
Time
8:10
8:10
8:10
12:00
12:00
14:50
14:40
14:18
13:50
13:30
15:35
15:35
Initials
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
Comments
Comments 8:55--noticed batch tank valve not open. Opened valve and now have process flow,
WEEK1
DAY 4 4/4/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
HOUR - 8
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Floe Tank
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
pH
Value
2.5
11.5
2.3
7.8
7.85
3.22
2.75
6.7
2.59
2.8
7
ORP
Value
61.8
204
-30.8
-223
458
Sampled
Time
8:10
8:10
11:50
11:50
14:45
14:32
14:20
14:00
13:46
15:40
15:40
Initials
BL
BL
DL
DL
Comments
Comments
WEEK1
DAY 5 4/5/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 2
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
Sample
Number
CC5-530
Sample
Port
Metal Reactor 2
Floe Tank
CCS
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
Sample
Analysis
pH
pH
Dissolved Metals (Fe,
As, Cu, Se)
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
Value
2.3
11.8
2.3
6.9
3.31
2.64
7.11
ORP
Value
366
-260
860
Sampled
Time
8:00
8:00
11:50
11:50
14:10
14:00
13:50
Initials
BL
BL
DL
DL
DL
DL
DL
Comments
-------
Table B-22. Catalyzed Cementation Process Demonstration Test Data Record Follow on Testing
HOUR - 6
HOUR - 8
HOUR - 8
CCS
Metal Reactor 2
Floe Tank
pH, ORP
pH
pH
2.34
3.7
7.4
547
13:45
15:50
15:50
DL
DL
DL
Comments
WEEK 2
DAY1 4/6/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
HOUR - 8
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Floe Tank
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
pH
Value
2.3
7.1
2.6
7.2
NR
NR
2.62
7.56
2.26
NR
NR
ORP
Value
NR
NR
-328
849
553
Sampled
Time
7:45
7:45
10:03
9:49
9:40
Initials
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
Comments
Comments
CC-Eff3 2.34 1 514 13:20 DL
WEEK 2
DAY 2 4/10/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
HOUR - 8
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Floe Tank
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
pH
Value
2.1
7.2
2.9
6.9
NR
3.49
2.66
6.68
3.33
3.2
7
ORP
Value
NR
22.4
-336
-547
148
Sampled
Time
8:50
8:50
12:50
12:50
15:50
15:30
15:05
14:44
15:58
15:58
Initials
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
Comments
Comments
WEEK 2 (WEEKLY)
DAY 3 4/11/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
Value
3.9
7.9
3
8.7
NR
3.53
2.93
8.33
2.89
2.3
ORP
Value
NR
302
-130
-686
431
Sampled
Time
7:59
7:59
11:59
11:59
14:21
14:10
14:00
13:34
15:50
Initials
DL
DL
DL
DL
DL
DL
DL
DL
DL
DL
Comments
-------
Table B-22. Catalyzed Cementation Process Demonstration Test Data Record Follow on Testing
HOUR - 8
Floe Tank |pH |6.8
15:50
DL
Comments
WEEK 2
DAY 4 4/12/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 8
HOUR - 8
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Metal Reactor 2
Floe Tank
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
pH
pH
Value
2.4
8.8
2.5
11.1
NR
2.85
2.66
4.49
2.9
11.1
ORP
Value
NR
416
-350
127.2
Sampled
Time
7:30
7:30
11:30
11:30
14:25
14:05
13:40
15:50
15:50
Initials
RS
RS
DL
DL
DL
DL
DL
DL
DL
DL
DL
Comments
Comments
WEEK 2 (FINAL)
DAYS 4/13/00
Sample
Time
HOUR - 0
HOUR - 0
HOUR - 4
HOUR - 4
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
HOUR - 6
Sample
Number
Sample
Port
Metal Reactor 2
Floe Tank
Metal Reactor 2
Floe Tank
CC1
CC2
CCS
CC4
CCS
Sample
Analysis
pH
pH
pH
pH
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH, ORP
pH
Value
2.3
6.5
2.6
7.3
NR
2.97
2.91
6.93
4.38
ORP
Value
NR
414
170
-504
1560
Sampled
Time
7:50
7:50
11:50
11:50
13:35
13:20
13:09
13:00
Initials
DL
DL
DL
DL
DL
DL
DL
DL
DL
Comments
Table B-23. Summary data for additional catalyzed cementation tests (aqueous)
Lab#
3291017
3291019
000330Q001
000330Q002
000330Q003
000330Q004
000330Q005
000330Q006
000330Q007
000330Q008
000330Q009
000330Q010
000330Q011
000330Q012
000330Q013
000331Q001
Sample Collect
Description Date
CC1-050 3/28/00
CC2-053
CC1-501
CC2-502
CC3-503
CC4-504
CC5-505
CC5-506
CC6-506
CC7-506
CC1-507
CC2-508
CC3-509
CC4-510
CC5-511
CC5-512
3/28/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/30/00
3/31/00
„ „ . Analyte Nitrate Sulfate , ° .
Collect ™nl „ , - Arsenic
Time V -. -. I"
Units mg/L mg/L
11:45 40
15:15
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
9:00
40
4.7 255 <29
<29
<29
<29
0.08 2090 <29
<29
<29
<29
<29
<29
30
Total
Copper
10
ug/L
30
4760
29
490
0.088
37
42
21
4900
120
55
48
380
Total Total Total by AA Dissolved Dissolved
Iron Selenium Selenium Arsenic Copper
300 40 1 10 10
ug/L ug/L ug/L ug/L ug/L
320 1880 N/A
320
<15
630000
670000
561000
581000
28
730
584000
550000
355000
500000
1910
1600
1600
210
220
44
1600
1600
360
270
230
650
N/A
N/A 40
47
<29
11
<29
<29
<29
<29
<29
<29
<29
<29
<29
<29
12
460
7
<1.8
29
27
26
<1.8
10
4600
29
<1.8
33
31
Dissolved Dissolved DissolvedbyAA
Iron Selenium Selenium
300 40 1
ug/L ug/L ug/L
33
500000
579000
264000
536000
389000
382
<15
29
600
527000
68000
328000
444000
1800
1700
570
490
410
410
440 DUPLICATE
<40 BLANK
1800
1700
690
420
520
980
-------
Table B-23. Summary data for additional catalyzed cementation tests (aqueous)
Lab#
000331Q002
000331Q003
000331Q004
000331QOOS
000331Q006
000331Q007
000331Q008
000404L007
000404L008
000404L009
000404L010
000404L011
000404L012
000405J001
00040SJ002
000405J003
000405J004
000405J005
000405J006
00040SJ007
000405J008
00040SP001
00040SP002
00040SP003
000405P004
00040SPOOS
000405P006
000406K001
000406K002
000406K003
4070927
000411J003
000411J004
000411JOOS
000411J006
000411P001
000411P002
000411P003
000411P004
000411POOS
000413K004
000413KOOS
000413K006
000413K007
0004141001
0004141002
0004141003
0004141004
0004141005
0004141006
0004141007
OOOS19POOS
OOOS19P006
OOOS19P007
Sample
Description
CC3-S12
CC1-513
CC2-S14
CC3-S1S
CC4-S16
CCS-S17
CC-EFF1
CCS-S18
CC1-519
CC2-S20
CC3-S21
CC4-S22
CCS-S23
CCS-S24
CC6-S24
CC7-S24
CC1-S2S
CC2-S26
CC3-S27
CC4-S28
CCS-S29
CCS-S30
CC-EFF2
CC2-S32
CC3-S33
CC4-S34
CCS-S3S
CC3-S39
CC4-S40
CCS-S41
CC-EFF3
CC2-S44
CC3-S4S
CC4-S46
CCS-S47
CCS-S48
CC2-SSO
CC3-SS1
CC4-SS2
CCS-SS3
CC2-SS6
CC3-SS7
CC4-SS8
CCS-SS9
CCS-S60
CC6-S60
CC7-S60
CC2-S67
CC3-S68
CC4-S69
CCS-S70
CC-Eff-3-0517
CCEff-4-OS17
CCEff-5-0517
Collect
Date
3/31/00
3/31/00
3/31/00
3/31/00
3/31/00
3/31/00
3/31/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/4/00
4/5/00
4/5/00
4/5/00
4/5/00
4/5/00
4/5/00
4/6/00
4/6/00
4/6/00
4/6/00
4/10/00
4/10/00
4/10/00
4/10/00
4/11/00
4/11/00
4/11/00
4/11/00
4/11/00
4/12/00
4/12/00
4/12/00
4/12/00
4/13/00
4/13/00
4/13/00
4/13/00
4/13/00
4/13/00
4/13/00
5/17/00
5/17/00
5/17/00
Analyte Nitrate Sulfate ,Tota! JOtal
Collect ' Arsenic Copper
Time ™DL °-\ S,, 10 10
Units mg/L mg/L
6 6 ug/L ug/L
9:00
13:00
13:00
13:00
13:00
13:00
13:00
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
9:50
10:40
9:50
9:50
9:50
9:50
N/T
N/T
N/T
13:30
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
N/T
9:30
9:30
9:30
9:30
N/T
N/T
N/T
N/T
N/T
N/T
N/T
14:15
14:15
14:15
<29
<29
36
45
<29
<29
<29
<29
<29
<29
<29
<29
<29
<29
75
42
<29
<29
<29
<29
<29
<29
<29
<29
<29
<29
<58
63
120
<58
31
62
100
< 50 1950 < 58
<29
86
<58
<58
<29
100
130
1.3 6000 <58
18
24
3200
88
57
18
23
23
6400
58
16
13
22
6500
58
120
96
39
6200
71
61
72
120
94
20
27
910
170
310
1.8
9700
560
410
64
9500
1500
810
800
9400
3900
3600
<1.6
Total Total Total by AA Dissolved Dissolved
Iron Selenium Selenium Arsenic Copper
300 40 1 10 10
ug/L ug/L ug/L ug/L ug/L
75500
22
340
405000
386000
53900
768000
<15
710
675000
270000
46900
210
1700
3690000
2030000
110000
67800
630
504000
420000
189000
473000
660000
29100
48000
746000
3100000
4110000
24500
882000
2710000
3140000
127000
341000
3460000
1880000
1520000
345000
5520000
4370000
2330000
790
1700
1600
720
720
850
120
1500
1500
350
320
740
1500
1500
<40
670
730
640
1500
840
770
730
870
770
750
810
370
<80
