THM_RD100-Siegal-2012_FINAL

R&D 100 • 2012

Exceptional service in the national interest

Parker THM Analyzer

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SANDIA NATIONAL LABORATORIES • R&D 100 2012 • ENTRY SUBMISSION

Parker THM Analyzer

1. Developer InformationA. Primary Submitter

Michael P. Siegal

Sandia National Laboratories

P.O. Box 5800, Mail Stop 1415

Albuquerque, NM, 87185-1415

USA

505-845-9453

Fax: 505-844-5470

[email protected]

www.sandia.gov

B. Joint Submitter

Using the Sandia National Laboratories concept for analyzing chemicals in

aqueous solutions, Parker Hannifi n Corporation created a commercial system

that includes a table-top tool and the software to run the system. First available

to the water utility industry, the Parker THM Analyzer is being readily accepted as

a low-cost alternative for high-resolution analysis of trace trihalomethane (THM)

concentrations in the water supply that are regulated by the U.S. Environmental

Protection Agency (US-EPA).

Kazi Z. A. Hassan

Parker Hannifi n Corporation

1005 A Cleaner Way

Huntsville, Alabama, 35805

USA

256-885-3879

[email protected]

2. Product InformationA. Product Name

Parker THM Analyzer

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B. Product Photo

Figure 1. The Parker THM Analyzer, the � rst product marketed based on Sandia’s nanoporous-carbon-coated surface acoustic wave (SAW) technology. This product was designed with input from water industry end users and experts. It provides water treatment operators with critical information in real-time needed to control THM formation.

3. Product Description This easy-to-operate, cost-effective, tabletop purge-and-trap gas chromatograph

ensures safe drinking water and monitors disinfection by-product formation at

water utilities in real-time without sample preparation or off-site analysis.

4. First MarketedThe Parker THM Analyzer was fi rst offered for sale in June 2011.

5. Has this product or an earlier version been entered in the R&D 100 awards competition previously? We entered a prototype of this technology, called the “Portable Sensor System for

the Analysis of Hazardous Chemicals in Water,” in 2010. It did not win.

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6. Principal InvestigatorMichael P. Siegal

Principal Member of the Technical Staff



Albuquerque, NM, 87185-1415

USA

505-845-9453

Fax: 505-844-5470

[email protected]

7. Product price$28,800

8. Patents1. Provisional Patent Application #2802-157-028. Filed 09/2011. ANALYTICAL

SYSTEM AND METHOD FOR DETECTING VOLATILE ORGANIC COMPOUNDS IN

WATER, Hassan, Doutt, Cost, Morse, and Geis.

2. Patent Application #13/032,254. Filed 02/22/2011. METHOD TO GROW

NANOPOROUS-CARBON FOR VOLATILE GAS SENSORS, Overmyer and Siegal

3. Patent Application #US 2008/0289397 A1. Filed 11/27/2008. PORTABLE

ANALYTICAL SYSTEM FOR DETECTING ORGANIC CHEMICAL IN WATER, Hassan,

Cost, Mowry, Siegal, Robinson, Whiting, and Howell.

9. Product’s Primary FunctionThe Parker THM Analyzer is a simple and easy-to-operate, cost-effective, fully

integrated table-top purge-and-trap gas chromatograph (GC) that ensures safe

drinking water and enables monitoring of disinfection processes at water utilities

in real-time without sample preparation or off-site analysis. It analyzes drinking

water samples in only 30 minutes for the presence of the four trihalomethanes

(THMs) simultaneously below part-per-billion (ppb) levels, greatly exceeding U.S.

Environmental Protection Agency (EPA) regulations.

One hundred years ago, typhoid and cholera epidemics were common throughout

the United States. Those diseases and others are still endemic in parts of the

This cost-effective,

table-top technology replaces an

entire chemical laboratory.

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world. For example, Haiti experienced outbreaks of typhoid and cholera in 2010.

In order to prevent similar outbreaks in the U.S., the US-EPA requires all water

utilities to monitor pathogen levels resulting from sewage discharges, leaking

septic tanks, and runoff from animal feedlots.

Ironically, the very chemical treatments of water so crucial for public health, e.g.,

chlorine and bromine, also react in water with trace natural organic matter to

create disinfection byproduct (DBP) chemicals, such as THMs, which are defi ned

as a group of chlorinated and brominated single-carbon compounds: chloroform

(CHCl3), dichlorobromomethane (CHCl2Br), dibromochloromethane (CHClBr2), and

bromoform (CHBr3). These four THMs are included in the US-EPA’s “suspected

negative health effects” category. Numerous toxicological and epidemiological

studies at high doses of THMs fi nd evidence for adverse reproductive 1, 2, 3, 4, 5 and

developmental effects 6, 7, 8, 9, 10, 11, while some low-dose studies show an association

to pancreatic 12, bladder 13, 14, 15, rectal and colon 16, 17 cancers.

The US-EPA requires all public water systems to use disinfection measures that

reduce DBP formation; in particular, total THMs are regulated to 80 ppb. State-

of-the-art analysis involves collecting water samples and sending them to a

specialized laboratory for chemical analysis, resulting in high cost and long wait-

times before results are reported. This time delay can cause critical problems for

public health and safety. Existing low-cost THM analysis systems barely meet US-

EPA limits and cannot measure the concentrations of each THM independently.

