&EPA
EPA 600/R-10/143 | December 2010 | www.epa.gov/ord
United States
Environmental Protection
Agency
Real Tech, Inc.
Real UV254 Security Monitor
TECHNOLOGY EVALUATION REPORT
Office of Research and Development
National Homeland Security Research Center
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Real Tech, Inc.
Real UV254 Security Monitor
TECHNOLOGY EVALUATION REPORT
Office of Research and Development
National Homeland Security Research Center
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Notice
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. Mention of trade names or commercial
products does not constitute official EPA approval, endorsement, or recommendation for use of a
specific product.
If you have difficulty accessing these PDF documents, please contact Nickel.Kathy@epa.gov or
McCall. Amelia a epa.gov for assistance.
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Acknowledgements
The authors wish to acknowledge Jell Szabo and Matthew Magnuson. U.S. Environmental
Protection Agency's (EPA) National Homeland Security Research Center. (NHSRC), Mike Henrie.
EPA Office of Water, and Yves Mikol, New York City Department of Environmental Protection
for providing reviews of the test/QA (i.e. quality assurance) plan and/or reports pertinent to this
technology evaluation.
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Contents
Notice iii
Acknowledgements iv
Abbreviations/Acronyms ix
Executive Summary xi
1.0 Introduction 1
2.0 Technology Description 3
3.0 Experimental Details 5
3.1 Portable Pipe Loop and Experimental Setup 5
3.2 Baseline Conditions 6
3.3 Portable Pipe Loop (PPL) Contaminant Injections 6
3.4 Small Loop Analysis 8
3.5 Contaminant Concentrations 9
3.6 Data Analysis 10
4.0 Quality Assurance/Quality Control (QA/QC) 11
4.1 Reference Method 11
4.2 Instrument Calibration 11
4.3 Audits 11
4.4 Quality Assurance/Quality Control (QA/QC) Reporting 12
5.0 Evaluation Results 13
5.1 Toxic Industrial Chemicals (TICs) in Drinking Water 13
5.2 Biological Contaminants (BCs) in Drinking Water 19
5.3 Small Loop Tests 24
5.4 Additional Tests 26
5.5 Operational Characteristics 27
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6.0 Performance Summary 29
6.1 Real UV254 Steady-state Response to Contaminant Injections 29
6.2 Operational Characteristics 29
7.0 References 31
Appendix 33
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Figures
Figure 2-1. Real UV254 3
Figure 3-1. EPA's portable pipe loop 5
Figure 3-2. First pass and steady-state response of Real UV254 to injections of nicotine 8
Figure 5-1. Transmittance of Real UV254 in response to injections of carbofuran 14
Figure 5-2. Real UV254 first pass response in addition to steady-state response in
chlorinated water. 18
Figure 5-3. Real UV254 first pass response in addition to steady-state response in
chloraminated water. 19
Figure 5-4. Transmittance of Real UV254 in response to injections of Bacillus thuringiensis 20
Figure 5-5. Real UV254 first pass response to biological contaminants (BCs) in addition to
steady-state response in chlorinated water. 23
Figure 5-6. Real UV254 first pass response to biological contaminants (BCs) in addition to
steady-state response in chloraminated water. 23
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Tables
Tabic 3-1 Source and Purity of Contaminants 7
Tabic 3-2. Contaminant List 9
Tabic 4-1. Summary of Total Organic Carbon (TOC) Reference Method 11
Table 4-2. Performance Evaluation Audit Results 11
Tabic 5-1. Change in Real UV254 Transmittance from Injections of Toxic Industrial Chemicals
(TICs) into Chlorinated Water 15
Tabic 5-2. Change in Real UV254 Transmittance from Injections of Toxic Industrial Chemicals
(TICs) into Chloraminated Water 17
Table 5-3. Change in Real UV254 Transmittance from Injections of Biological Contaminants
(BCs) into Chlorinated Water 21
Tabic 5-4. Change in Real UV254 Transmittance from Injections of Biological Contaminants
(BCs) into Chloraminated Water 22
Tabic 5-5. Response of Real UV254 to Contaminants in Small Loop Chlorinated Water 25
Tabic 5-6. Response of Real UV254 to Contaminants in Small Loop Chloraminated Water 25
Tabic 5-7. Steady-state Response of Real UV254 with Elevated Total Organic Carbon (TOC)
Concentrations 26
Table 5-8. Steady-state Response of Real UV254 with Elevated Ionic Strength 27
Table 5-9. Change in UV254 Response to Varying Monochloraminc Concentrations 27
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Abbreviations/Acronyms
BC
biological contaminant
cm
centimeter
E
error
EPA
U.S. Environmental Protection Agency
L
liter
m
meter
max
the % transmittance at a minimum %T level, truncated
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
OA
quality assurance
QC
quality control
QMP
quality management plan
SCADA
supervisory control and data acquisition
SOP
standard operating procedure
T
transmittance
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
Mg/L
microgram per liter
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Executive Summary
The U.S. Environmental Protection Agency's (EPA's)
National Homeland Security Research Center (NHSRC)
Technology Testing and Evaluation Program (TTEP) is
helping to protect human health and the environment
by carrying out performance tests on homeland security
technologies. Under TTEP, Battelle recently evaluated
the performance of several online total organic carbon
(TOC) analyzers and ultraviolet spectrometers including
the Real UV254 Security Monitor (hereafter referred
to a.s the Real UV254). The primary objective of
this evaluation was to determine the response of the
TOC analyzers and ultraviolet spectrometers upon the
introduction of contaminants such as toxic industrial
chemicals (TICs) and biological contaminants in
drinking water. The other TOC analyzers are covered
in separate reports. This objective was accomplished
by operating the Real UV254 in conjunction with EPA's
portable pipe loop (PPL), which simulates a drinking
water distribution system, and injecting 14 different
contaminants into both chlorinated and chloraminated
water. For the purposes of this study, one criterion for a
"response" (change from background) was subjectively
determined to be a post-injection change in percent
transmittance exceeding at least three times the standard
deviation of the baseline transmittance for the five
minutes prior to and after the contaminant injection.
Relatively low contaminant concentration levels (0.01
- 10 milligrams/liter (mg/L) were purposefully chosen
for this evaluation of ultraviolet spectrometers because
many of the contaminants posed health risks at the low
drinking water concentrations tested. Deployment and
operational factors were also documented and reported.
Real UV254 Response to Contaminant
Injections
Contaminant injections were performed for aldicaib.
caibofuran. colchicine, diesel fuel, disulfoton, mevinphos.
nicotine, potassium cyanide, sodium lluoroacetate. Bacillus
globigii, Bacillus thuringiensis, Chlorella, ovalbumin, and
ricin. The contaminant injection solutions were prepared
within 24 hours preceding testing (most within 8 hours)
in the same water tliat was within the PPL. Since this
water contained disinfectants it could cause degradation
or transformation of the injected contaminants prior to
injection. In chlorinated water, the Real UV254 measured
a response for 0.01 mg/L injections of colchicine as well
as 0.1 and 1 mg/L of aldicaib, caibofuran. colchicine.
mevinphos, and nicotine. Those five TICs as well as
potassium cyanide and sodium lluoroacetate were detected
by the Real UV254 at 10 mg/L.
In chloraminated water, the Real UV254 measured a
response for 0.01 mg/L of carbofuran. colchicine, and
nicotine. Those three toxic industrial chemicals, as well
as aldicarb and mevinphos were detected by the Real
UV254 at 0.1 mg/L, 1 mg/L, and 10 mg/L. The Real
UV254 measured a response for two of the three 10
mg/L injections of sodium lluoroacetate. No response
was measured for any injection of potassium cyanide
into chloraminated water.
Real UV254 responses for the biological contaminants
were similar in chlorinated and chloraminated water.
The Real UV254 detected neither Chlorella nor Bacillus
globigii at any concentration tested in either chlorinated
or chloraminated water. The Real UV254 measured a
response upon injection of 107 organism/L of a mixture
of spores and vegetative cells of Bacillus thuringiensis
in both chlorinated and chloraminated water. Injections
of 105 organism/L of a stock solution containing only
spores of Bacillus thuringiensis into chloraminated water
produced a response. The Real UV254 responded to 1
and 10 mg/L injections of ovalbumin.
Disulfoton. diesel fuel, and ricin were evaluated in a
small-loop configuration because those contaminants
were late additions to the evaluation. They were added
at the same time as ricin which required an experimental
setup in a biosafety hood, therefore, these contaminants
were evaluated using the same experimental setup. In
chlorinated water, disulfoton was detected at 0.1 and 1
mg/L, diesel fuel was not detectable at any concentration
level and ricin was detected at 1 and 10 mg/L. The
results were considerably different in chloraminated
water. There was no response to disulfoton. Diesel fuel,
though not soluble, was added to water and analyzed
using the Real UV 254, but the results were inconsistent
and difficult to interpret. Ricin responded in the same
way tliat it had for chlorinated water. Carbofuran was
also evaluated in the small loop configuration and
the instrument responded at 0.1 mg/L and 1 mg/L in
chlorinated water and only at 1 mg/L in chloraminated
water. In addition to these measurements, limited
experiments were performed to examine the effect of
elevated TOC, ionic strength, and iiionochloramine
concentrations on the Real UV254 TOC measurements.