<48
520
360
<48
<48
<48
490
<48
<48
<48
480
<48
<48
<48
730
150
140
<29
60
<29
<29
<29
<29
<29
<29
41
48
<29
<29
<29
<29
<29
<29
38
<29
48 <29
<29
<29
<29
<29
34
<29
<29
<29
<29
<29
<29
<29
<58
9 60
42 <58
<29
60
<150
18 <58
13 <58
13 <58
32
14 <150
44 <58
35 <58
<58
<290
<29
<150
14 <150
8 <58
13 <150
11
20
3200
24
<1.8
10
11
15
19
6100
20
3
10
260
260
<2
15
6200
17
<18
91
140
38
6000
22
4
70
75
<1.8
18
27
10300
28
<1
1900
310
10000
66
15
360
9600
400
520
810
<14
<18
<1.8
9700
1000
4
<4
Dissolved Dissolved
Iron Selenium
300 40
ug/L ug/L
82800
25
310
419000
81100
60900
1000000
26000
21
700
607000
176000
45200
201000
204000
25
17
2000
3600000
228000
113000
404000
71800
810
520000
21
209000
495000
<15
30800
48000
846000
3580000
305000
24600
495000
947000
139000
67500
2940000
315000
3560000
1780000
1630000
3130000
3240000
<15
337000
5910000
2990000
2580000
890
2000
1800
1000
970
890
660
880
1800
1600
140
280
800
470
460
<40
1700
1600
<40
540
790
460
710
1700
650
840
720
700
920
820
810
400
<58
<48
490
<48
<190
<48
<48
<48
530
<48
<48
<48
<48
<400
<40
630
<48
<48
<48
DissolvedbyAA
Selenium
1
ug/L
DUPLICATE
BLANK
28
4
12
<1
<1
<1
<1
<1
13
11
<1
1
<1
2.4
-------
Table B-24. Summary data for additional catalyzed cementation tests (solid)
Sam le Collect Collect TCLP TCLP TCLP TCLP Total Total Total Total Total Total Total Total Total Total Lead
Lab# . . . Arsenic Barium Cadmium Selenium Arsenic Barium Cadmium Calcium Chromium Copper Iron Mercury Selenium Zinc mg/kg
escnp ion e ime m^/L m^/L m^/L m^/L mg/|Cg mg/kg mg/kg mg/kg mg/kg mg/L mg/kg mg/kg mg/kg mg/kg
4111040 CC-Filtercake 4/7/00 10:30 < 0.029 0.057 0.07 <0.04 10.9 11.7 13.2 37300 57.1 256 5E+05 0.054 19.2 2610 <6
-------
APPENDIX C
Sampling Schedule and Analytical Protocols
Cl
-------
C.O INTRODUCTION
The following sections describe the analytical protocols, the field measurement protocols, and the
sampling schedules for each technology.
C.1 TOTAL SELENIUM, SELENITE, AND SELENATE
Selenium and selenite were determined using a hydride generation inductively coupled plasma-mass
spectrometry (ICP-MS) procedure at KEL according to SW-846 Method 7742 (Modified Cutter
Method) as outlined in Test Methods for Evaluation of Solid Waste-Physical/Chemical Methods (SW-
846) (Ref. 1). Selenite was determined directly by hydride generation. Total selenium was
determined by oxidizing all selenium in the sample to selenate in a potassium persulfate-nitric acid
digestion followed by reduction to selenite with hydrochloric acid (HC1). Selenate was calculated as
the difference between total selenium and selenite.
C.2 DISSOLVED, TOTAL RECOVERABLE, AND TOXICITY CHARACTERISTIC
LEACHING PROCEDURE METALS ANALYSIS BY INDUCTIVELY COUPLED
PLASMA SPECTROMETER
Dissolved and total recoverable metals will be determined using SW-846 Method 601 OB using an
inductively coupled plasma atomic emission spectrometer (ICP-AES) or SW-846 Method 6020 using
ICP-MS. The samples were prepared for ICP analysis as outlined in SW-846 Method 3005A.
The ICP-AES was calibrated according to the procedures outlined in SW-846 Method 601 OB and the
equipment manufacturer's instructions. The ICP-MS was calibrated according to the procedures
outlined in SW-846 Method 6020 and the manufacturer's instructions.
C.3 pH
Although process pH measurements were made through installed probes, some pH measurements were
done manually using a hand-held probe. A pH meter with automatic temperature compensation
capable of measuring pH at the demonstration site to ±0.1 pH units was used for this project. The pH
probe was calibrated daily using two fresh buffer solutions that bracket the expected pH. Temperature
values were also be recorded from the readout during pH measurements.
C.4 ORP
An ORP meter with a silver/silver chloride reference electrode was used to determine the ORP at the
demonstration site. The electrode was calibrated using a solution of known ORP. The calibration
procedures were conducted for every measurement set, and measurements for the biological process
were performed under anerobic and anaerobic conditions.
C2
-------
C.5 DISSOLVED OXYGEN
Dissolved oxygen was measured using a dissolved oxygen meter at the demonstration site. The meter
was calibrated using a sodium sulfite with a trace of cobalt chloride solution to represent 0% dissolved
oxygen and atmospheric air to represent 100% dissolved oxygen. Adjustments for barometric pressure
and salinity were made following calibration, as indicated in the manufacturer's instructions.
C.6 SULFATE
Sulfate analyses were performed according to SW-846 Method 9036. The auto-analyzer was calibrated
using at least five calibration standards of appropriate concentrations.
C.7 TOTAL SUSPENDED SOLIDS/TOTAL DISSOLVED SOLIDS
To determine how the filtering system was functioning, total suspended solids (TSS) and total
dissolved solids (TDS) were determined at KEL according to EPA Method 160.2 and EPA Method
160.1, respectively. These methods are contained in EPA's Methods for Chemical Analyses of Water
and Wastes (Ref. 2).
C.8 IRON SPECIATION
The concentration of dissolved iron will be determined by ICP-AES at KEL. The concentration of
ferrous iron will be determined using the colorimetric Standard Methods for the Examination of Water
and Wastewater (Ref. 3) Method 3500-Fe B and phenanthroline as the color developer.
C.9 TOXICITY CHARACTERISTIC LEACHING PROCEDURE (TCLP)
Solid materials from the ferrihydrite adsorption and catalyzed cementation processes were subjected to
the TCLP procedure outlined in SW-846 Method 1311 at KEL. If sufficient sample was not available
from filter-cake samples, the TCLP procedure was modified according to the weight of the solids
submitted for analysis. The amount of extraction fluid added to the sample was determined by the
weight of the sample and was adjusted according to the sample weight. All reagent additions will be
adjusted accordingly. The resulting extraction fluids from the TCLP were digested according to
procedures outlined in SW-846 Method 3005A for total recoverable metals. Digested samples were
analyzed by ICP-AES according to SW-846 Method 6010B. Splits of TCLP extracts were
prepared/analyzed for mercury by cold vapor atomic absorption (CVAA) according to procedures
outlined in SW-846 Method 7470A.
C3
-------
C.10 TOTAL METALS
The solid samples were characterized for total metals by ICP SW-846 Method 6010B at KEL.
Samples were digested according to SW-846 Method 3050A. The ICP-AES was calibrated according
to SW-846 Method 601 OB. Mercury in solid samples was determined according to procedures
outlined in SW-846 Method 7471 A.
C.11 PERCENT MOISTURE
The percent moisture of each solid sample was determined at KEL using the method outlined in
Exhibit D, Part F of the USEPA Contract Laboratory Program Statement of Work to Inorganics
Analysis, Document Number IlmOS.O (Ref. 4). The percent moisture data will be used to report the
metals on a dry weight basis. Although the method specifies percent solids, percent moisture was be
reported by the laboratory.
C.12 MICROBIAL ISOLATION AND CHARACTERIZATION
All samples were stored at • 4 «C to inhibit microbial growth until analysis. Before samples were
tested they were allowed to warm to ambient temperature and vortexed to ensure a representative
sample for plating. Plate counts were obtained using the standard laboratory procedure using 0.1 mL
of sample or sample dilution.
All plate counts, including plating to isolate individual colony types, were done at room temperature
on trypticase soy agar (TSA) plates and TSA plates containing 25-mg/L selenium. Plates were
incubated 24 to 48 hr in a constant temperature incubator at 28 °C, at ambient temperature, and in a
COY anaerobic chamber.