The Parker THM Analyzer is a cost-effective, table-top technology that replaces

an entire chemical laboratory. It provides easy-to-use, on-site analysis at water

utilities in 30 minutes (compared to the current times of days-to-weeks) with

no sample preparation of DBPs. With detection levels greatly exceeding US-

EPA requirements and comparable to large and expensive analytical laboratory

equipment, our product greatly benefi ts public health and safety.

10. How Does It Operate?The Parker THM Analyzer is designed for high-precision, high-accuracy

measurement of THMs and offers a full complement of calibration and

quantifi cation routines. With the push of a single button, helium (He) gas purges

volatile chemicals from a water sample and selectively captures the THMs in a

preconcentrator trap. The trap is then heated to desorb the THMs and carry them

in a He fl ow to a heated GC column that separates the THM components from

Toxicological and

epidemiological studies correlate

THM exposures to adverse

reproductive and developmental

effects, and increased

incidence of pancreatic,

bladder, rectal and colon

cancers.

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one another, with the individual THMs being detected by the nanoporous-carbon

(NPC)-coated surface acoustic wave (SAW) device for analysis. These functions

are shown schematically in Figure 2. The software program identifi es each THM

as it exits the GC column and analyzes their individual concentrations. The

ability to obtain THM results quickly and reliably without sample preparation

provides water treatment operators with the information they need to control the

formation of THMS.

Figure 2. The Parker THM Analyzer plumbing schematic

Running a sample on the Parker THM Analyzer begins with collecting a treated

water sample in a 40 mL EPA vial and pouring it into the sample holder that

screws into the analyzer, shown on the left side of the analyzer in Figure 3. The

operator then clicks on the “START” icon on the laptop screen, names the sample,

clicks “OK”, and waits only 28 minutes for the detailed results.

Figure 3. Analyzer and laptop for system control and analysis

“Purge” is to release the

volatile gases from water by

bubbling air or some inert

gas. “Trap” is to trap the volatile gases

one is interested in detecting.

We use a preconcentrator

that preferentially

holds, or traps, the THM gases.

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The software can display the results in several easy-to-interpret ways for the

operator’s convenience. One example is shown in Figure 4. The data panel at the

top tabulates the details of the chromatography. This particular result measured

a 10 ppb standard sample for calibration purposes. The concentration of each

THM is recorded separately, as well as totaled because the EPA currently regulates

the Total THMs, or TTHMs, in treated water. In addition, the chromatogram itself

is shown in the lower panel. Note that the SAW response peak heights get larger

with the mass of the THMs. This is due to the higher sensitivity of the analyzer

for the heavier THM molecules with higher boiling points, and is discussed in the

reference Siegal, M. P.; Mowry, C. D.; Pfeifer, K. B., “Nanoporous-carbon coated

surface-acoustic-wave device for the detection of sub-nanogram quantities of

trihalomethanes,” submitted to Analytical Chemistry. The reports can be printed or

pasted as an image into another document. In addition, the operator can transfer

the data into Excel, Word, or other programs for later use.

Figure 4. Analysis run window from the laptop program showing the processed chromatogram after a completed analysis run.

The analyzer is easily calibrated by running a set of standard samples. The samples

contain a mixture of each THM at a specifi c concentration. The software package

tabulates this data and provides an easy-to-understand display. A calibration for

chloroform is shown in Figure 5, plotting the SAW response peak heights against

the known concentrations.

The breakthrough that enables

this miniature and inexpensive

detector is our development

and use of NPC sorbent coatings

on the SAW device.

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Figure 5. Calibration window for viewing current and previous calibrations

The accuracy and reliability of THM analysis was performed independently at

several water plants around the country, each using an EPA Certifi ed Laboratory

for comparison. Table 1 shows a sample from the Nevada water plant where each

THM was measured independently. Note that the Parker THM Analyzer is always

within ± 10 – 15 % of the EPA certifi ed lab measurements, with the individual

THM results within ± 2 ppb.

Table 1. THM and TTHM results from a Nevada Water Plant and an EPA Certi� ed Laboratory

Tables 2, 3, and 4 show similar TTHM results from water plants in Alabama, Texas,

and South Carolina, all compared to an EPA certifi ed laboratory. Most water

utilities focus on the TTHM level because that is what the EPA presently regulates.

Again, all the results agree within ± 10 – 15 % and ± 7 ppb for TTHM.

Parker has hit a home run with this instrument

– Professor Christopher M.

Miller, Department of Civil Engineering,

The University of Akron

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Table 2. TTHM results from an Alabama Water Plant and an EPA Certi� ed Laboratory

Table 3. TTHM results from a Texas Water Plant and an EPA Certi� ed Laboratory

Table 4. TTHM results from a South Carolina Water Plant and an EPA Certi� ed Laboratory

11. Building Blocks of Our TechnologyCrucial factors for the development of this remarkable breakthrough technology

include the use of NPC as a sorbent material for SAW device sensors and the

ability to optimize it to achieve parts-per-billion to parts-per-trillion detection

levels depending on the analyte. Parker and Sandia have worked together on the

development of this NPC-coated SAW sensor system for THM detection since 2006.

