WO2001009041A9 - System for protection of building water supplies against chemical and biological warfare agents - Google Patents

System for protection of building water supplies against chemical and biological warfare agents

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Publication number
WO2001009041A9
WO2001009041A9 PCT/US2000/019729 US0019729W WO0109041A9 WO 2001009041 A9 WO2001009041 A9 WO 2001009041A9 US 0019729 W US0019729 W US 0019729W WO 0109041 A9 WO0109041 A9 WO 0109041A9
Authority
WO
WIPO (PCT)
Prior art keywords
water
treatment
recited
potable
agent
Prior art date
Application number
PCT/US2000/019729
Other languages
French (fr)
Other versions
WO2001009041A3 (en
WO2001009041A2 (en
Inventor
Clifford A Megerle
Original Assignee
Lockheed Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lockheed Corp filed Critical Lockheed Corp
Priority to AU13261/01A priority Critical patent/AU1326101A/en
Publication of WO2001009041A2 publication Critical patent/WO2001009041A2/en
Publication of WO2001009041A3 publication Critical patent/WO2001009041A3/en
Publication of WO2001009041A9 publication Critical patent/WO2001009041A9/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18Water
    • G01N33/1826Water organic contamination in water
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/008Control or steering systems not provided for elsewhere in subclass C02F
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18Water
    • G01N33/1826Water organic contamination in water
    • G01N2033/184Water organic contamination in water herbicides, pesticides, fungicides, insecticides, or the like

Definitions

  • This application claims the benefit of the co-pending U.S. provisional application 60/144,730 filed on July 20, 1999 pursuant to Title 35 USC Section 119(e).
  • This invention relates to a system and method designed to detect the presence of harmful or toxic agents in potable water systems and to provide treatment to water in response to the detection.
  • Buildings in urban and suburban areas including government buildings, commercial buildings, arenas, hospitals and private residences in most circumstances rely upon local municipal water supplies. Because these buildings must rely on external water systems that are outside the control of any security system, the water source for a building is a natural target for terrorists or saboteurs.
  • Terrorists can remotely introduce potentially harmful agents into the water system disrupting normal operations, instill fear to the populace and could potentially cause severe illness or death to large numbers of people who use the water supply of the building.
  • Embassies, consulates, military bases, schools, churches and other locations where citizens living abroad may congregate are particularly vulnerable targets. Such locations have a relatively high density population and most individuals share common citizenship. Furthermore, the water systems frequently do not have high quality treatment. Populations living abroad do not have the ability or authority to monitor the water system or provide for the security of the water system upon which they rely. Accordingly the locations identified above are frequently identified as potential targets for attack by terrorist groups or by unfriendly governments. A further potential target which share similar attributes as U.S.
  • botulinum toxin a highly toxic agent, an ounce or two in a reservoir of 10 million gallons would, in theory, kill anyone who drank a half-pint of water. Fortunately, there is a difference between theoretical and practical toxicity. It would be extremely difficult to disseminate the toxin evenly throughout the water supply; its presence would probably be detected, and boiling the water would suffice to make it harmless. Even at lower levels of heat, botulinum toxin rapidly loses its effect.
  • a biological or chemically harmful agent may be introduced to a municipal system from the secure privacy of any neighboring residence with a faucet by using a suitable pump having sufficient back pressure. Agents could also be directly introduced to a water main in the vicinity of the targeted building and outside the area that is controlled by the security force of the building.
  • the present invention involves an integrated system for the detection and subsequent removal of chemical and biological warfare agents from water supplies.
  • the system is designed to detect both toxic chemicals and pathological biological agents in water supplies and more particularly, to detect the presence of biological pathogens in water systems which are amenable to intentional contamination.
  • the system includes real time sensor and detection equipment, a sampling system, a manifold system, and treatment steps to provide parallel water systems that provide both potable and uncontaminated but non-potable water supplies to a particular building or other secured location such as an encampment or airport or port.
  • the system is controlled by a central processing unit that receives input from the detectors, processes the signal and provides output to the manifold system that directs the water supply to the treatment steps.
  • the system employs a biological agent detector/identifier such as a modified Joint Biological Point Detection System
  • JBPDS which is adapted for the detection of water borne pathogens or agents that can be effectively delivered by water.
  • the system further includes a detector or series of detectors that can detect typical chemical warfare agents within a water system.
  • a central manifold directs influent water from the inlet supply to a water reservoir or series of water reservoirs that are provided for treatment of the incoming water.
  • the manifold system diverts water from the inlet conduit to the treatment system in response to a signal from a central controller.
  • the treatment system which includes a series of reservoirs for preliminary treatment steps, is designed to render target agents harmless. Although the water exiting the primary treatment system would not cause illness, water exiting the primary treatment stage is not intended for potable use. Such water may be appropriate for use for fire systems, irrigation, or air conditioning systems. Water that is intended for consumption or personal hygiene is subjected to further treatment steps including distillation.
  • FIG. 1 is a schematic drawing of the system of the present invention.
  • Fig. 2 is a schematic drawing of the primary treatment system of the present invention.
  • a secured water system is depicted in a schematic format.
  • Water from an unsecured source 101 enters a secure area 103 through conduit 105 and a portion is continuously shunted to a side stream 107.
  • Side stream 107 is then again split to both detection devices 109a and 109b and a sampling system 111.
  • the sampling system 111 periodically captures a predetermined volume of water from side stream 107 at predetermined intervals and retains the sample in a magazine.
  • the time when the sample was taken and the location where the sample was retrieved is printed on label having pressure sensitive adhesive and is then automatically applied to container used to retain the sample and then stored within the magazine.
  • the sample collection system would collect and retain samples for later independent laboratory analysis and confirmation.
  • Both the detection devices and the sampling system communicate with a central controller 113. hi response to input from detectors 109a and 109b controller 113 can alter the frequency of sampling by the sampling system 111.