The baseline microbial characterization portion of the testing included microbial isolations and plate
counts. Microbial isolations were performed on trypticase soy agar (TSA) using the streak-plate
method. All culturing was performed in a Class II Laminar Flow hood. Isolates were initially
characterized by colony morphology and gram stain, and isolates were slanted on appropriate media
for future testing. Microbial counts were performed on the provided waters using the standard plate
count method (Ref. 3). Samples with low numbers of organisms present in the sample were
concentrated 1:50 using centrifugation to achieve a representative plate count. Plate counts are
reported in colony forming units (CFU)/mL. Selected site isolates capable of selenate to elemental
selenium reduction were further characterized using the BIOLOG™ metabolic profiling system and by
MIDI Labs fatty acid analysis. The following characterizations were completed on all samples
collected:
- total heterotrophs—nonselenium reducers (CPU);
- total aerobes (CFU);
- total anaerobes (CFU);
- total selenium reducers—aerobic (CFU); and
- total selenium reducers—anaerobic (CFU).
C4
-------
The following analyses were completed on selected samples:
- BIOLOG™;
- MIDI profiles of predominant heterotrophs (nonselenium reducers); and
- MIDI profiles of selenium reducers.
C.12.1 Total Heterotrophs/Total Selenium Reducers
Plate counts of total heterotrophs and total selenium reducers were made under aerobic and anaerobic
conditions to profile the site microorganisms and to determine potentially interfering nonselenium
reducing microbes. This profile was later used to judge the general reactor conditions with respect to
the desired microbial population. Total heterotroph plate counts were conducted using standard log
dilutions and plating techniques that used 0.1 mL per TSA plate. Colonies forming on the plates were
enumerated within 24 to 48 hr under aerobic conditions and up to two week for anaerobes. Selenium
reducers were enumerated using the same techniques with the exceptions of using TSA plates with
25-mg/L sodium selenate added.
C.12.2 BIOLOG™ and MIDI Fatty Acid Analysis
Where appropriate, BIOLOG™ plates were used to provide tentative microbial identification, and to
help characterize the metabolic profiles of microbes important in the selenium reduction process.
BIOLOG™ plates provide a profile of 96 carbon sources or selected carbon sources to profile the
metabolic character or individual microorganisms.
MIDI fatty acid profiles were used where appropriate to fingerprint the microbial population for
bioreactor tests. Selected heterotrophic and selenium reducing isolates were obtained by plating an
isolate for purity a minimum of three times on TSA plates. The isolate was streaked through four
quadrants and incubated at 28 °C for 24 hr, harvesting approximately 50 to 75 mg of microbial cells
from the third and forth quadrants. These microbial cells were used to prepare a hexane fatty acid
extract. The fatty acid extracts were injected into a micro-bore gas chromatograph column designed to
separate fatty acids and analyzed using MIDI microbial identification software and databases.
C.13 SAMPLING LOCATIONS/SCHEDULE
The sampling locations for each process as well as the sampling schedule for each process are defined
in the following tables. The sampling schedules were originally developed in the project-specific
QAPP. Table C-l describes the sampling locations for the ferrihydrite adsorption process, and
Table C-2 is the sampling schedule for the ferrihydrite adsorption process. Table C-3 describes the
sampling locations for the catalyzed cementation process, and Table C-4 is the sampling schedule for
the catalyzed cementation process. Table C-5 describes the sampling locations for the BSeR™ process,
and Table C-6 is the sampling schedule for the BSeR™ process. The preservative, holding times, and
analytical protocols for each sample type are summarized in Table C-7. The frequency of field QC
sampling is summarized in Table C-8.
C5
-------
Table C-l. Sample port/location descriptions and sample matrix at each
location for the ferrihydrite process.
Sample Port/Sample Location
FH1
FH2
FH3
FH4
FH5
FH Filter cake
FE/FT
ORP
DH
Description
Process influent
Process influent after FeCl2 addition
Process influent with HC1 and CaO addition
Treated water discharge
Unfiltered discharge
Sludge product
Flow Totalizer
Tank 101
Tanks 201, 203, and 204 pH monitors
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Solid
Aqueous
Aqueous
Aqueous
Table C-2 Noncritical and critical measurements for the ferrihydrite adsorption tests.
Measurement
pH
pH
ORP
Total Flow
Selenium Speciation
Selenium Speciation
Iron Speciation
Sulfate
Nitrate-Nitrite as N
Total Suspended
Solids
Total Dissolved
Solids
Total Recoverable
Metals (Ca, Fe, Mg,
Na, As, Ba, Cu,
Mo, Se)
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Classificatio
n
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Sample Frequency
Initially, every 4 hr for 2 days,
every 8 hr for 3 days, daily
Initial, every 24 hr
Initially, every 4 hr for 2 days,
every 8 hr for 3 days, daily
Initially, every 4 hr for 2 days,
every 8 hr for 3 days, daily
Initial, every tanker truck
delivery, final
Initial, daily for 5 days, weekly
Initial, every tanker truck
delivery, final
Initial, every 48 hr of operation,
final
Initial, every 48 hr of operation,
final
Initial, weekly, final
Initial, weekly, final
Initial, every 48 hr of operation,
final
Sample Location
pH probes in tank 101,
tank 102, and tank 103
FH5
ORP probes in tank 102
FE/FT (Total flow
indicator)
FH1
FH5
FH1
FH1, FH5
FH1, FH5
FH4 and FH5
FH4 and FH5
FH1, FH2, FH3, FH4,
FH5
Total
Number of
Samples
114
22
38
38
4
8
4
24
24
10
10
60
C6
-------
Table C-2 Noncritical and critical measurements for the ferrihydrite adsorption tests.
Measurement
Dissolved Metals
(Ca, Mg, Na, Ba,
Cu, Mo, Se)
Dissolved Metals
(As, Fe)
Total Metals (As,
Ba, Cd, Cr, Cu, Fe,
Pb, Se, Ag, Zn, Ca)
% Moisture
TCLP (As, Ba, Cd,
Cr, Pb, Hg, Se, Ag)
Dissolved Metals
(Se)
Matrix
Aqueous
Aqueous
Solid
Solid
Solid
Aqueous
Classificatio
n
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Critical
Sample Frequency
Initial, every 48 hr of operation,
final
Initially, every 24 hr of operation
Each sludge sample
Each sludge sample
Each sludge sample
Initially, every 4 hr for 2 days,
every 8 hr for 3 days, daily
Sample Location
FH1, FH2, FH3, FH4,
FH5
FH3, FH5
FH Filter cake
FH Filter cake
FH Filter cake
FH5
Total
Number of
Samples
60
44
3
3
3
38
Note: Sample collection will begin after the one system volume has been processed.
Table C-3. Sample port/location descriptions and sample matrix at each location for the
catalyzed cementation process.
Sample Port/Sample Location
CC1
CC2
CCS
CC4
CCS
CC Filter cake
FE/FT
ORP
pH
Description
Process influent
Process influent after reagent addition
Process influent with additional reagents
Unfiltered discharge
Treated water discharge
Sludge product
Flow totalizer
Tanks 108 and 109
Tanks 201, 203, and 204 pH monitors
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Solid
Aqueous
Aqueous
Aqueous
C7
-------
Table C-4. Noncritical and critical measurements for catalyzed cementation process
demonstration (3-week test).
Measurement
pH
pH
ORP
ORP
Total Flow
Selenium Speciation
Selenium Speciation
Iron Speciation
Sulfate
Nitrate-Nitrite as N
Total Suspended Solids
Total Dissolved Solids
Total Recoverable Metals
(Ca, Fe, Mg, Na, As, Ba,
Cu, Mo, Se)
Dissolved Metals (Ca, Mg,
Na, Ba, Cu, Mo, Se)
Dissolved Metals
(As, Fe)
Total Metals (As, Ba, Cd,
Cr, Cu, Fe, Pb, Se, Ag, Zn,
Ca)
% Moisture
TCLP (As, Ba, Cd, Cr, Pb,
Hg, Se, Ag)
Dissolved Metals (Se)
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Solid
Solid
Solid
Aqueous
Classification
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Critical
Sample Frequency
Initially, every 4 hr for 2
days, every 8 hr for 3
days, daily
initial, every 24 hr
Initially, every 4 hr for 2
days, every 8 hr for 3
days, daily
Initial, every 24 hr
Initially, every 4 hr for 2
days, every 8 hr for 3
days, daily
Initial, every tanker truck
delivery
Initial, daily for 5 days,
weekly
Initial, every tanker truck
delivery
Initial, every 48 hr of
operation, final
Initial, every 48 hr of
operation, final
Initial, weekly, final
Initial, weekly, final
Initial, every 48 hr of
operation, final
Initial, every 48 hr of
operation, final
Initially, every 24 hr of
operation
Each Sludge Sample
Each Sludge Sample
Each Sludge Sample
Initially, every 4 hr for 2
days, every 8 hr for 3
days, daily
Sample Location
pH probes in tanks
108 and 109
PCS
ORP probes in
tanks 108 and 109
PCS
FIT (Total flow
indicator)
PCI
PCS
PCI
PCI, PCS
PCI, PCS
PC4 and PCS
PC4 and PCS
PCI, PC2, PCS,
PC4, PCS
PCI, PC2, PCS,
PC4, PCS
PCS, PCS
PC Filter cake
PC Filter cake
PC Filter cake
PCS
Total
Number of
Samples
76
22
76
22
38
4
8
4
24
24
10
10
60
60
44
3
3
3
38
Note: Sample collection will begin after the one svstem volume has been processed.
C8
-------
Table C-5. Sample port/location descriptions and sample matrix at each location for the
biological selenium reduction process.
Sample Port/
Sample Location
BR01
BR02
BROS
BR04
BROS
BR06
BR07
BROS
Bioreactor
Flowmeter/Totalizer
Description
Process influent
Process influent after nutrient addition and first reactor
Process water exiting second reactor
Process water exiting third reactor
Process water after exiting fourth reactor
Process water after exiting fifth reactor
Process water after exiting sixth reactor
Final process effluent after slow sand filter
Selenium precipitate product
Flowmeter/totalizer for biological reduction system
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Solid
Aqueous
Table C-6. Noncritical and critical measurements for demonstration of the biological selenium
reduction (1-week test at residence times of approximately 24 hr, 12 hr, 6 hr, 3 hr, and repeat
of optimum).