Since our R&D 100 Award submission two years ago for a prototype device, Parker

has greatly improved the overall system by transforming the original briefcase-

sized detector into a small table-top instrument (Figure 1), accommodated all

electrical circuitry onto a single PC board, improved the GC, modifi ed the trap

(now also allowing for easy replacement), and is presently marketing the Parker

THM Analyzer based on this technology.

The NPC-coated SAW sensor is the heart of the product. We focus pulsed 248-

nm radiation from a krypton fl uoride (KrF) excimer laser to ablate a rotating

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graphite target, as shown in Figure 6. We control the kinetic energy of the ablated

carbon species by introducing a controlled pressure of argon (Ar), ranging from

100 – 200 mTorr, into the pulsed laser deposition (PLD) vacuum chamber. As

the Ar background pressure increases, the kinetic energy of the ablated species

decreases, resulting in lower NPC mass densities. We have reported mass densities

ranging from 0.08 – 2.0 g/cm3.

Figure 6. Photograph of the pulsed-laser deposition process used to create nanoporous-carbon � lms.

We grow NPC directly onto ST-cut quartz surfaces between the 97 MHz gold

interdigitated transducers of a SAW delay line, shown in Figure 7(a), using PLD.

NPC self-assembles during deposition and consists of nano-fragments of several

aligned graphene sheets that have interplanar spacings expanded by as much as

55% compared to crystalline graphite. Intercalation of molecules into graphite

is well known. Increasing the interplanar spacing eases the diffusion of gas

analyte molecules both in and out of NPC. The ideal NPC mass density is both

a function of this nanoporosity and the mechanical integrity of the material in

order to pass a surface acoustic wave across a highly-disordered surface without a

signifi cant loss in signal strength. This combination of critical factors is optimized

for NPC coatings with mass density ~ 1.0 g/cm3. Figure 7(b) is a scanning electron

microscope (SEM) image showing the surface morphology of an optimized NPC

fi lm coating, which despite its apparent roughness, is still suffi ciently mechanically

stiff to pass the acoustic wave.

Figure 7(c) is a transmission electron microscope (TEM) image showing the internal

structure of optimized NPC. The dark lines are actually individual planes of

graphene sheet segments. (Graphene is a one-atom thick layer of carbon atoms.)

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We fi nd two structural features that help explain the ability for NPC to act as such

a strong absorbent for volatile chemicals. First, the yellow arrow points to a void

with a diameter ~ 1 nanometer that can store analyte molecules. Second, and more

signifi cantly, the yellow line crosses over several aligned graphene sheet fragments.

The average distance between these fragments is ~ 0.45 nanometers, compared

to 0.35 nanometers for crystalline graphite. NPC consists of these small graphene

sheet clusters clumped together in every possible direction – very much like grains

of sand on the beach, where each grain is analogous to a cluster. These clusters are

separated by domain, or grain, boundaries. This image shows that such boundaries

exist every few nanometers. Essentially, NPC is an all-grain-boundary material

whose internal crystalline structure is expanded, with both features enabling rapid

diffusion in and out of the material, with nearly every internal graphene sheet

fragment acting as an available surface for chemical sorption.

Figure 7. (a) Photo of an NPC-coated 100 MHz SAW device on a U.S. quarter. This device replaces either a full chemistry laboratory or a mass spectrometer for detecting the presence of THMs to below ppb levels. (b) SEM image showing a 1-micrometer-thick NPC � lm surface with an optimized mass density of 1 g/cm3, exhibiting lots of ‘nooks and crannies’ for chemical species to penetrate into the bulk of the � lm. (c) TEM image showing internal structure of an ultra-sorbent self-assembled NPC coating that represents the heart of our invention. The yellow arrow points to a nanopore with ~ 1 nanometer diameter. The yellow line crosses several graphene sheet fragments and � nds that the interplanar spacing is ~ 0.45 nanometers.

The limits-of-detection (LOD) of the optimized NPC-coated SAW sensor device

are measured together by injecting quantifi ed mixed solutions, ranging from

1.3 – 183 ppb directly into a GC column. (Note that this GC column is NOT the

same as used in the Parker THM Analyzer and has NOT been optimized for these

tests.) The results are shown in Figure 8(a). Figure 8(b) is an expanded view of

the testing performed for the lowest THM concentration solutions. The THMs are

released from the GC in order of their molecular weights, which also corresponds

to their boiling points. Therefore, chloroform is released fi rst, followed by

dichlorobromoform, dibromochloroform, and fi nally bromoform.

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Figure 8. (a) The peak response of an optimized NPC-coated SAW device to all four THMs at exposure levels of 1.3, 9, 93, and 183 ppb. (b) An expanded view of the responses for the lowest THM exposure levels tested.

The raw data from Figure 8 is analyzed to quantify the SAW response of each

THM as a function of total exposure. This can be done either by determining

the maximum response for each THM (as is currently done by the Parker THM

Analyzer), or by integrating the total area under each response peak. While

the latter method provides greater sensitivity, the former method is more than

suffi cient to meet the needs of the water utility industry to assist in compliance

with EPA regulations.

Figure 9. Analysis of the NPC-coated SAW device responses to various exposures using the maximum SAW device response for each analyte. This method is used in the current Parker THM Analyzer software.