  • Biological agents or target agents identified as likely to be used in view of toxicity and ease of acquisition to contaminate water or food supplies of civilian populations include anthrax, tularemia, yersina pestis, shigella flexneri, s. dysenteriae (shiga bacillus) and salmonella species such as salmonella typhi.
  • Another bacterial agent that is both particularly amenable to exposure through the gastrointestinal track and virulent is cholera.
  • other bacterial agents that are both debilitating and amenable to exposure through the gastrointestinal tract include salmonella, and escherichia coli. The bacterium identified above are easily obtainable and could quickly defeat antibacterial agents in a municipal water system.
  • Toxins of particular concern include mycotoxins, ricin, staph enterotoxin B, NX and botulinum toxin. Many of these biotoxins have been identified as potential target agents that may be used to contaminate water supplies. In addition to the agents identified above, other potential target agents include PCP, LSD, other hallucinogenic drugs and conventional chemical agents such as sarin, cyanogen chloride, soman, and hydrogen cyanide. Sarin is a colorless and practically odorless liquid that dissolves well in water and organic solvents. Although the basic military use of sarin is that of a gas and a persistent aerosol, it could be delivered by water. Sarin is a highly toxic agent with a clearly defined myopic effect, symptoms of intoxication appear quickly without any period of latent effect. Therefore, detection devices 109a and 109b are designed to detect these particular agents or other predetermined potential target agents.
  • the primary detection method and device 109a of the preferred embodiment is a continuous or intermittent sampling of inlet water using a flow cytometer.
  • Flow cytometers are designed for rapid enumeration and analysis of bacterial cells, algae, yeast, mammalian cells and particles between 0.4 and 15 ⁇ m in diameter.
  • Flow cytometry involves the analysis of fluorescence and light scatter at a single cell level. Samples are stained with fluorescence-labeled reagents such as antibodies or organelle probes that are specific for the application in a sheath fluid. The labeled cells are illuminated by laser and emission of the fluorocliromes (fluorescence intensity) is recorded using a photodetector.
  • the flow component is a fluidics system that precisely delivers the cells at the intersection of the laser beam and light gathering lens by hydrodynamic focusing.
  • the physical properties of cells that can be measured include forward light scatter (FS) and orthogonal or side light scatter (SSC). In forward light scatter the cell interrupts the laser beam and the light that passes around the cell is measured. This measurement is an indication of cell diameter or size.
  • Cellular side scatter is the light that is reflected 90° to the laser beam (all fluorescence is emitted at this angle also) and is an indication of cytoplasmic density or cell surface granularity.
  • Cells such as bacteria have proteins (antigens) on their surface, which are unique to that cell and antibodies (immunoglobulins) specifically bind to these cell surface antigens.
  • Antigen is defined as any material (usually foreign) that elicits and/or is specifically bound by an antibody.
  • a pathogen is any disease-producing agent such as a bacterium or virus.
  • PMT's Photomultiplier tubes detect the faint fluorescent signals and amplify them. These signals can then be transmitted to the controller. Cytoplasmic proteins and nuclear membranes can also be breached (permeabilized) to introduce antibodies against these intracellular proteins or stain nucleic acids with intercalating dyes.
  • a flow cytometer can be configured to detect a wide variety of parameters including the presence of cellular material, the presence of specific antigens and the presence of DNA.
  • water from the sample stream is directed to a mixing chamber and mixed with the required salts, pH buffering agents, detergent and reagents for the desired detection step.
  • the detector would be initially operated at pre-selected intervals to determine if there were biological agents present in the supply water.
  • the detector would be automatically operated to identify the specific biological warfare agent in the water by altering the reagents and/or detection methodology.
  • sample system 111 is collecting samples of incoming water for later laboratory analysis and confirmation.
  • the reagents for the detector may be customized for specific threats based upon intelligence data.
  • marked antibodies for certain antigens that are more likely to be used based upon the delivery route (water), virulence through the gastrointestinal tract, availability and intelligence would be pre-selected for the detection apparatus.
  • organisms which could not survive the necessary transit time in water having the same pH and ionic strength as the supply water and viral agents which would not be amenable to delivery would be secondary priorities.
  • the detection device 109a is designed to make a first detection step which can broadly identify the presence of any biological agent, and a second detection step to particularly detect the presence of specific antigens within a liquid sample.
  • a flow cytometer measures light that is scattered by cells or light which cells emit by fluorescence. Typically the cells flow through a laser which serves as the light source or otherwise excites a fluorescent marker attached to the cell (or antigen).
  • a fluorescent activated cell sorted is a type of flow cytometer that can be used to select certain cells from the sample streams.
  • An alternative related detection methodology useful for the rapid detection of specific antigens within a liquid or water sample is immunofluorescence microscopy.
  • This technique involves providing modified antibodies specific to the selected antigen or any macromolecule. Dyes such as rhodamine (that will emit red light) and or fluorescein (that will emit green light) when excited by light at specific wavelengths have a low nonspecific affinity for biological molecules. Attachment of the dyes to purified antibody results in a marker comprised of a fluorescent dye-antibody complex. The marker molecule is introduced to the incoming water sample and will bind with any complementary antigen (in this case the intact cell) that may be present in the sample. When the complex is illuminated by the exciting wavelength, the molecule will light up and can be detected by a photodetector.
  • the photodetector or photodetector array then sends a signal or signals to microprocessor 113 that may reflect both the magnitude, color, and duration of the emitted light as it passes the detector.
  • Microprocessor 113 then process the signal with respect to both the presence and magnitude of the signal. In the event a signal is detected that exceeds a predetermined strength, an output signal is sent to the valves in the manifold to divert incoming water flow from the building water supply line to the treatment system.
