EPA/600/R-12/05 | December 2012 | www.epa.gov/ord
United States
Environmental Protection
Agency
Technology Evaluation Report
s::can Measuring Systems
Spectro::lyser
ii
Office of Research and Development
National Homeland Security Research Center
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Technology Evaluation Report
s::can Measuring Systems
Spectro::lyser™
U.S. Environmental Protection Agency
Cincinnati, OH 45268
11
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Contents
Disclaimer v
Acknowledgements vii
Abbreviations/Acronyms viii
Executive Summary ix
1.0 Introduction 1
2.0 Technology Description 2
3.0 Experimental Details 4
3.1 Portable Pipe Loop (PPL) and Experimental Conditions 4
3.2 Baseline Conditions 5
3.3 Portable Pipe Loop (PPL) Contaminant Injections 6
3.4 Small Loop Analysis 9
3.5 Contaminant Concentrations 9
4.0 Quality Assurance/Quality Control 12
4.1 Reference Method 12
4.2 Instrument Calibration 12
4.3 Audits 12
5.0 Evaluation Results 15
5.1 Toxic Industrial Chemicals (TICs) in Drinking Water 15
5.2 Results for Biological Contaminants (BCs) in Drinking Water 22
5.3 Small Loop Tests 27
5.4 Additional Evaluation 30
5.5 Operational Characteristics 33
6.0 Performance Summary 35
6.1 Spectrolyser Steady- State Response to Contaminant Injections 35
6.2 Operational Characteristics 37
7.0 References 38
Appendix A 39
Appendix B 43
Figures
Figure 2-1. Spectrolyser 2
Figure 3-1. EPA's portable pipe loop 5
Figure 3-2. First pass and steady-state response to injections of colchicine 8
Figure 5-1. Spectrolyser response to injections of nicotine 16
Figure 5-2. First pass and steady-state response to Toxic Industrial Chemicals in
chlorinated water 21
Figure 5-3. First pass and steady-state response to Toxic Industrial Chemicals in
chloraminated water 21
Figure 5-4. Spectrolyser to injections of Bacillus thuringiensis 23
Figure 5-5. First pass and steady-state responses to Biological Contaminants in
chlorinated water 27
Figure 5-6. First pass and steady-state responses to Biological Contaminants in
chloraminated water 27
in
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Tables
Table ES-1. Response Due to Injection of Toxic Industrial Chemicals into Chlorinated
Water xi
Table ES-2. Response Due to Injection of Toxic Industrial Chemicals into
Chloraminated Water xii
Table ES-3. Response to Biological Contaminants in Chlorinated Water xiii
Table ES-4. Response to Biological Contaminants in Chloraminated Water xiv
Table ES-5. Response to Contaminants in Small Loop Chlorinated Water xv
Table ES-6. Response to Contaminants in Small Loop Chloraminated Water xvi
Table 3-1 Source and Purity of Contaminants 7
Table 3-2. Contaminant List 10
Table 4-1. Summary of Total Organic Carbon Reference Method 12
Table 4-2. Performance Evaluation Audit Results 13
Table 5-1. Response Due to Injection of Toxic Industrial Chemicals into Chlorinated
Water 17
Table 5-2. Response Due to Injection of Toxic Industrial Chemicals into Chloraminated
Water 18
Table 5-3. Response to Biological Contaminants in Chlorinated Water 24
Table 5-4. Response to Biological Contaminants in Chloraminated Water 25
iv
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Disclaimer
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development's National Homeland Security Research Center, funded and managed this
technology evaluation through a blanket purchase agreement under General Services
Administration contract number GS23F0011L-3 with Battelle. This report has been peer
and administratively reviewed and has been approved for publication as an EPA
document, but does not necessarily reflect the Agency's views. Mention of trade names
or commercial products does not constitute endorsement or recommendation for use of a
specific product. EPA does not endorse the purchase or sale of any commercial products
or services.
Questions concerning this document should be addressed to:
Shannon D. Serre, Ph.D.
National Homeland Security Research Center
Office of Research and Development
U.S. Environmental Protection Agency
109 T.W. Alexander Drive, E343-01
Research Triangle Park, NC 27711
919-541-3817
serre.shannon@epa.gov
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with
protecting the nation's air, water, and land resources. Under a mandate of federal
environmental laws, the Agency strives to formulate and implement actions leading to a
compatible balance between human activities and the ability of natural systems to support
and nurture life. To meet this mandate, EPA's Office of Research and Development
(ORD) provides data and science support that can be used to solve environmental
problems and to build the scientific knowledge base needed to manage our ecological
resources wisely, to understand how pollutants affect our health, and to prevent or reduce
environmental risks.
In September 2002, EPA announced the formation of the National Homeland Security
Research Center (NHSRC). The NHSRC is part of the Office of Research and
Development; it manages, coordinates, supports, and conducts a variety of research and
technical assistance efforts. These efforts are designed to provide appropriate, affordable,
effective, and validated technologies and methods for addressing risks posed by
chemical, biological, and radiological terrorist attacks. Research focuses on enhancing
our ability to detect, contain, and decontaminate in the event of such attacks.
NHSRC's team of world renowned scientists and engineers is dedicated to understanding
the terrorist threat, communicating the risks, and mitigating the results of attacks. Guided
by the roadmap set forth in EPA's Strategic Plan for Homeland Security, NHSRC ensures
rapid production and distribution of security-related products.
The NHSRC has created the Technology Testing and Evaluation Program (TTEP) in an
effort to provide reliable information regarding the performance of homeland security
related technologies. TTEP provides independent, quality assured performance
information that is useful to decision makers in purchasing or applying the tested
technologies. It provides potential users with unbiased, third-party information that can
supplement vendor-provided information. Stakeholder involvement ensures that user
needs and perspectives are incorporated into the test design so that useful performance
information is produced for each of the tested technologies. The technology categories of
interest include detection and monitoring, water treatment, air purification,
decontamination, and computer modeling tools for use by those responsible for protecting
buildings, drinking water supplies and infrastructure, and for decontaminating structures
and the outdoor environment.
vi
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Acknowledgements
Contributions of the following individuals and organizations to the development of this
document are gratefully acknowledged.
United States Environmental Protection Agency (EPA)
Mike Henrie
Matthew Magnuson
Jeff Szabo
New York City Department of Environmental Protection
Yves Mikol
Battelle (contract number GS23F0011L-3)
vii
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Abbreviations/Acronyms
BC
biological contaminant
CTOC
calculated total organic carbon
cm
centimeter
EPA
Environmental Protection Agency
L
liter
m
meter
mm
millimeter
m/s
meter per second
mg/L
milligram per liter
NHSRC
National Homeland Security Research Center
PBS
phosphate buffered saline
PE
performance evaluation
PPL
portable pipe loop
ppm
parts per million
QA
quality assurance
QC
quality control
QMP
quality management plan
SCADA
supervisory control and data acquisition
SOP
standard operating procedure
T&E
testing and evaluation
TIC
toxic industrial chemical
TOC
total organic carbon
TSA
technical systems audit
TTEP
Technology Testing and Evaluation Program
UV
ultraviolet
UVS
ultraviolet spectrometer
Hg/L
microgram per liter
viii
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Executive Summary
The U.S. Environmental Protection Agency's (EPA's) National Homeland Security
Research Center, Technology Testing and Evaluation Program, is protecting human
health and the environment from adverse impacts resulting from acts of terror by testing
homeland security technologies. The primary objective of this series of evaluations was
to determine the response of the TOC and UVS analyzers upon the introduction of
contaminants such as toxic industrial chemicals (TICs) and biological contaminants
(BCs) in drinking water. Under the program, the performance of several online total
organic carbon (TOC) analyzers and ultraviolet spectrometers (UVS) were recently
evaluated. In this study, the s::can Measuring Systems Spectro::lyser™ (hereafter
referred to as the Spectrolyser) was tested in conjunction with EPA's portable pipe loop,
which simulates a drinking water distribution system. A total of 14 different
contaminants were injected into both chlorinated and chloraminated water. Relatively
low contaminant concentration levels (0.01 - 10 mg/L) were purposefully chosen for this
evaluation because many of the contaminants pose health risks at the low drinking water
concentrations tested.
The Spectrolyser does not measure TOC, but rather, based on s::can's experience with
analysis of wide range of drinking waters, it uses ultraviolet absorbance to calculate a
value representative of the TOC concentration. Hereafter, these calculated TOC
concentrations will be referred to as "CTOC" concentrations. For the purposes of this
study, a "CTOC response" (change from background) was determined to be a post-
injection change in Spectrolyser readings that was at least three times the standard
deviation of the baseline reading for the five minutes prior to the injection and three times
the standard deviation of the post-injection reading.
Measurements of TOC were made daily using a laboratory reference method. A
comparison to the reference measurements was conducted for the Spectrolyser and an
overall average percent difference is reported. Deployment and operational factors were
also documented and reported.
Spectrolyser Response to Contaminant Injections
Contaminant injections were performed for aldicarb, carbofuran, colchicine, diesel fuel,
disulfoton, mevinphos, nicotine, potassium cyanide, sodium fluoroacetate, Bacillus
globigii (a surrogate for Bacillus anthracis), Bacillus thuringiensis (a surrogate for
Bacillus anthracis), Chlorella, ovalbumin (a surrogate for ricin), and ricin. The
contaminant injection solutions were prepared within 24 hours (most within 8 hours) in
the same water that was within the portable pipe loop. Since this water contained
disinfectants it could cause degradation or transformation of the injected contaminants
prior to injection. The change in CTOC concentration is reported for each individual
injection that was performed. The summary below indicates what contaminants were
IX
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detectable by the Spectrolyser. In parentheses next to the indication is the number of
injections out of the total injections (usually three) that the contaminant was detectable.
Spectrolyser responses for TICs were similar in chlorinated and chloraminated water as
shown in Figures ES-1 and ES-2. Four TIC concentrations were tested: 0.01, 0.1, 1.0
and 10.0 mg/L. However, only the lowest detected concentrations (i.e., in 2/3 or 3/3
injections) are summarized here; where higher concentrations were tested, all injections
(3/3) produced CTOC responses. Injections of 0.01 mg/L of colchicine (2/3, chlorinated
and chloraminated) produced CTOC responses. Injections of 0.1 mg/L of aldicarb (3/3,
chlorinated; 2/3 chloraminated) and mevinphos (3/3, both waters) produced CTOC
responses. Injections of 1.0 mg/L of carbofuran (2/3, chlorinated;3/3 chloraminated) and
nicotine (3/3, both waters) produced CTOC responses. Injections of 10 mg/L of sodium
fluoroacetate (3/3, chlorinated; 2/3, chloraminated) produced CTOC responses. However,
injections of 10 mg/L of potassium cyanide produced a CTOC response in chlorinated
water (3/3) but none in chloraminated water.
x
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Table ES-1. Response Due to Injection of Toxic Industrial Chemicals into
Chlorinated Water
Contaminant
Injected
Cone.
(mg/L)
Average
Reference
Method
ATOC
(mg/L)
Injection
1
Injection
2
Injection
3
ACTOC
(mg/L)
ACTOC
(mg/L)
ACTOC
(mg/L)
Aldicarb
0.01
-0.05
0.00
0.00
0.00
0.1
0.08
0 (>2
0 o2
II III
1
0.46
u 24
u 2<>
i) 25
Carbofuran
0.01
-0.03
-0.01
0.00
0.00
0.1
0.04
-0.01
0.00
0.00
1
0.52
0 01
i] Hi
ii o2
10
4.05
u i:
0 |o
0 2<>
Colchicine
0.01
0.02
0 01
mi!
ii u|
0.1
0.07
u 15
u 1"
ii l<>
1
0.66
1 (iS
1 "(i
1 "1
10
8.02
in;i\
m;i\
ma\
Mevinphos
0.01
-0.01
I) DO
(i on
ii nil
0.1
0.04
0 o2
ii u2
ii o2
1
0.36
i) |'i
ii |'j
0 18
Nicotine
0.01
0.06
ii mi
ii u|
0.1
0.03
I) DO
ii u|
ii 02
1
0.67
I) 'O
ii 28
ii ^1
10
7.01
1 si
1 <>2
1 ""
Potassium
Cyanide
0.01
0.03
-0.01
-0.02
-0.01
0.1
0.02
-0.01
-0.01
-0.01
1
0.02
-( ) 0 1
-0 i i i
-0 i i i
10
0.34
III)'
ii u2
ii u|
Sodium
Fluoroacetate
0.01
0.02
-0.01
0.00
0.00
0.1
0.01
0.00
0.00
0.00
1
0.25
I) DO
ii mi
II III)
10
1.98
I) I) |
ii u|
II III
Water
Controls
None
0.01
0.00
0.00
0.00
0.00
0.00
0.00#
CTOC responses (indicated by shading) was at least three times the baseline standard deviation,
f max =change in CTOC resulted in a measured CTOC concentration greater than the upper range of the Spectrolyser.
* Only two replicates of the 0.01 mg/L nicotine injections were performed.
# Average of water controls.
XI
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Table ES-2. Response Due to Injection of Toxic Industrial Chemicals into
Chloraminated Water
Contaminant
Injected
Cone.