Figure 9 plots the THM peak heights vs. known concentrations. The thick dashed

lines through the data points are a best fi t. To measure the LOD for each THM,

the minimum SAW response above the noise level must be determined. This is

estimated from Figure 8(b). The noise-level is approximately 0.15˚ with a standard

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deviation of 0.07˚. A SAW response three-times greater than the standard deviation

of the noise level will provide a reliable detection limit. This sets the limit to

0.21˚ above the baseline and is shown in Figure 9 as a dashed horizontal line. The

intersection of the thin lines extrapolated from the power-law to this detection

limit provides the LOD for each individual THM and is listed as parts-per-trillion

in Table 5. The LODs for CF, DCBM, DBCM, and BF are 440, 150, 110 and 100 ppt,

providing precision and accuracy well in excess of EPA regulations.

Table 5. THM limits-of Detection (LODs) determined from both the peak height and integrated peak methods using an optimized NPC-coated SAW device sensor.

Figure 10. Analysis of the NPC-coated SAW device responses to various exposures using the integrated peak SAW device response for each analyte.

As noted above, the data from Figure 8 can be analyzed more accurately by

integrating the total area under each analyte response peak. These are plotted

in Figure 10. The thick dashed lines through the data points are a best fi t. To

The Parker THM Analyzer

provides precision and accuracy well

in excess of EPA regulations.

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measure the LOD for each THM, the minimum SAW response above the noise level

using this method must be determined. This can again be estimated from Figure

8(b), and is shown as a dashed horizontal line in Figure 10. The intersection of

the thin lines extrapolated from the power-law to this detection limit provides

the LOD for each individual THM and is also listed in parts-per-trillion in Table 5.

These LODs for CF, DCBM, DBCM, and BF are 77, 18, 0.7, and 0.3 ppt, signifi cantly

better than the peak height analysis used by the current Parker THM Analyzer

software, and offering a simple improvement to gain several orders-of-magnitude

of improved sensitivity for DBP analysis without making any physical changes to

the existing product.

12. Product Comparison Many methods for measuring THM concentrations in water exist. Most typically

have four sequential processes: purge, trap, separate, and detect. The fi rst three

are routine. Purge involves bubbling, or sparging, a gas through a specifi c volume

of water for a suffi cient period of time to extract all the volatile organic chemicals

(VOCs) from the water into a gas phase. This gas fl ow passes through a collector,

or preconcentrator, that traps VOCs but allows water vapor to pass through. The

preconcentrator material is typically specifi c for whatever VOCs are of interest.

Tenax® TA, a porous polymer resin based on 2.6-diphenylene oxide, is commonly

used for THMs. Upon heating, the collector releases the trapped species that then

enter a separator, such as a gas chromatograph. Finally a detector senses the

presence of VOCs, including THMs.

A variety of detectors can be used in combination with GC, such as mass

spectrometry (MS). GC-MS is a highly sensitive method for THM detection in

water and was used to discover many DBPs in water 18. THM limits-of-detection

range from parts per billion to a few parts per trillion.19, 20, 21 A more common

THM detector for GC is electron capture detection (ECD).22 Used in combination

with purge and trap, GC-ECD can also achieve LODs < 1 ppb for individual

THM detection; however, all of these methods require some form of sample

preparation.23, 24, 25, 26, 27, 28 Other detectors with GC have also been successfully

demonstrated, including microwave plasma emission,29 thermal conductivity

detection,30 and atomic emission detection.31

There are also several other methods that measure THM concentrations without

the use of a separation procedure. These include Fourier transform infrared

(FT-IR) spectroscopy using attenuated total refl ectance elements; however, the

“Because of the new-found convenience of

being able to perform THM

analyses in-house in 30

minutes, and the cost savings per sample, we

are now more proactive than

ever before about collecting THM samples.”

– Jeff Pendergrass, Water Treatment Plant Supervisor,

Scottsboro, Alabama Water, Sewer, and

Gas Board

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LODs are not as sensitive as the GC methods.32, 33 Ultrasonication has been used

to break carbon-chlorine (C-Cl) bonds, followed by detecting changes in Cl-1

ion concentration via pH/ion selective electrode meters; however, this method

requires signifi cant sample preparation, cannot distinguish the origin of Cl-1 ions,

and has limited sensitivity.34 Fluorescence spectroscopy has been used to measure

both Total Trihalomethanes (TTHMs) and total haloacetic acid (another DBP)

concentrations; however, it requires a chemical reaction with nicotinamide and

cannot measure DBPs independently.35, 36

Impedance spectroscopy based on analyte adsorption onto a surface has also

been utilized. Detection of brominated DBPs has been demonstrated from analyte

adsorption onto ten different conducting polymer coatings on gold microelectrode

sensing units; however, the combinations of polymers necessary to identify a

large number of mixed chemicals, such as exist in real water samples, can become

large.37

Surface acoustic wave device sensors offer greater resolution; an array of six SAW

device sensors was demonstrated to detect VOCs in water in combination with

purge-and-trap methods; however, similar to the impedance spectroscopy study, it

requires a sophisticated pattern recognition program to deconvolute the resulting

data, becoming both more complex and less reliable as the number of individual

VOCs present in a given sample increase.38

SAW devices have been studied more extensively as gas phase sensors.39 SAWs

measure the mass of materials that absorb to their surface as a fundamental

change in the propagation speed of a surface wave as a function of surface mass

density. This effect can be observed as a shift in center frequency of the transfer

