NZ749640A - Methods and system for evaluating and maintaining disinfectant levels in a potable water supply - Google Patents
Methods and system for evaluating and maintaining disinfectant levels in a potable water supplyInfo
- Publication number
- NZ749640A NZ749640A NZ749640A NZ74964017A NZ749640A NZ 749640 A NZ749640 A NZ 749640A NZ 749640 A NZ749640 A NZ 749640A NZ 74964017 A NZ74964017 A NZ 74964017A NZ 749640 A NZ749640 A NZ 749640A
- Authority
- NZ
- New Zealand
- Prior art keywords
- water
- chlorine
- orp
- ammonia
- sample
- Prior art date
Links
- 230000000249 desinfective Effects 0.000 title claims abstract description 128
- 235000012206 bottled water Nutrition 0.000 title claims description 47
- 239000003651 drinking water Substances 0.000 title claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 503
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000000460 chlorine Substances 0.000 claims abstract description 140
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 140
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000000463 material Substances 0.000 claims abstract description 91
- 238000005259 measurement Methods 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 66
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000005070 sampling Methods 0.000 claims abstract description 32
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N Dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QEHKBHWEUPXBCW-UHFFFAOYSA-N Nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 10
- 238000004364 calculation method Methods 0.000 claims abstract description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 39
- 238000001303 quality assessment method Methods 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 13
- 238000004891 communication Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 description 37
- 239000000126 substance Substances 0.000 description 20
- 241000894007 species Species 0.000 description 16
- 241000196324 Embryophyta Species 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 10
- 231100000673 dose–response relationship Toxicity 0.000 description 10
- 230000001590 oxidative Effects 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 9
- 239000002349 well water Substances 0.000 description 9
- 235000020681 well water Nutrition 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000645 desinfectant Substances 0.000 description 5
- 230000001603 reducing Effects 0.000 description 5
- 230000001105 regulatory Effects 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- -1 fully-combined a Chemical compound 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000001717 pathogenic Effects 0.000 description 3
- 244000052769 pathogens Species 0.000 description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L Ammonium iron(II) sulfate Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- 241000220225 Malus Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 235000021016 apples Nutrition 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000001546 nitrifying Effects 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 238000011012 sanitization Methods 0.000 description 2
- 229940044174 4-phenylenediamine Drugs 0.000 description 1
- PQRDTUFVDILINV-UHFFFAOYSA-N BCDMH Chemical compound CC1(C)N(Cl)C(=O)N(Br)C1=O PQRDTUFVDILINV-UHFFFAOYSA-N 0.000 description 1
- 210000002421 Cell Wall Anatomy 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N Hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 241000229754 Iva xanthiifolia Species 0.000 description 1
- WXFIGDLSSYIKKV-RCOVLWMOSA-N L-Metaraminol Chemical compound C[C@H](N)[C@H](O)C1=CC=CC(O)=C1 WXFIGDLSSYIKKV-RCOVLWMOSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N P-Phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000001413 cellular Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001809 detectable Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 230000036449 good health Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial Effects 0.000 description 1
- 239000012569 microbial contaminant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
Abstract
method of determining a disinfectant composition of a municipal water supply from a water sample that includes: (a) obtaining a water sample from a water source at a sampling location; (b) adding a chlorine-containing material to the water sample in the presence of an oxidation reduction potential (ORP) measurement device; (c) generating a plurality of ORP measurements during addition of the chlorine-containing material to the water sample; (d) estimating a concentration of one or more of free ammonia, fully combined ammonia, monochloramine, or a mixture of dichloramine and trichloramine in the water sample in which the estimation is derived from the relationship between the added chlorine material and the plurality of ORP measurements; and (e) determining a disinfectant composition of the water source at the water sampling location from the concentration calculation. A method of determining free ammonia composition is also included. (ORP) measurement device; (c) generating a plurality of ORP measurements during addition of the chlorine-containing material to the water sample; (d) estimating a concentration of one or more of free ammonia, fully combined ammonia, monochloramine, or a mixture of dichloramine and trichloramine in the water sample in which the estimation is derived from the relationship between the added chlorine material and the plurality of ORP measurements; and (e) determining a disinfectant composition of the water source at the water sampling location from the concentration calculation. A method of determining free ammonia composition is also included.
Description
METHODS AND SYSTEM FOR TING AND MAINTAINING DISINFECTANT
LEVELS IN A E WATER SUPPLY
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of United States Provisional Patent Application
No. 62/356,718 filed June 30, 2016, which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to methods and devices for evaluating the disinfectant
composition of a e water supply and, in particular, methods of determining the presence
of and estimation of the s of one or more of free ammonia, mono-, di- or tri- chloramines
therein as well as systems for measuring and maintaining the chloramination and free ammonia
levels of a potable water supply.