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Because the Real UV254 was able to make
measurements every second, the change in contaminant
concentration during mixing of the pipe loop was
observable. For example, the initial injection of
each contaminant caused a highly concentrated slug
of contaminant to pass by the Real UV 254 until it
became well-mixed into the PPL. Results show the
capability of the Real UV 254 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
During the evaluation of the Real UV254, the follow ing
general operational characteristics were observed.
Installation and operation of the Real UV254 were
straight forward with no routine maintenance required.
Operation of the Real UV254 softw are was intuitive
and. as used during this evaluation, the data files were
easily obtained in a text-delimited format for convenient
transfer into a spreadsheet. This evaluation did not
consider other possible data retrieval methods (e.g.,
supervisory control and data acquisition (SCAD A)) that
could be utilized with the Real UV254.
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1.0
Introduction
The U.S. EPA's National Homeland Security Research
Center (NHSRC) is helping to protect 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. NHSRC is working to develop tools and
information that will help to detect the intentional
introduction of chemical or biological contaminants
in buildings or water systems, to contain these
contaminants, to decontaminate buildings and/or water
systems, and to disposal of material resulting from clean-
ups.
NHSRC's Technology Testing and Evaluation Program
(TTEP) works with stakeholder groups consisting of
buyers and users of homeland security technologies,
with individual technology developers who participate in
carrying out performance testing on such technologies,
and with recognized testing organizations. The program
evaluates the performance of innovative homeland
security technologies by developing evaluation plans that
are responsive to the needs of stakeholders, conducting
tests, collecting and analyzing data, and 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
arc 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
tliat user needs and perspectives arc incorporated into the
evaluation design so that useful performance information
is produced for each of the evaluated technologies.
Under TTEP, Battelle recently evaluated the performance
of the Real UV254 Security Monitor (hereafter referred
to as the Real UV254). The primary objective of this
evaluation was to determine the ability of the Real
UV254 to detect changes in ultraviolet transmittance 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 Real UV254 was conducted because
the instrument reports ultraviolet transmittance rather
than a TOC (total organic carbon) concentration. 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) for
the TTEP and associated amendments.'
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2.0
Technology Description
This report provides results for the evaluation of the Real
UV254. Following is a description of the Real UV254
based on information provided by the vendor.
be adjusted as often. Once the detector is in the proper
range, the transmittance is set to 100%. These actions
are performed with a knob and a button that reside on
the side of the instrument case. Because chloraminated
water absoibs UV light better than chlorinated water, the
Real UV254 has a switch that changes the offset of the
transmittance to a scale that is appropriate for the current
water matrix.
The Real UV254 requires no reagents for operation. The
only ongoing maintenance includes replacement of the
UV lamp which has a rated lifetime of 12,000 hours of
operation. The total cost of the instrument as configured
is $7,000 and the estimated yearly non-labor operation
and maintenance costs are $100 for a replacement UV
lamp.
Figure 2-1. RealUV254
Figure 2-1 shows the Real UV254 which is housed in
a single enclosure containing a flow cell, optics, and
controls. The enclosure for the Real UV254 is 38
centimeters (cm) wide, 20 cm deep and 33 cm tall.
The Real UV254 measures transmittance of ultraviolet
(UV) light at a single wavelength, 254 nanometers,
through water moving through the flow cell. The Real
UV254 uses a configuration that includes a light source
and detector that rotates around the flow cell, providing
transmittance measurements at different 90 degree
orientations with each successive measurement.
Data collection and visualization is accomplished
through the use of a software package that shows the
UV254 transmittance on a real time plot. The software
has the capacity to display the signal standard deviation
and, while not evaluated here, also has an alarm
feature that can be activated when the signal crosses
a user-defined threshold. Data files can be saved and
downloaded as space delimited text.
Prior to deployment, the Real UV254 UV (ultraviolet)
detector sensitivity must be adjusted into a working
range. In this experimental design, this signal
adjustment took place before each set of injections, but
in an operational context it would not be expected to
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3.0
Experimental Details
The primary objective of this evaluation was to
determine the capability of total organic carbon (TOC)
analyzers and ultraviolet spectrophotometer (UVSs) to
measure changes in TOC level due to the introduction
of contaminants in drinking water. Four technologies
were evaluated, two TOC analyzers and two UVSs. 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 portable pipe loop (PPL) and four
contaminants were analyzed using a small loop sampling
approach.
This evaluation took place between June 3, 2009 and
September 24, 2009. Q A oversight of this evaluation
was provided by Battelle and EPA. Battelle QA staff
conducted a technical systems audit (TSA) and an audit
of data quality.
3.1 Portable Pipe Loop and
Experimental Setup
This evaluation was conducted using EPA's PPL which
is shown in Figure 3-1 and 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 (in) of 7.6 cm
diameter stainless steel pipe (316L grade). The two
racks were connected together for use during this
evaluation. All four TOC analyzers and UVSs evaluated
were connected to the PPL by one of the eight separate
sample ports with 6.35 millimeter (mm) (or one quarter
inch) inner diameter flexible 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 meters per second (m/s)). The
Real UV254 did not add reagents to the PPL water so the
water from the Real UV254 was collected in a common
reservoir and continuously pumped back into the mixing
tank using the peristaltic pump. Flow through the Real
UV254 was maintained between 1 and 1.5 L/min during
testing.
Figure 3-1. EPA's portable pipe loop
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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 milligrams/liter
(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.® To briefly summarize this
SOP, 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
Each Method 10200.® 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
RealUV254.
3.3 Portable Pipe Loop (PPL)
Contaminant Injections
The toxic industrial chemicals (TICs) and biological
contaminants (BCs) were injected into the PPL.
Concentrated 250 mL solutions were prepared within
8 hours of injection (with the exception of the discrete
samples which were prepared the day before) using the
same water used within the PPL, either chlorinated or
solutions in water containing disinfectants could cause
degradation or transformation of the contaminant. For
example, it is possible that the interaction of the cyanide
ion with chlorinated water may have formed cyanogen
chloride which could have continued to breakdown
to the cvanate ion. These reactions are dependent
on the dissolution water so the results presented lie re
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 contaminant 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 gentle
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. Tliese
transformational products may or may not retain the
same UV absorbance characteristics as the original
chemical.
The biological organisms were injected in a solution of
phosphate buffered saline (PBS). The final BC culture
was pelleted by centrifugation and washed in PBS three
times. The washed pellet cake was then resuspended in
PBS. The BC solution was enumerated and injection
solutions were prepared by diluting the BC to the
appropriate concentrations. The two Bacillus species
were grown in nutrient broth while the Chlorella was
grown in Bold 1NV Medium"". 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.
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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
LTltra 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
series of single contaminant injections was made into the
circulating water of the PPL. Figure 3-2 shows that with
each injection the response from the Real UV254 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 Real UV254. The contaminant concentration
within the slug was higher than the eventual steady-state
contaminant concentration within the PPL, therefore
causing a laiger decrease in transmittance than the ultimate
steady-state concentration decrease in transmittance. 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 Real
UV254 transmittance measurement (approximately once
every second) allowed evaluation of the Real UV254 with
respect to the first pass of a contaminant through the PPL in
addition to the steady-state response.
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 Real UV254. 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.
Nicotine was the example contaminant used in Figure
3-2, but nicotine was typical of the TIC contaminants
that were detected by the Real UV254. To ensure that
the contaminant concentration had reached steady-state,
a 20 minute stabilization period was allowed after a
contaminant injection. After this 20 minute stabilization
period, 30 minutes of data from each instrument were
collected at the post-injection steady-state concentration.
In addition to being used to determine the steady-state
response following each injection, the last 5 minutes of
this steady-state period were also used as the baseline
for the next 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.
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120 -i
N?
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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. As described in the
test/QA plan(1), TIC injection concentrations were
selected based on previous testing performed at EPA's
Testing and Evaluation (T&E) Facility™. BC injection
concentrations were based on relevant toxicological
data (e.g., infective dose)(5) as well as concentrations
recommended by Technology Testing and Evaluation
Program (TTEP) Water Security Stakeholders.