(mg/L)
Average
Reference
Method
ATOC
(mg/L)
Injection
1
Injection
2
Injection
3
ACTOC
(mg/L)
ACTOC
(mg/L)
ACTOC
(mg/L)
Aldicarb
0.01
-0.04
0.00
0.00
0.00
0.1
(I 15
o o2
o o |
o o2
1
o V)
0 21
0 21
0 21
Carbofuran
0.01
0.11
0.00
0.00
0.00
0.1
0.03
0.00
0.01
0.00
1
o (. i
o o2
0 0"
o o2
10
4 SS
o r
0 l<>
o IS
Colchicine
0.01
-o 02
o o |
O 0 |
o o2
0.1
I) OS
O l(>
0 l<>
o r
1
O 0
1 "O
10
(.41
m;i\
m;i\
in;i\
Mevinphos
0.01
() () |
O 00
O 00
O 00
0.1
o 05
o o2
o o2
o o2
1
O 1(1
o IS
o IS
O |'J
Nicotine
0.01
0.03
0.00
0.01
0.00
0.1
0.08
0.01
0.04
0.01
1
o (iS
o r
o I1)
o IS
10
(i X(i
1 (."!
1 "4
1 ~'J
Potassium
Cyanide
0.01
0.02
0.00
-0.01
0.00
0.1
0.01
-0.02
-0.02
-0.02
1
o o;
-0.10
-0.11
-0.11
10
O
-0.08
-0.09
-0.08
Sodium
Fluoroacetate
0.01
ool
0.00
0.00
0.00
0.1
Dili
0.00
0.00
0.01
1
O 'O
0.00
0.00
-0.02
10
: r
0.00
0.01
o o |
Water
Controls
None
0.01
0.00
0.00
0.00
0.00
0.00
0.00#
CTOC responses (indicated by shading) was at least three times the baseline standard deviation.
t max =change in CTOC resulted in a measured CTOC concentration greater than the upper range of the Spectrolyser.
Spectrolyser responses for the BCs were also similar in chlorinated and chloraminated
water as shown in Figures ES-3 and ES-4. The Spectrolyser detected neither Chlorella
nor Bacillus globigii at any concentration tested in either chlorinated or chloraminated
water. Injections of 107 organism/L of a mixture of spores and vegetative cells of
Bacillus thuringiensis produced a CTOC response in both chlorinated (2/3) and
chloraminated water (1/1). Injections of 105 organism/L of a solution containing only
spores of Bacillus thuringiensis into chloraminated water produced a CTOC response
(2/3). Injections of ovalbumin at 0.01 mg/L and 0.1 mg/L in chloraminated water
produced a CTOC response (1/3, both concentrations), but injections of 1 mg/L and 10
-------
mg/L resulted in CTOC responses for all ovalbumin injections (3/3, both chlorinated and
chloraminated water).
Table ES-3. Response to Biological Contaminants in Chlorinated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Average
Reference
Method
ACTOC
(mg/L)
Injection
1
Injection
2
Injection
3
ACTOC
(mg/L)
ACTOC
(mg/L)
ACTOC
(mg/L)
Bacillus
globigii
105
-0.09
-0.01
-0.01
0.00
106
0.01
0.00
0.00
0.00
107
-0.03
0.00
0.00
0.00
Bacillus
thuringiensis
105
-0.03
-0.01
-0.01
0.00
106
-0.02
0.00
0.02
0.00
107
-0.02
(I 05
0.02
o.o4
Chlorella
103
-0.04
-0.01
-0.01
-0.03
104
-0.04
0.00
-0.01
0.00
105
-0.04
0 00
0.00
0.00
Ovalbumin
0.01
0.01
1) in
O 00
O 00
0.1
0.02
0.0 |
O 0(>
O 00
1
0.09
0 0"
O 0(>
0.0"
10
1.10
0.2"
o 2(i
o 2<>
Water
Controls
None
0.01
0.00
0.00
0.00
0.00
0.00
0.00#
PBS/nutrient
broth
Equivalent to
107 Bacillus
-0.02
-0.01
0.00
0.00
0.00
0.01
-0.01
PBS/Bold
1NV medium
Equivalent to
107 Chlorella
-0.01
-0.01
0.00
0.00
-0.01
0.00
-0.01
CTOC responses (indicated by shading) was at least three times the baseline standard deviation.
# Average and standard deviation of water controls.
Xlll
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Table ES-4. Response to Biological Contaminants in Chloraminated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Average
Reference
Method
ATOC
(mg/L)
Injection
1
Injection
2
Injection
3
ATOC
(mg/L)
ATOC
(mg/L)
ATOC
(mg/L)
Bacillus
globigii
103
-0.01
-0.01
-0.01
0.00
104
-0.03
0.00
0.00
0.00
105
-0.01
0.00
0.00
0.00
107
-0.05
f
f
0.00
Bacillus
thuringiensis
103
-0.03
0.00
0.00
f
104
-0.03
0 00
O 00
f
105
-0.02
o.o4
o.o4
0.00
106
-0.04
f
f
0.00
107
-0.01
f
f
o.o4
Chlorella
103
-0.05
-0.01
0.00
-0.01
104
-0.04
0.00
0.00
0.00
105
-0.02
0.00
0.00
0.02
Ovalbumin
0.01
-0.01
0.00
0.00
0.00
0.1
0.04
0.00
0.00
0.00
1
o
0.0 I
0.0 I
o.o I
10
1 U
o r
o r
o l<>
Water
Controls
None
0.01
0.00
0.00
0.00
0.00
0.00
0.00#
PBS/nutrient
broth
Equivalent
to 107
Bacillus
-0.02
-0.01
0.00
0.00
0.00
0.01
-0.01
PBS/Bold
1NV medium
Equivalent
to 107
Chlorella
-0.01
-0.01
0.00
0.00
-0.01
0.00
-0.01
CTOC responses (indicated by shading) was at least three times the baseline standard deviation,
f Fewer than three injections performed at this concentration.
# Average and standard deviation of water controls.
Disulfoton, diesel fuel, and ricin were evaluated in a small-loop configuration because
those contaminants were late additions to the evaluation, added at the same time as ricin.
Because ricin required an experimental setup in a biosafety hood, these contaminants
were evaluated using the same experimental setup. A summary of the small loop results
is shown in Figures ES-5 and ES-6. All were tested at 0.1 and 1.0 mg/L; diesel fuel and
ricin were also tested at 10 mg/L. Disulfoton was detected at 0.1 mg/L (3/3) and 1 mg/L
(3/3) in chlorinated water while in chloraminated water, there was no CTOC response to
disulfoton. Ricin was detected at 1 mg/L (3/3) and 10 mg/L (3/3) in chlorinated water.
There was a response to ricin in chlorinated water, however, the sodium azide phosphate
buffer blank samples were also detectable; however, each of these responses were much
larger than the response from the sodium azide phosphate buffer blank made at
equivalent concentrations. Therefore, for all but one injection (10 mg/L) into
xiv
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chloraminated water, the response due to the ricin samples did not exceed three times the
response of the blank, causing them to be considered non-detectable.
Although diesel fuel is not soluble, diesel fuel was added to water and analyzed using the
Spectrolyser. Diesel fuel was not detectable at any concentration in chlorinated water.
For all concentrations, diesel fuel produced small but detectable CTOC responses in
chloraminated water. Carbofuran was also evaluated in the small loop configuration.
Carbofuran was detectable at 0.1 mg/L (3/3), but not at 1 mg/1 in chlorinated water.
Carbofuran was detected at 0.1 mg/1 (2/3) and 1 mg/L in chloraminated water (3/3). In
addition to these measurements, limited experiments were performed to examine the
effect of elevated TOC, ionic strength, and monochloramine concentrations on the
Spectrolyser measurements.
Table ES-5. Response to Contaminants in Small Loop Chlorinated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Injection
1
Injection
2
Injection
3
ACTOC
(mg/L)
ACTOC
(mg/L)
ACTOC
(mg/L)
Carbofuran
0.1
0.02
(i.(i2
0.02
1
-0.01
0.00
0.00
Diesel fuel
0.1
-0.05
-0.05
-0.05
1
-0.09
-0.09
-0.09
10
-0.03
-0.04
-0.06
Disulfoton
0.1
0.09
i) 1 1
0 |(l
1
n 14
(i IS
o 20
Ricin
0.1
-0.01
-i) i) I
-i 1111
1
0.05
0 04
0 0.;
10
0.47
()43
o
Sodium azide
(ricin blank)
0.1
0.00
f
1
( i on
10
o i>5
CTOC Responses (indicated by shading) must be at least the baseline standard deviation,
f One set of blank replicate samples were analyzed.
xv
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Table ES-6. Response to Contaminants in Small Loop Chloraminated Water
Contaminant
Injected
Cone.
Injection
1
Injection
2
Injection
3
(organism/L
ACTOC
ACTOC
ACTOC
or mg/L)
(mg/L)
(mg/L)
(mg/L)
Carbofuran
0.1
i) 03
(i.(i2
-i) i) I
1
0.04
i) 03
o.o2
0.1
0.06
i) i)4
(i (13
Diesel fuel
1
0.06
0.05
o o4
10
0.08
o o7
0 Oh
Disulfoton
0.1
0.00
-0.01
-0.01
1
-0.01
-0.02
-0.02
0.1
0.01
0.01
0.00
Ricin
1
0.04
0.04
0.03
10
D.30
0.26
0.23
Sodium azide
0.1
0.01
1
0.02
f
(ricin blank)
10
0.10
CTOC responses (indicated by shading) must be at least three times the baseline standard
deviation.
f One set of blank replicate samples were analyzed.
The Spectrolyser detected most of the TICs of interest at the higher concentration levels
in both chlorinated and chloraminated water. The response with BCs was limited to a
few compounds. Because the Spectrolyser was able to make measurements
approximately every 30 seconds, the change in contaminant concentration during mixing
of the pipe loop was able to be observed. For example, the initial injection of each
contaminant caused a highly concentrated slug of contaminant to pass by the Spectrolyser
until becoming well-mixed in the portable pipe loop. Results show the capability of the
Spectrolyser to monitor such changing concentrations that could occur as the result of a
contamination event or as the result of an operational event.
Operational Characteristics
Installation and operation of the Spectrolyser were straight forward with no routine
maintenance required. Operation of the Spectrolyser software was intuitive and the data
files were easily downloaded as comma delimited text files and convenient for transfer
into a spreadsheet. This evaluation did not consider other possible data retrieval methods
(e.g., SCAD A) that could be utilized with the Spectrolyser.
xvi
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1.0 Introduction
The U.S. Environmental Protection Agency's National Homeland Security Research
Center (NHSRC) is protecting human health and the environment from adverse impacts
resulting from intentional acts of terror. With an emphasis on decontamination and
consequence management, water infrastructure protection, and threat and consequence
assessment, NHRSC is developing tools that will detect the intentional introduction of
chemical or biological contaminants in buildings or water systems, and will provide
information needed for the containment of these contaminants, the decontamination of
buildings and/or water systems, and the disposal of material resulting from clean-ups.
NHSRC's Technology Testing and Evaluation Program (TTEP) works in partnership
with recognized testing organizations; with stakeholder groups consisting of buyers and
users of homeland security technologies and with the participation of individual
technology developers in carrying out performance testing such technologies. The
program evaluates the performance of innovative homeland security technologies by
developing evaluation plans that are responsive to the needs of stakeholders, by
conducting tests, by collecting and analyzing data, and by preparing peer-reviewed
reports. All evaluations are conducted in accordance with rigorous quality assurance
(QA) protocols to ensure that data of known and high quality are generated and that the
results are defensible. TTEP provides high-quality information that is useful to decision
makers in purchasing or applying the evaluated technologies. It provides potential users
with unbiased, third-party information that can supplement vendor-provided information.
Stakeholder involvement ensures that user needs and perspectives are incorporated into
the evaluation design so that useful performance information is produced for each of the
evaluated technologies.
Under TTEP, the performance of the s::can Measuring Systems Spectro::lyser™
(hereafter referred to as the Spectrolyser) was recently evaluated. The primary objective
of this evaluation was to determine the ability of the Spectrolyser to detect changes in
water quality, specifically, ultraviolet (UV) absorbance in response to the introduction of
contaminants in drinking water. Another objective was to document deployment and
operational characteristics. No evaluation of the accuracy of the Spectrolyser was
conducted because the unit measures ultraviolet absorption and calculates a total organic
carbon (TOC) concentration based on an algorithm for wavelength dependant absorption
for a typical mixture of organic compounds. This calculated TOC concentration will
hereafter be referred to as the CTOC. This evaluation was conducted according to a peer-
reviewed test/QA plan that was developed according to the requirements of the quality
management plan (QMP)(1).
1
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2.0 Technology Description
This report provides results for the evaluation of the Spectrolyser. Following is a
description of the Spectrolyser based on information provided by the vendor.
A computer residing within the control box performs data collection and visualization.
The control box is equipped with a touch screen that performs instrument control and
data visualization actions. Data files containing the calculated water quality parameters
as well as the complete spectrum for each measurement are automatically generated and
saved in the instrument memory and can be downloaded using a USB drive. Data files
are saved as comma delimited text.
Figure 2-1 shows the Spectrolyser
connected to the portable pipe
loop (PPL). The Spectrolyser
consists of a flow-through ultra-
violet (UV)/visible spectrometer
with a 100 mm path length as well
as a separate control and data
visualization box. The
Spectrolyser detects the
absorbance at different wave
lengths caused by the measured
medium. These "spectral
fingerprints" are measured in a
range between 200 and 750
nanometers. The Spectrolyser
uses "global calibrations", or
standard spectral algorithms
available for specific conditions of
typical applications (e.g.,
municipal waste water, river
water, drinking water) to calculate
Figure 2-1. Spectrolyser water quality parameters from
those spectral fingerprints. The
CTOC, one of the water quality parameters that the Spectrolyser calculates, was the
measurement parameter used during this evaluation. While not evaluated here, other
calculated water quality parameters that can be reported by the Spectrolyser include
turbidity, nitrate, and dissolved organic carbon. Local calibrations can be performed by
measuring spectral fingerprints and then performing corresponding laboratory analyses to
improve the accuracy of the calculated water quality parameters.