Description of Related Art
Water used for human or animal consumption must be d to remove pathogens
and contaminants. After treatment, a “residual disinfectant” is usually applied to the water to
prevent the regrowth of pathogens. This is also termed “secondary ection.” In municipal
water systems, chlorine or chloramines (monochloramine: NHzCl) are typically used for this
purpose. Many pal water systems in the United States and abroad increasingly use
chloramines, which are chemically more stable and less reactive, and, thus, can persist longer
in the distribution system.
With the increased use of mines as a strategy to reduce disinfection byproduct
levels in the municipal water supplies, in ular those used to deliver potable water to
consumers, enhanced analysis and treatment techniques are needed. Municipal water systems
are mandated by mission, as well as regulatory regimes, to ensure that water remains safe for
human consumption, not only at the treatment plant location, but at all ons in the delivery
system, including at or near the faucet where the water is finally delivered to the consumer.
ing with the demand for safety is the need to reduce off-tasting materials in the water,
which, while not necessarily unsafe, can result in consumer tion that the water is
unsanitary. As an additional issue, managers of water supplies must endeavor to treat water
using the most cost-effective methods available, which means that accurate measurement of
required chemical levels and process controls for delivering those als are required to
ensure that money is not wasted.
Chloramine chemistry has been bed for some time, especially in regard to
wastewater treatment and the disinfection of water cooling towers used in air conditioning
systems. In these applications, the goal generally is to reduce the amount of biological
contaminants present in order to also reduce the possibility of humans or other biological
systems from becoming ill from such contamination.
ining proper chloramine chemistry throughout a water distribution k is
difficult. At least some free ammonia is lly maintained in water systems—generally less
than about 0.1 mg/L—to better ensure that chloramination remains effective hout a water
distribution network. Because the chlorine in the molecule reacts with organic matter in the
water, some amount of chlorine will be deactivated from use as a disinfectant. As a result, with
time, the water can accumulate excess free ammonia. For other water sources that may be used
as potable water, such as wells, free ammonia may be natively present in the water due to
biological and water source artifacts. The presence of free ammonia greatly increases the risk
of nitrification — a microbial process that converts ammonia to e and then nitrate. Elevated
levels of nitrate can make the water unfit for human consumption. Nitrification is a common
occurrence in chloraminated e water systems. Accordingly, water system operators
spend large amounts of time attempting to prevent or mitigate ication, mainly by closely
monitoring and managing free ammonia levels in the water supply.
minated water s must be lly monitored at multiple points in a
water distribution network to appropriately detect the onset of nitrification and portions of the
water system are d to remove water with low disinfectant residual or elevated nitrite
levels. Flushing not only wastes water and resources, the process is time consuming and can
disrupt water supplies.
Many ng analysis and water treatment methods for use with chloramine
disinfection do not contemplate that the mine treated water will be ingested by a human
or will otherwise be used to provide hydration to a biological system. Moreover, water may
test as within appropriate limits at a treatment plant, but as the water travels though the water
system, the chloramination level can change markedly, resulting in water that is either not
adequately disinfected by the time it exits the faucet of a consumer, or that exhibits an off-taste
due to the presence of di- or trichloramines.
Standard methods to measure monochloramine only are available. The
monochloramine can be determined amperometrically or titrated with ferrous ammonium
sulfate (FAS) using a colorimetric DPD (N,N Diethyl-l,4 Phenylenediamine Sulfate) indicator
under controlled conditions. These methods are best used in a lab ion and require a higher
WO 05952
degree of skill and care to perform the analysis. Both methods require good control of the
reagents added to limit dichloramine interference and can also have interference from organic
chloramines. Accordingly, these standard methodologies are generally not suitable to ongoing
measurement within a municipal water delivery system, especially in regard to obtaining real
time measurements of potable water that is in the process of being delivered to consumers.
Ammonia detection is also nt in a municipal water distribution system. Because
the presence of excess free ammonia y increases the risk of nitrification, efforts must be
made to minimize free ammonia levels in chloraminated potable water systems. Free ammonia
levels can be measured with a variety of field and laboratory methods. However, many of the
field techniques have reliability issues at the low concentrations that occur in properly
functioning potable water systems, for example, generally below 0.1 mg/l.