Table 3-2. Contaminant List
Type
Agent
Analysis Method
Injected Concentrations
Medium
Toxic Industrial
Chemicals
Aldicarb
PPL
0.01. 0.1. 1 (mg/L)
Water
Carbofuran
PPL, discrete
0.01.0.1. 1. 10 (mg/L)
Water
Colchicine
PPL
0.01.0.1. 1. 10 (mg/L)
Water
Diesel fuel
Discrete
0.1. 1. 10 (mg/L)
Water
Disulfoton
Discrete
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
Potassium cyanide
PPL
0.01.0.1. 1. 10 (mg/L)
Water
Sodium fluoroacetate
PPL
0.01.0.1. 1. 10 (mg/L)
Water
Biological
Contaminants
Bacillus thuringiensis
(surrogate for Bacillus
anthracis)
PPL
103.10". 105. 106. 107 (spores/L)
PBS and Nutrient Broth
Bacillus globigii (surrogate for
Bacillus anthracis)
PPL
103.10". 105. 106. 107 (spores/L)
PBS and Nutrient Broth
Chlorella (surrogate for
Cryptosporidium)
PPL
103. 10". 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
Discrete
0.1. 1. 10 (mg/L)
Buffered sodium azide
Controls
Water
PPL
t
Water
PBS/nutrient broth
PPL
t
Water
PBS/Bold 1NV medium
PPL
t
Water
Buffered sodium azide
Discrete
t
Water
PBS- phosphate buffered saline
PPL - portable pipe loop
"I" No 10 mg/L injections due to a response at 1 mg/L and prohibitive cost
J Concentrations (or volumes for water injections) equivalent to those present in contaminant injections
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3.6 Data Analysis
During the evaluation, the Real UV254 made a
transmittance measurement approximately once every
second. The baseline transmittance is defined as the
average transmittance over the 5 minute baseline
measurement period before each injection. Baseline
measurement periods began 45 minutes after an
injection. For the purposes of this study, one criterion
for an anomalous change or "response" was subjectively
determined to be the detection by the Real UV 254 of a
post-injection change in percent transmittance (%T) at
least three times the standard deviation of the baseline
transmittance for the five minutes prior to and after the
contaminant injection. For this evaluation, most of the
time this was a decrease in %T, indicated by a negative
number in the data tables and text. However, while not
as common during this evaluation, a response can also
be the result of a %T becoming more positive. When
these conditions, and one other (see below). were met,
the Real UV254 was defined to have "responded" to
an injected contaminant. To simplify wording, in this
report an anomalous change will be referred to as a
"response" to the contaminant injection. Depending on
operational parameters of a water system, a change in
%T that exceeds three times the standard deviation of the
baseline, may or may not indicate that a contamination
event has occurred.
The second criterion defining a "response" was to
avoid having responses attributable to water injections
from being considered responses. So. 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 Real UV254. Water
for control injections was removed from the PPL and
then injected back into the PPL within 4 hours. Five
such injections resulted in an average %T response of
1.55%T with a standard deviation of 2.10%T. So, for
most control samples, the average %T response was
between -0.55 and 3.65. Therefore, in addition to the
requirement for a response previously described in this
section, a second requirement is that a response must not
reflect the average response to a control injection (1.55%
±2.10%T); a response must be more negative than -0.55
or more positive than 3.65.
The magnitude of a change in transmittance (also
referred to as steady-state response) was calculated and
expressed as AT. The AT for the Real UV254 calculated
using Equation 1:
A T = T-TbaseUne (1)
where T is the average post-injection %T measured by
the Real UV254; and T, .. is the average baseline %T
7 baseline
as determined by the Real UV254. Generally, increases
in contaminant concentration result in a decrease in the
transmittance measured by the Real UV254. Results
for AT are reported as negative numbers when the
transmittance decreased after injection of a contaminant.
10
-------
4.0
Quality Assurance/Quality Control (QA/QC)
Quality assurance/quality control (QA/QC) procedures
were performed in accordance with the program QMP(2)
and the test/QA plan(1) for this evaluation.
4.1 Reference Method
EPA Method 415.3(6) was used to analyze reference
samples for TOC concentration. The reference
instrument was a Teledyne-Tekmar (Mason OH) Fusion
TOC Analyzer™. 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 summarized in
Table 4-1 along with the acceptable tolerance for the
performance evaluation audit that validates the accuracy
of the reference method. As mentioned above, the
reference method was not used to evaluate the accuracy
of the Real UV254.
Table 4-1. Summary of Total Organic Carbon (TOC) Reference Method
Instrument
Method
Measurement
Principle
Detection
Limit
Maximum Holding Time
Acceptable
Tolerance
Teledyne-Tekmar Fusion
TOC Analyzer™
(Mason, OH)
EPA 415.36
(Standard Method 5310C)
UV/persulfate
oxidation
0.2 Jig/L
28 days with acidification to pH <2
20%
Jlg/L = micrograms per liter
4.2 Instrument Calibration
The Real UV254 was connected to the PPL by Battelle
with support from the vendor via telephone. No
calibration using certified calibration standards was
performed for the Real UV254. However, each day prior
to testing, the arbitrary response units were adjusted
using a knob on the right side of the Real UV254. The
adjustment was made to ensure that the Real UV254
UV detector was in an optimal working range. This
adjustment is described more thoroughly in Section
5.5.3 on the operation of the UV254. In addition to the
adjustment of response units, the transmittance was reset
to 100 percent. This was the only calibration activity
performed for the Real UV254.
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
(Enviromnental Resource Associates), Arvada, Colorado)
and analyzed. Accuracy of the TOC measurement
was expressed in terms of the percent error (%E), as
calculated from the following equation:
%E = -——xlOO
Cr
(2)
where C 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 result 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)
The Battelle QA Manager conducted a Technical
Systems Audit (TSA) at the Columbus, Ohio testing
location to ensure that the evaluation was performed in
accordance with the test/QA plan(1) and the Technology
Testing and Evaluation Program (TTEP) QMP.(2) As
part of the audit, the Battelle QA Manager reviewed the
reference sampling and analysis methods used, compared
actual evaluation procedures with those specified in
the test/QA plan,(1) and reviewed data acquisition and
handling procedures. No significant adverse findings
were noted in this audit. The records concerning the TSA
are permanently stored with the Battelle QA Manager.
-------
4.3.3 Amendments/Deviations
One amendment was made to the test/QA plan for
this evaluation. The amendment dealt with the list of
contaminants to be tested. The amendment removed
cesium, as well a.s the chemical warfare agents VX,
soman, and sarin from the contaminant list and added
ricin. disulfoton. mevinphos, and sodium Huoroacetate
to the list of injected contaminants. The amendment
stipulated that sodium Huoroacetate and mevinphos
be evaluated in the PPL and ricin and disulfoton be
evaluated as discrete samples. The amendment 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 only the reference
TOG instrument. However, both TOG vendors had
provided TOG standards (independently) that had
been measured accurately by the reference method
repeatedly during preparation for the evaluation.
Therefore, there was a high degree of confidence in
the accuracy of the reference method/instrument.
Instead of holding up the evaluation, testing
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(7)), a test for
monochloramine (Hach Method 10200®) 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 TIGs.
Some of the participating technologies 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, these tests were not performed.
• For the elevated TOG component of the testing, the
TOG was elevated by approximately 1 mg/L rather
than 2 mg/L because of the change in the source
water's background TOG on testing day.
• Concentrations of the BGs were increased to include
samples at 106 and 107 organisms/L to identify
detectable levels.
• While not applicable to the Real UV254, percent
difference was used to compare the reference
method with results from the TOG technologies.
4.3.4 Data Quality Audit
At least 10% of the data acquired during the evaluation
were audited. The Battelle 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.
4.4 Quality Assurance/Quality Control
(QA/QC) Reporting
Each assessment and audit was documented in
accordance with the test/QA plan'1' and the QMP.(2) Once
an assessment report was prepared by the Battelle Q A
manager, it was routed to the EPA Task Order Leader
and Battelle TTEP Manager for review and approval.
The Battelle Q A manager then distributed the final
assessment report to the EPA task order project officer,
QA manager, and Battelle stall.
-------
5.0
Evaluation Results
This section presents the results of the evaluation
including the ability of the Real UV254 to measure
changes in UV absorbance in response to the injections
of TICs and BCs in drinking water. Also given are the
operational characteristics of the Real UV254 that were
observed during the evaluation.
5.1 Toxic Industrial Chemicals (TICs) in
Drinking Water
5.1.1 Real UV254 Steady-State Response to
Toxic Industrial Chemical (TIC) Injections
A total of seven TICs were individually injected into the
PPL at the concentration levels given in Table 3-2. 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
3.6.1 describes the change in transmittance that was
considered a "response" due to a contaminant injection.
After each set of TIC injections, the PPL was Hushed
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 into the PPL.
Figure 5-1 shows an example of the Real UV254
response to one set of injections of carbofuran into
chlorinated water. Injections of carbofuran are marked
on Figure 5-1 with vertical lines and labeled with the
concentration level. The transmittance over the time
period prior to the first injection was used as the baseline
transmittance for the 0.01 mg/L injection. In the set
of injections shown, the Real UV254 did not have a
response to the 0.01 mg/L injection of carbofuran but
did have a response to the 0.1, 1, and 10 mg/L injections.