  • Another related technique which can rapidly provide information relating to the presence of specific antigens or entire cellular bodies involves enzyme immunoassay techniques including both rapid assay and conventional EIA kits. These techniques also take advantage of the specific antibody-antigen bonding and use an enzyme conjugate as the marker.
  • antibody is attached to the surface of a microwell or microtiter plate.
  • the microwell is flooded with the water sample and any antigen within the sample will bind.
  • the antigen selected for detection consists of intracellular material
  • the cell wall of the bacteria is first ruptured or lysed. Lysis can be preformed by sonication, changes in osmotic pressure, mechanical force (liquid shear, X-press), with an agent such as lysozymes or by the use of detergents (i.e. sodium dodecyl sulfate).
  • an enzyme conjugate is introduced to the microwells.
  • the enzyme conjugate that contains a marker that can be read by a spectrometer.
  • the conjugate will bind with any antigen that has bound with the antibody on the microwell.
  • the microwell is then read by the spectrometer and a signal is generated and directed to the controller in the event that a target antigen is present.
  • the series of reagents, washes and buffers can be automatically introduced to the plates at predetermined intervals, and at the end of the sequence, a spectrometer is automatically activated in response to instructions from a central controller.
  • the detection system may also be provided with additional detector technologies 109b that are optimized for the detection of chemical agents that are both debilitating and amenable to delivery by water as identified above on a second conduit 121 branching from conduit 107 from the incoming water supply line 105.
  • additional detector technologies 109b that are optimized for the detection of chemical agents that are both debilitating and amenable to delivery by water as identified above on a second conduit 121 branching from conduit 107 from the incoming water supply line 105.
  • certain drugs such as lysergic acid diethylamide (LSD), quinuclidinyl benzilate (BZ) and phencyclidine (PCP) have been as considered as target agents which could result in serious psychological effects.
  • LSD lysergic acid diethylamide
  • BZ quinuclidinyl benzilate
  • PCP phencyclidine
  • certain conventional chemical warfare agents identified above can be dissolved in water and are thus potential target agents.
  • HPLC High performance liquid chromatography
  • HPLC is a chromatographic separation technique wherein the stationary phase is a thin layer of powdered absorbent.
  • the detector for an HPLC emits a response due to the eluting sample compound and subsequently signals a peak on the chromatogram. It is positioned immediately posterior to the stationary phase in order to detect the compounds as they elute from the column.
  • the bandwidth and height of the peaks may usually be adjusted using the coarse and fine-tuning controls, and the detection and sensitivity parameters may also be controlled.
  • RI Refractive Index
  • UN Ultra-Niolet
  • ⁇ ear-IR Fluorescent
  • MS Radiochemical
  • NMR Nuclear Magnetic Resonance
  • LS Light Scattering
  • a mass spectrometer may also be employed to detect chemical agents. Frequently a sample is introduced to the mass spectrometer probe by the intermediary of chromatography device (e.g. gas chromatography, liquid chromatography, capillary electrophoresis, etc.).
  • a mass spectrometer consists of an inlet system, and ion source, an analyzer and a detector. Once in the source, sample molecules are subjected to ionization and ions formed in the source (molecular and fragment ions) acquire kinetic energy and leave the source.
  • a calibrated analyzer then analyzes the passing ion function of their mass to charge ratios. The ion beam exiting the analyzer assembly is then detected and the signal is analyzed.
  • Different kind of analyzer(s) can be used including magnetic, quadrulpole, ion trap, Fourier transform, and time of flight.
  • the application of mass spectroscopy techniques to identify chemical agents is well known in the art.
  • the controller 113 will automatically send a signal to the central manifold 115 to close the water service to the primary inlet supply 117 and direct the water to conduit 119 to the treatment system.
  • Other outputs from the central controller may include a signal to the sampling system 111 wherein the frequency of the sampling will increase in response to detection event and a command for the sampling system 111 to retain all samples.
  • an alarm 121 is also activated to alert both those responsible for the safety of the water supply and the potential end users of the system.
  • Treatment system 123 consists of both a potable treatment system 125 and a non-potable system 127.
  • non-potable system 127 the influent water from conduit 119 is treated to render biological and chemical agents harmless.
  • NaOH sodium hydroxide
  • Water is retained within the first tank a predetermined residence time in order to allow the alkaline environment to degrade chemical or biological warfare agents. Elevating the pH is very effective in destroying a wide range of chemical warfare agents including nerve, blister and blood agents as well as a wide range of pathogenic organisms.
  • a third treatment stage involves a third tank 208 in which conventional bleach is added at port 210 which is also highly effective at mitigating the virulence of biological contaminants. Bleach can be neutralized before the water is directed to the non- potable system 212. In alternative embodiments additional treatment steps such as ozonolysis or ultraviolet irradiation may also be incorporated to destroy any residual biological organisms.
  • the objective of the foregoing stage is to render any chemical or biological agent harmless and the water, although it would not be considered suitable for potable water sources primarily due to the presence of salts or bleach, would not be a hazard to health.
  • a portion of the water exiting the non-potable treatment system 127 is directed to a potable water treatment system 125.
  • the potable treatment system consists of a distillation system which removes all salts and any residual levels of chemicals or other toxic materials.
  • water containing contaminants is heated so that water enters the gas phase.
  • the distillation step involves filling a chamber with water and heating the water to the boiling point, 212°F (100°C). Boiling the water will kill most bacteria, cysts and viruses and the detritus remains within the chamber.
  • Toxins such as botulinium and ricen are also rendered harmless by extreme heat in the boiling process.
  • the steam rises into a stainless steel coil, leaving behind dissolved solids, salts, heavy metals and any other particles and materials having a lower vapor pressure than water. Heavy elements will not rise with the steam formed during the boiling process stay behind and become concentrated in the boiling tank.