2
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The Spectrolyser can report alarm parameters for indicating deviations from baseline
water quality. These alarm parameters are most sensitive following training on the
specific water matrix being measured. The total cost of the unit ranges from $15,000 to
$30,000 depending on the features that are selected.
3
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3.0 Experimental Details
The primary objective of the series of TTEP evaluations was to determine the capability
of TOC and UVS analyzers to measure changes in TOC level due to the introduction of
contaminants in drinking water. In all, four technologies were evaluated, two TOC
analyzers and two UVS analyzers. Two drinking water matrices were used for all of the
testing conducted in this evaluation: (1) finished drinking water from Columbus, OH
(chlorinated and filtered surface water), and (2) water prepared to simulate water from a
utility that uses chloramination as its primary means of disinfection. Eleven
contaminants were injected using the EPA's PPL and four contaminants were analyzed
using a small loop sampling approach.
The Spectrolyser, a UV based analyzer, evaluation took place between June 3, 2009 and
September 24, 2009. A technical systems audit (TSA) and an audit of data quality were
conducted during the evaluation.
3.1 Portable Pipe Loop (PPL) and Experimental Conditions
This evaluation was conducted using EPA's PPL, which is shown in Figure 3-1. The PPL
consists of: (1) an equipment rack that contains a 78 liter (L) stainless steel mixing tank, a
recirculating pump, a peristaltic pump, and three contaminant injection ports and (2) a
piping rack that contains approximately 29 meters (m) of 7.6 cm diameter stainless steel
pipe (316L grade). The two racks were connected for use during this evaluation. All
four TOC analyzers and UVSs evaluated in the series of studies were connected to the
PPL by one of the eight separate sample ports with 6.35 millimeter (mm) (or one quarter
inch) inner diameter tubing.
The PPL flow was controlled by the variable flow recirculating pump which allowed the
operator to set flow rates from 44 liters per minute (L/min) to 440 (L/min) in the PPL.
For testing, the PPL contained approximately 250 L of water (including the mixing tank
and pipe) with a flow rate of approximately 88 L/min (linear velocity of 0.33 m/s). The
Spectrolyser did not add reagents to the PPL water so water from the Spectrolyser was
collected in a common reservoir and continuously pumped back into the mixing tank
using the peristaltic pump. Flow through the Spectrolyser was maintained between 1 and
1.5 L per minute during the testing.
4
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Figure 3-1. EPA's portable pipe loop
3.2 Baseline Conditions
Prior to the start of daily testing, the PPL was filled with drinking water using a hose
(15.9 mm or 5/8" ID) that connected the laboratory water supply to the mixing tank of the
PPL using a hose-thread to sanitary-fitting coupler. During the chlorinated water testing,
this water was used with no alterations after the free chlorine level was measured using
U.S EPA Method 330.5' Over the course of the evaluation, free chlorine
concentrations in the chlorinated water ranged from 1.0 to 1.6 mg/L with an average of
1.3 mg/L. In addition, the pH of the water was always between 7.4 and 8.1.
The chloraminated test water matrix was prepared by mixing chlorine and ammonia in
the proper ratio to yield approximately 2 mg/L monochloramine, following an EPA
Testing & Evaluation (T&E) Facility standard operating procedure (SOP) for preparation
of chloraminated water. The total chlorine concentration was measured and then chlorine
was added to the PPL to increase the total chlorine concentration to 2 mg/L. The total
chlorine concentration was then measured again to confirm the total chlorine
concentration was within 10% of 2 mg/L. Ammonia was then added to the PPL to form
monochloramine at a concentration of 2 mg/L in the PPL. Prior to the injection of a
contaminant, the monochloramine concentration was confirmed by Hach '! Method
5
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10200(4). Throughout the evaluation, the monochloramine concentrations ranged from
1.8 to 2.3 mg/L with an average of 2.0 mg/L. Once the applicable chlorine measurement
had been completed, a 30 minute baseline measurement was conducted with the
Spectrolyser.
3.3 Portable Pipe Loop (PPL) Contaminant Injections
The toxic industrial chemicals (TICs) and biological contaminants (BCs) were injected
into the PPL as concentrated 250 mL solutions that were prepared within 24 hours of
injection. Solutions of TICs, ovalbumin, and ricin were prepared using the same water
contained in the PPL, either chlorinated or chloraminated. The preparation of
contaminant injection solutions in water containing disinfectants could cause degradation
or transformation of the contaminant. For example, the interaction of the cyanide ion with
chlorinated water may have formed cyanogen chloride which could have continued to
breakdown to the cyanate ion. These reactions are dependent on the dissolution water so
the results presented here should be interpreted carefully and not extrapolated too
broadly. However, the experimental plan was intended to simulate an actual
contamination event during which the use of tap water as the dissolution solvent would
be expected. In addition, even if the contaminant degrades, the degradation products
would likely still be present in the injected solution. Of course, these degradation
products may or may not retain the same UV absorbance characteristics as the original
chemical.
Table 3-1 shows the sources of each TIC and toxin contaminants as well as the purity.
The purities of the TICs varied substantially from 89% to 99%. Information about the
content of the impurities for each contaminant was not available so it is possible that the
impurities included compounds with UV absorbing functional groups. In addition,
aldicarb, carbofuran, and disulfoton were difficult to get into solution and required
heating to encourage them into solution. Heating these solutions could have favored
transformations preventing the stated contaminant (and, instead, transformational
products) from being injected into the PPL. These transformational products might or
might not retain the same UV absorbance characteristics as the original chemical.
Originally, the two Bacillus species were grown in nutrient broth while the Chlorella was
grown in Bold 1NV Medium(5). The final BC cultures were pelleted by centrifugation
and washed in phosphate buffered saline (PBS) three times. The washed pellet cake was
then resuspended in PBS. The BC solution was enumerated by plating the solution and
counting the colonies and injection solutions were prepared by diluting the BC to the
appropriate concentrations in PBS. The concentration of each injection solution was such
that injection of 250 mL of the solution into 250 L of water in the PPL gave the desired
steady-state concentration in the PPL.
6
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Table 3-1 Source and Purity of Contaminants
Contaminant
Supplier
Purity
Aldicarb
Ultra Scientific (North Kingston, RI)
99%
Carbofuran
Sigma-Aldrich (St. Louis, MO)
98%
Colchicine
Sigma-Aldrich (St. Louis, MO)
97%
Diesel
Marathon (Columbus, OH)
Retail-grade (from pump)
Disulfoton
Chem Service (West Chester, PA)
98.7%
Mevinphos
Ultra Scientific (North Kingston, RI)
89.4%
Nicotine
Acros Organics (Geel, Belgium)
98%
Ovalbumin
MP Biomedicals (Solon, OH)
98%
Potassium Cyanide
Sigma-Aldrich (St. Louis, MO)
96%
Ricin
Vector Laboratories (Burlingame, CA)
5 mg/mL (in phosphate buffered
sodium azide)
Sodium Fluoroacetate
Sigma-Aldrich (St. Louis, MO)
99%
Sodium Fluoroacetate
Pfaltz & Bauer (Waterbury, CT)
95%
Upon establishing a steady response in the PPL and collecting a minimum of 30 minutes
of baseline data, a set of single contaminant injections were made into the circulating
water of the PPL. Figure 3-2 shows that with each injection, the response from the
Spectrolyser oscillated until the water within the PPL became well-mixed and a steady-
state contaminant concentration throughout the PPL was reached. As the contaminant
injection solution was introduced into the intake side of the recirculating pump of the
PPL, the initial contaminant "slug" made a first pass through the Spectrolyser. The
contaminant concentration within the slug was higher than the eventual steady-state
contaminant concentration within the PPL. As the contaminant slug flowed throughout
the PPL, it entered the mixing tank, becoming greatly diluted, and then continued to
recirculate until a steady-state concentration was reached within approximately 10
minutes. The time scale for mixing of the PPL in the context of the evaluation
(approximately 10 minutes) and the time scale of the Spectrolyser absorption
measurement (approximately once every 30 seconds) allowed evaluation of the
Spectrolyser with respect to the first pass of a contaminant through the PPL.
Starting with the lowest concentration level for each contaminant, the contaminant
injection solution was pumped into the circulating water of the PPL at a rate that made
the concentration of the contaminant 10 times greater than the eventual steady-state
concentration in the water moving past the Spectrolyser. This injection lasted for 15-20
seconds, which at a flow rate of 88 L/min (linear velocity of 0.33 m/s) corresponds to
approximately a 4.5 m long (-25 L) slug of injected contaminant.
Colchicine was the example contaminant used in Figure 3-2, but colchicine was typical of
the TIC contaminants that were detected by the Spectrolyser. In order to ensure that the
contaminant concentration had reached steady-state, a 20 minute stabilization period was
allowed after a contaminant injection. After this 20 minutes stabilization period, 30
minutes of data were collected at the post-injection steady-state concentration. In
addition to being used to determine the steady-state response for each instrument, the last
5 minutes of this steady-state period were also used as the baseline for the next
7
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5.0
4.5
4.0
m 3.5
E
u
O
ai
N
>
U
ai
a.
i/>
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Mixing Steady-Stat
0.01 mg/L
^ Injection
Mixing Steady-State
i , i
Mixing Steady-State
25
50
0.1 mg/L
Injection
75 100
Time (minutes)
1 mg/L
^ Injection
125
150
175
Figure 3-2. First pass and steady-state response to injections of colchicine.
contaminant injection. The next higher concentration level of contaminant was
introduced using the identical procedure. Therefore, a minimum of 50 minutes of time
passed between contaminant injections.
Each set of contaminant injections with increasing concentration levels (some
contaminants had three concentration levels, some had four concentration levels)
represented one replicate. Three replicate sets of injections were made for each
contaminant. Between the replicate sets of injections, the system was exchanged at least
five times with contaminant-free water (from the laboratory supply). As this
uncontaminated water filled the PPL, the online measurements returned to the original
baseline. Once five water exchanges had been completed (approximately 30 minutes of
water exchange) and the response from each technology steadied so it deviated from the
average by less than 10% over 30 minutes, testing proceeded with the next replicate set of
injections for that contaminant.
The mass transport and mixing properties that occur within the PPL are not thoroughly
understood which is why the focus of this evaluation is on the steady-state concentration
after the PPL becomes well mixed. One might expect that the first pass of the
8
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contaminant slug as well as the successive passes prior to reaching a steady-state
concentration would behave like a simple dilution process. However, a constant ratio
between the first pass response and the steady-state response is not observed. Similar
inconsistent mixing phenomena may or may not occur in an operational water system.
3.4 Small Loop Analysis
Three contaminants (diesel fuel, disulfoton, and ricin) were analyzed by the Spectrolyser
in a small loop configuration rather than injections into the PPL. This experimental
approach was used because ricin must be contained within a biosafety hood preventing
use of the PPL for the ricin injections. Disulfoton was added to the experimental plan
late in the testing through the same test/QA plan amendment as the ricin, so was analyzed
in the same fashion. Diesel fuel was analyzed in the small loop out of concern for
carryover of diesel fuel after injection into the PPL. Carbofuran was analyzed in the
small loop in addition to the PPL so that one contaminant would be analyzed using both
experimental approaches.
Volumes of drinking water ranging from 3 to 7 L (depending on the contaminant) were
contaminated at the desired contaminant concentration. Initially, non-contaminated
chlorinated or chloraminated drinking water was drawn through the Spectrolyser using a
peristaltic pump. When a baseline had been established, the inlet was moved to a sample
container with the lowest concentration water sample. When a new baseline response
was established with that concentration level, the inlet was transferred directly into the
next higher concentration sample and the process repeated until the highest concentration
level for the contaminant was reached. Three replicate sets of small loop analyses were
performed.
For small loop analysis, the 0.01 mg/L concentration was not evaluated. Due to limited
solubility, disulfoton and carbofuran were not analyzed at 10 mg/L in the small loop
configuration. Diesel fuel was not soluble in water and separated upon mixing with
water, but analysis at each concentration was still performed.
3.5 Contaminant Concentrations
Table 3-2 gives the injected contaminants and their corresponding concentrations. TIC
injection concentrations were selected based on previous testing performed at EPA's
Testing and Evaluation (T&E) Facility(2). BC injection concentrations were based on
relevant toxicological data(6) as well as concentrations recommended by TTEP Water
Security Stakeholders.