The initial response following each injection is due to
the first pass concentration of the contaminant while
the eventual steady-state concentration was 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 Real UV254 was able to measure these
changes because of its relatively high measurement
frequency and rapid response to the dynamic
concentration gradient. For the 10 mg/L carbofuran
injection, the first pass response was more gradual,
without an anomalous first pass result. This resulted
because a larger volume was injected due to the limited
solubility of carbofuran at the concentration required for
the contaminant injection solution.
13
-------
SP
ai
u
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in
IN
>
D
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a>
c£
120
100
80
60
40
20
0
Baseline
0.01 mg/L
Injection
/
0.1 mg/L
^Injection
1 mg/L
Injection
¦ •
10 mg/L
Injection
0
30
60
90
210
120 150 180
Time (minutes)
Figure 5 1. Transmittance of Real UV254 in response to injections of carbofuran
240
270
300
Table 5-1 gives the contaminant injected, the concentration
of the injected contaminant, and the average steady-state
response (AT) for each TIC injection Also given next to
each average response is the standard deviation that each
average response had to exceed (by a factor of three) to be
considered anomalous. That standard deviation was the
greater of the standard deviation of the steady-state response
in the 5 minutes before the injection or the 5 minutes after
the contaminant became well mixed in the PPL. Those
injections which were determined to produce a response
in the transmittance (as defined previously) measured
by the Real UV254 are highlighted in gray. During this
evaluation as the concentration of TICs increased in the
water, the transmittance of UV light in that water decreased.
Therefore, most of the changes in transmittance are given as
negative numbers in the table. There were a few instances
where contaminant injections resulted in a response.
At 0.01 mg/L, the Real UV254 responded for two
out of three injections of colchicine and one injection
of nicotine. At the 0.1 mg/L concentration, the
transmittance measured by the Real UV254 decreased by
more than 25% in response to colchicine. This response
made colchicine the TIC that was most sensitive to
UV detection. Aldicarb, carbofuran mevinphos, and
nicotine were also detected by the Real UV254 at 0.1
mg/L, with small changes in transmittance, ranging from
-0.5%T - -3.5%T.
-------
Table 5-1. Change in Real UV254 Transmittance from Injections of Toxic Industrial Chemicals (TICs) into
Chlorinated Water
Injected Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
0.01
0.71
0.11
0.05
0.02
0.80
0.14
Aldicarb
0.1
-1.36
0.60
-1.67
0.03
-0.51
0.10
1
-28.64
0.21
-28.16
0.22
-27.10
0.35
0.01
0.79
0.08
1.45
0.16
0.16
0.10
Carbofuran
0.1
1.06
0.05
-1.10
0.13
-0.52
0.05
1
-6.80
1.31
-14.41
0.22
-12.87
0.21
10
-49.60
0.57
-46.32
2.48
-66.03
0.21
0.01
-3.24
0.05
-2.38
0.48
-0.21
0.25
Colchicine
0.1
-28.95
0.14
-30.43
0.26
-25.71
0.27
1
max'
0.70
max
0.24
max
0.35
10
max
0.00
max
0.01
max
0.00
0.01
-0.22
0.03
-0.07
0.06
0.09
0.04
Mevinphos
0.1
-1.44
0.02
-1.30
0.03
-1.29
0.04
1
-11.59
0.03
-11.33
0.02
-10.92
0.02
0.01
t
t
-7.38
0.33
-1.10
0.80
Nicotine
0.1
-0.55
0.16
-3.50
0.22
1.69
1.21
1
-57.72
0.10
-58.39
0.24
-70.53
0.62
10
max
0.26
max
1.22
max
0.16
0.01
2.00
0.45
1.46
0.14
1.35
0.09
Potassium Cyanide
0.1
2.50
0.24
1.09
0.08
1.32
0.06
1
5.34
0.18
3.86
0.06
3.46
0.06
10
-0.92
0.15
-0.75
0.11
0.03
0.12
0.01
0.08
0.09
0.01
0.10
-0.18
0.04
Sodium Fluoroacetate
0.1
0.09
0.04
-0.03
0.08
0.04
0.04
1
0.14
0.03
0.33
0.07
-0.21
0.04
10
-3.54
0.05
-3.09
0.05
-3.10
0.02
Water controls
None
4.82
0.34
2.49
0.36
-0.10
0.67
0.35
0.14
0.18
0.40
1.55*
2.10*
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
"|" max = the % transmittance dropped to a minimum %T level and was truncated
J Only two replicates of the 0.01 mg/L nicotine injections were performed.
# Average and standard deviation of water controls.
-------
Aldicarb, carbofuran, colchicine, mevinphos, and
nicotine, the same TICs that were detected by the
Real UV254 with small responses at 0.1 mg/L, were
detected with much larger decreases at the 1 mg/L
concentration. At this concentration, the Real UV254
response to aldicarb was less than -27%T, carbofuran
-7%T - -14%T, colchicine -53%T - -72%T, mevinphos
-11%T - -12%T, and nicotine -58%T - -71%T. When
the continuous Real UV254 data were plotted over time
for each of these contaminant injections, the change
in transmittance was easily observed. Only potassium
cyanide and sodium Huoroacetate were not detected with
Real UV254 responses of more negative than -10%T.
Injections of 10 mg/L of contaminants were performed
for all but aldicarb and mevinphos. For those TICs that
were detected with decreases of at least -10%T at
1 mg/L, the decreased response was greater in magnitude
for the 10 mg/L injections. The carbofuran responses
were -46%T - -66%T, and colchicine and nicotine
caused the Real UV254 response to diminish to the
point that the detector response bottomed out into a flat
response at the bottom of the working range.
The Real UV254 measured a small but significant
decrease in transmittance for two of the 10 mg/L
injections of potassium cyanide, but none of the other
injections at any concentration. At lower concentrations,
the Real UV254 response increased slightly after
injection of potassium cyanide. While it is not clear
why, it is possible that interaction between the cyanide
and chlorine caused this behavior. Sodium Huoroacetate
was detected by the Real UV254 upon all three
injections of 10 mg/L with changes in transmittance
of -3%T - 4%T. The injections of 10 mg/L of sodium
Huoroacetate were performed using an injection solution
prepared from a standard with 95% purity rather than
the standard with 99% purity that had been used for the
other injections. It is possible that this very small change
in transmittance was due to the presence of an impurity
and not due to sodium Huoroacetate.
Table 5-2 presents the same information for injections
made into the chloraminated water matrix. In general,
the results are similar for chlorinated and chloraminated
water. The Real UV254 detected some very small but
significant decreases in the transmittance for aldicarb
and carbofuran at 0.01 mg/L and 0.1 mg/L. The
transmittance then decreased substantially during the
higher concentration injections for both of those TICs.
The Real UV254 results for colchicine and mevinphos
were also very similar to the chlorinated results. The
colchicine was detected with decreases of more than
-32%T at 0.1 mg/L and the Real UV254 responded
to mevinphos at approximately -11%T at 1 mg/L. As
had been the case for the chlorinated water, the Real
UV254 responded minimally to potassium cyanide and
sodium Huoroacetate at all concentrations. The biggest
difference between the chlorinated and chloraminated
response was for nicotine at 0.1 mg/L. In chloraminated
water, the Real UV254 detected the response to be
between -9%T and -12%T. The response in chlorinated
water was between -1%T and -4%T.
The standard deviation of the individual injection data
presented above could be used to calculate the amount
of change that would be required for detection of a
contamination event. For example, if a set of replicate
injections is precise (e.g., 0.1 mg/L mevinphos) and
therefore, has a low standard deviation, a small change
would be detectable. Conversely, a set of replicates tliat
were somewhat imprecise and therefore, have a higher
standard deviation would require a relatively large
change in %T to attain a detectable concentration. 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 may
exist in the context in an operational setting.