In this regard, one secondary disinfectant control strategy uses a very small (ppb) free
ammonia concentration to ensure that monochloramine is the predominant species, with the
goal to provide secondary ection without creating the foul g di- and trichloraminated
species. If the free ammonia concentration is kept very low, the potential of nitrifying bacteria
developing in the distribution system is minimized. However, in practicality, the control of free
ammonia at the low ppm range, especially in the water distribution environment, is difficult
e of other variables that affect the ability to accurately and closely monitor such a low
level of free a in a large volume of water, especially when adding ammonia precisely
to a large volume while still managing chlorine levels to remain within specification. If too
much ammonia containing material is added, more chlorine will have to be added, otherwise
excess of ammonia will be present as a food source for the ication process. If too much
chlorine containing material is added, di- or trichloramines can be created, and free ammonia
will have to be back added to reset the levels to 5:1 (by weight) or to 1:1 (by stoichiometry)
ed for monochloramine speciation. Alternatively, the systems will need be flushed, as
discussed earlier.
Moreover, existing free ammonia analysis requires reagents that are some to
deploy in field settings. The xity of free ammonia testing, coupled with the high stakes
involved in ensuring safe potable water for consumers, lly requires highly trained
nel to conduct the testing, a reality that further limits deployment of free ammonia
analysis in the field. In short, today there is no free ammonia test methodology that can provide
truly accurate results when the test is conducted e of a laboratory. As a result of these
deficiencies in analysis techniques, water system operators have a ult time in optimizing
and maintaining chloramine try in potable water systems, thus leaving water s
vulnerable to ication and/or over-chlorination or both.
Oxidation reduction potential (ORP) has been used to measure chlorine (and other
oxidant) levels in water. Measurements of ORP in water can reflect the ability of certain
chemical components in the water to accept or lose ons. In laboratory settings where
ongoing electrode calibration and process controls are available, ORP can exhibit high
reliability. However, they are not used for analysis and treatment of municipal water supplies
or well water because of inaccuracies inherent in the measurements that can result from at least
pH, temperature, and water source effects (e.g., metals, CaCO3, etc., that are present as a
on of the location where the water is sourced and/or the path it travels during delivery to
the consumer). The ORP electrodes themselves are highly sensitive to deposits that affect ORP
measurement kinetics and require frequent maintenance to remove buildup that occurs on the
electrode surface. While pH, temperature, dissolved materials and electrode t effects that
may affect ORP measurements can be readily addressed in laboratory settings to enable the
method to provide te chloramination information, ORP cannot readily be deployed in
field settings for the measurement and management of chloramination disinfection of
pal water supplies, especially in on to estimation of the amount of free ammonia
present in a water . Put simply, ORP is not seen to be reliable in indicating
chloramination levels in water systems. Therefore, this ology is not deployed by health
departments to evaluate safe disinfectant .
There remains a need for methods to better measure and manage disinfectant
composition in municipal water supplies at locations downstream from water treatment
facilities or in wells. Methodologies to measure and manage chloraminated speciation and free
ammonia levels to a more controlled degree are also needed. There is also need for methods
that can be deployed by technicians without sophisticated chemical training and skills or that
can be deployed inline using automated processes.
SUMMARY OF THE INVENTION
In certain non-limiting embodiments, the t invention is directed to a method of
determining a disinfectant composition of a municipal water supply from a water sample that
includes: (a) ing a water sample from a water source at a sampling location; (b) adding
a chlorine-containing al to the water sample in the presence of an oxidation reduction
potential (ORP) measurement device; (c) generating a plurality of ORP measurements during
addition of the chlorine-containing material to the water sample; (d) estimating a concentration
of one or more of free a, fully combined ammonia, monochloramine, or a mixture of
dichloramine and trichloramine in the water sample from which the estimation is derived based
on the relationship between the added chlorine material and the plurality of ORP
measurements; and (e) determining a disinfectant composition of the water source at the water
sampling location from the concentration ation. Further, as to the step of obtaining a
water sample: (i) the water sample is derived from a water treatment facility; (ii) a chlorine—
containing material and an ammonia-containing material are present in the water ; and
(iii) the sampling location is located ream from the water treatment facility.
In some non-limiting embodiments, the concentration is estimated by monitoring the
rate of change of ORP measurement in millivolts as a function of the amount of chlorine-
containing material added to the water sample. In addition, the concentration can also be
estimated by calculating a slope ed by plotting the ORP of the water sample versus the
amount of chlorine-containing material added to the water sample. Moreover, the disinfectant
composition is determined as a real-time measurement.