Measurement
pH
Temperature
Dissolved Oxygen
ORP
Flow Rate/Total Flow
Total Recoverable Metals (Ca,
K, P, Mg, Na, As, Ba, Cu,
Mo, Se)
Dissolved Metals (Ca, K, P,
Mg, Na, As, Ba, Cu, Mo, Se)
Nitrate-Nitrite as N
Cell Count
MIDI Fatty Acid Analysis
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous/Solid
Aqueous/Solid
Classification
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Noncritical
Sample Frequency
Daily
Daily
Daily
Daily
Daily
Weekly
Weekly
Weekly
Initial, weekly,
final
Initial and final
Sample Location
BR01 through
BROS
BR01 through
BROS
BR01 through
BROS
BR01 through
BROS
Flowmeter/Totalize
r
BR01 through
BROS
BR01 through
BROS
BR01 through
BROS
Bioreactors
Bioreactors
Total
Number of
Samples
up to 1,224
up to 1,224
up to 1,224
up to 1,224
up to 153
up to 176
up to 176
up to 176
up to 144
up to 12
C9
-------
Table C-6. Noncritical and critical measurements for demonstration of the biological selenium
reduction (1-week test at residence times of approximately 24 hr, 12 hr, 6 hr, 3 hr, and repeat
of optimum).
Measurement
Selenium Speciation
Total Metals (As, Ba, Cd, Cr,
Cu, Fe, Pb, Se, Ag, Zn)
% Moisture
Dissolved Metals (Se)
Matrix
Aqueous
Solid
Solid
Aqueous
Classification
Noncritical
Noncritical
Noncritical
Critical
Sample Frequency
Initially, daily
during residence
times tests, then
weekly
Each product
sample
Each product
sample
Initially, daily
during residence
times tests, then
weekly
Sample Location
BR01 through
BROS
Bioreactor
Bioreactor
BROS
Total
Number of
Samples
up to 424
up to 5
up to 5
53
Note: Sample collection will begin after the one system volume has been processed.
CIO
-------
Table C-7. Preservatives, holding times, containers, method types, and references.
Parameter
Selenium
Speciation
Iron Speciation
pH
Dissolved Oxygen
Temperature
ORP
Flow Rate/Total
Flow
Sulfate
Nitrate-Nitrite asN
IDS
rss
Total Recoverable
Metals (Al, As,
Cd, Cu, Fe, Pb,
P, Zn by ICP)
Dissolved Metals
(Se by ICP-MS)
Dissolved Metals
by ICP-AES or
ICP-MS
Total Metals by
ICP-AES (Hg by
CVAA)
MIDI Fatty Acid
Analysis
Cell Counts
% Solids
TCLP Metals (Hg
by CVAA)
Matrix
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
N/A
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Solid
Aqueous/
Solid
Aqueous/
Solid
Solid
Solid
Preservative
•4-C,
Filter,
pH- 2 HC1
•4-C,
Filter,
pH- 2 HC1
None
None
None
None
None
•4°C
•4-C, pH-2
H2S04
•4°C
•4°C
•4-C, pH-2
HNO3
•4-C,
Filter,
pH- 2 HNO3
•4-C,
Filter,
pH- 2 HNO3
None
None
None
None
None
Holding Time
Analyze
immediately
Analyze
immediately
Analyze
immediately
Analyze
immediately
Analyze
immediately
Analyze
immediately
Analyze
immediately
28 days
28 days
7 days
7 days
6 Months
6 Months
6 Months
6 Months
48 hr after colony
isolation
48 hr
6 Months
7 days to extraction,
40 days after, 28
days until extraction,
28 days until
analysis of extract
Sample Size &
Container
500-mL HDPE
500-mL HDPE
100-mL HDPE
100-mL HDPE
100-mL HDPE
100-mL HDPE
N/A
500-mL HDPE
500-mL HDPE
500-mL HDPE
500-mL HDPE
500-mL HDPE
500-mL HDPE
500-mL HDPE
8 oz CWM
15mL HDPE
15 mL HDPE
Taken from solid
sample
at least 100 g
16 oz CWM
Method Type
AA hydride
generation
Colorimetric
pH meter
DO meter
Thermometer
ORP meter
Flowmeter/
Totalizer
Colorimetric
Colorimetric
Filter/Weigh
Filter/Weigh
ICP
ICP-MS
ICP
ICP
Gas
Chromatograph
(GC)
Plate Count
Drying/
Weighing
ICP
Reference
See Section 5.1, Modified
SW-846 Method 7742
Standard Methods
3500-Fe B, Appendix C
EPA
(SW-846) Method 9040
EPA
(SW-846) Method 9040
EPA
(SW-846) Method 9040
Equip. Manufacturer
instructions
Manufacturer's
Instructions
EPA Method 375. 2
EPA Method 353.3
EPA Method 160.2
EPA Method 160.1
EPA SW-846 Preparation
Method 3005 A/
ICP Method 601 OB
EPA SW-846 Preparation
Method 3005A/ICP-MS
Method 6020
EPA SW-846 Preparation
Method 3005 A/
ICP Method 601 OB or
6020
EPA SW-846 Preparation
Method 3050A/ICP
Method 601 OB (Hg
Method 7471A)
See Section 5. 12
See Section 5. 12
CLP SOW 3/90 Exhibit
D, Part F and Appendix C
EPA SW-846 Extraction
Method 1 3 1 1 /Preparation
Method 30053/ICP
Method 601 OB (Hg
Method 7470A1
Cll
-------
Table C-8. Field QC sampling for each process demonstration.
Process
ABC Biological Process
MSB Catalyzed
Cementation
MSB Berrihydrite
Adsorption
Field Duplicates
Frequency
weekly
weekly
weekly
Field Cross Contamination
Blanks Frequency
weekly
weekly
weekly
Total Number of Field QC
Samples
23 field duplicates and 23 field
blanks
4 field duplicates and 4 blanks
4 field duplicates and 4 blanks
1 Bield QC samples are to be taken at the initial sampling event and then weekly for each technology demonstration.
The field duplicate samples will be taken from the effluent location of each process.
REFERENCES
1. U.S. Environmental Protection Agency, "Test Methods for Evaluating Solid Waste—Physical/
Chemical Methods," U.S. EPA, Washington D.C., 1990 through Update IIB, January 1995.
2. U.S. Environmental Protection Agency, "Methods for Chemical Analyses of Water and Wastes."
3. American Public Health Association (APHA), "Standard Methods for the Examination of Water
and Wastewater," 16th Edition, 1985.
4. U.S. Environmental Protection Agency, "USEPA Contract Laboratory Program Statement of
Work to Inorganics Analysis," Document number ILM03.0, Washington D.C., June 1992.
C12
-------
APPENDIX D
Microbial Screening and Laboratory Testing
-------
D.1 MICROBIAL SELENIUM REDUCTION SCREENING
Endpoint, qualitative, and quantitative selenium reduction assays were utilized as screening tools to
assess selected microbial strains and microbial support materials for selenium reduction. The selenium
test water used for the screening series consisted of Garfield Wetlands-Kessler Springs water collected
by KUCC and used unspiked (2-mg/L selenium) and spiked (25-mg/L selenium). Screening tests used
log-phase microbial cultures prepared in trypticase soy broth (TSB), washed and resuspended in sterile
saline, and inoculated into 15-mL culture tubes containing selenium test water at a concentration of 2 x
109 cells per mL. Sterile saline served as the abiotic control. Tubes were incubated in both an aerobic
environment and a COY anaerobic chamber at room °C for 24 to 48 hr and then evaluated for
selenium reduction.
D.2 NUTRIENT SCREENING
Endpoint, qualitative, and quantitative selenium reduction assays were utilized as screening tools to
assess selected microbial strains and microbial support materials for selenium reduction using various
supplementary nutrients. The selenium test water used for the screening series consisted of Garfield
Wetlands-Kessler Springs water collected by KUCC and used unspiked and spiked to a final selenate
concentration of 25 mg/L. Screening tests used log-phase microbial cultures prepared in TSB, washed
and resuspended in sterile saline, and inoculated into 15-mL culture tubes containing selenium test
water and or selected nutrient(s) at a concentration of 2 x 109 cells per mL. Nutrients screened for
selenium reduction included acetate, an acetate nutrient mix-1, methanol, several proprietary molasses-
based nutrient mixes, ammonium phosphate, ammonium phosphate nutrient mix-1, and a peptone-
based nutrient. Nutrient mixes are proprietary and significantly effect selenium reduction over
extended periods. Nutrient-selenium containing media without microorganisms and selenium
containing media without nutrients were used as controls. Tubes were incubated in both aerobic
environments and a COY anaerobic chamber at room °C for 24 to 48 hr and then evaluated for
selenium reduction.
D.3 MICROBIAL SUPPORT MATERIALS
Microbial support materials were evaluated for selenium-reduction at the Garfield Wetlands-Kessler
Springs site because of KUCC's desire to test alternative biofilm support materials. Materials tested
included slag and biosolids obtained from KUCC that were screened to +8 mesh, Darco charcoal +8
mesh, Celite, and continuous-release microbe-containing alginate beads. Continuous release beads
were prepared for sustained reactor inoculation with desired microbes. Controls were used to
determine possible sorption of dissolved selenium to materials used in the proposed testing. Sorption
tests were conducted with biofilm support materials (50% by volume to approximate reactor
conditions) under static conditions at ambient temperature for 2, 4, and 8 hr. Tests used prewetted
biofilm support materials, 25-100 mL of actual process water, and were conducted as shown in Table
D-l below.