16
-------
Table 5-2. Change in Real UV254 Transmittance from Injections of Toxic Industrial Chemicals (TICs) into
Chloraminated Water
Injected Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
0.01
-0.55
0.07
0.04
0.05
-0.02
0.07
Aldicarb
0.1
-3.03
0.26
-0.49
0.05
-1.90
0.07
1
-35.91
0.29
-35.60
1.42
-35.37
0.20
0.01
0.06
0.03
-0.86
0.20
-0.82
0.06
Carbofuran
0.1
-0.65
0.03
-3.83
0.22
-0.60
0.06
1
-13.09
0.05
-18.25
1.27
-13.55
0.11
10
-56.03
0.11
-45.54
0.22
-58.64
0.27
0.01
-2.87
0.66
-3.18
0.09
-3.59
0.29
Colchicine
0.1
-31.59
0.05
-33.74
0.09
-34.09
0.07
1
maxt
0.07
max
0.09
max
0.08
10
max
0.01
max
0.01
max
0.01
0.01
-0.01
0.02
0.20
0.03
0.20
0.05
Mevinphos
0.1
-0.61
0.03
-0.64
0.02
-0.76
0.07
1
-11.24
0.04
-9.47
0.10
-11.20
0.06
0.01
0.00
0.11
-0.83
0.08
-0.58
0.11
Nicotine
0.1
-8.68
0.12
-11.65
0.09
-10.39
0.09
1
-63.08
0.11
-62.44
0.09
-60.16
0.15
10
max
0.04
max
0.05
max
0.02
0.01
0.35
0.02
1.33
0.11
0.63
0.07
Potassium Cyanide
0.1
0.68
0.04
2.22
0.04
1.93
0.02
1
0.23
0.02
3.57
0.11
1.62
0.06
10
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.47
0.04
0.06
0.06
0.42
0.11
Sodium Fluoroacetate
0.1
0.41
0.12
0.16
0.10
0.23
0.05
1
0.17
0.06
-0.47
0.05
0.49
0.12
10
0.06
0.24
-2.54
0.05
-2.26
0.07
Water controls
None
4.82
0.34
2.49
0.36
-0.10
0.67
0.35
0.14
0.18
0.40
1.55*
2.10*
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
"|" max = the % transmittance dropped to a minimum %T level and was truncated
# Average and standard deviation of water controls.
-------
5.1.2 Real UV254 First Pass Response during
Toxic Industrial Chemical (TIC) 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 Real UV254. The first pass
response was defined as the maximum Real UV254
response immediately after contaminant injection. This
maximum response typically occurred within three
minutes of the injection for the Real UV254.
Figure 5-2 and Figure 5-3 show bar graphs of the
absolute value 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 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 of -28%T at
the steady-state concentration. The average additional
decrease due to the first pass of each concentration
level is approximately -58%T and represented by the
lighter gray bar extending up to approximately 86%T.
Nearly all of the injections of aldicarb, carbofuran,
colchicine, mevinphos, and nicotine produced responses
registered by the Real UV254 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 in chlorinated water. However,
the ratio between the change in transmittance due to the
first pass and the change due to the steady-state are not
constant. Clearly there are unique mixing phenomena
occurring in the PPL which may or may not translate
into an operational setting. Overall, three injections
caused the transmittance to be completely diminished,
thus, dropping the Real UV254 transmittance to
approximately 0%T. This occurred for the first pass and
steady-state for the 1 mg/L and 10 mg/L injections of
colchicine and the 10 mg/L injection of nicotine in both
chlorinated and chloraminated water.
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100
90
80
70
60
50
40
30
20
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-------
For both the chlorinated and chloraminated water, there
were several instances that the first pass results increased
the Real UV254 response from a small steady-state
response of less than 5% to over 10%. This occurred for
injections of aldicarb, colchicine, and nicotine 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 %T for each first pass injection of the TICs
are given in the appendix.
100
H
" =
oN
C
90
=>
50
(5
4)
tc
40
o
20
0
<
1
1
-J
h
¦
&
J?
First pass
i Steady-state
Figure 5-3. Real UV254 first pass response in addition to steady-state response in chloraminated water
5.2 Biological Contaminants (BCs) in
Drinking Water
5.2.1 Real UV254 Steady-state Response to
Biological Contaminant (BC) Injections
Three biological organisms 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
5-3 shows one set of injections for Bacillus thuringiensis
into chlorinated water. The Real UV254 did not exhibit
a response (as defined in Section 3.6) to the injections
at 105 and 106 organism/L of Bacillus thuringiensis
shown in Figure 5-3 but did exhibit a response to the
injection at 107 organism/L. Initially, concentrations of
103, 104, and 105 organism/L were to be injected into the
PPL for each organism. After the results of the initial
injections showed no significant changes in response to
these injections, the concentrations were increased to
include a maximum concentration of 107 organism/L for
Bacillus globigii and Bacillus thuringiensis (the higher
concentration Bacillus thuringiensis was a mixture of
vegetative cells and spores). Limitations on the amount
of stock solution available prevented increasing the
concentrations of Chlorella in a similar manner.
19
-------
120
SP
o\
aj
u
E
1/1
*3"
in
IN
>
D
75
ai
C£
100
80
60
40
20
0
Baseline
105 organism/L
Injection
10s organism/L
Injection
/
107 organism/L
Injection
0 30 60 90 120 150 180 210
Time (minutes)
Figure 5-4. Transmittance of Real UV254 in response to injections of Bacillus thuringiensis
Table 5-3 gives the contaminant injected, the
concentration of the injected contaminant, and the
average and standard deviation of the measured
transmittance for each BC injection. Those injections
which were determined to produce a response in
transmittance as measured by the Real UV254 are
highlighted in gray.
The Real UV254 measured a change in transmittance
in response to injections of Bacillus thuringiensis at 107
organism/L, but not at lower concentrations. Ovalbumin
a protein surrogate for biological toxins such as ricin or
botulinum, did result in a response in the transmittance
as measured by the Real UV254 for injections at 1 and
10 mg/L.
20
-------
Table 5-3. Change in Real UV254 Transmittance from Injections of Biological Contaminants (BCs) into
Chlorinated Water
Contaminant
Injected Contaminant
Concentration
(organism/L or mg/L)
Injection 1
Injection 2
Injection 3
AT
(%T)
Std Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
Bacillus globigii
105
1.16
0.33
1.37
0.13
0.21
0.03
106
0.44
0.14
0.85
0.04
0.54
0.09
107
0.04
0.07
-0.32
0.05
0.27
0.03
Bacillus thuringiensis
105
0.61
0.10
-0.18
0.08
0.28
0.08
106
-0.09
0.08
0.42
0.07
-0.22
0.10
107
-4.57
0.05
-4.05
0.06
-3.82
0.11
Chlorella
103
1.02
0.06
0.97
0.11
-1.66
0.68
10"
0.76
0.06
1.12
0.14
0.33
0.19
105
0.48
0.04
0.48
0.07
-0.16
0.12
Ovalbumin
0.01
-4.84
0.62
-1.47
0.39
-0.98
0.19
0.1
1.78
0.41
2.46
0.79
1.50
0.18
1
-13.82
0.51
-12.24
0.34
-10.45
0.37
10
-32.85
0.26
-30.05
1.38
-40.26
0.52
Water controls
None
4.82
0.34
2.49
0.36
-0.10
0.67
0.35
0.14
0.18
0.40
1.55*
2.10*
PBS/nutrient broth
(Bacillus control)
Equivalent to 107Bacillus
0.33
0.02
0.38
0.03
0.57
0.03
0.50
0.10
0.33
0.06
0.66
0.07
PBS/Bold 1NV
medium (Chlorella
control)
Equivalent to 107 Chlorella
0.24
0.02
-0.11
0.03
1.60
0.01
1.12
0.16
0.06
0.10
0.43
0.04
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
# Average and standard deviation of water controls.
Table 5-4 presents the responses to injections of the BCs
and ovalbumin into chloraminated water. Significant
Real UV254 responses are highlighted in gray. Initial
injections of Bacillus globigii were performed at
10\ 104, and 105 organism/L. One injection of 107
organism/L of Bacillus globigii was included with the
final replicate set of injections to confirm the results
determined during the chlorinated water injections.
None of the Bacillus globigii or Chlorella injections
resulted in an anomalous change in the transmittance
measured by the Real UV254. The first two sets of
injections of Bacillus thuringiensis were performed at
10\ 104, and 105 organism/L. Those injections resulted
in Real UV254 responses of approximately 3%T for
the 105 organism/L so for the last set of injections, the
concentrations were increased to include concentrations
of 105, 106, and 107 organism/L. The only Real UV254
response caused by these injections was approximately
3% to the 107 organism/L injection. The higher
concentration injections of Bacillus thuringiensis were
a mixture of vegetative cells and spores while the initial
injections were spores only. Based on the Real UV254
response, the vegetative cells absorbed ultraviolet light
less than the spores as the 107 organism/L concentration
generated a response similar to that of the spores-
only injection at 105 organism/L. This also may be an
optical effect that of spores blocking more light than the
vegetative cells. The Real UV254 measured a change in
transmittance in response to injections of ovalbumin at 1
and 10 mg/L.
In addition to the injections of BCs, controls of growth
media were injected into the PPL. The controls had
no organisms added and were handled in the same
manner as the stock solutions of the BCs. Triplicate
sets of injections of the washed growth media for both
the Bacillus organisms and Chlorella were made into
chlorinated and chloraminated water. None of the 12
injections produced a response from the Real UV254.