3.6 Data Analysis
During the evaluation, the Spectrolyser made a transmittance (absorption) measurement
approximately once every 30 seconds. The absorption spectrum generated every 30
9
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seconds was used by the Spectrolyser to internally calculate a CTOC concentration. The
baseline CTOC concentration is defined as the average CTOC concentration over the
Table 3-2. Contaminant List
Type
Agent
Analysis
Method
Concentrations
Medium
TICs
Aldicarb'
PPL
0.01,0.1, 1 (mg/L)
Water
Carbofuran
PPL, small
loop
0.01, 0.1, 1, 10 (mg/L)
Water
Colchicine
PPL
0.01, 0.1, 1, 10 (mg/L)
Water
Cyanide
PPL
0.01, 0.1, 1, 10 (mg/L)
Water
Diesel fuel
small loop
0.1, 1, 10 (mg/L)
Water
Disulfoton
small loop
0.1, 1 (mg/L)
Water
Mevinphos'
PPL
0.01,0.1, 1 (mg/L)
Water
Nicotine
PPL
0.01, 0.1, 1, 10 (mg/L)
Water
Sodium fluoroacetate
PPL
0.01, 0.1, 1, 10 (mg/L)
Water
BCs
Bacillus thuringiensis
(surrogate for Bacillus
anthracis)
PPL
103,104, 105, 106, 107
(spores/L)
PBS and
Nutrient
Broth
Bacillus globigii
(surrogate for Bacillus
anthracis)
PPL
103,104, 105, 106, 107
(spores/L)
PBS and
Nutrient
Broth
Chlorella (surrogate for
Cryptosporidium)
PPL
103, 104, 105 (cells/L)
PBS and Bold
1NV Medium
Toxins
Ovalbumin (surrogate
for botulinum toxin and
ricin)
PPL
0.01, 0.1, 1, 10 (mg/L)
Water
Ricin
small loop
0.1, 1, 10 (mg/L)
Buffered
sodium azide
Controls
Water
PPL
t
Water
PBS/nutrient broth
PPL
%
Water
PBS/Bold 1NV medium
PPL
%
Water
Buffered sodium azide
small loop
%
Water
PBS- phosphate buffered saline
¦f No 10 mg/L injections due to a CTOC response at 1 mg/L and prohibitive cost
} Concentrations (or volumes for water injections) equivalent to those present in contaminant injections
five minute baseline measurement period before each injection. Baseline measurement
periods began 45 minutes after the previous injection. Following a contaminant injection,
the Spectrolyser was considered able to detect a "CTOC response" if the change
(ACTOC) in CTOC, post contaminant injection, was at least three times the standard
deviation of the baseline CTOC concentration prior to the contaminant introduction and
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three times the standard deviation of the post-injection CTOC concentration. When these
conditions were met, the Spectrolyser was defined to exhibit a CTOC response to an
injected contaminant. In order to simplify the wording within this report, hereafter, this
report will refer to this scenario as the Spectrolyser having "responded" to the injection of
a contaminant.
In addition to the injection of the 14 contaminants, control injections of both chlorinated
water and chloraminated water were performed to determine if the act of injecting water
into the PPL caused a response for the Spectrolyser. Water for control injections was
removed from the PPL and then injected back into the PPL within 4 hours. Five such
injections resulted in no detectable CTOC concentrations. Therefore, no additional
injection blank correction was required.
The magnitude of a signal change was calculated and expressed as ACTOC. The signal
change of the Spectrolyser as ACTOC was calculated using Equation 1:
ACTOC = CTOC-CTOCbaselme (1)
where CTOC is the average post-injection CTOC concentration calculated by the
Spectrolyser absorbance measurements; and CTOCbaseiine is the average baseline CTOC
concentration as reported by the Spectrolyser.
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4.0 Quality Assurance/Quality Control
Quality Assurance (QA)/quality control (QC) procedures were performed in accordance
with the program QMP(1) and the test/QA plan for this evaluation.
4.1 Reference Method
EPA Method 415.3(7) was used to analyze reference samples for TOC concentration. The
reference instrument was a Teledyne-Tekmar (Mason, OH) Fusion TOC Analyser™.
Reference samples were collected immediately after contaminant injections as well as
after the contaminant had become well-mixed in the PPL (steady-state). The analysis
method is described in Table 4-1. Because the Spectrolyser does not measure TOC
directly, its results were not compared directly to the reference method.
Table 4-1. Summary of Total Organic Carbon Reference Method
Instrument
Method
Measurement
Detection
Maximum
Principle
Limit
Holding Time
Teledyne-
EPA
UV/persulfate
0.2 |a,g/L
28 days with
Tekmar Fusion
415.36
oxidation
acidification to
TOC
(Standard
pH <2
Analyser™
Method
(Mason, OH)
5310C)
4.2 Instrument Calibration
The Spectrolyser was installed at the testing contractor's facility by a vendor
representative during a one day visit. The Spectrolyser had been calibrated by the vendor
prior to connection to the PPL. The instrument calibration used an algorithm to convert
the absorption spectrum measured by the Spectrolyser to a CTOC concentration using a
theoretical mixture of organic compounds typically found in drinking water.
4.3 Audits
4.3.1 Performance Evaluation (PE) Audit
A PE audit was conducted to assess the accuracy of the TOC reference method. A PE
sample containing 5 mg/L organic carbon as potassium hydrogen phthalate was obtained
(Pharmaceutical Resource Associates [Environmental Resource Associates], Arvada,
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CO) and analyzed. Accuracy of the TOC measurement was expressed in terms of the
percent error (%E), as calculated from the following equation:
%/¦; = d~Cu x i oo (2)
Cr
where CR was the standard or reference concentration of the PE sample and d is the
measurement obtained using the reference method. Ideally, if the reference value and the
measured value are the same, there would be a percent difference of zero percent. Table
4-2 shows that the results of the PE audit was below the maximum allowed %E for TOC.
Table 4-2. Performance Evaluation Audit Results
Reference Sample
Expected Result
Actual
Result
%E
Maximum
Allowed (%E)
TOC (Pharmaceutical Resource
Associates, Arvada, CO)
5.00 mg/L
5.30 mg/L
6.0
20
4.3.2 Technical Systems Audit (TSA)
A TSA was conducted at the Columbus, OH testing location to ensure that the evaluation
was performed in accordance with the test/QA plan and the TTEP QMP.(1) As part of the
audit, the the reference sampling and analysis methods used were reviewed; actual
evaluation procedures were compared with those specified in the test/QA plan; and data
acquisition and handling procedures were reviewed. No adverse findings were noted in
this audit. The records concerning the TSA are permanently stored with the QA Manager.
4.3.3 Amendments/Deviations
One amendment was made to the test/QA plan for this evaluation. To accommodate the
latest needs of EPA's homeland security mission the amendment changed the list of
contaminants to be tested. The amendment removed cesium, as well as the chemical
warfare agents VX, soman, and sarin from the contaminant list and added ricin,
disulfoton, mevinphos, and sodium fluoroacetate to the list of injected contaminants. The
amendment stipulated that sodium fluoroacetate and mevinphos be evaluated in the PPL
and ricin and disulfoton be evaluated as discrete samples, and also changed the tests with
diesel fuel from using the PPL to testing diesel as discrete samples.
Throughout the course of testing, there were a few instances of slight deviation from the
test/QA plan.
• The PE sample for the reference method was not analyzed until after the first tests
were conducted rather than before testing began. The first attempt at the PE audit
was not successful due to the use of PE audit samples that unknowingly contained
chemical constituents that interfered with the reference measurement. However,
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two TOC standards (one provided by the vendor) were measured accurately by
the reference method repeatedly during preparation for the evaluation. Therefore,
the evaluation staff had a high degree of confidence in the accuracy of the
reference method/instrument. Instead of holding up the evaluation, we proceeded
while obtaining interferent-free PE audit samples.
• An alternate test method for monochloramine was used. Rather than using the
difference between total and free chlorine (EPA method 330.5(3)), a test for
monochloramine (Hach Method 10200(4)) was used to determine the
monochloramine level in the water used for the chloraminated tests.
• Injections at 0.01 mg/L were included in the test matrix in addition to the levels
specified in the test/QA plan (0.1, 1, and 10 mg/L) for the TICs. Some of the
participating technologies already tested by TTEP in this series of technology
evaluations were more sensitive than anticipated to the 0.1 mg/L injections. The
injections at 0.01 mg/L were added to better understand the performance of the
analyzers at the low end of their measurement range. In addition, because the 1
mg/L injections of aldicarb and mevinphos were detected by all the technologies
and the injection of 10 mg/L would have been extremely expensive, they were not
performed.
• For the elevated TOC component of the testing, the TOC was elevated by
approximately 1 mg/L rather than 2 mg/L because of the change in background
TOC of the source water on the day of testing.
• Concentration of the BCs were increased to include samples at 106 and 107
organisms/L in order to attempt to identify detectable levels.
• Percent difference was used to compare the reference method with results from
the TOC technologies.
4.3.4 Data Quality Audit
At least 10% of the data acquired during the evaluation were audited. The QA manager
traced the data from the initial acquisition, through reduction and statistical analysis, to
final reporting, to ensure the integrity of the reported results. All calculations performed
on the data undergoing the audit were checked.
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5.0 Evaluation Results
This section presents the results of the evaluation including the ability of the Spectrolyser
to measure changes in contaminant concentrations in response to the injection of TICs
and BCs in drinking water. Also given are the operational characteristics of the
Spectrolyser that were observed during the evaluation.
5.1 Toxic Industrial Chemicals in Drinking Water
5.1.1 Spectrolyser Steady-State Response to Toxic Industrial Chemical Injections
A total of seven TICs were individually injected into the PPL at the concentration levels
given in Table 3-1. As described in Section 3.3, contaminant injections were performed
in sets. Each set consisted of sequential injections of increasing concentration to attain
the target concentrations of contaminants in the PPL. Three sets of injections were
performed for each contaminant. Section 3.6 describes the change in CTOC that was
considered a "CTOC response" due to a contaminant injection. After each set of TIC
injections, the PPL was flushed with uncontaminated drinking water before the next set
of injections was performed. The results presented in this report reflect the scenarios
specific to those defined by the test/QA plan for this evaluation. As discussed in Section
3.3, it is possible that chemical transformations took place during the solution preparation
prior to contaminant injections in the PPL.
Figure 5-1 shows an example of the Spectrolyser CTOC response to one set of injections
of nicotine into chlorinated water. Injections of nicotine are marked on Figure 5-1 with
vertical lines and labeled with the concentration level. The CTOC concentration over the
time period prior to the first injection was used as the baseline CTOC concentration for
the 0.01 mg/L injection. In the set of injections shown, the Spectrolyser did not have a
CTOC response to the 0.01 mg/L injection of nicotine but the Spectrolyser did have a
CTOC response to the 0.1, 1, and 10 mg/L injections of nicotine. The initial response is
due to the first pass concentration of the contaminant while the eventual steady-state
concentration is reached after mixing in the PPL (as discussed in Section 3.3 and shown
in Figure 3-2). It took approximately 2-3 minutes for a contaminant to circulate through
the PPL. Therefore, the Spectrolyser was able to measure these changes because of its
relatively high measurement frequency and rapid response to the dynamic concentration
gradient.
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o 2.0
1 mg/L
0.1 mg/L
0.01 mg/L
Injection
Base in
Injection
Injection
25 50 75 100 125 150 175
Time (minutes)
10 mg/L
^/injection
200 225 250
Figure 5-1. Spectrolyser response to injections of nicotine.
Table 5-1 gives the contaminant injected, the concentration of the injected contaminant
and the average steady-state response for each TIC injection. Also given next to each
average response is the standard deviation that each average response had to exceed in
order to be considered a CTOC response. That standard deviation was the greater of the
standard deviation of the steady-state response in the 30 minutes before the injection or
the 30 minutes after the contaminant became well mixed in the PPL. Those injections
which were determined to produce a CTOC response (as defined previously) measured
by the Spectrolyser are highlighted in gray.
The Spectrolyser measured CTOC response at 0.01 mg/L for two injections of colchicine
and one injection of nicotine, but none of the other TIC injections. The Spectrolyser
responded to all of the 0.1 mg/L injections of aldicarb, colchicine, and mevinphos, and
one of the 0.1 mg/L injections of nicotine. All injections of aldicarb, carbofuran,
colchicine, mevinphos, and nicotine produced a CTOC response from the Spectrolyser at
1 and 10 mg/L with the exception of one 1 mg/L injection of carbofuran. The colchicine
injections at 10 mg/L resulted in CTOC concentrations that were higher than the
maximum concentration that could be measured by the Spectrolyser.
16
-------
Table 5-1. Response Due to Injection of Toxic Industrial Chemicals into
Chlorinated Water
Contaminant
Injected
Cone.
(mg/L)
Average
Reference
Method
ATOC
(mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
Std.
Dev.
ACTOC
(mg/L)
Std.
Dev.
ACTOC
(mg/L)
Std. Dev.
Aldicarb
0.01
-0.05
0.00
0.001
0.00
0.001
0.00
0.001
0.1
0.08
0 (>2
0.003
0 (>2
0.002
(1 III
0.003
1
0.46
u 24
0.009
u 2<>
0.008
o 25
0.009
Carbofuran
0.01
-0.03
-0.01
0.012
0.00
0.002
0.00
0.001
0.1
0.04
-0.01
0.011
0.00
0.004
0.00
0.001
1
0.52
0 01
0.008
i] Hi
0.004
(i (P
0.002
10
4.05
u i:
0.004
0 |o
0.005
() 2<>
0.002
Colchicine
0.01
0.02
0 01
0.002
mi!
(Kill
(i (i |
0.001
0.1
0.07
u 15
0.005
u 1"
11(104
(i l(>
0.002
1
0.66
1 (iS
0.009
1 "(i
(KI05
l."l
0.004
10
8.02
in;i\
0.009
m;i\
(KI05
ni;i\
0.004
Mevinphos
0.01
-0.01
I) DO
0.002
(i on
(1(102
(i on
0.002
0.1
0.04
0 o2
0.001
ii o2
(1(102
ii (P
0.004
1
0.36
i) |'i
0.001
ii |'j
(1(106
0 IS
0.004
Nicotine
0.01
0.06
t
t
0.00
0.002
(i (i |
0.002
0.1
0.03
0.00
0.002
0.01
0.009
(i (P
0.002
1
0.67
I) 'O
0.007
ii :x
0.009
(i.^l
0.008
10
7.01
I Si
0.002
i <>:
0.015
1 ""
0.008
Potassium
Cyanide
0.01
0.03
-0.01
0.002
-0.02
0.003
-0.01
0.002
0.1
0.02
-0.01
0.002
-0.01
0.002
-0.01
0.002
1
0.02
-0.03
0.002
-0.03
0.002
-0.03
0.002
10
0.34
0.03
0.006
0.02
0.008
0.01
0.004
Sodium
Fluoroacetate
0.01
0.02
-0.01
0.003
0.00
0.003
0.00
0.002
0.1
0.01
0.00
0.003
0.00
0.003
0.00
0.002
1
0.25
I) DO
0.003
0.00
0.001
0.00
0.002
10
1 <>X
I) I) |
0.002
0.01
0.002
0.01
0.002
Water
Controls
None
0.01
0.00
0.002
0.00
0.002
0.00
0.001
0.00
0.001
0.00
0.002
0.00#
0.001#
CTOC responses (indicated by shading) was at least three times the baseline standard deviation,
f max =change in CTOC resulted in a measured CTOC concentration greater than the upper range of the Spectrolyser.