-------
Table D-l. Support material test matrix.
Test Condition
Test Material
Carbon Support
Biosolids Support
Live Cells
Heat Inactivated Cells
Process Water
X
X
X
X
Process Water with Nutrients
X
X
X
X
Process Water with Se (25 mg/L)
X
X
X
X
D.4 LABORATORY BIOREACTOR/BIOPROCESS TESTS
Staggered sets of anaerobic up-flow bioreactors were used to evaluate preliminary BSeR™ operating
parameters, economics, retention time, flow rate, system kinetics, nutrients and overall system
performance. All tests were conducted in one-inch diameter columns operated in single-pass, up-flow
mode with retention times ranging from 3 to 24 hr, at ambient temperature (• 24 • C). The bioreactors
used a defined microbial cocktail of Pseudomonas and other site bacteria to provide scale-up estimates
for pilot-scale application. All tests used provided KUCC waters and live microbial biofilms.
Bioreactors used an agricultural-grade molasses based media. Kinetic determinations were made over
a 2-week period by varying retention time and measuring selenium in the effluent. Controls used
granular activated carbon, slag, Celite and/or biosolids without microorganisms.
D.5 RESULTS
Results of the microbial screening and laboratory testing are discussed in the following sections.
D.5.1 Microbial Isolation and Characterization
Microbes were characterized through plating samples, noting colony morphology, gram stains,
BIOLOG™ plates, and MIDI fatty acid profiles when appropriate. Multiple site and previously
collected microbial isolates were tested for the ability to remove selenium in unspiked and spiked
KUCC waters and synthetic waters (to 25 mg/L selenium as sodium selenate). Each isolate was plated
on TSA containing 25 mg/L selenium. These plates were incubated in both aerobic and anaerobic
environments and screened for selenium reduction. Microbial characterization results are shown in
Table D-2.
A number of site isolates were also nonselenium reducers. Table D-3 below lists some of the
nonselenium reducers of concern in developing a selenium reducing microbial cocktail biofilm that
would resist replacement by indigenous nonselenium reducing microbes.
D3
-------
Table D-2. Garfield Wetlands-Kessler Springs microbial characterization.
Sample Name
KS001
Stake 1
KS002
E. Seep Black
KS003
White N of Stake
KS004
E. Seep
KS005
Stake 2
KS006
Sample from pool with stake
KS007
Sample from pool with stake
KS008
Sample from pool with stake
KS009
Sample from pool with stake - Channel
Total Plate Count
2.05E+04
1.60E+06
1.71E+05
1.40E+06
9.00E+04
1.90E+05
1.63E+04
3.60E+05
4.00E+05
Selenium
Reducers
7.50E+03
Four different
colonies
1.53E+05
Three different
colonies
1.50E+05
Three different
colonies
7.00E+05
Three different
colonies
7.90E+04
Four different
colonies
1.80E+05
Four different
colonies
1.48E+04
Three different
colonies
3.00E+05
Three different
colonies
1.95E+05
Three different
colonies
Non-Selenium
Reducers
1.30E+03
Three different
colonies
6.00E+03
One colony
2.10E+04
One colony (rapid
growth)
7.00E+05
Four different
colonies
1.10E+04
One colony
l.OOE+04
One colony
1.50E+03
Two different
colonies
6.00E+04
Three different
colonies
2.05E+05
Two different
colonies
D4
-------
Table D-3. Nonselenium reducing site isolates.
Nonselenium
Reducers
KS003AX
KS001CX
KS009E
KS001E
KS007D
KS003F
KS007E
KS004A
KS005CX
Aerobic
Growth
+
+
+
+
+
+
+
+
+
Anaerobic
Growth
-
-
-
-
-
-
-
-
-
Gram-Stain
-
-
-
-
-
+
-
-
-
Biolog ID
Pseudomonas
fluorescens type c
No Identification
No Identification
Pseudomonas putida
Pseudomonas corrugata
Bacillus sp.
Pseudomonas frag/
Psudomonas fluorescens
type G
Pseudomonas mendocina
D.5.2 Microbial Selenium Reduction Screening
Selected microbes were tested for their ability to reduce selenium in an economical proprietary
molasses-based nutrient mix. Results of this screening are presented in Figure D-l. Top performing
microbes from this screening were selected for bioreactor testing. Previously collected selenium-
reducing strains were selected based on their original source of isolation (high selenium containing
mining and industrial process waters) and their ability to perform a reduction on selenium and other
oxyanionic contaminants. Figure D-2 shows endpoint screening results of microbial strains tested for
selenium reduction in synthetic laboratory water. Four laboratory isolates demonstrating the best
selenium reduction in KUCC waters were selected for further testing—Pseudomonas putida, P.
pseudoalcalagenes, P. stutzeri, Cellulomonas flavis. Isolates tested are naturally occurring,
nonpathogenic facultative anaerobes. Isolates that reduced selenium by 95% in this screening were
selected for a further study to determine relative selenium reduction rates.
The microorganisms reducing selenium in the above screenings were subsequently tested in KUCC
waters containing • 14.7 and • 2.0 mg/L selenium for their ability to reduce selenium. Tests were
conducted in 15-mL tubes under static conditions at ambient temperature for 7 days. Results of this
screening are in Figures D-3 and D-4 and demonstrate the effect that site waters have on selenium
reduction at this site. Different microbes were shown to have different levels of effectiveness in the
two KUCC provided waters. This information was processed with additional information obtained
from the testing described herein to formulate a microbial cocktail that would effectively remove
selenium from both waters.
D5
-------
c
o
B
m
|
2
Figure D-l. Isolate screen for selenium reduction (spiked laboratory waters
containing 50-mg/L selenium).
loo.oon |f|ffYflfVfVfYPlfWlflfV?v?V7L*L*i
90.00- ' If
80.00- '
70.00- '
60.00- '
50.00- x
40.00- 1
30.00- x
20.00- 1
10.00- 1
0.00
1 \ 4fyft7W\j7L0Lj»
9 jn .n
' f e\
0
a
ff —
n — i — i — rn — i — i — rn — i — rn — i — i — rn — i — rn — i — i — i — rn — i — f
ir ir ir W ir ir ir ir ir i? ir ir ir ir ir 03 ir ir ir
Isolate
Figure D-2. Isolate screen for relative selenium reduction (spiked laboratory waters
containing 50-mg/L selenium).
D6
-------
« 90"
g 80-
| 70-
* 60-
OT 50-
^ 40-
^ 30-
B 20-
^ 10-
rv; „
"• U ^
f rfirt
rn
-*r ^-- -c ^>
Microorganism
Figure D-3. Relative selenium reduction in KUCC water (• 14.7 mg/L).
.
3S .2
^- +••
0)
a:
100n
90-
80-
70-
60-
50-
40-
30-
20-
10-
c
e:
^
^
^
^
£=
•-
*-
e
^
r=]
Microorganism
Figure D-4. Relative selenium reduction in KUCC water (• 2 mg/L).
D.5.3 Nutrient Screening
Microbes demonstrated to be effective in KUCC waters containing • 2.0 mg/L selenium were grown
for 24 hr in 50-mL volumes containing TSB at ambient temperature. Each sample was subsequently
diluted or concentrated to a cell density of • 2.0 x 109/mL. The cells were washed with saline,
resuspended in site waters with selected nutrients and incubated at ambient temperature for 6 days.
Figures D-5, D-6 and D-7 show the effectiveness of selected nutrients for selenium reduction in site
water. As can be seen in these figures, different nutrient mixes affect selenium reduction by different
microbes differently. Molasses-based nutrient mixes were shown to be most effective for selenium
reduction by site and other selected microbes using KUCC waters.
D7
-------
II III F^J 1 1 F^i 1 1 FT"! 1 1 FT"I 1 1 FT~~^ 1 1 r^
II rlllril 1 1 iH 1 1 1 iH Illril II PTI II"
MlnM^lfmll
UJ IraJ IraJ IraJ IraJ mU ft
111 rd ri rH ri r
1 ^•AJ | 1 l^-l 1 1 P"rt 1 1 1 '-I 1 1 P"rt 1 1 HT" 1
^B
v\
1
-2
-1.5
Relative Selenium
"1 Reduction
-0.5
n
1 I III
! ! 1 11
Figure D-5. Nutrient screening for selenium reduction in KUCC waters (• 2 mg/L).
Molasses Blend
#4
Figure D-6. Nutrient screening for selenium reduction in KUCC waters (• 2 mg/L).
D8
-------
Relative (%
Selenium
reduction
100-
90
80
70-
60
50
40
30
20
10-
n
d
d
d
d
=
f=
C
C
^
=
,C
A° ^
Microorganism
Figure D-7. Selenium reduction with proprietary molasses-based nutrient blend.
Test series used KUCC water at • 2.0 mg/mL spiked to final selenium concentration
of25 mg/L.
D.5.4 BIOLOG™ and MIDI Fatty Acid Analysis
BIOLOG™ plates were used to help determine metabolic profiles of potential key microbial cocktail
microorganisms and potentially interfering nonselenium-reducing microbes. The results of these tests
are presented here instead of with the rest of the microbial characterization results to represent the
relative sequence in which the testing was conducted. Metabolic and site profiles were compared to
develop a microbial cocktail that resembled the existing microbial population but that reduced selenium
under site conditions using an economical nutrient source. Example BIOLOG™ screening plates are
presented in Figure D-8.