  • the vapor is introduced to the coil that is cooled and the steam will condense.
  • the water is then allowed to percolate through a filter and collects in a storage tank as pure distilled water. Distillation provides consistently pure water and will completely remove a wide range of water contaminants including algae, viruses, cysts, bacteria, arsenic, benzene, chloride, chlorine, copper, fluoride, lead, mercury, nitrates, pesticides, rust, salt and sulfates.
  • the system has a separate system 129 for potable water exiting the potable water treatment system for supply to the building.
  • distillation is a preferred treatment method
  • other water treatment methods could be employed to remove the salts, ionic materials and undissolved contaminants.
  • These alternative methods may include ion exchange techniques or revere osmosis filtration followed by carbon filtration.
  • Ion exchange resins consisting of both anion and cation exchange resin, will remove both dissolved and undissolved ionic contaminants from the supply water.
  • Carbon filtration will effectively remove organic contaminants and serves to both remove any discoloration and odor.
  • Conventional media filtration is also recommended downstream of the carbon filter to ensure particulate matter is not introduced to the portable water system.
  • a further alternative method to provide potable water is the use of reverse osmosis, sometimes referred to as ultrafiltration.
  • Reverse osmosis will also effectively remove both salts and organic based contaminants, however pretreatment is recommended to ensure that the membranes used in the system do not become fouled.
  • Further features of the system include a feedback loop sampling feature which samples water exiting the non-potable and potable treatment systems and a second sample retention system which periodically samples the treated water for independent analysis.
  • the feedback loop feature provides a check to ensure that the water is safe for its intended application. In the event the detectors from the loop system are triggered, the central control will interrupt water supply within the facility.

Abstract

Integrated system for the detection and subsequent removal of chemical and biological warfare agents from water supplies. The system is designed to detect both toxic chemicals and pathological agents in water supplies and more particulary, to detect the presence of biological pathogens in water systems which are amandable to intentional contaminants. The system includes real time sensors and detection equipment, a sampling system, a manifold system, and treatment steps to provide both potable and uncontaminated non-potable supplies to particular building or other secured location such as an encampment or airport or port. The system is controlled by a central processing unit that receives input from the protectors, processes the signal and provides output to the manifold system that directs the water supply to the treatment steps.

Description

SYSTEM FOR THE PROTECTION OF BUILDING WATER SUPPLIES AGAINST TERRORIST ATTACK WITH CHEMICAL AND BIOLOGICAL
WARFARE AGENTS
BACKGROUND OF THE INVENTION
This application claims the benefit of the co-pending U.S. provisional application 60/144,730 filed on July 20, 1999 pursuant to Title 35 USC Section 119(e). This invention relates to a system and method designed to detect the presence of harmful or toxic agents in potable water systems and to provide treatment to water in response to the detection. Buildings in urban and suburban areas including government buildings, commercial buildings, arenas, hospitals and private residences in most circumstances rely upon local municipal water supplies. Because these buildings must rely on external water systems that are outside the control of any security system, the water source for a building is a natural target for terrorists or saboteurs. Terrorists can remotely introduce potentially harmful agents into the water system disrupting normal operations, instill fear to the populace and could potentially cause severe illness or death to large numbers of people who use the water supply of the building. Embassies, consulates, military bases, schools, churches and other locations where citizens living abroad may congregate are particularly vulnerable targets. Such locations have a relatively high density population and most individuals share common citizenship. Furthermore, the water systems frequently do not have high quality treatment. Populations living abroad do not have the ability or authority to monitor the water system or provide for the security of the water system upon which they rely. Accordingly the locations identified above are frequently identified as potential targets for attack by terrorist groups or by unfriendly governments. A further potential target which share similar attributes as U.S. consulates and embassies abroad and are thus a potential target are U.S. military installations. It is further contemplated that a system according to the invention could also be used either aboard ships or in connection with port facilities to mitigate the potential for contamination of a water supply on board. The successful penetration of the water supply for the U.S. military with a biological or chemical agent could have a devastating effect not only on the health of the personnel but also on the mission.
In general, there are a number of obstacles to effectively penetrate a general water source such as a reservoir or other surface water source. In view of the dilution factors involved, the purification and treatment steps employed by the water authority including the widespread use of disinfectants such as chlorine, a successful penetration of a large municipal water source with a pathogen would be difficult.
Although the scenario of terrorists poisoning the water supply of a population center by dumping a biological agent into its reservoir has been frequently contemplated, there is some consensus that the introduction of a small quantity of a 'supertoxin' or biological agent into the general water supply would be virtually impossible to poison a large water supply because of hydrolysis, chlorination, and the quantity of the toxin which would be required. Moreover, many of the highly lethal biological agents are not effectively transmitted by water and would be further debilitated by conventional purification systems. The contamination of a municipal water supply would require compensation for a significant dilution factor and hence the quantities of the biological agent that would be required are beyond what terrorists might find it easy to acquire, transport or introduce without detection. Finally, in most circumstances municipal water supply is screened for contamination.
For example, with regard to botulinum toxin, a highly toxic agent, an ounce or two in a reservoir of 10 million gallons would, in theory, kill anyone who drank a half-pint of water. Fortunately, there is a difference between theoretical and practical toxicity. It would be extremely difficult to disseminate the toxin evenly throughout the water supply; its presence would probably be detected, and boiling the water would suffice to make it harmless. Even at lower levels of heat, botulinum toxin rapidly loses its effect. Notwithstanding, there appears to be some disagreement and dispute among experts and some have warned that a terrorist with no particular expertise could feed the bacteria [referring to escherichia coli] into the water system or other public facilities and it has been reported that while one kilogram 'might not' harm a very large city, several kilograms would be enough to defeat the antibacterial agents in the water system. Others have suggested that measures such as chlorination would not necessarily kill such germs as the hardened anthrax created during the military's chemical and biological warfare programs. There is some consensus that anthrax spores can survive in boiling water and have been known to survive in soil for decades after the original contamination. There is also a concern that genetically engineered bacteria could be dumped into the water supply of a medium-sized city, resulting ultimately through the contagion in the deaths of millions. The US
Congressional Office of Technology Assessment has cited experts who have made claims that the effect that a person drinking 100 milliliters (less than half a cup) of untreated water from a 5 million liter reservoir would become severely sick and perhaps die if the reservoir had been contaminated by 1/2 kg of salmonella typhi (the cause of typhoid fever), 5 kg of botulinum toxin, or 7 kg of staphylococcal toxin, whereas it would require 10 tons of the chemical agent potassium cyanide to contaminate the reservoir to the same level of toxicity.