In certain non-limiting embodiments, the chlorine—containing material is added to the
water sample in a known volume while generating the plurality of ORP measurements to
ine the relationship between the added chlorine material and the plurality of ORP
measurements. In some non-limiting embodiments, the method further es comparing the
plurality of ORP measurements obtained from the water sample located downstream from the
water treatment facility to ORP measurements obtained from a water sample obtained at the
water treatment ty to ine disinfection efficacy. In certain non—limiting
embodiments, the estimation provides the concentration of both free ammonia and
monochloramine in the water sample.
In some miting embodiments, the method further includes, after determining
the disinfectant composition of the water source, adding additional chlorine-containing
als and ammonia containing materials to the water source to achieve a desired level of
the disinfectant composition. Moreover, an amount of the added additional chlorine—containing
materials and ammonia-containing materials can be independent of a concentration of the
chlorine—containing materials and ammonia-containing materials. In addition, in some non-
limiting embodiments, a volume of the water sample obtained from the water source is known.
In certain miting embodiments, the present invention is directed to a method of
determining a free ammonia composition of a water supply. The method includes: (a) obtaining
a water sample from a water supply at a sampling location; (b) adding a ne—containing
material to the water sample in the ce of an ion reduction potential (ORP)
measurement device; (c) generating a plurality of ORP measurements during addition of the
chlorine-containing material to the water sample; and (d) estimating a concentration of free
ammonia in the water sample in which the estimation is derived from the relationship between
the added chlorine material and the plurality of ORP measurements.
In some non-limiting embodiments, the method also includes maintaining a
concentration of free ammonia in the water supply within a range of greater than 0 mg/L and
less than about 0.1 mg/L. In on, in certain non-limiting embodiments, the water sample
is derived from a water treatment facility and the sampling location is located ream from
the water treatment facility. The method of determining free ammonia composition can also
be substantially free of a reagent other than chlorine and ammonia—containing materials.
In some non-limiting embodiments, the concentration of free ammonia is estimated
from monitoring the rate of change of ORP measurement in millivolts as a function of the
amount of ne-containing al added to the water sample. Further, in some non-
limiting embodiments, the method r includes adding additional chlorine—containing
materials when the estimated ammonia concentration is above a desired ammonia
tration range.
In n miting embodiments, the present invention is directed to a system for
ining the disinfectant level of a potable water . The system can include: (a) a
water quality assessment module that includes (i) a plurality of sensors sing at least an
oxidation reduction potential sensor (ORP), and (ii) a control module in operational
engagement with the plurality of sensors; (b) a water supply intended for delivery of potable
water to a consumer; (c) a water sampling device comprising a fluid delivery means configured
to provide a sample of water derived from the water supply to the water quality assessment
; and (d) a chlorine feed source and an ammonia feed source in which each of the
sources are, independently: (i) in operational ment with the water quality assessment
module; and (ii) in fluid communication with the water supply. Further, the system is
ured to measure and adjust the chloramination level and the free ammonia levels of a
portable water supply prior to delivery of the water supply to the consumer.
In some non-limiting embodiments, the water quality assessment module is
configured to e information regarding at least a disinfectant level of the water supply.
Further, the water supply can be maintained in a water storage tank. In certain non-limiting
embodiments, the water storage tank includes a mixing module.
In certain non-limiting embodiments, the water sampling device further includes a
pump. In on, in some non—limiting embodiments, a volume of the sample of water
provided by the delivery means is known. The plurality of sensors used with the system can
also include a pH sensor and a temperature .
The present invention is also directed to the following s:
Clause 1: A method of determining a ectant composition of a municipal water
supply from a water sample comprising: (a) obtaining a water sample from a water source at a
sampling location, wherein: (i) the water sample is derived from a water treatment facility; (ii)
a ne-containing al and an a-containing material are present in the water
source; and (iii) the sampling location is located downstream from the water treatment facility;
(b) adding a chlorine-containing material to the water sample in the presence of an oxidation
reduction potential (ORP) measurement device; (c) generating a plurality of ORP
measurements during addition of the chlorine-containing material to the water sample; ((1)
estimating a concentration of one or more of free ammonia, fully ed ammonia,
loramine, or a e of dichloramine and trichloramine in the water sample, wherein
the determination is derived from the relationship between the added chlorine material and the
plurality of ORP measurements; and (e) determining a disinfectant composition of the water
source at the water sampling location from the concentration calculation.
Clause 2: The method of clause 1, wherein the concentration is estimated from
monitoring the rate of change of ORP measurement in millivolts as a function of the amount
of chlorine—containing al added to the water sample.