MIDI analysis was conducted to develop profiles of important selenium reducers and nonselenium
reducers to monitor biofilm development and performance throughout the pilot-scale tests. Examples
of the monitored profiles are shown in Figure D-9. The MIDI profiles were also used to monitor
microbial establishment and persistence in the bioreactors.
D9
-------
Nutrient Utilization Profiles
KS001EX
i- i
Ms**
I-
ftmte
4.
' «H). 4"
g«'*Mb*ift t qlaeem
m
n-B
. ne
IKMSt
+ 1 m L
T
r +
C"
SlKJffS*
~!fl
3-
£itmM
1
iWICUMC ^>rim
W I H
» + ( 0-
gly^MatWH:
ft C* |
•MB DL 4-
vaivle a^ie lacxaoo
= -H 4- ^+ !
MM
19
" 4, =
freoonc tyjfftiod
(1U
ft-
-f
8' I
I 1. I
$l««$»ne l *^*«iw
'^ 4-'
1 f* 1 i
1 gM»fiC
i -*
__r
•i 11
. fwwsnp*
! Mtfl
1 O.L-* •
•fKj*-j
frwayms
ftt
D
"* 4
i 0- I
met^l
pr^vaie
Ell""
sa^oe
aoc
g«*TM.
a»aae-K
acad
0.. "I'
'« _t_
^ifll^L !
^in*p%«
_jpie ___
giK
7-*K*t>
Mrvwtf
5tucrae-f t ^hi£OJH^-6
y(K!K*Wt* p^lCWBPasB
KS003AX
_j_
m«l
-r
9-™**
l«
4-
fll
BUW
' —( '
1 23^.'
*
+
a J_
I- +
*«**
4.
~t
•p _j_ " j ! H
•it i«« .
! !dL_ l '
1 m&tr#jm i tspKi
i en
'- o-
**B-™. I
Figure D-8. BIOLOG metabolic screening plates.
i
"T
til
D -4-
BWMb
Ion
*** _L
i- "T™
r +:«:
+ ;
D10
-------
Figure D-9. MIDI profiles ofbioreactor microbes.
Dll
-------
D.5.5 Microbial Support Materials
The 20 best selenium reducers from previous screening tests were screened for their ability to growth
to a cell density of • 5 x 109/mL on different reactor materials (see Table D-4). One milliliter of
• 2 x 109/mL cells was added to 9 mL of reactor materials and TSB under static conditions for 4 days.
Celite is not listed because it was determined that it required pretreatment to obtain high microbial
growth and the tests conducted were not designed to take this into account and were, therefore, biased
in this respect.
Dissolved selenium sorption controls were run on the alginate, biosolids, and carbon. Using KUCC
water at • 2.0 mg/L selenium, the alginate, as expected, sorbed considerably more that the carbon or
biosolids, as shown below in Table D-5.
Table D-4. Reactor matrix/biafilm testing.
Microbe Name
SF046
KS008EX
KS008D
KS007C
SF077
SF047
SF024
SF050
SF123
KS008A
KS001C
KS009DX
KS006B
KS004C
KS008FX
SF057
KS005A
KS004B
KS004D
KS004F
KS005B
Crushed Rock
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Carbon
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Alginate
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Biosolids
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Table D-5. Matrix sorption controls.
Sample
Kestler Spring Water
Biosolids Ig/lOmL
Carbon Ig/lOmL
Alginate Ig/lOmL
[Se] mg/L
1790
1660
1600
1182
%
N/A
7
11
34
D12
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D.5.6 Laboratory Bioreactor/Bioprocess Tests
The first series of reactors tested used calcium alginate beads configured to evaluate microbial cocktail
compositions in the following process (SeO42~) • (Se°) and slag and activated carbon sized to +8.
Celite was not included in these tests. Slag and carbon reactors were treated to enhance biofilm
establishment and then inoculated with the top performing microorganisms as shown in Figure D-10
(Pseudomonas stutzeri, RC-large, KS005A, KS006A, KS001B, SF037, and SF001). Reactors were
inoculated in a manner to ensure establishment of this microbial cocktail as the predominant
microorganisms in the carbon and biosolids reactors. With a 24-hr retention time and KUCC waters
containing • 14.7 mg/L selenium, the carbon and alginate reactors were removing • 96% of the
selenium. At day 10, the reactors were switched to KUCC waters containing • 2.0 mg/L selenium and
a 12-hr retention time. The microbes took a couple of days to adjust to the new water but then
continued to remove 90% to 97% of the selenium for about 2 weeks. The slag reactor did not perform
as well, removing up to 74% of the selenium in 12 hr. At this point, the first series of reactors was
discontinued and a second series of reactors containing alginate beads, carbon, and a carbon-biosolids
mixture was started using KUCC water containing • 2.0 mg/L selenium.
The second reactor series was operated with a 12-hr retention time. Alginate beads were again used to
evaluate different microbial cocktail compositions. As can been seen in Figure D-l 1, the microbial
compositions tested in alginate did not perform as well as the first alginate test series and were
discontinued at day 25. The microbial cocktails tested in series one were optimized for the KUCC
water containing • 2.0 mg/L selenium. In these second series tests, the carbon bioreactor again
performed slightly better than the carbon biosolids reactors. However, both the carbon and carbon
biosolids reactors were removing selenium to well below target levels; reaching low microgram to
nondetectable levels. The low-level microgram selenium spikes are probably due to elemental
selenium that was observed to migrate through the reactors in both test series.
Control reactors consisted of alginate, slag, carbon, and carbon-biosolids without microorganisms.
Slight initial dissolved selenium sorption was observed in all control columns except for the slag
column. This sorption leveled out within a few days and control selenium levels were near reactor
feed values. Reactor configurations tested are shown in Figure D-l2 (initial laboratory reactors) and
Figure D-l3 (second series of laboratory reactors).
D.5.7 Nutrient Feed Testing
A pulse versus continuous reactor feed was tested in the bench-scale reactors. Both systems delivered
the same amount of nutrient over the test period. Both feed delivery systems sufficiently supported
selenium reduction in the reactors. However, in the continuous feed reactor, excess biomass formation
was noted at the nutrient delivery site, resulting in poor fluid transfer through the reactor matrix.
Based on these observations, a pulsed nutrient feed was implemented in the field reactors.
D13
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16000
Figure D-10. Laboratory Bioreactor Series 1. The initial carbon, slag, and
alginate columns that were used to measure selenium reduction using KUCC
waters (• 14.7 mg/L). Columns used a 24-hr retention time until day 10
when they were switched to a 12-hr retention time. Columns were run at
ambient temperature under anaerobic conditions. The alginate column was
used to measure relative effectiveness of various different selenium reducing
microbes.
I Alginate
Microbes
] Carbon Biofilm
D Carbon
Unautoclaved
Biosolids
• Carbon
Autoclaed
Biosoilds
Days
Figure D-ll. Laboratory Bioreactor Series 2. The second series of carbon,
carbon-biosolids, and alginate columns used to measure selenium reduction
using KUCC waters (• 2 mg/L). Columns used a 12-hr retention time and
were run at ambient temperature under anaerobic conditions. The alginate
column was used to measure relative effectiveness of various different
selenium reducing microbes.
D14
-------
Figure D-12. Laboratory bioreactor test configuration.
Figure D-13. Second series of BSeR ™ laboratory reactors.
D15
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APPENDIX E
Enzymatic Selenium Reduction Laboratory Project
El
-------
ENZYMATIC SELENIUM REDUCTION
LABORATORY PROJECT
Prepared for:
Helen Joyce
MSB Technology Applications, Inc.
PO Box 4078
Butte, Montana 84098
January 31,2001
Prepared by:
Applied Biosciences Corp.
P.O. Box 520518
Salt Lake City, UT 84152
(800) 280-7852
www.bioprocess.com
E2
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Executive Summary
This project was focused on furthering the development of enzymatic selenium removal for
demonstration in pilot-scale tests. Applied Biosciences has demonstrated, in bench scale tests,
enzymatic selenium reduction from economical extracts of microbial cells. This document
describes testing conducted toward development of an prototype enzymatic treatment system for
demonstration at pilot scale. Enzymatic systems have the potential for greater kinetics, do not
appear to be affected by contaminant levels that would kill live microbial cells and do not require
nutrients. Furthermore, enzyme preparations have been demonstrated to reduce selenium in
environments inhibitory to live microorganisms. Selenium was reduced in the presence of >100
mg/L cyanide, a cyanide concentration inhibitory to or toxic to all selenium reducing microbes
tested to date.
Methods to economically prepare stable enzyme preparations and enzyme preparations from
different microorganisms were investigated. Several immobilization polymers were evaluated to
increase enzyme operational longevity. Of the polymers tested, Calcium alginate performed the
best in regards to ease of handling, toxicity, cost, and performance. Problems with stability or
possibly loss of an electron donor system were problematic throughout the testing, and are
thought to be responsible for the variation in stability or performance observed between various
tests. Even though enzymatic selenium reduction was demonstrated for periods ranging from 2-6
months, the stability or electron donor systems of the preparations tested was not sufficiently
reproducible to warrant pilot scale tests at this time. In summary, although successful in furthering
preparation of economical selenium reducing enzyme extracts, more research is required to
enhance the stability and/or electron donor systems for pilot-scale tests.
E3
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ENZYMATIC SELENIUM REDUCTION LABORATORY PROJECT
Introduction
This document is a report for the Applied Biosciences Corp. (ABC) Enzymatic Selenium
Reduction Laboratory Project. The Enzymatic Selenium Reduction Laboratory Project is a
project within the Mine Waste Technology Program (MWTP). The MWTP is funded by the
U.S. Environmental Protection Agency (EPA) and is jointly administered by the U.S.