function in frequency space or a phase change in the time domain. Small shifts

in the device wave propagation speed relate to the sorption of species. Sorbent

coatings, such as polymers or sol gels, are used to enhance this frequency shift

by allowing greater mass to adhere onto the surface.40, 41 An effective SAW coating

must be able to both sorb the desired gases and transmit an acoustic wave across

its surface without a signifi cant insertion-loss increase. This latter condition places

additional requirements on an effective SAW coating. It must be suffi ciently rigid

to maintain the acoustic wave and have minimal residual stress such that the

coating does not buckle or crack, and hence, dampen the wave. Also, the coating

cannot be discontinuous: all particles, grains, domains, etc., must maintain

good physical contact with the substrate to enable the passing of a surface wave.

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Assuming these parameters are met, there also exists a thickness constraint for a

coating; too much mass will dampen a surface acoustic wave, limiting the relative

response to analyte sorption.

These critical coating requirements are met with nanoporous-carbon (NPC). NPC

is a nanocrystalline-to-amorphous form of graphite that has no residual stress,

is thermally stable to 600˚C, and is hydrophobic (advantageous for a water

testing material). NPC grows at room temperature on any substrate surface

using line-of-sight pulsed-laser deposition. Mass density, and hence porosity and

surface area, can be controlled by the deposition energetics from 2.0 g/cm3 to

less than 0.1 g/cm3. The internal structure of NPC self-assembles during growth

and mainly consists of nano-fragments of several aligned graphene sheets that

have interplanar spacings expanded by as much as 55% compared to crystalline

graphite. Intercalation of molecules into graphite is well known. Increasing

the interplanar spacing eases the diffusion of species both in and out of NPC.43

NPC even demonstrates a large capacity to store alkali ions for electrochemical

capacitors and energy storage applications with relatively high charge and

discharge rates.44 More relevantly, NPC-coated SAW devices have been used to

detect a large variety of VOCs, similar to the THMs, with results suggesting LODs

well below 1 ppb for most of the analytes tested.45

Comparison Matrix

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Improvements Over Competitive Products

The US-EPA passed in March 2006 and began implementing in January 2012

the Stage 2 Disinfectants and Disinfection Byproducts Rule (DBPR) to reduce

potential cancer risks and address concerns with potential reproductive and

developmental risks from DBPs. The Stage 2 DBPR is designed to reduce the

level of exposure from DBPs without compromising the control of microbial

pathogens. A main component of this rule is to reduce to below 80 ppb the

concentration of total THMs that are present in water disinfected with chlorine or

chloramine. Furthermore, while TTHM is monitored for compliance, its presence

is representative of many other chlorination DBPs that also occur in water, so a

reduction in TTHM generally indicates an overall reduction of DBPs. Previously,

the rule required water plants serving a population base > 10,000 people to only

report the average of four TTHM measurements taken from different places within

their plant and distribution system. However, a recent rule change requires all

four site measurements be reported independently and be below 80 ppb TTHM.

The EPA currently recognizes TTHM measurements performed using approved

EPA analytical chemistry methods. The continuous cost of having these analyses

performed by outside vendors gets very high. Furthermore, under best-case

scenarios, a water utility get results within a few days, during which time fi nished

drinking water is delivered to everyone within the district served by that utility.

The Hach THM Plus systems are low-cost tools to help provide water utilities

with in-house TTHM data that can be used to more closely monitor the usage

of treatment chemicals without constantly going through the EPA certifi ed

laboratories. Some shortcomings in the Hach systems include the requirement

of a skilled worker to prepare water samples for TTHM analysis, the ongoing

costs for sample preparation kits, the time (several hours) for a single laborious

sample prep and measurement, the limited resolution (10 ppb), and the fact

that the individual THMs cannot be determined, just the four THMs in aggregate.

In addition, the Hach THM Plus methods can result in false positives due to

interference from other chlorinated DBPs. These considerations place severe

constraints on the utility and limit the overall usefulness of the device, preventing

the Hach product line from truly being competitive with the Parker THM Analyzer.

The Infi con systems provide signifi cantly better information than the Hach

instrumentation, indeed more than suffi cient to meet the requirements of the EPA

regulations. Similar to the Parker THM Analyzer, these gas chromatography and

The Parker THM Analyzer

is the only cost-effective

chemical detection

system that reports each

chemical separately

and detects low levels

(< 1 ppb) of all four THMs.

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GC/mass spectrometry instruments can measure individual THM levels to limits

ranging from 1 ppt to 1 ppb. However, the Infi con systems range in cost from

$45,000 to $140,000 for a complete analytical system and require a signifi cant

level of personnel training to operate and interpret the results.

The Parker THM Analyzer is the only cost-effective chemical detection system that

reports each chemical separately and detects low levels (< 1 ppb) of all four THMs.

The Parker THM Analyzer combines all the necessary system features (purge, trap,

separate, and detect) using a low-cost, small, light-weight sensor based on mature

SAW device technology, but greatly improved with highly sensitive, reliable,

reproducible, and thermally stable NPC-sorbent coatings. The use of NPC-coated

SAW sensor devices enables the Parker THM Analyzer to achieve the detection

resolution and speciation of the high-cost Infi con product lines, but at signifi cantly

lower cost. Most importantly, the Parker THM Analyzer is easier to use than any of

the competitive products, requiring signifi cantly less training and lower skill levels

to perform chemical analyses: simply pour in the water and push a single button!