Although the contamination of the municipal water source such as a river or large reservoir does not appear to be a severe threat or highly vulnerable target, there nevertheless remains a concern. More particularly there is a concern with directed, local, smaller-scale attacks such as one confined to a small area but still capable of causing massive casualties. Generally, the smaller the target population, the more likely terrorists are to succeed, especially if the target population resides or works within a single building. Many believe that biological warfare within a city will most likely be directed against specific buildings or specific limited parts of the population. Dangerous bacteriological organisms or chemical agents can be introduced to a building a number of ways, and an optimal manner is through the water system. The water source for a particular building is limited in volume and the source may be accessible to a terrorist group. By introducing the harmful agent near the building, there is less dilution and less time when the agent is in contact with purification chemicals such as chlorine which could mitigate the effect of harmful biological agents. Although security personnel can monitor, maintain and control the immediate physical surrounding they cannot easily monitor the source of the water nor is the detection of contamination easily made. For example, a biological or chemically harmful agent may be introduced to a municipal system from the secure privacy of any neighboring residence with a faucet by using a suitable pump having sufficient back pressure. Agents could also be directly introduced to a water main in the vicinity of the targeted building and outside the area that is controlled by the security force of the building.
While the technologies to purify water are well known, as demonstrated above, there is a particular need for an integrated system which can both detect the presence of harmful agents, communicate an immediate alarm upon the detection of the presence of the agents, and provide a measured and complementary response to mitigate or remove the threat of the particular agent. It is accordingly an object of the invention to provide a manner to detect such an attack by sensing the presence of chemical and biological warfare agents in a water supply and to remove them or render them harmless in an inexpensive and effective way.
SUMMARY OF THE INVENTION
The present invention involves an integrated system for the detection and subsequent removal of chemical and biological warfare agents from water supplies. The system is designed to detect both toxic chemicals and pathological biological agents in water supplies and more particularly, to detect the presence of biological pathogens in water systems which are amenable to intentional contamination. The system includes real time sensor and detection equipment, a sampling system, a manifold system, and treatment steps to provide parallel water systems that provide both potable and uncontaminated but non-potable water supplies to a particular building or other secured location such as an encampment or airport or port. The system is controlled by a central processing unit that receives input from the detectors, processes the signal and provides output to the manifold system that directs the water supply to the treatment steps. The system employs a biological agent detector/identifier such as a modified Joint Biological Point Detection System
(JBPDS) which is adapted for the detection of water borne pathogens or agents that can be effectively delivered by water. The system further includes a detector or series of detectors that can detect typical chemical warfare agents within a water system. A central manifold directs influent water from the inlet supply to a water reservoir or series of water reservoirs that are provided for treatment of the incoming water. The manifold system diverts water from the inlet conduit to the treatment system in response to a signal from a central controller. The treatment system, which includes a series of reservoirs for preliminary treatment steps, is designed to render target agents harmless. Although the water exiting the primary treatment system would not cause illness, water exiting the primary treatment stage is not intended for potable use. Such water may be appropriate for use for fire systems, irrigation, or air conditioning systems. Water that is intended for consumption or personal hygiene is subjected to further treatment steps including distillation.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic drawing of the system of the present invention.
Fig. 2 is a schematic drawing of the primary treatment system of the present invention. DETAILED DESCRIPTION
Now referring to Fig. 1, a secured water system according to the invention is depicted in a schematic format. Water from an unsecured source 101 enters a secure area 103 through conduit 105 and a portion is continuously shunted to a side stream 107. Side stream 107 is then again split to both detection devices 109a and 109b and a sampling system 111. The sampling system 111 periodically captures a predetermined volume of water from side stream 107 at predetermined intervals and retains the sample in a magazine. Preferably the time when the sample was taken and the location where the sample was retrieved is printed on label having pressure sensitive adhesive and is then automatically applied to container used to retain the sample and then stored within the magazine. The sample collection system would collect and retain samples for later independent laboratory analysis and confirmation. Both the detection devices and the sampling system communicate with a central controller 113. hi response to input from detectors 109a and 109b controller 113 can alter the frequency of sampling by the sampling system 111.
Biological agents or target agents identified as likely to be used in view of toxicity and ease of acquisition to contaminate water or food supplies of civilian populations include anthrax, tularemia, yersina pestis, shigella flexneri, s. dysenteriae (shiga bacillus) and salmonella species such as salmonella typhi. Another bacterial agent that is both particularly amenable to exposure through the gastrointestinal track and virulent is cholera. Although not as lethal as cholera, other bacterial agents that are both debilitating and amenable to exposure through the gastrointestinal tract include salmonella, and escherichia coli. The bacterium identified above are easily obtainable and could quickly defeat antibacterial agents in a municipal water system. Toxins of particular concern include mycotoxins, ricin, staph enterotoxin B, NX and botulinum toxin. Many of these biotoxins have been identified as potential target agents that may be used to contaminate water supplies. In addition to the agents identified above, other potential target agents include PCP, LSD, other hallucinogenic drugs and conventional chemical agents such as sarin, cyanogen chloride, soman, and hydrogen cyanide. Sarin is a colorless and practically odorless liquid that dissolves well in water and organic solvents. Although the basic military use of sarin is that of a gas and a persistent aerosol, it could be delivered by water. Sarin is a highly toxic agent with a clearly defined myopic effect, symptoms of intoxication appear quickly without any period of latent effect. Therefore, detection devices 109a and 109b are designed to detect these particular agents or other predetermined potential target agents.