Clause 3: The method of clauses 1 or 2, wherein the concentration is determined by
calculating a slope obtained by plotting the ORP of the water sample versus the amount of
ne-containing material added to the water sample.
Clause 4: The method of any of clauses 1 to 3, wherein the disinfectant composition
is determined as a real-time measurement.
Clause 5: The method of any of clauses 1 to 4, wherein the chlorine-containing
material is added to the water sample in a known volume while generating the plurality of ORP
measurements to determine the onship between the added chlorine material and the
plurality of ORP measurements.
Clause 6: The method of any of clauses 1 to 5, further comprising comparing the
ity of ORP measurements obtained from the water sample located downstream from the
water treatment facility to ORP measurements obtained from a water sample obtained at the
water treatment facility to determine disinfection efficacy.
Clause 7: The method of any of clauses 1 to 6, wherein the estimation provides the
concentration of both free a and monochloramine in the water sample.
Clause 8: The method of any of clauses 1 to 7, r comprising, after determining
the disinfectant composition of the water source, adding additional chlorine-containing
materials and ammonia-containing materials to the water source to e a desired level of
the disinfectant composition.
Clause 9: The method of clause 8, wherein an amount of the added additional
chlorine-containing materials and ammonia-containing materials is independent of a
concentration of the chlorine-containing materials and ammonia-containing materials.
Clause 10: The method of any of clauses 1 to 9, wherein a volume of the water sample
obtained from the water source is known.
Clause 11: A method of determining free ammonia ition of a water supply
sing: (a) ing a water sample from a water supply at a sampling location; (b) adding
a chlorine-containing material to the water sample in the presence of an oxidation reduction
potential (ORP) measurement device; (c) generating a plurality of ORP measurements during
addition of the chlorine-containing material to the water sample; and (d) estimating a
concentration of free ammonia in the water sample, wherein the estimation is derived from the
onship between the added chlorine material and the ity of ORP measurements.
Clause 12: The method of clause 11, wherein a volume of the water sample obtained
from the water source is known.
Clause 13: The method of clauses 11 or 12, wherein the water is derived from a water
treatment facility and the sampling location is located downstream from the water treatment
facility.
Clause 14: The method of any of clauses 11 to 13, further sing maintaining a
concentration of free ammonia in the water supply within a range of greater than 0 mg/L and
less than about 0.1 mg/L.
Clause 15: The method of any of clauses 11 to 14, wherein the method of determining
free ammonia composition is ntially free of a t other than chlorine and ammonia-
containing materials.
Clause 16: The method of any of clauses 11 to 15, n the concentration of free
ammonia is estimated by monitoring the rate of change of ORP measurement in millivolts as a
function of the amount of chlorine—containing material added to the water sample.
Clause 17: The method of any of clauses 11 to 16, further comprising adding
chlorine-containing als when the estimated ammonia concentration is above a desired
ammonia concentration range.
Clause 18: A system for maintaining the disinfectant level of a potable water supply
comprising: (a) a water quality assessment module comprising: (i) a plurality of sensors
comprising at least an oxidation reduction potential sensor (ORP); and (ii) a control module in
operational engagement with the plurality of sensors; (b) a water supply intended for delivery
of potable water to a consumer; (c) a water sampling device comprising a fluid delivery means
configured to provide a sample of water derived from the water supply to the water y
assessment module; ((1) a chlorine feed source and an ammonia feed source, wherein each of
the sources are, independently: (i) in operational engagement with the water quality assessment
module; and (ii) in fluid communication with the water supply, wherein the system is
configured to measure and adjust the chloramination level and the free ammonia levels of a
potable water supply prior to ry of the water supply to the consumer.
Clause 19: The system of clause 18, wherein the water quality assessment module is
configured to provide information regarding at least a disinfectant level of the water supply.
Clause 20: The system of clause 19, wherein the water supply is maintained in a water
storage tank.
Clause 21: The system of clause 20, wherein the water storage tank includes a mixing
module.
Clause 22: The system of any of clauses 18 to 21, wherein the water sampling device
further ses a pump.
Clause 23: The system of any of clauses 18 to 22, wherein the volume of the sample
of water provided by the delivery means is known.
Clause 24: The system of any of s 18 to 23, wherein the plurality of sensors
further comprise a pH sensor and a temperature sensor.
BRIEF DESCRIPTION OF THE DRAWINGS
illustrates a method of determining disinfectant composition of e water
by measurement of ORP; and
illustrates an exemplary system in which the inventive ology can be
implemented.