Limitations of product

• The Parker THM Analyzer is not an online or in-process instrument.

Parker’s THM Analyzer is designed to perform analysis on grab-samples taken

from multiple collection sites. While an on-line instrument could offer municipal

plant operators continuous process monitoring feedback at one site, customer

discovery indicated most operators preferred the ability to analyze samples

taken from multiple collection sites to control the process from initial raw water

treatment to clear well and on throughout the distribution system.

• Parker’s THM Analyzer is not portable

The THM Analyzer is a transportable, tabletop design weighing approximately 14

pounds. It was developed to operate in a plant lab environment and can easily

be transported from one plant to another.

• The Parker THM Analyzer does not feed data directly to a SCADA (Supervisory

Control and Data Acquisition) system.

The Analyzer’s grab-sample design confi guration allows users the fl exibility

to input custom sample names and information by collection site. Full report

features and data logging are supported.

• Parker’s THM Analyzer is not EPA Certifi ed.

The Parker THM Analyzer is a process-monitoring instrument designed to

Our product is easier to use than any of

the competitive products, requiring

signi� cantly less training

and lower skill levels: simply

pour in the water and push a single button!

19


provide municipal water treatment plants with timely data that can be used

to control their process and optimize the effi ciency of their operation. It is not

an US-EPA-compliance instrument and does not replace the need for US-EPA-

required compliance testing. This is also true for other competitive products

on the market.

13. Product UsePrincipal Applications and Bene� ts

The Parker THM Analyzer will greatly benefi t public health and safety by

enabling on-site detection of hazardous chemicals in the nation’s water supplies

at lower levels in real time. Furthermore, past work at Sandia demonstrates this

technology is easily extended to detect other volatile organic and toxic industrial

compounds, both in solution and in air, at similar levels, i.e., near part-per-

trillion limits-of-detection.

Three hundred million people in the United States rely on public water systems

for safe, clean water. One hundred years ago, typhoid and cholera epidemics were

common throughout American cities. Disinfection, typically using chlorine, was

a major factor in reducing these epidemics and is still an essential part of water

treatment today. In 1990, the US-EPA Science Advisory Board cited drinking water

contamination as one of the most important environmental risks and indicated

that disease-causing microbial contaminants (i.e., bacteria, protozoa, and viruses)

were still the greatest remaining health-risk management challenge for drinking

water suppliers. This recognition was prompted by the concern about the number

of waterborne disease outbreaks in the United States, with over 500,000 cases

of waterborne disease reported between 1980 and 1994. In 1993, an outbreak

of Cryptosporidium, a microbial pathogen, caused 403,000 people in Milwaukee

to experience intestinal illness;46 over 4,000 were hospitalized, and at least 104

deaths were attributed to the disease.47 Not surprisingly, these problems exist

throughout the world.

The Safe Drinking Water Act (SDWA) was fi rst passed by Congress in 1974 and

amended in 1986 and 1996. The US-EPA requires all public water systems to

closely monitor pathogen levels, including a few types of bacteria, viruses,

protozoa, and other organisms, which are frequently a result of fecal matter from

sewage discharges, leaking septic tanks, and runoff from animal feedlots into

bodies of water.

Three hundred million people

in the United States rely on public water

systems for safe, clean water.

20


As chemical detection developed over the years, scientists and engineers gained

greater abilities to identify and measure exactly what is in our water supplies.

Ironically, chemical treatment of drinking water that is critical for health, such as

chlorine, ozone, and chlorine dioxide, also react with trace natural organic matter

to create disinfection byproduct chemicals, such as the trihalomethanes. The

presence of THMs in the water supply was fi rst reported in 1974.48 Different DBPs

result from different combinations of source water and disinfection processes, but,

in fact, only a few are monitored and regulated by the US-EPA. A major challenge

for water suppliers is how to balance the risks from microbial pathogens and

DBPs. The 1996 amendments to the SDWA required the US-EPA to develop rules to

achieve these goals.

In December 1998, the EPA established the Stage 1 Disinfectants/ Disinfection

By-products Rule, requiring all public water systems to use treatment measures

that reduce the formation of DBPs and meet specifi c standards. Today, TTHMs

are regulated at a maximum allowable annual average of 80 ppb. THMs

are characterized in the “suspected negative health effects” category, and

epidemiological and toxicological studies at high doses of THMs demonstrate clear

adverse reproductive and developmental effects, while some low-dose studies

show an association, rather than a causal link, to bladder, rectal, and colon

cancers. While the degree of risk has long been debated, the US-EPA requires

measurement and reporting of THMs in our water, preferring to err on the side of

safety while scientists continue studying these correlations.

The true variation in THM concentrations for any utility is not known, but

generally is assumed to vary daily due to a variety of source quality and treatment

factors. Indeed, seasonal variations are known due to the increased abundance

of natural organics in water during warmer weather. Unfortunately, the US-EPA

is forced to balance the health risks with the low costs of provision by water

consumers, and therefore only requires testing and reporting quarterly or

annually, depending on the size of the utility. Because of the unknown risk of each

individual THM, the diffi culty in providing simultaneous individual measurements,

and the natural variation by locality, the four THMs are reported together as a

group.