Department of Energy (DOE) and the EPA. This project tested selenium reducing enzyme
preparations for stability and operational functionality. The project approach used an
optimized mixture of naturally occurring bacterial enzymes from heterotrophic bacteria
previously isolated from selenium-contaminated mining waters and soils, to reduce selenate
and selenite to elemental selenium in mining wastewaters. Enzymatic selenium reduction
was evaluated to make a decision for scale up and pilot testing. Project goals are to:
• Test enzyme extracts from microbes with the best demonstrated selenium reduction
capabilities and from mixtures of these microbes to examine selenium-reduction
kinetics
• Optimize selenium enzyme extraction/purification protocols
• Examine select, immobilization/encapsulation formulations to increase the stability and
extend the functional time of the selenium-reducing enzyme(s) preparation
• Evaluate the immobilized/encapsulated enzyme preparation's durability, enzyme
function (kinetics and stability).
• Determine initial bench-scale process operational parameters, estimated costs, and
any pretreatment recommendations
Background
Selenium is a common water contaminant throughout the world and represents a major
environmental problem in the U.S., being a problem contaminant in at least nine western
states. This contamination, originating from mining operations, mineral processing, abandoned
mining sites, petroleum processing and agricultural run-off. Microbes have been identified
and cultured with very high selenium tolerance and accelerated selenium reduction
capabilities. These live microorganisms assembled in the Applied Biosciences' BSeR™
selenium bioprocess serve as a baseline for selenium reduction and removal. The high
selenium tolerance and selenium reducing capabilities of these microorganisms were the basis
for initial testing of the enzymatic selenium reduction process.
Enzyme technologies are revolutionizing all biotechnology disciplines. Enzyme technologies
are commonplace in the pharmaceutical industry, medical and environmental diagnostics, and
are found in household products such as laundry detergent and degreasing products. In the
area of pollution control, various enzyme technologies have been demonstrated. In water
treatment, enzymatic contaminant removal is considered an emerging technology, potentially
applicable to waste and drinking water treatment. For removal of selenium from waters,
Applied Biosciences has demonstrated that cell free extracts have been able to reduce and
remove selenium from various mining waters at the bench scale.
E4
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Proprietary enzyme technologies for contaminant removal have been demonstrated, by
Applied Biosciences at bench scale. The prototype enzymatic selenium reduction system
functioned equally well in both synthetic and actual mining wastewaters. The potential of
enzymatic selenium reduction is based on proprietary enzyme extraction/purification methods
combined with unique immobilization/encapsulation techniques that keep the selenium
reducing enzyme(s) in a functional arrangement within an immobilization matrix. Enzyme
extraction methods and immobilization matrices require improvement to make a pilot-scale
evaluation of enzymatic selenium reduction system practical.
Materials and Methods
General
Enzyme preparations were produced from selenium-reducing microorganisms by lysing
bacterial cells in a bead-mill type cell homogenizer, extracting/purifying specific cellular
fractions and subsequently immobilizing the preparation in several different
immobilization/encapsulation matrices. Preparations immobilized in a standard calcium
alginate polymer were formed into beads for base line tests and comparisons.
Microbes
Microbes were screened to select microorganisms with the greatest potential for selenium
reduction and would therefore be good candidates for enzyme sources. Microbial strains were
collected from sites with a long history of selenium contamination. Select Pseudomonas and
Alcaligenes sp. were used for the selenium-reducing immobilized enzyme preparations.
These strains have unique selenium-reducing characteristics and have been utilized in
selenium removal systems at bench, pilot, and full scale in the BSeR™ process.
Controls
Comparative tests with biofilms, immobilized live cells, and immobilized enzymes used controls
consisting of support materials without biofilms and immobilized heat-inactivated cells or
enzymes. Immobilized live cells and enzyme preparations used the same starting live
microbial cell concentrations.
Endpoint selenium reduction assays
Endpoint selenium reduction assays were utilized as a screening tool to assess selected
microbial strains, enzyme preparations, and immobilization supports for selenium reduction
capabilities. The test water used for the screening series consisted of collected Kennecott
Utah Copper Corporation (KUCC) water, unspiked, and spiked to a concentration of 50 or 100
mg/L Se. For the microbial screening, log-phase cultures were prepared in Trypticase Soy
Broth (TSB). Cultures were washed and re-suspended in sterile saline. 15-ml culture tubes
containing test water were inoculated with log phase suspended cultures, at a concentration
of 2 x 108 cells per ml. Sterile saline served as the abiotic control.
The tubes were incubated at 22° C for 24 hours, and periodically assayed for selenium
reduction. Relative selenium reduction was determined by the formation of a red amorphous
selenium precipitate. For enzyme extracttesting, cell free extracts were immobilized in calcium
alginate beads, or other polymers listed in Table 2. Beads containing one ml of enzyme extract
E5
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were tested as described above. Control tubes containing blank beads were prepared using
sterile saline. All testing was done with actual site waters.
Cell-free Extract Preparation
In general, cell free extracts were prepared using a bead mill containing 0.2 mm beads in
disruption buffer (HEPES buffered saline, pH 7.5). Non-disrupted cells and cell debris were
removed using low speed centrifugation (1000xg, 20 min). Controls on all enzyme test
materials included two tests: (1) direct microscopic examination of the enzyme preparation for
live cells and (2) plating 1.0 ml of enzyme preparation on trypticase soy agar (ISA). Initially,
an additional control sample was plated, 1.0 ml of a 10-fold concentration of the enzyme
preparation, with no observable live cells on ISA. Data from the enzyme preparations were
not used if any live microorganisms were present.
Immobilization Testing
Various immobilization schemes were screened, tested, and compared in the laboratory,
including: Alginic acid, high viscosity (Sigma #A7003); Alginic Acid, low viscosity (Sigma
#A2158); Bulk Sodium Alginate (WEGO Chemical Corp.); Agarose (BBL#11849); Carrageen
Type I (Sigma C1013; Carrageen, Type II (Sigma C1138); Polyacrlyamide; polysulfone;
nitrocelluose membrane (SpectraPor #132680); and granular activated carbon.
For testing a prototype enzyme system, alginic acid as calcium alginate was selected as the
best initial encapsulation polymer. Low viscosity calcium alginate was selected because it
stabilized the enzyme preparation more than other matrix materials, ease of handling during
matrix preparation, negligible toxicity, cost, and observed stability in KUCC test water.
Strains demonstrating the highest selenium reduction capabilities from the microbial screening
were selected for preparation of enzyme extracts and additional screening. Extracts
immobilized in calcium alginate were tested individually, and then as a mixture using the
described endpoint selenium reduction assay. A control using empty immobilized matrix
material was also tested. Heat inactivated (denatured) extracts (80°C for 15 minutes), were
utilized as a negative (dead enzyme) control.
Results
Microbial Screening
Multiple microbial isolates, including the microbes used in the BSeR™ process, were tested
for their ability to reduce selenium in spiked (to 50 mg/L Se) and un-spiked synthetic and
actual KUCC waters, Figure 1. Strains were selected based on their original source of
isolation (high selenium containing mining and industrial process waters) and their ability to
perform a reduction on other oxyanionic contaminants such as selenate All isolates tested are
naturally occurring, non-pathogenic facultative anaerobes. Some of the isolates tested for
selenium reduction are shown in Table 1.
E6
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Microbe
C1-la
(53)9-26
C1-lb
A-27
P. stuzeri 1
R.C. Large
SF123
SF077
KSOOSa
KS004d
C. flavis
P. putida
KS006A
Microbial
Se Red. In
synthetic
water
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
Microbial
Se Red. in
KUCC test
water
+++
+++
+++
+++
++
++
+
+++
++
+++
+
+
++
Enzymatic
Se Red. (cell-
free prep)
+++
++
+++
++
+
+
ND
0
0
*
ND
*
0
Table 1. Microbial Screening. Selenium reducing strains were initially screened for selenium
reduction in synthetic waters, and then actual KUCC test water. Cell free preps for the strains
that scored ++or higher were prepared and evaluated. The top 4 cell free preps (scoring +++)
were selected for use in additional evaluations.
Enzyme preparation testing
Top performing microbial cultures (C1-la, (53)9-26, C1-lb, and A-27) from the microbial
screening were utilized as a source material for enzyme preparation, and as cultures for the
live microbial biofilm reactors. Cell-free extracts were screened in an immobilized form in
calcium alginate beads. Controls included denatured enzyme preparations, immobilized live
microbial cells and immobilization polymers. The live microbial controls contained the same
number of cells used to prepare the enzyme extracts so that a direct comparison could be
made. Results of the screening are detailed in Figures 2 and 3. The tests were evaluated for
and screened for the formation of elemental selenium over a 2 month period. With the
optimized preparations, the enzymatic preparations exceeded the initial selenium reducing
activity of the live cell beads.
However, a loss in stability was observed in the cell-free preparations that was not observed
in the living system. This loss in stability contributed to variation between cell free preps of
the same origin and unpredictable operational longevity of the system, Figure 4.
Immobilization Support Testing
Granular activated carbon support material performed the best for a live microbial system, and
was utilized for reactor testing. Based on the testing and evaluation of various other supports,
bulk sodium alginate was selected as the best immobilization material for the enzyme system.
Sodium alginate was cross-linked with Ca3+ to form the calcium alginate matrix. Calcium
alginate was selected as an encapsulation polymer for due to function of the immobilized
E7
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reduction system, ease of handling during matrix preparation, low toxicity, cost, and observed
stability. As a microbial support, the calcium alginate beads have been demonstrated to
remain intact for periods greater than two years, without loss of microbial function or support
structural breakdown. The support materials are ranked in Table 2.