* Only two replicates of the 0.01 mg/L nicotine injections were performed.
# Average and standard deviation of water controls.
The Spectrolyser measured very small (less than 0.03 mg/L) CTOC responses to all three
10 mg/L injections of potassium cyanide and sodium fluoroacetate. The injections of
sodium fluoroacetate which produced a response were made with 95% purity rather than
the standard with 99% purity that had been used for the other injections. It is possible
that these very small changes were due to the presence of an impurity and not due to
sodium fluoroacetate. The Spectrolyser measured CTOC responses at or below the levels
measured by the reference instrument for all TICs except for sodium fluoroacetate.
17
-------
Table 5-2 presents the same information for injections made into the chloraminated water
matrix. The only injections which produced a CTOC response at 0.01 mg/L in
chloraminated water were two of the three 0.1 mg/L colchicine injections. The
Spectrolyser measured a CTOC response for two of three injections of aldicarb and for all
of the 0.1 mg/L injections of colchicine and mevinphos.
Aldicarb, carbofuran, colchicine, mevinphos, and nicotine all produced CTOC responses
measured by the Spectrolyser at injected concentrations of 1 mg/L or greater. The
colchicine injections at 10 mg/L resulted in CTOC concentrations that were higher than
Table 5-2. Response Due to Injection of Toxic Industrial Chemicals into
Chloraminated Water
Contaminant
Injected
Cone.
(mg/L)
Average
Reference
Method
ATOC
(mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
Std.
Dev.
ACTOC
(mg/L)
Std.
Dev.
ACTOC
(mg/L)
Std.
Dev.
Aldicarb
0.01
-0.04
0.00
0.002
0.00
0.010
0.00
0.002
0.1
(I 15
o o2
n 002
0.01
0.010
o o2
nno2
1
o
0 21
o 003
0.21
0.003
0 21
o o03
Carbofuran
0.01
o 1 1
o 004
0.00
0.012
O 00
o o02
0.1
O O 1
o 002
0.01
0.007
O 00
o o03
1
O (. i
o o2
o 002
0 0"
0.007
o o2
o o03
10
4 SS
o r
0.005
o l<>
0.009
o IS
o o08
Colchicine
0.01
-uu:
O 0 |
0.002
o o |
0.005
o o2
o o02
0.1
0 OS
O l(>
0.002
o l<>
0.005
o r
o o02
1
0 o
0.004
1 "O
o o03
10
(.41
m;i\
o 003
m;i\
0.004
in;i\
o o03
Mevinphos
0.01
()()|
o 002
O 00
0.002
O 00
o o02
0.1
mis
002
0.002
o o2
0.002
o o2
o o02
1
O 1(1
o IS
0.002
o IS
0.002
i) |'i
o o02
Nicotine
0.01
Dili
0.002
O 0 |
0.010
O 00
o o09
0.1
DOS
ool
0.004
o 04
0.025
0.01
O.U09
1
O (iS
o r
0.006
O I1)
0.031
O IS
0.013
10
(i X(i
1 (."!
0.006
1 "4
0.031
1 -'J
0.013
Potassium
Cyanide
0.01
0.02
0.00
0.003
-0.01
0.002
0.00
0.001
0.1
0.01
-0.02
0.002
-0.02
0.002
-0.02
0.001
1
0.03
-0.10
0.010
-0.11
0.010
-0.11
0.010
10
or
-0.08
0.010
-0.09
0.010
-0.08
0.010
Sodium
Fluoroacetate
0.01
0.01
0.00
0.002
0.00
0.002
0.00
0.007
0.1
0.03
0.00
0.002
0.00
0.002
0.01
0.020
1
O 'O
0.00
0.002
0.00
0.008
-0.02
0.020
10
: r
0.00
0.002
o o |
0.002
o o |
0.002
Water
Controls
None
0.01
0.00
0.002
0.00
0.002
0.00
0.001
0.00
0.001
0.00
0.002
0.00#
0.001#
CTOC responses (indicated by shading) was at least three times the baseline standard deviation.
t max =change in CTOC resulted in a measured CTOC concentration greater than the upper range of the Spectrolyser.
# Average and standard deviation of water controls.
18
-------
the maximum concentration that could be measured by the Spectrolyser. The
Spectrolyser responded minimally to two of the 10 mg/L injections of sodium
fluoroacetate. The Spectrolyser did not respond to any of the potassium cyanide
injections into chloraminated water. Across all the contaminants, the results in
chloraminated water were very similar to those in chlorinated water.
The standard deviation of the CTOC of the background drinking water could be used to
calculate the amount of change that would be required for detection of a contamination
event. For example, if the background CTOC measurements during the time of
observation are precise and therefore, have a low standard deviation, a small change
would be detectable. Conversely, if the background CTOC measurements were
somewhat imprecise during the time of observation and therefore, have a higher standard
deviation, this situation would require a relatively large change in CTOC to for detection
of an injected contaminant. In this instance, the precision is not only dependent on the
instrument, but also on experimental factors having to do with the PPL operation.
However, similar variables can exist in operational settings.
As described in Section 2, the Spectrolyser does not measure TOC directly but the TOC
concentrations reported by the Spectrolyser (referred to as the CTOC values in this
report) are calculated based on the absorption characteristics of the water. The
Spectrolyser comes with a "global calibration" established by the vendor that determines
the concentration of TOC that is reported. This global calibration was used during this
evaluation to report the CTOC values that are present in the data tables and are used to
determine the response to contaminant injection. That is, there was not a local calibration
performed to base the calibration of calculated water quality parameters on the water
being measured. The CTOC concentrations were compared to the reference method TOC
concentrations determined from grab samples collected during steady-state conditions
following contaminant injections. Overall, the average percent deviation (%D) between
the CTOC reported by the Spectrolyser and that reported by the reference method was -
33% ± 6% in chlorinated water and -23% ± 10% in chloraminated water. Therefore, the
Spectrolyser reported CTOC concentrations were generally lower than the reference
results regardless of the water matrix.
The Spectrolyser has alarm functionality, meaning that an algorithm monitors changes in
the shape of four different wavelength ranges of the measured spectrum. Following this
TTEP evaluation, the Spectrolyser vendor trained the alarm parameters of the
Spectrolyser on the spectral data that had been collected during time periods when the
Spectrolyser was connected to flowing water in the PPL, but contaminants were not
present. Then, the Spectrolyser vendor reprocessed the spectral data through the
algorithm that produces the alarm values. Appendix A gives the results of this additional
analysis of the data that was conducted by s::can without oversight by TTEP evaluation
staff.
19
-------
5.1.2 First Pass Response during Toxic Industrial Chemical Testing
In addition to the steady-state responses discussed in Section 5.1.1, first pass responses to
the TIC injections were determined for the Spectrolyser. The first pass response was
defined as the maximum change in the CTOC concentration reported by the Spectrolyser
immediately after contaminant injection. This maximum response typically occurred
within three minutes of the injection for the Spectrolyser. This section describes the
response due to the first pass as well as the steady-state response whereas the previous
section only accounted for the change in steady-state response.
Figure 5-2 and Figure 5-3 show bar graphs of the first pass response for chlorinated and
chloraminated water, respectively. The response due to the steady-state contaminant
concentration is shown as a dark gray bar and above that the response due to the first pass
of the contaminant slug for each concentration level (as described in Section 3.3) is
shown as a lighter bar. Aldicarb and mevinphos were injected at three concentration
levels (0.01, 0.1, and 1 mg/L) and the other TICs were injected at those concentration
levels as well as 10 mg/L. Therefore, aldicarb and mevinphos are shown in both figures
with three bars (with increasing concentration from left to right) and the other TICs with
four bars. For example, the 1 mg/L injection of aldicarb in chlorinated water (shown in
Figure 5-2) is the third bar and represents an average response for the three 1 mg/L
injections.
At least two out of three injections of each concentration level of aldicarb, carbofuran,
colchicine, mevinphos, and nicotine produced CTOC responses measured by the
Spectrolyser during the first pass of the contaminant slug in both chlorinated and
chloraminated water. The only exceptions were the 0.01 mg/L injections of carbofuran
into chlorinated water. All of the injections at 1 and 10 mg/L for colchicine and 10 mg/L
injections for nicotine produced a first pass CTOC concentration that exceeded the
maximum concentration measurable by the Spectrolyser (shown by the bars extending to
the top of the graphs). All of the 10 mg/L injections of potassium cyanide into
chlorinated water produced a first pass response from the Spectrolyser, but none of the 10
mg/L injections into chloraminated water produced a CTOC response. All of the 10
mg/L injections of sodium fluoroacetate produced a very small, but first pass CTOC
response from the Spectrolyser.
20
-------
5.0
4.5
5 4,0
O
w 3.5
£
a 3.0
c
o
s- 2.5
a;
C£L
5 2.0
N
>
X 1.5
a> 1.0
Q-
0.5
0.0
-------
For both the chlorinated and chloraminated water, there were four instances that the first
pass results increased the Spectrolyser response from a small steady-state response of less
than 0.25 mg/L CTOC to close to or more than 1 mg/L. This occurred for injections of 1
mg/L aldicarb, mevinphos, and nicotine and 0.1 mg/L injections of colchicine for both
water matrices. This capability of identifying short-lived events could be important in
deciphering the change in response due to water utility operational changes versus
changes due to the injection of a contaminant. The changes in measured CTOC
concentration for each first pass injection of the TICs are given in Appendix B.
5.2 Results for Biological Contaminants (BCs) in Drinking Water
5.2.1 Steady-State Response to Biological Contaminant Injections
Three BCs and one toxin surrogate were injected into the PPL. These injections were
performed in the same manner as the TIC injections with a concentrated injection
solution injected into the PPL over approximately 15-20 seconds. The same injection and
flush procedures were used and response determination was performed in the same way.
Figure 5-4 shows one set of injections for Bacillus thuringiensis into chlorinated water.
The Spectrolyser did not exhibit a CTOC response (as defined in Section 3.6.1) to the
injections at 105 and 106 organisms/L of Bacillus thuringiensis shown in Figure 5-4, but
did exhibit a CTOC response to the injection at 107 organisms/L.
22
-------
5.0
4.5
4.0
3.5
3.0
<-> 2.5
-------
Table 5-3. Response to Biological Contaminants in Chlorinated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Average
Reference
Method
ACTOC
(mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTO
C
(mg/L)
Std.
Dev.
(mg/L)
Bacillus
globigii
105
-0.09
-0.01
0.001
-0.01
0.002
0.00
0.001
106
0.01
0.00
0.001
0.00
0.002
0.00
0.001
107
-0.03
0.00
0.001
0.00
0.001
0.00
0.001
Bacillus
thuringiensis
105
-0.03
-0.01
0.004
-0.01
0.009
0.00
0.001
106
-0.02
0.00
0.001
0.02
0.027
0.00
0.002
107
-0.02
0.05
0.001
0.02
0.027
0.04
0.002
Chlorella
103
-0.04
-0.01
0.002
-0.01
0.002
-0.03
0.024
104
-0.04
0.00
0.002
-0.01
0.002
0.00
0.011
105
-0.04
0.00
0.002
0.00
0.006
0.00
0.005
Ovalbumin
0.01
0.01
mi'
0.001
0.00
0.004
0.00
0.004
0.1
0.02
II.Ill
0.002
OIK.
0.004
0.00
0.004
1
0.09
mi-
0.002
(1 IK.
0.004
u.tr
0.003
10
l.lu
ll :_
0.006
U.2(>
0.010
U.2(>
0.062
Water
Controls
None
0.01
(MM)
0.002
0.00
0.002
0.00
0.001
0.00
0.001
0.00
0.002
0.00#
0.001#
PBS/nutrient
broth
Equivalent to
107 Bacillus
-0.02
-0.01
0.002
0.00
0.001
0.00
0.002
0.00
0.001
0.01
0.021
-0.01
0.008
PBS/Bold
1NV medium
Equivalent to
107 Chlorella
-0.01
-0.01
0.001
0.00
0.001
0.00
0.001
-0.01
0.002
0.00
0.002
-0.01
0.002
CTOC responses (indicated by shading) was at least three times the baseline standard deviation.
# Average and standard deviation of water controls.
24
-------
Table 5-4. Response to Biological Contaminants in Chloraminated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Average
Reference
Method
ATOC
(mg/L)
Injection 1
Injection 2
Injection 3
ATOC
(mg/L)
Std.f
Dev.
(mg/L)
ATOC
(mg/L)
Std.f
Dev.
(mg/L)
ATOC
(mg/L)
Std.f
Dev.