In order to meet the 80 ppb regulation for Total THMs, many utilities are

considering changing their disinfection process to an alternative, but less-

understood process using chloramine-based chemicals. There are known DBPs

21


generated by this process as well, however, there is little data suggesting that they

have lowered risk factors. It is conceivable that increased knowledge of THM levels

will infl uence utility decisions regarding the switch to chloramines.

The ability to detect each THM separately with rapid and low-cost technology

will have wide-ranging impacts on the 300 million water consumers in the U.S.,

their utilities, and the epidemiological community. Implementation of the Stage

1 DBP Rule requires utilities to take samples across their distribution network to

determine approximate variations and concentration excursions. Enabling utilities

to measure THMs quickly and cheaply will allow them to:

a. monitor and optimize their disinfection processes for increased safety and

regulatory compliance, and

b. save money by more precisely determining locations to collect laboratory

samples, reducing the cost of compliance and monitoring.

The ability to detect each THM separately with on-site and rapid detection

technology will enable the epidemiological community to perform lower-

cost studies that also have improved data quality and frequency because the

measurements are:

a. in situ (local and not sent back to the lab)

b. more rapid (30 minutes versus waiting weeks for lab results)

c. economical due to no laboratory testing expenses.

The Parker THM Analyzer will enable improved risk assessments and

understanding of local variations, providing long-term health benefi ts to

water consumers.

Other Applications

While the initial focus of our product is monitoring THMs in water, we have

demonstrated detection of other chemicals of commercial value and health

interest. This includes both water and air analysis. Some specific examples

are discussed below, but the great advantage of the NPC-coated SAW is its

sensitivity and non-specific nature – potentially useful in a variety of chemical

monitoring applications.

The analyzer system is not limited to THMs in water. A host of chemical

contaminants can be detected. Figure 11 shows the analysis, using the

physical system without modification, of a water sample containing ppb

22


levels of several common fuel components of concern in fuel storage and

water quality applications.

Figure 11. Analysis of a water sample containing common fuel components.

Other hazardous solvents of concern to drinking water and wastewater

applications include chlorinated compounds such as those detected by the system

and shown in Figure 12. We anticipate additional applications with respect to

water monitoring. The measurement of chemicals in water is important for issues

ranging from:

• Homeland Security

• regulatory compliance

• taste and odor concerns

• remediation

• containment, cleanup, or tracking of chemical spills.

Figure 12. Analysis of hazardous chlorinated compounds

We also anticipate that this technology will be useful for air monitoring. Only

slight modifi cations will be required to collect and analyze air samples. The speed

and cost effectiveness of the system will allow, for example, occupational health

exposure monitoring. Breath monitoring in health-system settings or for disease

research is also anticipated.

23


Sandia has demonstrated NPC-coated SAW sensor devices detecting airborne

chemicals that are critical to public health and national security needs, including

volatile organic compounds (VOC), toxic industrial chemicals (TIC), chemical

warfare agents (CWA), and explosive and explosive residue compounds, such

as triacetone triperoxide (TATP), used in failed terrorist attempts on airliners.

Nearly all of these compounds are detected as readily as the THMs shown in this

application to LODs ranging from 1 ppb to better than 1 ppt.

Figure 13 demonstrates detection using a heated SAW of explosives-related

compounds. The ability to use a heated SAW makes the system useful for industrial

applications and is unique among coated-SAW developments.

Figure 13. Detection of explosives related compounds using a heated SAW.

Sandia has also applied NPC coatings as the adsorbent material for

micropreconcentrator devices where the analyte of interest is semi-volatile, such

as those commonly used for CWA and explosives. Such devices are routinely fl ash

heated to elevated temperatures near 200˚C to release the captured analytes

into some analytical system (GC, SAW, mass spectrometer, etc.). However, high

residual stresses in commonly used polymer or sol-gel coatings lead to fi lm

delamination and membrane cracking with thermal cycling, constraining fi lms to

submicrometer thicknesses that limit the available adsorbent surface area. The

NPC coatings do not have these limitations.

NPC-coatings for both SAW-coated sensors and preconcentrators can be readily

confi gured to develop a portable detection system for airborne chemicals with

minor alterations to the present confi guration, greatly expanding its fi eld-of-use

beyond chemical detection in aqueous systems.

NPC-coated SAW sensor rapidly

detects airborne chemicals that are critical to public health and national

security needs: volatile organic

compounds, toxic industrial

chemicals, and chemical

warfare agents.

24


14. SummaryThe Parker THM Analyzer is an integrated purge-and-trap gas chromatograph

that provides results without sample preparation. This device can help operators

optimize water treatment at the plant and evaluate water age in the distribution

system for improved control over the formation of THMs. The Parker THM Analyzer

provides drinking water treatment plants and water distribution facilities with an

important tool to help deliver safe drinking water to the public.

The Parker THM Analyzer provides high-precision, high-accuracy measurement

of THMs and offers a full complement of calibration and quantifi cation routines.

With the push of a button, the analyzer provides sample purging, THM component

separation, precise and accurate detection, and data analysis.