Table 2. Immobilization Materials
Support Material
Alginic Acid, low
viscosity
Alginic Acid, high
viscosity
Bulk Sodium
Alginate
Agarose
Carrageen
Polyacrylamide
Nitrocelluose
membrane
Granular
Activated
Carbon*
r v
Ease of
Handling
4
2
4
4
3
1
1
5
j\j\ i ^- —
Toxicity
Low
Low
Low
Low
Low
High*
Low
Low
Cost
High
High
Low
Med
Low
Med
High
Low
•J \JUUU
Relative
Performance
(Cell Free)
4
4
4
2
1
1
2
N/D
Relative
Performance
(Microbes)
4
4
4
2
1
1
2
5
Overall
Rating
3
3
4
2
2
1
2
5*
* Tested with microbial system only
Electron Donor System Testing
Various electron donor systems tested in the laboratory include cellular components, nutrient
components, and electron-carrying dyes. An electro-bioreactor test system was designed to
provide a constant supply of electrons to the matrix as an attempt to increase the operational
longevity of the system. Test material was prepared for the system by incorporating the
electron-carrying dyes (Azur A and Bromophenol Blue) into an alginate matrix. A bead
preparation without an electron-carrying dye (enzyme extract only) served as a control. The
supplied DC current, with and without the electron carrying dyes did not appear to have an
appreciable effect on enhancement of the longevity of selenium reduction (data not shown).
None of the other tested electron donor systems, including the nutrient components (acetate,
H2 and molasses) increased the operational longevity of the enzymatic matrix.
Reactor Testing
Bench scale testing has demonstrated the proof of concept for use of enzyme technologies
for water treatment. Bench-scale up-flow columns were set up as demonstrated in Figure 5.
Selenium removal from the mining process solutions has been tested using a consortium of
E8
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selenium-reducing bacteria, both as live microbes and as an immobilized enzyme preparation.
The data indicates that the selenium concentration was reduced to approximately the same
levels in both the live immobilized microbe column and the immobilized enzyme column. The
selenium concentrations were lowered from 23.1 mg/L in the feed, to <0.10 mg/L in the
effluent in 9hr, Figure 6. For this testing a 9-hour retention time was used.
A second test series was conducted using immobilized enzymes to determine if cyanide and
selenium could be removed simultaneously from the process solution. Enzyme preparations
used in proprietary cyanide-oxidizing enzyme preparations and the selenium-reducing enzyme
preparations were immobilized separately and combined in a column for testing. Test results,
presented below show that the cyanide level decreased from 102 to <1 mg/L and the selenium
concentration decreased from 31.1 to 1.6 mg/L, Figure 7. Simultaneous removal using live
microbes would not be possible because the cyanide level of -100 mg/L is toxic for the live
selenium-reducing bacteria. An 18-hour retention time was used to allow contaminant diffusion
into the alginate beads.
Enzymatic selenium reduction was compared with an enhanced encapsulated live microbial
biofilm preparation, Figure 8. Stabilized microbial enzyme preparations were able to remove
selenium to or below 0.01 mg/L in a single-pass reactor from a feed solution containing 0.62-
mg/L selenium for over four months. In comparison, the enhanced immobilized biofilm also
reduced selenium in these tests to below 0.01 mg/L for over nine months.
Discussion
Applied Biosciences has demonstrated, at bench scale, a proof-of-concept proprietary enzyme
technology for selenium reduction and removal. The prototype functioned equally well in both
synthetic and various actual wastewaters for limited times. This metal reducing technology is
based on proprietary enzyme extraction/purification methods combined with unique
immobilization/encapsulation techniques that keep the selenium reducing enzyme(s) in a
functional arrangement within an immobilized/encapsulated matrix.
Advantages of cell-free systems over live systems include (1) the potential for greatly
increased kinetics, (2) nutrients are not required, and (3) the effects of toxic process solutions
can be eliminated. Cell-free bioreactors can be engineered to be resistant to microbial
overgrowth and degradation. To construct an enzyme bioreactor, one needs readily available
sources of the stable enzymes. Although several enzymes of microbial origin have been
isolated and characterized, some are membrane-bound and difficultto purify and retain activity
in vitro. Pure enzymatic metal reduction systems are currently cost prohibitive to treat large
water volumes
Because enzymes are biological catalysts, they promote the rate of reactions and are not
themselves consumed in the reactions; they may be used repeatedly for as long as they
remain active. However, in most industrial, analytical, and clinical enzymatic processes,
enzymes are mixed in a solution with substrates and cannot be economically recovered after
the exhaustion of the substrates. This single use approach is obviously quite wasteful when
the cost of enzymes is considered. Thus, there is an incentive to use enzymes in an
E9
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immobilized form so that they may be retained in a bioreactor to catalyze a feed stream. The
use of immobilized enzymes would make it economically feasible to operate an enzymatic
process in a continuous mode.
Numerous methods exist for microbe and enzyme immobilization. These include biofilms,
matrix entrapment, micro-encapsulation, adsorption, and covalent binding. Many entrapment
methods are used today, and all are based on the physical occlusion of live microbes and/or
enzyme molecules within a "caged" gel structure such that the diffusion of active components
to the surrounding medium is severely limited, if not rendered totally impossible. What creates
the "wires" of the cage is the cross-linking of polymers. A highly cross-linked gel has a fine
"wire mesh" structure and can more effectively hold smaller enzymes in its cages. The degree
of cross-linking depends on the condition at which polymerization is carried out. Ideally the
network of cross-linking should be coarse enough so that the passage of substrate and
product molecules in and out of a gel bead is as unhindered as possible.
With any oxidation/reduction reaction, an electron donor or acceptor must be present to
complete the desired contaminant transformation. In a living microbial system, the electrons
are provided as carbon substrates are oxidized. One can anticipate both live microbial and
enzymatic systems to function only as long as a suitable electron donor/acceptor system is
available. Many materials can function at electron donors both for live microbial cells and for
immobilized enzyme systems. These materials include many metal ions, microbial cellular
components, nutrient components, dyes, and direct electric current.
Scale Up Recommendations
Due to the instability or lack or an appropriate electron donor system, of the enzymatic reactor
matrix, enzymatic selenium removal cannot be recommended as an economical process at this
time, nor is it ready to be recommended for pilot-scale testing. The current limitation to the
deployment of an enzymatic selenium reduction system lies in the cost and/or ability to
produce a stable enzymatic reactor matrix.
Purified enzyme preparations of plant origin, are currently commercially available. However,
these plant-based preparations are much too expensive to be applied to water treatment. The
use microbial enzyme preparations are expected to eventually reduce these costs. However,
more work is needed to gain a better understanding of what is occurring in the immobilization
of the enzymes and the linking of electron donors with in any immobilization technique used.
If the enzyme-matrix can be demonstrated to be stable for 6 to 9 months, the process could
possibly be considered as an economical treatment alternative. However, with the current
operational longevity at 3 weeks to just several months, treatment costs become prohibitive.
The enzymatic system still has the potential to operate at higher kinetics and outperform live
microbial systems in many ways. Enzymatic technologies are still in the prototype
development stages, but are viewed by many to have the potential to revolutionize drinking
water and wastewater treatment. .
Conclusions
Based on this laboratory study, the following conclusions can be made:
E10
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Microorganisms are an alternative source for inorganic contaminant reducing enzymes
Selenium reduction in the presence of cyanide is possible using select cell free
preparations
As an encapsulation polymer, calcium alginate performed the best in regards to ease of
handling, toxicity, cost, and performance.
Research to further develop the electron donor system and enhance the operational
longevity of the system is needed to complete prototype development
SELENIUM REDUCTION SCREEN
5
4
3 RB.ATIVE Se
2 REDUCTION
1 1
(f>
DAYS < m 5
Figure 1. Multiple microbial isolates were tested for their ability to reduce
selenium in synthetic and actual mining waters.
Ell
-------
Immobilized Live Cells / Enzyme Comparison
(100 mg/LSe)
Relative Selenium
Reduction
Live Cells
DEnzyme Prep 1
DDenatured Enzyme
DEnzyme Prep 2
Evaluations
Figures 2 and 3. Enhanced selenium removal was observed in cell free
preparations when compared to a live microbial system. Testing used actual
KUCC mining water spiked to 50 and 100 mg/L Se.
Immobilized Live Cells / Enzyme Comparison
(50 mg/L Se)
Relative Selenium
Removal
DEnzyme Prep 1
DDenatured Enzyme
DEnzyme Prep 2
Evaluations
Figure 3. (See caption in Figure 2).
E12
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Stability of Cell-Free Preparations
Age of Prep
Figure 4. Multiple preparations were tested for stability over time. Preps
were allocated and placed into selenium containing water at 1 week intervals.
By the forth week, all preps had lost selenium reducing capabilities.
Figure 5. Bench scale reactor test apparatus.
E13
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Enhanced Biofilm - Immobilized Enzyme Comparison
Feed
Control
Microbes
Enzymes
Figure 6. Enhanced Biofilm and Immobilized Enzyme Comparison
Mine Waste Water, pH 10.6
Retention Time
18 hours
100 —
"Si
75 E
I J s_
E
3
50
25
C
-------
Selenium (mg/L)
1.2
Enzyme • Biofilm Comparison
(Wastewater at pH 7.9)
8 21 35
83 97 111 127 141
54 68
Days
Wastewater"C-Control QC-Biofilm
Enzyme a Enzyme Control
Figure 8. Proof-of concept reactor testing compares enzymatic selenium
reduction to live microbial systems.
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