(mg/L)
Bacillus
globigii
103
-0.01
-0.01
0.004
-0.01
0.006
0.00
0.001
104
-0.03
0.00
0.001
0.00
0.002
0.00
0.002
105
-0.01
0.00
0.001
0.00
0.001
0.00
0.002
107
-0.05
f
f
f
f
0.00
0.002
Bacillus
thuringiensis
103
-0.03
0.00
0.001
0.00
0.002
t
t
104
-0.03
0.00
0.002
0.00
0.002
t
t
105
-0.02
0.04
0.002
0.04
0.003
0.00
0.001
106
-0.04
f
f
f
f
0.00
0.001
107
-0.01
f
f
f
f
0.1)4
0.001
Chlorella
103
-0.05
-0.01
0.014
0.00
0.002
-0.01
0.004
104
-0.04
0.00
0.001
0.00
0.002
0.00
0.002
105
-0.02
0.00
0.001
0.00
0.001
0.02
0.028
Ovalbumin
0.01
-0.01
0.00
0.002
0.00
0.002
0.00
0.006
0.1
0.04
0.00
0.003
0.00
0.002
0.00
0.002
1
0
().()|
0.003
I) I) 1
0.002
II.Ill
0.002
10
1 U
ii. r
0.003
ii r
0.002
II. I<>
0.004
Water
Controls
None
0.01
0.00
0.002
0.00
0.002
0.00
0.001
0.00
0.001
0.00
0.002
0.00#
0.001#
PBS/nutrient
broth
Equivalent
to 107
Bacillus
-0.02
-0.01
0.002
0.00
0.001
0.00
0.002
0.00
0.001
0.01
0.021
-0.01
0.008
PBS/Bold
1NV medium
Equivalent
to 107
Chlorella
-0.01
-0.01
0.001
0.00
0.001
0.00
0.001
-0.01
0.002
0.00
0.002
-0.01
0.002
CTOC responses (indicated by shading) was at least three times the baseline standard deviation,
f Fewer than three injections performed at this concentration.
# Average and standard deviation of water controls.
Table 5-4 presents the response determinations for injection of the BCs and ovalbumin
into chloraminated water. Initial injections of Bacillus globigii were performed at 103,
104, and 105 organisms/L. One injection of 107 organisms/L was included with the final
replicate set of injections. The 105 organism/L injection was made with a stock
consisting of only spores while the 107 organism/L injection that produced a CTOC
response was made with a stock containing a mixture of spores and vegetative cells.
None of the Bacillus globigii or Chlorella injections resulted in a CTOC response
measured by the Spectrolyser. Three injections of Bacillus thuringiensis resulted in a
CTOC response measured by the Spectrolyser, two of three at 105 organisms/L, no
CTOC response to the one injection at 106, and one CTOC response to the one injection
at 107 organisms/L. The Spectrolyser measured a CTOC response to injections of
ovalbumin at 1 and 10 mg/L, but not at 0.01 or 0.1 mg/L.
25
-------
In addition to the injections of BCs, control injections of growth media, without
organisms added, which was handled in the same manner as the stock solutions of the
BCs were injected into the PPL. Triplicate sets of injections of the washed growth media
for both the Bacillus organisms and Chlorella were made into chlorinated and
chloraminated water. Of 12 total injections, only one injection produced a very small
(0.01 mg/L) CTOC response from the Spectrolyser.
5.2.2 First Pass Response during Biological Contaminant Testing
As described in Section 5.1.2 for the TIC injections, first pass response determinations
were also made for BC injections. Therefore, this section describes the response due to
the first pass and steady-state response for BCs whereas the previous section only
accounted for the steady-state response. The change in CTOC due to the steady-state
contaminant concentration in dark gray and the change in CTOC above that due to the
first pass of the contaminant slug for each concentration level (as described in Section
3.3).
1.0
0.9
_ I -I
f # #
/ / * S
/
¦ First pass
¦Steady-state
26
-------
Figure 5-5. First pass and steady-state responses to Biological Contaminants in
chlorinated water.
1.0
0.9
_ 0.8
—i
u"
g 0.7
10
£
-0.6
c
o
8" 0.5
a
g 0.4
_>
£ 0.3
o
O)
EL
" 0.2
0.1
0.0
if
J?
&
,c&
\On
,r
-J L_
¦ First pass
I Steady-state
Figure 5-6. First pass and steady-state responses to Biological Contaminants in
chloraminated water.
The Spectrolyser did not measure a CTOC response to any of the Chlorella injections in
either chlorinated or chloraminated water. The Spectrolyser did measure an extremely
small CTOC response for 107 organism/L injections of Bacillus globigii in chlorinated
water and another extremely small change for two of the 104 organism/L injections of
Bacillus globigii in chloraminated water. The Spectrolyser measured a CTOC response
for the injections of Bacillus thuringiensis into chlorinated water at both 106 and 107
organisms/L. In chloraminated water, the Spectrolyser measured a CTOC response to
one injection of Bacillus thuringiensis at 104 and two at 105 organisms/L for injections
made with the pure spore culture and at 106 and 107 organisms/L for injections made with
the contaminant injection solution that was a mixture of spores and vegetative cells. At
least two out of three concentrations of ovalbumin into chlorinated water produced a
CTOC response by the Spectrolyser. In chloraminated water, the Spectrolyser measured
a CTOC response for the two highest concentration level injections. The changes in
measured TOC concentration for each first pass injection of the TICs are given in
Appendix B.
5.3 Small Loop Tests
As described in Section 3.4, four contaminants, carbofuran, diesel fuel, disulfoton, and
ricin, were evaluated in the small loop configuration. Three replicates of each
concentration level were performed in both chlorinated and chloraminated water.
27
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Because each contaminant solution flowed directly through the Spectrolyser, the
Spectrolyser was never exposed to a first pass slug of higher concentration as was the
case for the PPL injections. Therefore, no first pass response determinations were made
for tests conducted in the small loop configuration.
Table 5-5 and Table 5-6 give the TIC, the concentration of the injected TIC, the
measured change in CTOC concentration, and the standard deviation for each
contaminant concentration level in chlorinated and chloraminated water, respectively.
Those tests that produced a CTOC response by the Spectrolyser are highlighted in gray.
The ricin was stored in the sodium azide phosphate buffer so along with each
measurement of ricin, the sodium azide phosphate buffer was analyzed at the
concentration at which it was present in the ricin solutions. Results of both the ricin tests
and the sodium azide tests are included in both tables Table 5-5 and Table 5-6.
5.3.1 Carbofurans
Carbofuran was analyzed at 0.1 and 1 mg/L in the small loop. No analysis in the small
loop of 10 mg/L carbofuran samples was conducted due to the limited solubility of
carbofuran. During the small loop analyses, the Spectrolyser measured a CTOC response
for three out of three 0.1 mg/L samples in chlorinated water and two of the three 0.1
mg/L samples in chloraminated water. The Spectrolyser measured a very small CTOC
response for the 1 mg/L tests in chloraminated water, but not in chlorinated water.
Table 5-5. Response to Contaminants in Small Loop Chlorinated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
Carbofuran
0.1
(i o2
0.006
(i o:
0.003
(i o2
0.003
1
-ool
0.006
(1 110
0.004
(1 (III
0.003
Diesel fuel
0.1
-0.05
0.002
-0.05
0.002
-0.05
0.001
1
-0.09
0.002
-0.09
0.002
-0.09
0.001
10
-0.03
0.002
-0.04
0.002
-0.06
0.003
Disulfoton
0.1
(i i)ij
0.001
i) 1 1
0.002
i) |0
0.001
1
() 14
0.001
(i IS
0.002
i) 2n
0.001
Ricin
0.1
-i) i) I
0.002
-i) i) I
0.002
-i) i) I
0.002
1
(i (15
0.001
i) i)4
0.002
i) o3
0.002
10
U.47
0.006
()43
0.005
() 3X
0.004
Sodium azide
(ricin blank)
0.1
0.00
0.001
f
1
0.00
0.001
10
(i (15
0.001
CTOC Responses (indicated by shading) must be at least the baseline standard deviation,
f One set of blank replicate samples were analyzed.
28
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Table 5-6. Response to Contaminants in Small Loop Chloraminated Water
Contaminant
Injected
Cone.
(organism/L
or mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
Carbofuran
0.1
i) o3
0.003
(i ()2
0.003
-0.01
0.003
1
ii.(i4
0.003
i) o3
0.003
o o2
0.003
Diesel fuel
0.1
1) (l(i
0.003
oo4
0.003
o o3
0.002
1
(1 ()h
0.002
o o5
0.003
o o4
0.002
10
I) OS
0.004
O.07
0.003
(i (ifi
0.003
Disulfoton
0.1
0.00
0.001
-0.01
0.001
-u.ul
0.001
1
-0.01
0.002
-0.02
0.001
-0.02
0.001
Ricin
0.1
0.01
0.003
0.01
0.003
0.00
0.003
1
0.04
0.003
0.04
0.002
0.03
0.002
10
D.30
0.003
0.26
0.003
0.23
0.005
Sodium azide
(ricin blank)
0.1
0.01
0.003
f
1
0.02
0.003
10
0.10
0.005
CTOC responses (indicated by shading) must be at least three times the baseline standard
deviation.
f One set of blank replicate samples were analyzed.
Carbofuran was also injected into the PPL at 0.1 and 1 mg/L. No injections at 0.1 mg/L
produced CTOC responses, but five out of six injections at 1 mg/L did product CTOC
responses that were all less than 0.04 mg/L, similar to the response in the small loop.
5.3.2 Diesel fuel
Small loop analysis of diesel fuel samples was conducted at 0.1, 1, and 10 mg/L. The
solubility of diesel was such that diesel was not soluble in water at any of the
concentrations evaluated. For each sample, two phases were visible with diesel on top of
water. Prior to each analysis, the samples were mixed, but over the course of the analysis
period the samples began to separate into a distinct diesel (organic) phase and aqueous
phase. The Spectrolyser measured negative CTOCs (opposite direction of change
compared with all other contaminants) for all of the diesel fuel tests in chlorinated water,
and measured a CTOC responses for all diesel fuel tests in chloraminated water. While
the different directions of response is not able to be explained, overall, it is difficult to
make any conclusions about the diesel fuel tests because of its lack of solubility.
5.3.3 Disulfoton
Small loop analysis of disulfoton samples was conducted at 0.1 and 1 mg/L. No small
loop analysis of 10 mg/L disulfoton samples was conducted due to the limited solubility
of disulfoton. The Spectrolyser measured CTOC responses for all of the disulfoton
29
-------
samples in chlorinated water, but did not measure a CTOC response for any of the
disulfoton samples in chloraminated water.
5.3.4 Ricin
Ricin tests were carried out inside a hood in a biological safety level 2 laboratory. Small
loop analysis of ricin samples was conducted at 0.1, 1, and 10 mg/L. The ricin solutions
were prepared from a stock of 5 mg/mL ricin in a sodium azide phosphate buffer
solution. Therefore, the sodium azide phosphate buffer was analyzed at the concentration
at which it was present in the ricin solutions to determine whether the Spectrolyser
measured a CTOC response due to the sodium azide phosphate buffer. The Spectrolyser
measured a CTOC response at 1 and 10 mg/L for ricin samples in chlorinated water.
Each of these responses were much larger than the response from the sodium azide
phosphate buffer blank made at equivalent concentrations. In chloraminated water, ricin
only produced a CTOC response for one injection at 10 mg/L. Most of the ricin
injections caused detectable changes in the baseline, but the corresponding blank samples
also caused a CTOC response in the baseline response. Only the first 10 mg/L injection
caused a change in the baseline that was at least three times the blank, the other changes
were not considered a CTOC response.
5.4 Additional Evaluation
5.4.1 Effect of Elevated Total Organic Carbon Injections on Spectrolyser Response
To determine if the background TOC level had any effect on the ability of the
Spectrolyser to respond to a contaminant injection, a very small component of this
evaluation included the injection of three sets of injections of nicotine at 0.1 and 1 mg/L
into chlorinated water which had been fortified with quinine to raise the background TOC
level. Quinine was added to the PPL to increase the background TOC concentration by
approximately 1 mg/L. Additional experiments would be needed to obtain more
definitive results, but Table 5-7 presents the response from the elevated TOC injections
as well as those from the injections of nicotine at the same levels without elevated
background TOC.
The 0.1 mg/L injections of nicotine at the elevated TOC level were not measured as a
CTOC response by the Spectrolyser. Only one of those injections had been measured as
a CTOC response when the TOC levels were background. For the 1 mg/L nicotine
injections at elevated TOC, the change in measured TOC was about half of what it was
for the background injections, but the CTOC response was still evident.
30
-------
Table 5-7. Steady-State Response in Elevated Total Organic Carbon
Concentrations
Injection 1
Injection 2
Injection 3
Contaminant
Concentration
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
Nicotine
(background
TOC)
0.1
0.00
0.002
0.01
0.009
0 02
0.002
1
1) 3(1
0.007
0 :x
0.009
()3I
0.008
Nicotine
0.1
1) 1)1)
0.006
Hoi
0.010
i) i) I
0.007
(elevated
TOC)
1
() 14
0.008
0 13
0.009
() 13
0.009
CTOC responses (indicated by shading) must be at least three times the baseline standard deviation
5.4.2 Effect of Elevated Ionic Strength on Spectrolyser Response
A second very small component of this evaluation included the injection of three sets of
injections of nicotine at 0.1 and 1 mg/L into chlorinated water which had been fortified
with calcium chloride to increase the calcium cation concentration from approximately
42 mg/L to 126 mg/L. The response from these elevated ionic strength injections was
used to determine if the ionic strength of the water had any effect on the ability of the
Spectrolyser to detect a change in response to a contaminant injection. Grab samples
collected before and after the addition of the calcium chloride were analyzed to confirm
that the calcium chloride addition tripled the background calcium concentration.