Offered in a complete analytical package, the Parker THM Analyzer features

a touch screen for status indication and basic data results displays. Analyzer

calibration is streamlined with detailed menu options, while push-button

operation simplifi es building calibration curves and quantifying sample results.

This cost-effective, tabletop technology replaces an entire chemical laboratory. It

provides easy-to-use, on-site analysis with no sample preparation of DBPs at water

utilities in 30 minutes (compared to the current times of days to weeks), greatly

benefi ting public health and safety. It is the only cost-effective tabletop sensor

system with better than ppb LOD levels for each THM simultaneously, greatly

enhancing the information necessary for epidemiological and toxicological studies

of these hazardous disinfection byproducts.

Furthermore, testing demonstrates the ability to readily detect many different

chemicals in water, including volatile organic compounds, toxic industrial

chemicals, and explosive-related compounds. Identifi cation of these chemicals in

a laboratory, followed by a simple calibration similar to what we have performed

for the THMs, will enable the analyzer to monitor a multitude of chemicals

simultaneously. Previously, only expensive mass spectrometry techniques have

been capable of individually detecting each of these other water contaminants in

a mixed sample to ppb levels.

The Parker THM Analyzer, with its ease of measurement at reasonable cost, can

enable the US-EPA to regulate additional chemicals in the future and further

improve the safety of our municipal drinking water systems.

The Parker THM Analyzer provides high-

precision, high-accuracy measurement of THMs and

offers a full complement of calibration and

quanti� cation routines. With

the push of a button,

the analyzer provides sample

purging, THM component

separation, and data analysis.

25


Finally, the small size and relatively low-cost of this system also suggest future use

as a permanent in situ diagnostic providing real-time monitoring of disinfection

processes. Such measurement improvements will not only create a safer fi nished

drinking water supply for the public, but can also help reduce the costs to

municipalities for their disinfection processes, and hence, lower the costs to the

ultimate users of the drinking water.

15. Af� rmationBy submitting this entry to R&D Magazine I affi rm that all information submitted

as a part of, or supplemental to, this entry is a fair and accurate representation of

this product.

Michael P. Siegal

26


Appendix A: Submitter Information1. Contact person to handle all arrangements on exhibits, banquet, and publicity.

Glenn Kubiak

Director, Sandia National Laboratories

P. O. Box 969, Mail Stop 9405

Livermore, CA

94551-0969

USA

925-294-3375

Fax: 925-294-3403

[email protected]

2. Contact person for media and editorial inquiries.

Glenn Kubiak

Director, Sandia National Laboratories

P. O. Box 969, Mail Stop 9405

Livermore, CA

94551-0969

USA

925-294-3375

Fax: 925-294-3403

[email protected]

APPENDIC

ES

27


Appendix B: Development Team Information Donald L. Overmyer

Member of the Technical Staff



Albuquerque, NM

87185-1415

USA

505-844-5435

Fax: 505-844-5470

[email protected]

Curtis D. Mowry

Senior Member of the Technical Staff



Albuquerque, NM

87185-0886

USA

505-844-6271

Fax: 505-844-2974

[email protected]

Kent B. Pfeifer




Albuquerque, NM

87185-1425

USA

505-844-8105

Fax: 505-844-1198

[email protected]

28


Appendix B: Development Team Information (cont.)Alex Robinson




Albuquerque, NM

87185-1080

USA

505-844-9520

Fax: 505-844-2081

[email protected]

William M. Cost

Applications Engineer

Parker Hannifi n, Instrumentation Products Division

1005 A Cleaner Way


USA

256-885-3810

[email protected]

Mike Doutt

Senior Project Engineer


1005 A Cleaner Way


USA

256-885-3834

[email protected]

Glenn Geis

Project Engineer - Systems


1005 A Cleaner Way


USA

256-885-3871

[email protected]

29


Appendix B: Development Team Information (cont.) John A. Morse

New Business Development Manager


1005 A Cleaner Way


USA

256-885-3850

[email protected]

30


Appendix C: Patent Application

Electronic Acknowledgement Receipt EFS ID: 10897864 Application Number: 61531974 Confirmation Number: 5183 International Application Number: Title of Invention: ANALYTICAL SYSTEM AND METHOD FOR DETECTING VOLATILE ORGANIC COMPOUNDS IN WATER First Named Inventor/Applicant Name: Kazi Z. A. Hassan Customer Number: 49458 Application Type: Provisional Time Stamp: 18:10:23 Filing Date: Receipt Date: 07-SEP-2011 Attorney Docket Number: P157P0028US Filer Authorized By: Filer: Michael P. Wendolowski

Payment information: Submitted with Payment yes Payment was successfully received in RAM $220 Payment Type Credit Card RAM confirmation Number 8206 Deposit Account 180988 Authorized User WENDOLOWSKI,MICHAEL P. The Director of the USPTO is hereby authorized to charge indicated fees and credit any overpayment as follows: Charge any Additional Fees required under 37 C.F.R. Section 1.16 (National application filing, search, and examination fees) Charge any Additional Fees required under 37 C.F.R. Section 1.17 (Patent application and reexamination processing fees)

31


Appendix C: Patent Application (cont.)

32


Appendix D: Letters of Support

33


Appendix D: Letters of Support (cont.)

34



35



36



37



38


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Exceptional service in the national interest

Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000

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