21
-------
Table 5-4. Change in Real UV254 Transmittance from Injections of Biological Contaminants (BCs) into
Chloraminated Water
Contaminant
Injected Contaminant
Concentration
(organism/L or mg/L)
Injection 1
Injection 2
Injection 3
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
Bacillus globigii
103
1.07
0.04
1.18
0.29
1.20
0.06
10"
0.45
0.10
0.77
0.11
0.74
0.07
105
0.40
0.06
0.39
0.06
0.30
0.09
107
t
t
t
t
0.57
0.04
Bacillus
thuringiensis
103
0.42
0.05
1.01
0.16
t
t
10"
0.16
0.04
0.24
0.12
t
t
105
-2.06
0.09
-3.08
0.09
0.60
0.06
106
t
t
t
t
-0.12
0.09
107
t
t
t
t
-3.06
0.05
Chlorella
103
0.74
0.10
0.52
0.03
0.44
0.06
10"
0.47
0.07
0.35
0.02
0.16
0.03
105
0.51
0.07
0.30
0.02
0.16
0.02
Ovalbumin
0.01
0.22
0.12
0.24
0.03
0.68
0.14
0.1
0.11
0.09
0.17
0.03
0.05
0.11
1
-1.69
0.12
-0.66
0.02
-1.35
0.16
10
-20.46
0.24
-17.82
0.21
-17.46
0.10
Water controls
None
4.82
0.34
2.49
0.36
-0.10
0.67
0.35
0.14
0.18
0.40
1.55*
2.10*
PBS/nutrient broth
(Bacillus control)
Equivalent to 107 Bacillus
0.33
0.02
0.38
0.03
0.57
0.03
0.50
0.10
0.33
0.06
0.66
0.07
PBS/Bold 1NV
medium (Chlorella
control)
Equivalent to 107 Chlorella
0.24
0.02
-0.11
0.03
1.60
0.01
1.12
0.16
0.06
0.10
0.43
0.04
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
"("Fewer than three injections performed at this concentration.
# Average and standard deviation of water controls.
5.2.2 Real UV254 First Pass Response during
Biological Contaminant (BC) Testing
First pass response determinations were also made for
BC injections. Figure 5-5 and Figure 5-6 show graphs
of the change in transmittance due to the steady-state
contaminant concentration in dark gray and the change
in transmittance above that due to the first pass of the
contaminant slug for each BC concentration level (as
described in Section 3.3).
As shown for both chlorinated and chloraminated
water, the first pass injections caused a response in the
Real UV254 for the highest concentration injections
of ovalbumin and two concentrations of Bacillus
thuringiensis from baseline results. The responses
for each first pass injection of BCs are provided in the
appendix.
22
-------
u
m
rsi
>
Z>
>
O
(A
_Q
<
First pass
I Steady-state
Figure 5-5. Real UV254 first pass response to biological contaminants (BCs) in addition to steady-state response
in chlorinated water
60
50
40
^ 30
a>
oc
o
o>
(TJ
>
o
20
10
First pass
i Steady-state
r
~
&
\°
Figure 5-6. Real UV254 first pass response to biological contaminants (BCs) in addition to steady-state response
in chloraminated water
-------
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. Because
each contaminant solution flowed directly through the
Real UV254, the Real UV254 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 contaminant, the Real UV254 response, and the
standard deviation for each contaminant concentration
level in chlorinated and chloraminated water,
respectively. Those tests which were determined to
produce a response are highlighted in gray. The ricin
was stored in the sodium a/ide phosphate buffer so
along with each measurement of ricin. the sodium a/ide
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 a/ide buffer tests are
included in Table 5-5 and Table 5-6.
5.3.1 Carbofuran
Carbofuran was analyzed at 0.1 and 1 mg/L in the
small loop. No analysis in the small loop of 10 mg/L
caibofuran samples was conducted due to the limited
solubility of caibofuran. During the small loop analyses,
the Real UV254 measured a response for one of the 0.1
mg/L tests in chlorinated water and two of the 0.1 mg/L
tests in chloraminated water. The Real UV254 measured
a response for all tests at 1 mg/L except for one of the
tests in chlorinated water. Caibofuran was also injected
into the PPL resulting in a response approximately three
times larger than small loop samples. The reason for this
discrepancy is not clear.
5.3.2 Diesel fuel
Small loop analysis of diesel fuel samples was conducted
at 0.1, 1, and 10 mg/L. However, 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 test, the samples were mixed,
but over the course of the test period the samples began
to separate into a distinct diesel (organic) phase and
aqueous phase. The Real UV254 measured significant
increases in transmittance (opposite direction of change
compared with most other contaminants) for all of the
diesel fuel tests in chlorinated water, and measured
significant decreases in transmittance for all diesel
fuel tests in chloraminated water. While the different
directions of response are not able to be explained,
overall, it is difficult to draw any conclusions about
diesel fuel test 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 Real UV254 measured
significant responses for all of the disulfoton tests in
chlorinated water, but with the exception of a 1 mg/L
test that demonstrated an increase in transmittance. it did
not measure a response for any of the disulfoton tests in
chloraminated water. The difference in results between
the two water matrices was not apparent.
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/
111L ricin in a sodium a/ide phosphate buffer solution.
Therefore, the sodium a/ide phosphate buffer was
analyzed at the concentration at which it was present in
the ricin solutions to determine whether the Real UV254
measured a response due to the sodium a/ide phosphate
buffer. The Real UV254 measured an anomalous
reduction in transmittance at ricin concentrations of
1 and 10 mg/L for tests in chlorinated water and all
three concentrations in chloraminated water. The Real
UV254 detected a positive response to the phosphate
buffered sodium a/ide solution in chlorinated water. The
positive response to the sodium a/ide phosphate buffer
in chlorinated water was not a concern because the ricin
decreased the transmittance at each concentration level.
In chloraminated water the sodium a/ide phosphate
buffer was detected with a negative response at the 10
mg/L concentration level. The ricin negative response
was more than five times greater so the presence of
the sodium a/ide phosphate buffer did not prevent the
detection of ricin.
24
-------
Table 5-5. Response of Real UV254 to Contaminants in Small Loop Chlorinated Water
Contaminant
Solution Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
Carbofuran
0.1
-2.03
0.92
-1.98
0.70
-3.93
0.40
1
-2.55
0.92
-2.66
0.52
-4.54
0.40
Diesel fuel
0.1
7.51
0.16
7.38
0.44
8.29
0.18
1
10.83
0.42
11.03
0.40
12.28
0.18
10
6.53
0.44
7.05
0.40
9.52
0.20
Disulfoton
0.1
-18.39
0.54
-21.33
0.46
-8.96
0.29
1
-26.28
0.64
-32.70
0.31
-27.55
0.29
Ricin
0.1
0.79
0.31
0.78
0.12
1.09
0.23
1
-11.58
0.26
-8.77
0.21
-6.56
0.23
10
-56.01
0.33
-53.60
0.23
-48.69
0.23
Sodium azide/
phosphate buffer
(ricin blank)
0.1
6.09
0.36
f
1
8.98
0.19
10
3.86
0.19
A "response" (indicated by shading) was at least three times the baseline standard deviation.
fOne set of blank replicate samples were analyzed.
Table 5-6. Response of Real UV254 to Contaminants in Small Loop Chloraminated Water
Solution Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
Carbofuran
0.1
-10.59
0.38
-7.22
1.69
-0.36
0.37
1
-16.94
0.28
-12.89
1.37
-7.79
1.06
0.1
-11.96
0.45
-7.48
0.98
-5.20
0.29
Diesel fuel
1
-12.63
0.41
-9.47
0.98
-8.42
0.29
10
-18.13
0.35
-14.64
0.98
-13.63
0.37
Disulfoton
0.1
0.72
0.58
0.79
0.15
0.31
0.04
1
6.25
0.32
1.74
0.15
0.40
0.04
0.1
-3.61
0.61
-1.67
0.47
-1.00
0.39
Ricin
1
-6.85
0.61
-5.62
0.47
-5.06
0.39
10
-32.96
0.61
-30.41
0.47
-28.86
0.39
Sodium azide/
phosphate buffer
(ricin blank)
0.1
-1.15
0.79
1
-1.72
0.79
t
10
-5.97
0.79
A "response" (indicated by shading) was at least three times the baseline standard deviation.
fOne set of blank replicate samples were analyzed.
25
-------
5.4 Additional Tests
5.4.1 Effect of Elevated Total Organic Carbon
(TOC) Injections on Real UV254 Response
In a minor component of this evaluation an additional
control was run to determine if the background TOC
level had any effect on the ability of the Real UV254
to detect a change in transmittance in response to a
contaminant injection. The controls included 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. 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 responses to the addition of approximately 1 mg/L
of quinine were similar so we concluded that there was
no effect on the response of the Real UV254 at 1 mg/L
of quinine. However, at 0.1 mg/L the Real UV254
measured a larger, response in transmittance for all three
injections at elevated background TOC but only two
of three injections without elevated background TOC.
Additional experiments would need to be performed to
make any interpretations from the presented results.
Table 5-7. Steady-state Response of Real UV254 with Elevated Total Organic Carbon (TOC) Concentrations
Contaminant
Injected Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
ATf
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std.