The primary detection method and device 109a of the preferred embodiment is a continuous or intermittent sampling of inlet water using a flow cytometer. Flow cytometers are designed for rapid enumeration and analysis of bacterial cells, algae, yeast, mammalian cells and particles between 0.4 and 15 μm in diameter. Flow cytometry involves the analysis of fluorescence and light scatter at a single cell level. Samples are stained with fluorescence-labeled reagents such as antibodies or organelle probes that are specific for the application in a sheath fluid. The labeled cells are illuminated by laser and emission of the fluorocliromes (fluorescence intensity) is recorded using a photodetector. The flow component is a fluidics system that precisely delivers the cells at the intersection of the laser beam and light gathering lens by hydrodynamic focusing. The physical properties of cells that can be measured include forward light scatter (FS) and orthogonal or side light scatter (SSC). In forward light scatter the cell interrupts the laser beam and the light that passes around the cell is measured. This measurement is an indication of cell diameter or size. Cellular side scatter is the light that is reflected 90° to the laser beam (all fluorescence is emitted at this angle also) and is an indication of cytoplasmic density or cell surface granularity. Cells such as bacteria have proteins (antigens) on their surface, which are unique to that cell and antibodies (immunoglobulins) specifically bind to these cell surface antigens. Antigen is defined as any material (usually foreign) that elicits and/or is specifically bound by an antibody. A pathogen is any disease-producing agent such as a bacterium or virus. By tagging each antibody with a different colored fluorochrome, the type and quantity of antigens expressed by each cell can be distinguished. Employing dichroic splitting mirrors, band pass filters and compensation colors can be resolved. Photomultiplier tubes (PMT's) detect the faint fluorescent signals and amplify them. These signals can then be transmitted to the controller. Cytoplasmic proteins and nuclear membranes can also be breached (permeabilized) to introduce antibodies against these intracellular proteins or stain nucleic acids with intercalating dyes.
Accordingly, a flow cytometer can be configured to detect a wide variety of parameters including the presence of cellular material, the presence of specific antigens and the presence of DNA. According to the invention, water from the sample stream is directed to a mixing chamber and mixed with the required salts, pH buffering agents, detergent and reagents for the desired detection step. In a preferred embodiment the detector would be initially operated at pre-selected intervals to determine if there were biological agents present in the supply water. In the event that the analysis of the signal indicated the presence of any organisms at a level that would be demonstrative or appropriate to an attack using biological warfare agents, the detector would be automatically operated to identify the specific biological warfare agent in the water by altering the reagents and/or detection methodology. At the same time, the system would confirm that sample system 111 is collecting samples of incoming water for later laboratory analysis and confirmation. The reagents for the detector may be customized for specific threats based upon intelligence data. Thus, marked antibodies for certain antigens that are more likely to be used based upon the delivery route (water), virulence through the gastrointestinal tract, availability and intelligence would be pre-selected for the detection apparatus. Moreover, organisms which could not survive the necessary transit time in water having the same pH and ionic strength as the supply water and viral agents which would not be amenable to delivery would be secondary priorities.
The detection device 109a is designed to make a first detection step which can broadly identify the presence of any biological agent, and a second detection step to particularly detect the presence of specific antigens within a liquid sample. A flow cytometer measures light that is scattered by cells or light which cells emit by fluorescence. Typically the cells flow through a laser which serves as the light source or otherwise excites a fluorescent marker attached to the cell (or antigen). A fluorescent activated cell sorted is a type of flow cytometer that can be used to select certain cells from the sample streams.
An alternative related detection methodology useful for the rapid detection of specific antigens within a liquid or water sample is immunofluorescence microscopy. This technique involves providing modified antibodies specific to the selected antigen or any macromolecule. Dyes such as rhodamine (that will emit red light) and or fluorescein (that will emit green light) when excited by light at specific wavelengths have a low nonspecific affinity for biological molecules. Attachment of the dyes to purified antibody results in a marker comprised of a fluorescent dye-antibody complex. The marker molecule is introduced to the incoming water sample and will bind with any complementary antigen (in this case the intact cell) that may be present in the sample. When the complex is illuminated by the exciting wavelength, the molecule will light up and can be detected by a photodetector. The photodetector or photodetector array then sends a signal or signals to microprocessor 113 that may reflect both the magnitude, color, and duration of the emitted light as it passes the detector. Microprocessor 113 then process the signal with respect to both the presence and magnitude of the signal. In the event a signal is detected that exceeds a predetermined strength, an output signal is sent to the valves in the manifold to divert incoming water flow from the building water supply line to the treatment system. Another related technique which can rapidly provide information relating to the presence of specific antigens or entire cellular bodies involves enzyme immunoassay techniques including both rapid assay and conventional EIA kits. These techniques also take advantage of the specific antibody-antigen bonding and use an enzyme conjugate as the marker. In a conventional arrangement, antibody is attached to the surface of a microwell or microtiter plate. The microwell is flooded with the water sample and any antigen within the sample will bind. In the event the antigen selected for detection consists of intracellular material, the cell wall of the bacteria is first ruptured or lysed. Lysis can be preformed by sonication, changes in osmotic pressure, mechanical force (liquid shear, X-press), with an agent such as lysozymes or by the use of detergents (i.e. sodium dodecyl sulfate). Next the microwell is washed and an enzyme conjugate is introduced to the microwells. The enzyme conjugate that contains a marker that can be read by a spectrometer. The conjugate will bind with any antigen that has bound with the antibody on the microwell. The microwell is then read by the spectrometer and a signal is generated and directed to the controller in the event that a target antigen is present. In a contemplated embodiment of using the EIA techniques the series of reagents, washes and buffers can be automatically introduced to the plates at predetermined intervals, and at the end of the sequence, a spectrometer is automatically activated in response to instructions from a central controller.