DESCRIPTION OF THE INVENTION
In the following detailed description, nce is made to the accompanying
drawings, which form a part hereof, and within which are shown by way of illustration n
embodiments by which the t matter of this disclosure may be practiced. It is to be
understood that other embodiments may be utilized and structural changes may be made
without departing from the scope of the sure. In other words, illustrative embodiments
and aspects are described below. It will, of course, be appreciated that in the development of
any such actual embodiment, numerous implementation-specific ons must be made to
achieve the developers’ specific goals, such as compliance with system-related and business-
related constraints, which may vary from one implementation to another. Moreover, it will be
appreciated that such development effort might be complex and time consuming, but would
nevertheless be a routine undertaking for those of ordinary skill in the art having the t of
this disclosure.
Unless d otherwise, all technical and scientific terms used herein have the same
g as is commonly understood by one of ordinary skill in the art to which this disclosure
belongs. In the event that there is a plurality of definitions for a term herein, those in this n
prevail unless stated otherwise.
Wherever the phrases “for example,99 ‘5such as,99 44'including,” and the like are used
herein, the phrase ”and without limitation” is understood to follow unless explicitly stated
ise.
The terms “comprising” and “including” and ving” (and similarly “comprises”
and “includes” and “involves”) are used interchangeably and mean the same thing.
Specifically, each of the terms is defined consistent with the common United States patent law
definition of “comprising” and is therefore interpreted to be an open term meaning “at least the
following” and is also interpreted not to exclude additional features, limitations, aspects, etc.
The term “about” is meant to account for variations due to experimental error. All
measurements or numbers are implicitly understood to be modified by the word about, even if
the measurement or number is not explicitly modified by the word about.
The term antially” (or alternatively “effectively”) is meant to permit deviations
from the descriptive term that do not negatively impact the intended purpose. Descriptive terms
are implicitly understood to be modified by the word substantially, even if the term is not
explicitly ed by the word substantially.
“Water supply” as used herein means water generated from a municipal water supply,
a well system or both.
The term “disinfectant composition” comprises the amounts of one or more of free
ammonia, fully-combined a, monochloramine, dichloramine, trichloramine, or free
ne that is present in the water supply. ection composition can be estimated from a
water sample d from the water supply as discussed elsewhere herein.
The term “municipal water ” means a water supply provided from a central
point and piped to individual users under pressure. Water sources used to generate municipal
water supplies can vary. As required by regulations, municipal water supplies will undergo
primary disinfection to make it suitable for use as potable water at the treatment facility.
Secondary disinfection with chloramination processes will also be provided at the water
treatment plant to ensure that the water will remain suitable for use as potable water as it travels
through the water system to the consumer.
“Well water” is water ed from a below-ground water source such as an aquifer,
and that is stored (or storable) for supply as potable water, among other uses. As would be
recognized, well water can natively comprise free a as a result of natural processes.
Well water may or may not be disinfected prior to use.
In certain non—limiting embodiments, the present invention comprises a method of
ining disinfectant compositions in potable water at ons in a municipal potable
water supply that are located downstream from a water treatment facility. In this regard, the
present invention relates to ining adequate secondary disinfection of a potable water
supply, where “secondary disinfection” means the maintenance of free or ed chlorine
levels in a water supply once the water is treated with primary disinfecting methods (e.g.,
sedimentation, ation, UV, chlorine gas, etc.). Yet r, the present ion relates
to systems in which the disinfectant level determination can be implemented.
As would be recognized, “primary disinfectants” are intended to kill or otherwise
deactivate pathogens that exist in a water source upon its arrival at a treatment plant, whereas
“secondary disinfectants” are intended to maintain the healthiness and cleanliness of the water
supply upon leaving the treatment plant throughout its path through a pal water system
until it reaches the faucet of a consumer.
The present invention relates, in some non-limiting embodiments, to estimating,
maintaining, and adjusting the secondary disinfectant composition of potable water supplies
where the ary ection is provided in part or in full by way of chloramines.
Disinfection composition is estimated and/or maintained by measuring the presence (or lack
thereof) of a disinfecting species of interest using an ORP electrode as discussed elsewhere
herein. In this regard, at the water treatment plant, for secondary disinfection, chlorine or a
chlorine-containing material will be added to the water supply. Ammonia or ammonia-
ning materials will also be added to the water supply during treatment, usually after
addition of the chlorine-containing material, when secondary ection is to be effected and
maintained by mination, as in the present invention. Note that, while ammonia is
generally added to water supplies to provide suitable secondary ection with chloramines,
some ammonia-containing als may be naturally present in the water source when it
reaches the treatment ty. Such naturally occurring ammonia material, which will vary
from water source to water , will be included in the discussions related to free ammonia
ion herein.