Dev. (%T)
Nicotine (background
TOC)
0.1
-0.55
0.16
-3.50
0.22
1.69
1.21
1
-57.72
0.10
-58.39
0.24
-70.53
0.62
Nicotine (elevated
TOC)
0.1
-15.78
0.41
-11.92
0.31
-12.25
0.10
1
-54.67
0.05
-61.80
0.15
-58.07
0.14
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
5.4.2 Effect of Elevated Ionic Strength on Real
UV254 Response
A second minor component of this evaluation was
used to determine if the ionic strength of the water had
any effect on the ability of the Real UV254 to detect
a change in response to a contaminant injection. The
injection of three sets of injections of nicotine at 0.1
and 1 mg/L were made into chlorinated water which
had been fortified with calcium chloride to raise the
calcium cation concentration from approximately 42
mg/L to 126 mg/L. 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. Table 5-8 presents
the responses 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
of the Real UV254 to nicotine at 1 mg/L. At 0.1 mg/L
the Real UV254 measured a larger and a response
in transmittance for all three injections at elevated
background hardness but only two of three injections
without elevated background hardness were detected as
significant responses by the Real UV254. Additional
experiments would need to be performed to make any
interpretations from the presented results.
26
-------
Table 5-8. Steady-state Response of Real UV254 with Elevated Ionic Strength
Injected Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std. Dev.
(%T)
AT
(%T)
Std.
Dev. (%T)
Nicotine (background
0.1
-0.55
0.16
-3.50
0.22
1.69
1.21
ionic strength)
1
-57.72
0.10
-58.39
0.24
-70.53
0.62
Nicotine (elevated
0.1
-10.15
0.11
-9.04
0.08
-8.84
0.08
ionic strength)
1
-57.64
0.15
-59.90
0.08
-60.39
0.09
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
5.4.3 Effect of Monochloramine Level on Real
UV254 Response
Lastly, a very limited experimental design was included
in this evaluation to make a preliminary determination
about whether or not UVSs could possibly 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 Real UV254 was used
to monitor water with three different concentrations
of monochloramine to determine whether the level of
monochloramine affected the Real UV254 response.
Monochloramine levels of 1.92, 5.72, and 7.54 mg/L
were prepared in the PPL following the procedure
described in Section 3.2.
Table 5-9 presents the Real UV254 transmittance
measurements for the tests conducted at different
monochloramine concentrations. The column at the
left of the table shows the different monochloramine
concentrations. The baseline transmittance for the Real
UV254 was 100%T at the lowest monochloramine
concentration of 1.92 mg/L. When the monochloramine
concentrations were raised, the Real UV254 did
measure a response in transmittance. Increasing the
monochloramine from 1.92 to 5.72 mg/L decreased the
Real UV254 response from 100% to approximately 37%.
At a monochloramine concentration of 7.54 mg/L the
Real UV254 response was only 19% of the transmittance
measured at 1.92 mg/L of monochloramine. Additional
evaluation would have to be performed to determine if
the Real UV254 could be used to monitor chloramines
quantitatively, but these results suggest that it may be a
possibility.
Table 5-9. Change in UV254 Response to Varying Monochloramine Concentrations
Monochloramine Concentration (mg/L)
Real UV254
T (%T)
Real UV254 Std. Dev.
(%T)
Real UV254
AT (%T)
1.92
100
0.21
Baseline
5.72
36.74
0.27
63.37
7.54
18.99
0.05
81.12
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
5.5 Operational Characteristics
Operational characteristics of the Real UV254 that were
encountered during 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
Real UV254 was a combination of training provided
by the vendor during phone conversations and printed
instructional material. The vendor did not recommend
an on-site visit to connect the Real UV254 to the
PPL so the Real UV254 was shipped to Battelle with
instructions for installation and operation. No problems
were encountered in the installation and start up of the
Real UV254.
27
-------
The instruction manual contained information on
installation of the Real UV254, operation of the
software, as well as instructions for adjusting the sensor
value and zeroing the Real UV254 to provide a baseline
for measurements.
5.5.2 Installation
Installation of the Real UV254 was straight-forward.
The vendor shipped the Real UV254 to Battelle along
with installation instructions. Installation of the Real
UV254 consisted of unpacking the instrument and
making two connections to the PPL via quick connect
fittings. The software was easily installed on a PC and
the instruction manual provided sufficient instructions
for software operation and data file generation. No
calibration of the Real UV254 was required other than
the daily sensor adjustment and zero procedure.
5.5.3 Operation
Prior to each set of contaminant injections, water
flow was initiated and then the Real UV254 UV
detector response was adjusted to between 33,000 and
36,000 response units using a knob on the right side
of the enclosure. This adjustment would not have to
be performed as often in an operational setting, but
was important for conducting this evaluation. The
adjustment was made to ensure that the Real UV254
UV detector was in an optimal working range, not
functioning in a maximum or saturated scenario, so
changes in transmittance in response to the injection of
contaminants would be measured. This adjustment also
corrected for any drift that occurred throughout each day
of testing. The need for adjustment as evaluated before
each of 72 sets of contaminant injections. Over the
course of the evaluation:
• thirty-four sets of injections required no adjustment
• nineteen sets required adjustment from 36,000 -
40,000 response units
• nine sets required an adjustment from 30,000 -
33,000 response units
• seven sets required an adjustment from 25,000 -
30,000 response units
• two sets required an adjustment from 40,000
response units (the maximum detector response)
• one set required an adjustment from 21,000 response
units.
Following this adjustment, the Real UV254
transmittance was set to 100 percent by pressing a button
on the left side of the enclosure. Pressing this button
set the transmittance to 100% in uncontaminated tap
water. The detector response adjustment and baseline
transmittance adjustment were performed prior to each
set of injections.
After the evaluation stall had become familiar with
using the Real UV254, operation was straight-forward.
The Real UV254 was found to be very sensitive to
changes in operating conditions. Small changes
to the flow rate through the instrument resulted in
changes in the transmittance measured by the Real
UV254. Additionally, when monitoring water, the
transmittance was found to fluctuate during times in
which no injections had been made. This fluctuation
did not affect this evaluation because the duration of
the contaminant injections was over 2-3 hours. A stable
transmittance was observed over such short timeframes
and contaminant injections exhibited the cliaracteristic
mixing pattern that could not be mistaken for other
changes in the water. Over the course of more than one
day and during operational activities involving the pipe
loop, fluctuations in the transmittance were observed.
No formal investigation into this observed behavior
was made, but it is possible that the Real UV254 was
detecting changes in the chlorine or monochloramine
concentration in the water.
5.5.4 Maintenance/Consumables
No consumables were required for operation of the
Real UV254. No maintenance was performed on the
instrument over the course of testing.
5.5.5 Software/Data Collection
The Real UV254 software allowed data to be visualized
in real time on the screen of a PC. The data files
generated by the software were in a space delimited
format. Because of the high frequency of data
collection, the data files often became very large. This
high frequency data collection was useful for measuring
changes in the transmittance signal for the first pass of
a contaminant but made data analysis and interpretation
more difficult. The high frequency of data collection
was helpful during this technology evaluation but it may
not be necessary or desired in an operational setting.
While the software has the capability to display the
standard deviation of the collected data on the computer
screen and alarm when pre-programmed transmittance
thresholds are passed, these components were not
evaluated.
28
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6.0
Performance Summary
Summary results from evaluation of the Real UV254
are presented below for each performance parameter
evaluated. Discussion of the observed performance can
be found in Section 5 of this report.
6.1 Real UV254 Steady-state Response
to Contaminant Injections
Contaminant injections were performed for aldicarb.
carbofuran, colchicine, diesel fuel, disulfoton,
mevinphos. nicotine, potassium cyanide, sodium
lluoroacetate. 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 contaminants
prior to injection. In chlorinated water, the Real
UV254 measured a response for 0.01 mg/L injections
of colchicine a.s well as 0.1 and 1 mg/L of aldicarb,
carbofuran, colchicine, mevinphos, and nicotine. Those
five TICs as well as potassium cyanide and sodium
lluoroacetate were detected by the Real UV254 at 10
mg/L.
In chloraminated water, the Real UV254 measured a
response for 0.01 mg/L of carbofuran. colchicine, and
nicotine. Those three TICS, as well as aldicarb and
mevinphos were detected by the Real UV254 at 0.1
mg/L, 1 mg/L. and 10 mg/L. The Real UV254 measured
a response for two of the three 10 mg/L injections of
sodium lluoroacetate. No significant response was
measured for any injection of potassium cyanide into
chloraminated water.
Real UV254 responses for the BCs were similar
in chlorinated and chloraminated water. The Real
UV254 detected neither Chlorella nor Bacillus globigii
at any concentration tested in either chlorinated or
chloraminated water. The Real UV254 measured a
response upon injection of 107 organism/L of a mixture
of spores and vegetative cells of Bacillus thuringiensis
in both chlorinated and chloraminated water. Injections
of 105 organism/L of a stock solution containing only
spores of Bacillus thuringiensis into chloraminated water
produced an anomalous Real UV254 response. The Real
UV254 measured a response to 1 and 10 mg/L injections
of ovalbumin.