Additional experiments would need to be performed to make more definite conclusions,
but Table 5-8 presents the response determinations from the elevated ionic strength
injections as well as those from the injections of nicotine at the same levels at
background ionic strength.
The addition of calcium chloride to increase the background ionic strength did not affect
the response determination of the Spectrolyser at 1 mg/L, but at 0.1 mg/L the
Table 5-8. Steady-State Spectrolyser Response with Elevated Ionic Strength
Contaminant
Concentration
(mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
ACTOC
(mg/L)
Std.
Dev.
(mg/L)
Nicotine
(background
Ionic
Strength)
0.1
0.00
0.002
0.01
0.009
0.02
0.002
1
O. iO
0.007
u.:x
1)009
0 1\
0.008
Nicotine
(Ionic
Strength)
0.1
0 o2
0.002
0 o2
1)002
o o2
0.002
1
0:.
0.008
i) 25
1)007
o 2<>
0.009
CTOC responses (indicated by shading) must be at least three times the baseline standard deviation.
31
-------
Spectrolyser measured a CTOC response for all three injections at elevated background
ionic strength but only one of three injections with background ionic strength.
5.4.3 Effect of Monochloramine Level on Spectrolyser Response
Lastly, a very limited experimental design was included in this evaluation to make a
preliminary determination about whether UVSs could be used to track the level of
chloramines in a water system. However, chloramines chemistry is highly dependent on
variable water conditions so the results here should be interpreted carefully. The
Spectrolyser was used to monitor water with three different concentrations of
monochloramine to determine whether the level of monochloramine had an effect on the
CTOC measurement from the Spectrolyser. Monochloramine levels of 1.92, 5.72, and
7.54 mg/L were prepared in the PPL following the procedure described above. The
Spectrolyser did show an increase in measured CTOC concentration with increasing
monochloramine level.
Table 5-9 presents the Spectrolyser CTOC measurements for the tests conducted at
different monochloramine concentrations. The column at the left of the table shows the
different monochloramine concentrations. The baseline CTOC for the Spectrolyser was
1.54 mg/L at the lowest monochloramine concentration was 1.92 mg/L.
Table 5-9. Change in Spectrolyser Response with Monochloramine Concentrations
Monochlorami
ne
Concentration
(mg/L)
Spectrolyser
CTOC
Spectrolyser
Std. Dev.
Spectrolyser
ACTOC
(mg/L)
(mg/L)
(mg/L)
1.92
1.54
0.002
Baseline
5.72
1.93
0.003
(i
7.54
2.17
0.003
() 24
CTOC responses (indicated by shading) must be at least three times the baseline standard deviation.
When the monochloramine concentrations were raised, the from 1.92 to 5.72 mg/L, the
Spectrolyser did measure a CTOC response. The CTOC increased from 1.54 mg/L to
approximately 1.93 mg/L. At a monochloramine concentration of 7.54 mg/L the CTOC
was 2.17 mg/L. Additional evaluation would have to be performed to determine if the
Spectrolyser could be used to monitor chloramines quantitatively, these results suggest it
may be possibility.
32
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5.5 Operational Characteristics
Operational characteristics of the Spectrolyser for this evaluation are organized into the
following categories:
• Training/Education Material
• Installation
• Operation
• Maintenance/Consumables
• Software/Data Collection.
5.5.1 Training/Educational Material
The training for operation and maintenance of the Spectrolyser was a combination of
vendor-provided, in-person training and printed instructional material. The testing
contractor was trained by an employee of Spectrolyser in the operation of the
Spectrolyser instrument and software. Multiple printed instruction manuals contained
information on installation of the Spectrolyser spectrometer probe and on the user
interface and proper operation of the software.
5.5.2 Installation
Installation of the Spectrolyser consisted of mounting the unit on a stand, and making
plumbing and power connections to the PPL. The Spectrolyser was set up with the
software and a global calibration pre-loaded so the instrument was up and running with
very little effort during installation.
5.5.3 Operation
After the evaluation staff had become familiar with using the Spectrolyser, operation was
straight forward. The Spectrolyser automatically collected data every 30 seconds while
in measurement mode. No calibrations were performed on the Spectrolyser. The
Spectrolyser was operated with minimal maintenance for the duration of the testing. For
the purpose of this evaluation, data files were automatically downloaded daily using an
USB drive. In an operation setting, the daily download of data would not be required.
Real time results were available for viewing on the touch screen of the control module.
5.5.4 Maintenance/Consumables
No consumables were required for operation of the Spectrolyser. One time during the 56
days of testing the vendor requested the flow cell be disassembled to check the
cleanliness of the windows. This procedure was accomplished in approximately 30
minutes with guidance from the vendor over the phone. No other maintenance was
performed on the Spectrolyser.
33
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5.5.5 Software/Data Collection
The Spectrolyser software allowed data to be visualized in real time on the front panel of
the control module. Results were updated on the screen every 30 seconds. Data files
were downloaded daily using an USB drive. The download procedure was very straight
forward as the unit displayed a prompt once the USB drive was inserted to ask if data
were to be downloaded. The download procedure was initiated by responding yes to this
prompt. Data files were downloaded as comma delimited text. Two files were
downloaded for each time period; one had the measurement results while the other
contained the absorption spectra. The measurement result files were used for all data
analysis for this evaluation.
34
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6.0 Performance Summary
Summary results from evaluation of the Spectrolyser are presented below. Discussion of
the observed performance can be found in Section 5 of this report.
6.1 Spectrolyser Steady- State Response to Contaminant Injections
Contaminant injections were performed for aldicarb, carbofuran, colchicine, diesel fuel,
disulfoton, mevinphos, nicotine, potassium cyanide, sodium fluoroacetate, Bacillus
globigii, Bacillus thuringiensis, Chlorella, ovalbumin, and ricin. The contaminant
injection solutions were prepared within 24 hours (most within 8 hours) in the same water
that was within the PPL. Since this water contained disinfectants it could cause
degradation or transformation of the injected contaminants prior to injection. The change
in CTOC concentration is reported for each individual injection that was performed. The
below summary indicates what contaminants were detectable by the Spectrolyser. In
parentheses next to the indication is the number of injections out of the total injections
(usually three) that the contaminant was detectable.
Spectrolyser responses for TICs were similar in chlorinated and chloraminated water.
Four TIC concentrations were tested: 0.01, 0.1, 1.0 and 10.0 mg/L. However, only the
lowest detected concentrations (i.e., in 2/3 or 3/3 injections) are summarized here; where
higher concentrations were tested, all injections (3/3) produced CTOC responses.
Injections of 0.01 mg/L of colchicine (2/3, chlorinated and chloraminated) produced
CTOC responses. Injections of 0.1 mg/L of aldicarb (3/3, chlorinated; 2/3
chloraminated) and mevinphos (3/3, both waters) produced CTOC responses. Injections
of 1.0 mg/L of carbofuran (2/3, chlorinated;3/3 chloraminated) and nicotine (3/3, both
waters) produced CTOC responses. Injections of 10 mg/L of sodium fluoroacetate (3/3,
chlorinated; 2/3, chloraminated) produced CTOC responses. However, injections of 10
mg/L of potassium cyanide produced a CTOC response in chlorinated water (3/3) but
none in chloraminated water.
Spectrolyser responses for the BCs were also similar in chlorinated and chloraminated
water. The Spectrolyser detected neither Chlorella nor Bacillus globigii at any
concentration tested in either chlorinated or chloraminated water. Injections of 107
organism/L of a mixture of spores and vegetative cells of Bacillus thuringiensis produced
a CTOC response in both chlorinated (2/3) and chloraminated water (1/1). Injections of
105 organism/L of a solution containing only spores of Bacillus thuringiensis into
chloraminated water produced a CTOC response (2/3). Injections of ovalbumin at 0.01
mg/L and 0.1 mg/L in chloraminated water produced a CTOC response (1/3, both
concentrations), but injections of 1 mg/L and 10 mg/L resulted in CTOC responses for all
ovalbumin injections (3/3, both chlorinated and chloraminated water).
Disulfoton, diesel fuel, and ricin were evaluated in a small-loop configuration because
those contaminants were late additions to the evaluation, added at the same time as ricin.
35
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Because ricin required an experimental setup in a biosafety hood, these contaminants
were evaluated using the same experimental setup. All were tested at 0.1 and 1.0 mg/L;
diesel fuel and ricin were also tested at 10 mg/L. Disulfoton was detected at 0.1 mg/L
(3/3) and 1 mg/L (3/3) in chlorinated water while in chloraminated water, there was no
CTOC response to disulfoton. Ricin was detected at 1 mg/L (3/3) and 10 mg/L (3/3) in
chlorinated water. Ricin responded in chlorinated water, however, the sodium azide
phosphate buffer blank samples were also detectable; however, each of these responses
were much larger than the response from the sodium azide phosphate buffer blank made
at equivalent concentrations. Therefore, for all but one injection (10 mg/L) into
chloraminated water, the response due to the ricin samples did not exceed three times the
response of the blank, causing them to be considered non-detectable.
Although diesel fuel is not soluble, diesel fuel was added to water and analyzed using the
Spectrolyser. Diesel fuel was not detectable at any concentration in chlorinated water.
For all concentrations, diesel fuel produced small but detectable CTOC responses in
chloraminated water. Carbofuran was also evaluated in the small loop configuration.
Carbofuran was detectable at 0.1 mg/L (3/3), but not at 1 mg/1 in chlorinated water.
Carbofuran was detected at 0.1 mg/1 (2/3) and 1 mg/L in chloraminated water (3/3). In
addition to these measurements, limited experiments were performed to examine the
effect of elevated TOC, ionic strength, and monochloramine concentrations on the
Spectrolyser measurements.
Spectrolyser responses for the BCs were similar in chlorinated and chloraminated water.
The Spectrolyser detected neither Chlorella nor Bacillus globigii at any concentration
tested in either chlorinated or chloraminated water. The Spectrolyser measured a
significant response upon injection of 107 organism/L of a mixture of spores and
vegetative cells of Bacillus thuringiensis in both chlorinated (2/3) and chloraminated
water (1/1). Injections of 105 organism/L of a contaminant injection solution containing
only spores of Bacillus thuringiensis into chloraminated water produced a significant
Spectrolyser response (2/3). For ovalbumin, a protein surrogate for biological toxins, the
Spectrolyser responded to one injection each at 0.01 mg/L (1/3) and 0.1 mg/L (1/3) in
chloraminated water and all injections of 1 mg/L (3/3) and 10 mg/L (3/3) injections in
both water types.
Disulfoton, diesel fuel, and ricin were evaluated in a small-loop configuration because
those contaminants were late additions to the evaluation, added at the same time as ricin.
Because ricin required an experimental setup in a biosafety hood, these contaminants
were evaluated using the same experimental setup. In chlorinated water, disulfoton was
detected at 0.1 mg/L (3/3) and 1 mg/L (3/3), diesel fuel was not detectable at any
concentration level, and ricin was detected at 1 mg/L (3/3) and 10 mg/L (3/3). In
chloraminated water, there was no response to disulfoton. While diesel fuel was not
soluble, diesel fuel was added to water and analyzed using the Spectrolyser producing
small but detectable responses. Ricin responded similarly as in chlorinated water,
however, the sodium azide phosphate buffer blank samples were also detectable.
Therefore, for all but one injection (10 mg/L) into chloraminated water, the response due
36
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to the ricin samples did not exceed three times the response of the blank, causing them to
be considered non detectable. Carbofuran was also evaluated in the small loop
configuration and was detectable in chlorinated water at 0.1 mg/L (3/3) and 1 mg/L (3/3)
in chloraminated water. In addition to these measurements, limited experiments were
performed to examine the effect of elevated TOC, ionic strength, and monochloramine
concentrations on the Spectrolyser measurements.
The Spectrolyser detected most of the TICs of interest at the higher concentration levels
in both chlorinated and chloraminated water. The response with BCs was limited to a
few compounds. Because the Spectrolyser was able to make measurements
approximately every 30 seconds, the change in contaminant concentration during mixing
of the pipe loop was able to be observed. For example, the initial injection of each
contaminant caused a highly concentrated slug of contaminant to pass by the Spectrolyser
until becoming well-mixed in the portable pipe loop. Results show the capability of the
Spectrolyser to monitor such changing concentrations that could occur as the result of a
contamination event or as the result of an operational event.
6.2 Operational Characteristics
Installation and operation of the Spectrolyser were straight forward with minimal routine
maintenance required. Operation of the Spectrolyser software was intuitive and the data
files were easily downloaded as comma delimited text files and convenient for transfer
into a spreadsheet. This evaluation did not consider other possible data retrieval methods
(e.g., SCAD A) that could be utilized with the Spectrolyser.
37
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7.0 References
1. Quality Management Plan for the Technology Testing and Evaluation Program,
Version 3.0, Battelle, Columbus, Ohio, January 2008.
2. Hall, John; Zaffiro, Alan D.; Marx, Randall B.; Kefauver, Paul C., Krishnan, E.
Radha; Haught, Roy C.; Herrmann, Jonathan G., "On-line water quality parameters as
indicators of distribution system contamination," Journal American Water Works
Association (AWWA), 99(l):66-77, January 2007.
3. U.S. EPA, EPA Method 330.5, Chlorine, Total Residual (Spectrophotometric, DPD) in
Methods for Chemical Analysis of Water and Wastes, EPA/600/4-79/020, March 1983.
4. Hach Method 10200, Nitrogen, Free Ammonia and Chloramine (Mono), Indophenol
Method (0-4.50 mg/L CI2 and 0-0.50 mg/L NH3-N) for finished chloraminated
drinking water. April 2004.