During one or more periods in the water distribution timeline and!or at one or more
locations in the water distribution network, the amount of one or more of the disinfectant
compositions of interest can be estimated by measuring the ORP of the sample during on
of chlorine (or a chlorine containing material) to the water sample. The amount of disinfectant
composition of interest in the water sample can then be estimated from one or more of
previously identified dose response curves, as discussed further herein.
In some non-limiting embodiments, the present invention relates to devices and
methods to estimate the free ammonia concentration in a water supply by extrapolating
concentrations estimated from a water sample obtained from the water supply. The free
ammonia estimation can be ted after the water leaves a water treatment facility and prior
to delivery of the water to a consumer, where the sampling is taken at one or more locations in
the water distribution network and!or at different times. The present invention allows a water
supply to be sampled and tested for free ammonia levels using simple and reliable testing
methodologies, in particular, ORP measurement of a water sample derived from the water
supply of interest. The ammonia tion of the present invention can also be ted on
water that has not previously been treated in a primary disinfectant regime, such as water
sourced from or otherwise present in a well, where free ammonia may be natively present
therein.
ORP can be used to determine or estimate the levels of chemical disinfectants that
work via the oxidation or reduction of the structures of microbial contaminants. For example,
chlorine, an oxidant, will strip electrons from the negatively d cell walls of some
bacteria, thus ing it harmless to the potable water consumer. The ors have found
that because ORP suitably measures the total chemical activity of a on—which in the
present invention correlates to a disinfecting species composition—ORP as described herein
can estimate the total composition of all, or substantially all, oxidizing and reducing
disinfectants in solution. While in the case of the t invention, the level of chloramines
(e.g., mono-, di- and tri-) are of primary nce, other oxidants that may be used in water to
act in a redox capacity to inactivate harmful materials in water are also analyzable according
to the ORP methods and devices herein: hypochlorous acid, sodium hypochlorite, UV, ozone,
peracetic acid, bromochlorodimethylhydantoin, etc.
When other factors in a water sample are substantially stable (temperature, pH, etc.),
ORP values are d to disinfectant composition in a water sample and, therefore, the water
supply from which the sample is derived. As the concentration of ne-containing material,
for example, chloramine species, in a water sample changes, the ORP value s.
Accordingly, ORP has been found to provide a reliable estimation of disinfectant composition
in a water sample that has been subjected to a mination disinfection methodology.
In some non-limiting embodiments the present invention substantially characterizes
a disinfectant composition in a water , as opposed to being a direct detection method of
a particular chemical or chemical species. That is, ORP indicates the effectiveness of those
disinfectant materials that work through oxidation and reduction. Use of this method by itself
cannot generally ine the exact concentrations of known species of chemical in on
without collection of additional information. However, when applied to test previously d
municipal water es, the regulatory regimes applicable to municipal water supplies greatly
restrict the types and amounts of chemicals and chemical species that may be present in potable
water. Moreover, since, in some non-limiting embodiments, the water samples evaluated herein
are derived from water supplies emanating from water treatment facilities, any ORP
measurements can be used to not only estimate the disinfecting composition of a water sample,
and, thus, the municipal water supply itself at the point of testing, but also to confirm the type
and amount of a sanitizing chemical that is providing the secondary disinfection to the potable
water in real time.
The present invention can also be used to estimate the free ammonia tration
of untreated water, such as well water. In this regard, chlorine (or chlorine-containing material)
is added to a water sample obtained from a water supply and the dose response curve is used
to generate a concentration estimation.
The present invention allows ORP to be deployed to test secondary disinfection
species composition in pal water supplies to obtain real time, online measurements.
Such real time, online measurements ent a substantial advance in the management of
municipal potable water supply s. That is, water systems ors have ically
been challenged to guarantee to potable water consumers that potable water maintains its safety
once it leaves the water treatment facility.
The complexities required to obtain accurate analysis of water has generally required
samples to be taken from water sources for analysis under tory conditions. Such
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complexities are exacerbated by the small quantities of materials that must be quantified to
ensure that potable water is safe and complies with the ive regulatory regimes. The
present invention y simplifies the analysis, and, therefore, provides heretofore
unavailable economies and ease of ment in the field to e “just in time” knowledge
about the disinfectant composition of a municipal water supply as the water travels through the
distribution network from the water treatment plant to the consumer. Still further, the present
invention enables the ted optimization of chloramine disinfectant ition and
concentration in the water distribution system, where such automation is discussed elsewhere
herein. Yet further, the present invention provides an improved methodology to estimate free
ammonia ition in water es, where such knowledge is of interest in determining
ication potential of the water supply from which the water sample is derived.