The detection system may also be provided with additional detector technologies 109b that are optimized for the detection of chemical agents that are both debilitating and amenable to delivery by water as identified above on a second conduit 121 branching from conduit 107 from the incoming water supply line 105. For instance certain drugs such as lysergic acid diethylamide (LSD), quinuclidinyl benzilate (BZ) and phencyclidine (PCP) have been as considered as target agents which could result in serious psychological effects. Likewise, certain conventional chemical warfare agents identified above can be dissolved in water and are thus potential target agents.
Additional detection technologies for chemical target agents include gas chromatography, a technique that can be used to separate and identify volatile organic compounds, High performance liquid chromatography (HPLC) or thin layer chromatography can also detect chemical agents and toxins. HPLC is a chromatographic separation technique wherein the stationary phase is a thin layer of powdered absorbent. The detector for an HPLC emits a response due to the eluting sample compound and subsequently signals a peak on the chromatogram. It is positioned immediately posterior to the stationary phase in order to detect the compounds as they elute from the column. The bandwidth and height of the peaks may usually be adjusted using the coarse and fine-tuning controls, and the detection and sensitivity parameters may also be controlled. Some of the more common detectors that can be used with HPLC include: Refractive Index (RI), Ultra-Niolet (UN), Fluorescent, Radiochemical, Electrochemical, Νear-Infra Red (Νear-IR), Mass Spectroscopy (MS), Nuclear Magnetic Resonance (NMR), and Light Scattering (LS).
A mass spectrometer may also be employed to detect chemical agents. Frequently a sample is introduced to the mass spectrometer probe by the intermediary of chromatography device (e.g. gas chromatography, liquid chromatography, capillary electrophoresis, etc.). A mass spectrometer consists of an inlet system, and ion source, an analyzer and a detector. Once in the source, sample molecules are subjected to ionization and ions formed in the source (molecular and fragment ions) acquire kinetic energy and leave the source. A calibrated analyzer then analyzes the passing ion function of their mass to charge ratios. The ion beam exiting the analyzer assembly is then detected and the signal is analyzed. Different kind of analyzer(s) can be used including magnetic, quadrulpole, ion trap, Fourier transform, and time of flight. The application of mass spectroscopy techniques to identify chemical agents is well known in the art.
In the event a biological or chemical target agent is detected by detector 109a or 109b, the controller 113 will automatically send a signal to the central manifold 115 to close the water service to the primary inlet supply 117 and direct the water to conduit 119 to the treatment system. Other outputs from the central controller may include a signal to the sampling system 111 wherein the frequency of the sampling will increase in response to detection event and a command for the sampling system 111 to retain all samples. In a preferred embodiment an alarm 121 is also activated to alert both those responsible for the safety of the water supply and the potential end users of the system.
Treatment system 123 consists of both a potable treatment system 125 and a non-potable system 127. In non-potable system 127 the influent water from conduit 119 is treated to render biological and chemical agents harmless. For example, referring now to Fig 2, in a first treatment tank 200 sodium hydroxide (NaOH) is added at inlet 202 to increase the pH. Water is retained within the first tank a predetermined residence time in order to allow the alkaline environment to degrade chemical or biological warfare agents. Elevating the pH is very effective in destroying a wide range of chemical warfare agents including nerve, blister and blood agents as well as a wide range of pathogenic organisms.
Water exiting the first tank 200 is directed to second tank 204 where the pH level is brought back to neutral using hydrochloric acid (HCL) introduced at inlet 206. The process creates water containing sodium chloride, a harmless salt. A third treatment stage involves a third tank 208 in which conventional bleach is added at port 210 which is also highly effective at mitigating the virulence of biological contaminants. Bleach can be neutralized before the water is directed to the non- potable system 212. In alternative embodiments additional treatment steps such as ozonolysis or ultraviolet irradiation may also be incorporated to destroy any residual biological organisms. The objective of the foregoing stage is to render any chemical or biological agent harmless and the water, although it would not be considered suitable for potable water sources primarily due to the presence of salts or bleach, would not be a hazard to health.
A portion of the water exiting the non-potable treatment system 127 is directed to a potable water treatment system 125. In a preferred embodiment the potable treatment system consists of a distillation system which removes all salts and any residual levels of chemicals or other toxic materials. In a distillation system water containing contaminants is heated so that water enters the gas phase. The distillation step involves filling a chamber with water and heating the water to the boiling point, 212°F (100°C). Boiling the water will kill most bacteria, cysts and viruses and the detritus remains within the chamber. Toxins such as botulinium and ricen are also rendered harmless by extreme heat in the boiling process. The steam rises into a stainless steel coil, leaving behind dissolved solids, salts, heavy metals and any other particles and materials having a lower vapor pressure than water. Heavy elements will not rise with the steam formed during the boiling process stay behind and become concentrated in the boiling tank. The vapor is introduced to the coil that is cooled and the steam will condense. The water is then allowed to percolate through a filter and collects in a storage tank as pure distilled water. Distillation provides consistently pure water and will completely remove a wide range of water contaminants including algae, viruses, cysts, bacteria, arsenic, benzene, chloride, chlorine, copper, fluoride, lead, mercury, nitrates, pesticides, rust, salt and sulfates. Thus most potentially harmful bacteria, pathogens, parasites, viruses, as well as herbicides, pesticides, organic and inorganic chemicals, along with heavy metals (arsenic, lead, etc.) are effectively removed by distillation. Many organic chemicals can boil over to the distillate when they volatilize to gas, combining with the water vapor during the boiling process, and then, condensing back into dissolved chemicals in the water to give the distillate. For this reason, a vented distillation system is required which will selectively release these lightweight organic molecules. In a preferred embodiment an activated carbon filter could also be used in conjunction with the distillation system to remove organic materials.