5. R.C. Statt and J. A. Zeikus. Utex—the culture collection of algae at the University of
Texas at Austin. J. Phycol. 29: 1-106, 1993.
6. Burrows, W. Dickinson; Renner, Sara E., "Biological warfare agents as threats to
potable water " Environmental Health Perspectives, 107 (12):975-984, December
1999.
7. U.S. EPA, EPA Method 415.3, Determination of Total Organic Carbon and Specific
UV Absorbance at 254 nm in Source Water and Drinking Water, EPA/600/R-05/055,
February 2005.
38
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Appendix A
S::can-generated Alarm Value Responses
Due to Subset of Contaminant Injections
This data was generated by the vendor and was not QA audited by the contractor.
39
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S::can provided the following alarm data which was generated by reprocessing the raw
data files from a subset of the contaminant injections.
The Spectrolyser detects the absorbance at different wave lengths caused by the measured
in a wavelength range between 200 and 750 nm. The Spectrolyser software calculated
various water quality parameters from the absorbance of specific ranges of wavelengths
across the available spectrum. These characteristic absorbances are referred to as
"fingerprints". The Spectrolyser comes equipped with a "global calibration" that
includes standard spectral algorithms available for specific conditions of typical
applications (e.g., municipal waste water, river water, drinking water). In the main body
of this report the global calibration results for CTOC was used to demonstrate the
sensitivity of the Spectrolyser to contaminant injections.
The Spectrolyser also has alarm functionality, meaning that an algorithm monitors
changes in the shape of four different wavelength ranges. Following the evaluation,
s::can trained the alarm values of the Spectrolyser on the spectral data that had been
collected during time periods when the Spectrolyser was connected to flowing water in
the PPL, but contaminants were not present. Then, s::can reprocessed the spectral data
through the algorithm that produced the alarm values and provided the data for inclusion
here. Depending on the resulting alarm values, the Spectrolyser generates three different
alarm indicators: OK (no indicator of change in absorbance spectrum), Warning
(preliminary indicator of change in absorbance spectrum), and Alarm (indicator of a
significant deviation in spectral shape and hence in water composition). A properly
calibrated alarm will produce an alarm value between 0 and 1 for non-contaminated
drinking water. The indicators are displayed according to the below specifications.
• OK: between -0.1 and 1.1
• Warning: between -1.0 and -0.1 as well as between 1.1 and 2.0
• Alarm: below -1.0 and above 2.0.
Table A-l and Table A-2 below give the results from the most sensitive of the four alarm
parameters for a subset of the contaminant injections performed during this evaluation.
The rest of the contaminants were not evaluated because the absorption data from the full
range of spectral data was not saved. Most of the lost data was from the time period
when injections were being made into chloraminated water.
40
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Table A-l. Alarm Data (unitless
from Toxic Industrial Chemical (TIC) Injections
Contaminant
Injected
Cone.
fmg/Ll
Injection 1
Injection 2
Injection 3
Value
Indicator
Value
Indicator
Value
Indicator
Aldicarb
0.01
1.3
t
0.65
OK
0.65
OK
0.1
().')
0.25
OK
0.2
OK
1
-2.5
Ahum
-3.8
Alarm
-1.2
Alarm
Carbofuran
0.01
0.68
OK
-0.15
Warning
-0.1
Warning
0.1
0.55
OK
-0.8
Warning
-0.7
Warning
1
-2.8
Alarm
-5.')
Alarm
-5.8
Alarm
10
-20.7
Ahum
-20
Alarm
-1,5.3
Alarm
Colchicine
0.01
0.1.")
OK
0.14
OK
0.1
-2.')
Ahum
-.)
Alarm
-3.1
Ahirm
1
-37.1
Ahum
-3').5
Alarm
-37.')
Alarm
10
-13
Ahirm!!
-13
Alarm!!
-12
Alarm!!
Disulfoton
0.1
().()}{
OK
0.1
OK
0.2 1
OK
1
(MM
OK
0.75
OK
0.73
OK
Disulfoton
(chloraminated)
0.1
0.23
OK
0.5
OK
0.71
OK
1
0.5
OK
0.7
OK
0.95
OK
Diesel
0.1
0.05
OK
0.04
OK
0.02
OK
1
0.38
OK
0.29
OK
0.22
OK
10
0.25
OK
0.21
OK
0.21
OK
Mevinphos
0.1
0.48
OK
0.48
OK
0.51
OK
1
-1.5
Ahirm
-1.15
Alarm
-1.44
Alarm
Mevinphos
(chloraminated)
0.01
().')¦1
OK
0.71
OK
().')»
OK
0.1
0.77
OK
0.50
OK
0.82
OK
1
-1.03
Ahirm
-1.2
Alarm
-1.05
Alarm
Nicotine
0.01
0.50
OK
-0.4
Warning
0.1
0.15
OK
-0.3
Warning
-1.3
Alarm
1
-0.4
Warning
- / .0
Alarm
-8.8
Alarm
10
-8
Ahirm
-50.2
Alarm
-50.')
Alarm
Nicotine (elevated TOC]
0.1
0.73
OK
0.71
OK
0.73
OK
1
-0.8')
Warning
-().')')
Warning
-0.8')
Warning
Nicotine (elevated ionic
strength)
0.1
-0.45
Warning
0.8
OK
-0.28
Warning
1
-0.7
Ahirm
-0.15
Warning
- /
Alarm
Nicotine
(chloraminated)
0.01
0.4
OK
0.05
OK
0.1
-0.2
Warning
-0.12
Warning
.
.
1
-C>. 1
Alarm
-7.15
Alarm
10
-55.3
Alarm
-5<).0
Alarm
Potassium cyanide
0.01
0.11
OK
0.15
OK
0.55
OK
0.1
0
OK
0
OK
0.4
OK
1
-0.8
Warning
-0.75
Warning
-0.48
Warning
10
-0.88
Warning
-0.85
Warning
-0.01
Warning
Sodium fluoroacetate
0.01
0.45
OK
0.45
OK
0.45
OK
41
-------
0.1
0.45
OK
0.45
OK
0.45
OK
1
0.45
OK
0.45
OK
0.45
OK
10
o.r,
OK
0.4.~>
OK
0.1,")
OK
Sodium fluoroacetate
(chloraminated)
0.01
0.35
OK
0.35
OK
0.35
OK
0.1
0.35
OK
0.35
OK
0.35
OK
1
().:¦?.">
OK
0.35
OK
0.35
OK
10
o.
OK
0.35
OK
o.
OK
Shading indicates a CTOC response from TOC as defined in the main body of the report
' Alarm indicator in background water - suspected carry over from previous injection
^Injections not performed at this concentration
* Alarm data not available
Table A-2. Alarm Data (Unitless) from Biological Contaminant (BC) Injections
Contaminant
Injected
Cone.
(org/L or
mg/L)
Injection 1
Injection 2
Injection 3
Value
Indicator
Value
Indicator
Value
Indicator
B. thuringiensis
105
0.67
OK
0.69
OK
0.84
OK
106
0.63
OK
0.64
OK
0.8
OK
107
0.17
OK
0.51
OK
0.78
OK
B. thuringiensis
(chloraminated)
105
0.2
OK
t
t
t
t
106
0.25
OK
t
t
t
t
107
0.18
OK
t
t
t
t
Chlorella
103
t
t
t
t
1.07
OK
104
t
t
t
t
1.05
OK
105
t
t
t
t
1.05
OK
Chlorella (chloraminated)
103
0.27
OK
0.32
OK
0.38
OK
104
0.32
OK
0.36
OK
0.43
OK
105
0.35
OK
0.42
OK
0.46
OK
Ovalbumin
0.01
0.3
OK
0.2
OK
0.1
0.23
OK
0.1
OK
1
-0.2.")
Wnniint>
-OA".
Wnrnin"
10
-I-.3
Alnrm
-1.73
Alnrm
-l..">3
Alnrm
Ricin
0.1
0.6
OK
0..").")
OK
0..", 1
OK
1
0
OK
0.1
OK
0.1.")
OK
10
-2.')
Alnrm
-2..")
Alnrm
-2.1
Alnrm
Sodium azide buffer
0.
0.08
OK
,
,
,
,
1
-0.22
OK
10
-1.2")
Alnrm
Shading indicates a CTOC response from TOC as defined in the main body of the report
' Data not available for analysis
* Alarm indicator in background water - suspected carry over from previous injection
Only one set of injections performed
42
-------
Appendix B
Tables of First Pass Changes in Calculated Total Organic Carbon (CTOC) Due to
Contaminant Injections
43
-------
Table B-l First Pass Calculated Total Organic Carbon (CTOC) Changes in
Response to Injections of Toxic Industrial Chemicals (TICs) in Chlorinated Water
Concentration
(mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
ACTOC
ACTOC
ACTOC
(mg/L)
(mg/L)
(mg/T.)
0.01
0.01
0 01
0 u|
Aldicarb
0.1
I) 1 1
o |n
I) OS
1
0.63
1 04
1 08
0.01
-0.01
I) DO
o o4
Carbofuran
0.1
0.00
I) I) |
o o2
1
0.09
O O"
o.l"
10
0.12
DOS
o 24
0.01
0.08
0 |o
O O"
Colchicine
0.1
0.96
() •)?
II. "4
1
>2.91
2 81
2
10
>0.68
0 l)5
0
0.01
0.01
0 o2
o o |
Mevinphos
0.1
0.07
I) 14
o I I
1
0.75
0.88
1 lo
0.01
NA
o 02
Oll'l
Nicotine
0.1
0.06
o.O'J
0.0"
1
0.60
1 14
O (i i
10
>2.85
2 "'J
2 8"
0.01
0.00
-o.ol
OOi
Potassium
0.1
-0.01
-0.01
0.00
Cyanide
1
-0.03
-mil
0 u|
10
0.02
0 01
O O |
0.01
0.00
0.00
0.00
Sodium
0.1
0.00
0.00
0.00
Fluoroacetate
1
0.00
0.00
0.00
10
0 o5
0 o4
oo5
44
-------
Table B-2 First Pass Total Organic Carbon (TOC) Changes in Response to
Injections of Toxic Industrial Chemicals (TICs) in Chloraminated Water
Contaminant
Concentration
(mg/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
ACTOC
(mg/1.1
ACTOC
fmg/T.)
Aldicarb
0.01
0.01
I) DO
0 u|
0.1
0.10
()()')
u 1 1
1
1.23
1) X<>
u "2
Carbofuran
0.01
0.03
I) DO
1)0'
0.1
0.00
I) (P
o o2
1
u 1 1
II 12
0.08
10
0.15
(I 12
o l<>
Colchicine
0.01
0.09
mi1)
O ()(>
0.1
0.88
0 ss
o 85
1
7?
2 (.'
2 (.8
10
>0.61
O
o l<>
Mevinphos
0.01
0.01
no I
o o|
0.1
0.08
()()')
o I I
1
0.73
u "2
1 n
Nicotine
0.01
0.01
I) ()(>
O 0 |
0.1
0.07
o |o
()()')
1
0.70
u.1) |
O "8
10
>2.90
2 81
1 ()')
Potassium
Cyanide
0.01
-0.01
-0.01
o.o5
0.1
-0.01
-0.01
O ()(>
1
-0.02
-0.03
o.o I
10
-0.04
-0.04
0.00
Sodium
Fluoroacetate
0.01
0.00
0.00
0.00
0.1
0.00
0.00
0.00
1
0.00
0.00
-0.01
10
0.01
0 (>4
o o5
45
-------
Table B-3 First Pass Response to Injections of Biological Contaminants (BCs) in
Chlorinated Water
Contaminant
Concentration
(mg/L or
organisms/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
ACTOC
(mg/L)
ACTOC
(mg/L)
Bacillus
globigii
105
0.00
0.00
0.00
10s
0.00
-0.01
0.00
107
0.02
0 <)2
0 (>2
Bacillus
thuringiensis
105
0.00
0 01
I) DO
106
0.01
mi;
0 o2
107
0.17
1) IS
i) r
Chlorella
103
0.00
0.00
-0.02
104
0.00
0.00
0.00
105
0.00
0.00
0.00
Ovalbumin
0.01
0.02
I) DO
I) I) 1
0.1
0.01
I) I) 1
I) ()(>
1
0.10
I) ()"
I) o"
10
0.77
0.(1 1
u 45
Table B-4 First Pass Response to Injections of Biological Contaminants (BCs) in
Chloraminated Water
Contaminant
Concentration
(mg/L or
organisms/L)
Injection 1
Injection 2
Injection 3
ACTOC
(mg/L)
ACTOC
(mg/L)
ACTOC
(mg/L)
Bacillus
globigii
103
0 00
0 o |
0.00
104
0 0(>
0 0 |
0.00
105
0.00
0.00
0.00
107
t
t
0.00
Bacillus
thuringiensis
103
0.00
-0 01
t
104
0.00
0 0 |
t
105
i) r
o In
0.00
106
t
t
0 u|
107
t
t
i) r
Chlorella
103
0.02
0.00
0.00
104
0.00
0.00
0.00
105
0.00
0.00
0.00
Ovalbumin
0.01
0.00
0.00
0.00
0.1
0.00
0.00
0.00
1
o o5
O 0(1
o 04
10
o U
0 5"
0 5'
T Fewer than three injections performed at this concentration.
46
-------
SEPA
United States
Environmental Protection
Agency
PRESORTED STANDARD
POSTAGE & FEES PAID
EPA
PERMIT NO. G-35
Office of Research and Development (8101R)
Washington, DC 20460
Official Business
Penalty for Private Use
$300
------- |