Disulfoton, diesel fuel, caibofuran, and ricin were
evaluated in a small-loop configuration because those
contaminants were added to the evaluation at the same
time as ricin which required a specific experimental
setup so they were evaluated using that same setup. In
chlorinated water, disulfoton was detected at 0.1 and 1
mg/L, diesel fuel was not detectable at any concentration
level and ricin was detected at 1 and 10 mg/L. The
results were considerable different in chloraminated
water. There was no response to disulfoton. Diesel fuel
was not soluble, but it was added to water and analyzed
using the Real UV 254; the results were inconsistent
and difficult to interpret. Ricin responded in the same
way that it had for chlorinated water. Carbofuran was
detectable in chlorinated water at 0.1 mg/L and 1 mg/L
and only 1 mg/L 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
Real UV254 TOC measurements.
Because the Real UV254 was able to make
measurements every second, the change in contaminant
concentration during mixing of the pipe loop was
observable. For example, the initial injection of
each contaminant caused a highly concentrated slug
of contaminant to pass by the Real UV 254 until it
became well-mixed into the PPL. Results show the
capability of the Real UV 254 to monitor such clianging
concentrations that could occur as the result of a
contamination event or as the result of an operational
event.
6.2 Operational Characteristics
During the evaluation of the Real UV254, the following
general operational characteristics were observed.
Installation and operation of the Real UV254 were
straight forward with no routine maintenance required.
Operation of the Real UV254 softw are was intuitive
and. as used during this evaluation, the data files were
easily obtained in a text-delimited format for convenient
transfer into a spreadsheet. This evaluation did not
consider other possible data retrieval methods (e.g.,
supervisory control and data acquisition (SCADA)) that
could be utilized with the Real UV254.
29
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30
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7.0
References
1. Test/QA Plan for the Evaluation of Online Total
Organic Carbon and Ultraviolet Spectroscopy
Analyzers, Technology Testing and Evaluation
Program. Version 1.0, March 19, 2009.
2. Quality Management Plan for the Technology
Testing and Evaluation Program, Version 3.0,
Battelle. Columbus. Ohio. January 2008.
3. U.S. EPA Testing and Evaluation Facility Technical
Standard Operating Procedure: Chloramine Source
Water Production. February 2009.
4. 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)1, January 2007.
5. Burrows, W. Dickinson; Renner. Sara E„
"Biological warfare agents as threats to potable
water," Environmental Health Perspectives, 107
(12), December 1999.
6. B. B. Potter and Wimsatt. J. C. Method 415.3,
Determination of Total Organic Carbon and
Specific UV Absorbance at 254 nin in Source
Water and Drinking Water. U.S. Environmental
Protection Agency. National Exposure Research
Lab: Cincinnati. Ohio. EPA/600/R-05/055, February
2005.
7. U.S. EPA. EPA Method 330.5, Chlorine. Total
Residual (Spect rophotomet ric. DPD) m Methods for
Chemical Analysis of Water and Wastes, EPA/600/4-
79/020, March 1983.
8. Hach Method 10200, Nitrogen. Free Ammonia and
Chloramine (Mono), Indophenol Method (0-4.50
mg/L CI, and 0-0.50 mg/L NH.-N) for finished
chloraminated drinking water, April 2004. U.S.
Patent 6,315,950 filed September 4, 1998 and issued
November 13, 2001.
9. R.C. Statt and J. A. Zeikus. 1993. Utex—the culture
collection of algae at the University of Texas at
Austin. J. Phycol. 29: 1-106.
31
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32
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Appendix
Tables of First Pass Changes in Transmittance
Due to Contaminant Injections
First Pass Change in Real UV254 Transmittance from Injections of Toxic Industrial Chemicals (TICs) into
Chlorinated Water (responses shown in gray)
Injected Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
AT
(%T)
AT
(%T)
AT
(%T)
0.01
-3.01
-1.06
-0.98
Aldicarb
0.1
-16.82
-15.06
-13.61
1
-84.74
-87.88
-85.27
0.01
0.04
0.19
-0.42
Carbofuran
0.1
-0.46
-4.46
-3.38
1
-31.45
-38.38
-30.07
10
-46.84
-49.33
-71.02
0.01
-16.23
-11.50
-5.59
Colchicine
0.1
-78.25
-70.90
-70.14
1
-58.39
-53.51
-72.18
10
-0.31
-0.27
-0.38
0.01
-0.79
-0.53
-0.71
Mevinphos
0.1
-5.76
-5.29
-4.26
1
-43.58
-39.35
-34.49
0.01
t
-6.83
-43.86
Nicotine
0.1
-28.06
-37.16
-33.05
1
-74.83
-82.25
-92.69
10
-18.43
-89.77
-22.59
0.01
0.67
0.16
0.07
Potassium Cyanide
0.1
2.38
1.18
1.09
1
3.72
3.22
2.80
10
-2.57
-1.75
-0.92
0.01
-0.12
-0.05
-0.19
Sodium Fluoroacetate
0.1
-0.17
-0.28
-0.06
1
-0.23
-0.02
-1.05
10
-10.33
-8.91
-11.59
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
"|" Only two replicates of the 0.01 mg/L nicotine injections were performed.
33
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First Pass Change in Real UV254Transmittance from Injections of Toxic Industrial Chemicals (TICs) into
Chloraminated Water (responses shown in gray)
Injected Contaminant
Concentration (mg/L)
Injection 1
Injection 2
Injection 3
Contaminant
AT
(%T)
AT
(%T)
AT
(%T)
0.01
-2.55
-0.39
-2.10
Aldicarb
0.1
-23.21
-10.61
-14.68
1
-88.09
-92.51
-81.53
0.01
-0.33
-0.65
-0.86
Carbofuran
0.1
-2.27
-6.60
-3.05
1
-31.18
-26.52
-33.25
10
-65.60
-55.00
-72.61
0.01
-8.51
-15.64
-16.00
Colchicine
0.1
-82.14
-79.50
-81.15
1
-60.45
-62.06
-61.81
10
-0.43
-0.44
-0.34
0.01
-0.61
-0.54
-0.56
Mevinphos
0.1
-5.90
-4.85
-3.93
1
-45.94
-44.91
-39.30
0.01
-2.43
-3.27
-3.52
Nicotine
0.1
-22.45
-28.07
-30.75
1
-87.33
-83.29
-85.72
10
-29.29
-24.01
-28.38
0.01
0.19
0.66
0.76
Potassium Cyanide
0.1
0.43
1.52
1.14
1
0.23
2.31
1.36
10
0.00
0.00
0.00
0.01
-0.20
-0.11
0.27
Sodium Fluoroacetate
0.1
0.13
-0.19
0.03
1
-0.06
0.10
0.03
10
0.04
-10.09
-6.00
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
-------
First Pass Change in Real UV254 Transmittance from Injections of Biological Contaminants (BCs) into
Chlorinated Water (responses shown in gray)
Injected Contaminant
Injection 1
Injection 2
Injection 3
Contaminant
Concentration
AT
AT
AT
(organism/L or mg/L)
(%T)
(%T)
(%T)
105
0.23
1.12
-0.09
Bacillus globigii
106
0.41
0.32
0.06
107
-1.51
-1.95
-1.29
105
0.44
-0.86
-0.31
Bacillus thuringiensis
106
-1.16
0.18
-1.09
107
-13.40
-10.00
-14.57
103
0.72
0.53
0.19
Chlorella
10"
0.45
0.58
0.43
105
0.14
0.61
-0.25
0.01
-3.04
-0.40
-1.49
Ovalbumin
0.1
-2.46
-0.74
-0.70
1
-14.57
-11.70
-6.62
10
-46.11
-49.24
-54.40
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
First Pass Change in Real UV254 Transmittance from Injections of Biological Contaminants (BCs) into
Chloraminated Water (responses shown in gray)
Injected Contaminant
Injection 1
Injection 2
Injection 3
Contaminant
Concentration
AT
AT
AT
(organism/L or mg/L)
(%T)
(%T)
(%T)
103
0.69
1.20
0.77
Bacillus globigii
10"
0.75
0.86
0.70
105
0.44
0.63
0.51
107
t
t
0.59
103
0.38
0.60
t
10"
-0.52
-0.51
t
Bacillus thuringiensis
105
-13.05
-13.09
0.06
106
t
t
-0.55
107
t
t
-9.24
103
0.50
0.67
0.28
Chlorella
10"
0.44
0.54
0.18
105
0.30
0.35
0.10
0.01
-0.14
-0.24
-0.39
Ovalbumin
0.1
-0.51
-0.45
-0.65
1
-7.25
-6.19
-7.31
10
-49.04
-57.21
-51.38
A "response" (indicated by shading) was at least three times the baseline standard deviation and exclude responses attributable to water injection
alone (i.e. 1.55%T ±2.10%T, see Section 3.6).
|Fewer than three replicates at this concentration
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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
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