In a preferred embodiment of the invention the system has a separate system 129 for potable water exiting the potable water treatment system for supply to the building. Although distillation is a preferred treatment method, other water treatment methods could be employed to remove the salts, ionic materials and undissolved contaminants. These alternative methods may include ion exchange techniques or revere osmosis filtration followed by carbon filtration. Ion exchange resins, consisting of both anion and cation exchange resin, will remove both dissolved and undissolved ionic contaminants from the supply water. Carbon filtration will effectively remove organic contaminants and serves to both remove any discoloration and odor. Conventional media filtration is also recommended downstream of the carbon filter to ensure particulate matter is not introduced to the portable water system. A further alternative method to provide potable water is the use of reverse osmosis, sometimes referred to as ultrafiltration. Reverse osmosis will also effectively remove both salts and organic based contaminants, however pretreatment is recommended to ensure that the membranes used in the system do not become fouled. Further features of the system include a feedback loop sampling feature which samples water exiting the non-potable and potable treatment systems and a second sample retention system which periodically samples the treated water for independent analysis. The feedback loop feature provides a check to ensure that the water is safe for its intended application. In the event the detectors from the loop system are triggered, the central control will interrupt water supply within the facility.

Claims

CLAIMS I claim:
1. A system for the protection of potable water supplies comprising an inlet conduit directing water from a water source, a side stream conduit connected to said inlet conduit directed to a fluid sampling system and a detector, said detector generating a signal in response to the presence of a predetermined target agent in said water, said signal received by a controller, said controller and analyze said signal and provide an output signal to control a valve on a manifold wherein said manifold directs flow of said fluid from a first primary inlet supply system to a secondary treatment system, wherein said secondary treatment system renders said target agent harmless.
2. The system recited in claim 1 wherein said detector comprises a flow cytometer.
3. The system as recited in claim 1 wherein said detector comprise immunoflourescence technology and a photodetector.
4. The system recited in claim 1 wherein said detector comprises immunoassay components and a spectrometer.
5. The system recited in claim 1 further comprising an alarm system wherein upon the detection of the presence of a predetermined target agent, said controller generates a signal to activate said alarm system.
6. The system recited in claim 1 wherein said treatment comprises two stages, a first stage to provide non-pathogenic non-potable water and a second stage to provide potable water.
7. The system recited in claim 6 wherein said first treatment stage comprises a plurality of treatment tanks, wherein said first tank is provided with inlet water and means for the addition of sodium chloride and a second tank is provided with treated water from said first tank and further provided with means for the addition of hydrochloric acid whereby any biologically active agent is rendered harmless.
8. The system recited in claim 6 wherein said second stage comprises distillation.
9. The system recited in claim 8 wherein said second treatment stage further comprising treatment with activated carbon.
10. The system recited in claim 6 wherein said second treatment stage comprises treatment with ion exchange resin followed by treatment with activated carbon.
11. The system as recited in claim 6 wherein said second treatment stage comprises treatment by reverse osmosis.
12. The system recited in claim 6 further comprising a dual delivery system wherein a first delivery system is provided for non-potable water from said first treatment stage and a second delivery system is provided for potable water requirements from said second treatment stage.
13. The system recited in claim 1 wherein said preselected target agents are amenable to delivery by water and at least one is selected from a group consisting of anthrax, tularemia, yersina pestis, shigella flexneri, s. dysenteriae (shiga bacillus), salmonella species, cholera, escherichia coli, mycotoxins, ricin, staph enterotoxin B, NX , botulinum toxin, PCP, LSD, hallucinogenic drugs, sarin, cyanogen chloride, soman, and hydrogen cyanide.
14. A method for maintaining the safety of a water supply for a secured location comprising a first step of analyzing water from an inlet conduit for the presence of at least one pre-selected target antigen or agent, a second step of diverting the flow of water from a supply conduit line in response to the detection of said target antigen or agent to a treatment system, and a third step of treating said water in said treatment system to render said target antigen or agent harmless.
15. The .method recited in claim 14 wherein said first detection step comprises employing a flow cytometer.
16. The method recited in claim 14 wherein said third treatment step comprises directing said water to a first retention tank and adding sodium chloride to said water, and then directing said water to a second retention tank and adding hydrochloric acid to said water wherein water exiting said second tank is harmless non-potable water.
17. The method recited in claim 16 further comprising directing said harmless non-potable water to a distillation apparatus wherein water exiting said distillation apparatus is potable water.
18. The method recited in claim 15 wherein said flow cytometer is provided with reagent antibody markers specific to biological agents and toxins amenable to delivery by water.
19. The method recited in claim 15 wherein said flow cytometer is provided with at least one reagent antibody markers specific to biological agents and toxins from a group consisting of anthrax, tularemia, yersina pestis, shigella flexneri, s. dysenteriae (shiga bacillus), salmonella species, cholera, escherichia coli, mycotoxins, ricin, staph enterotoxin B, NX , and botulinum toxin.
20. The method recited in claim 14 wherein said pre-selected target agent is at least one from a group selected from a group consisting of lysergic acid diethylamide (LSD), quinuclidinyl benzilate (BZ) and phencyclidine (PCP), sarin, cyanogen chloride, soman, and hydrogen cyanide.
PCT/US2000/019729 1999-07-20 2000-07-20 System for protection of building water supplies against chemical and biological warfare agents WO2001009041A2 (en)

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