As used herein, “substantially accurate estimation of disinfectant ition in
potable water” means the ability to distinguish between potable water with excess free
ammonia and potable water with excess di- or oramine species, as well as free chlorine,
if the system has moved past the chlorine breakpoint, as such materials and terms are known
to those of ordinary skill in the art.
Still further, the present invention provides a previously unavailable ology to
enable water supply operators to maintain the secondary disinfection regime substantially at all
times in the water delivery network in the monochloramine species part of the tion curve.
(See . Yet further, the present invention allows substantially precise control of the
monochloramine disinfectant regime so as to allow the amount of free ammonia in a potable
water supply to be maintained within the desired range of from greater than 0 mg/L to less than
about 0.1 mg/L, where such range is the optimum for managing chloraminated systems. In
short, the present invention provides effective chloramination disinfection while still ng
the potential for the chloraminated water supply to undergo nitrification, as discussed
after.
In use, a cian can manually obtain a sample of water from a location
downstream of the water treatment facility, that is, after the water has undergone primary
disinfection and is in the process of being delivered to consumers for use. Alternatively, an
automatic inline process can be used to sample the potable water after it leaves the treatment
facility. The locations where the water can be sampled for disinfectant composition are
expansive, however, it may generally be more suitable to test in locations where the water
collects for storage or is otherwise staged for delivery. In this regard, if it is determined that the
potable water is out of compliance for disinfection composition, the stored or collected potable
water can be treated in that location or, if necessary, diverted so that the out-of—compliance
water is not delivered to the er. In some non-limiting ments, the water is
sampled at or near a water storage tank or water storage location that is downstream from the
water treatment facility. Water can also be manually or automatically sampled from a well
source.
The relevance of free ammonia to disinfectant composition in water systems where
secondary disinfection includes chloramination has increased the availability of free a
sensors in recent years. Notably, existing free ammonia estimate techniques require the use of
additional reagents. The use of reagents that must be stored, measured, and re-supplied y
increases the complexity of free ammonia measurements. Thus, the ability to easily estimate
the amount of free ammonia in a water sample derived from a municipal water supply, as in
the present invention, es significant benefits. In some non—limiting embodiments, the
methodology of the present invention is substantially free of a reagent besides chlorine and
ammonia—containing materials because ORP probes used, according to the description herein,
use an electrical circuit to generate the measurements. The substantial absence of reagents
needed to te free ammonia estimation using the present invention is a marked
improvement over existing methodologies. Still further, free ammonia estimation, ing to
the present invention, does not require concurrent determination of the monochloramine
concentration using metric determination in order to obtain an estimation of the amount
of free ammonia in real-time.
ication is the two-stage biological s of converting ammonia first into
nitrite and then into nitrate. Nitrification can occur in e water systems containing natural
ammonia, in chloraminated systems where free ammonia exists in excess from the
chloramination process, or from decomposition of the chloramines themselves. Elevated levels
of nitrate can be l and, thus, reduction or elimination of es is a desirable outcome
for municipal water supply managers. Because chloraminated water disinfection necessarily
gives rise to the possibility of nitrification, it is desirable to maintain the amount of free
ammonia present in a potable water supply as low as le, while still providing a small
amount. A carefully controlled amount of total chlorine to total ammonia is, ore,
necessary. Moreover, even if free ammonia is absent when the water supply leaves the water
treatment plant—where chemical dosing and detection methodologies can be more closely
monitored and controlled—free ammonia can be released as the water s to the er
as the disinfectant s bacteria or reacts with organics that generally exist in any distribution
system. The released free ammonia acts as a food source for nitrifying bacteria. This can lead
to nitrification and biofilm re-growth in the distribution system. The nitrification and biofilm
re—growth process consumes the effectiveness of disinfectants and can lead to ion in the
distribution system. Beyond the health and regulatory issues, er taste and odor
complaints can result directly from nitrification or from free chlorine reversions used to treat
the issue. If uncontrolled, costly and disruptive line flushes may be required. In this regard, it
is cial to be able to accurately and easily estimate free ammonia levels after the water
leaves the treatment plant.
In certain non-limiting embodiments, therefore, the present invention also comprises
methods and s for detecting the presence and relative amounts of free ammonia in a
water sample derived from a water supply of interest. The present invention also provides
methods and s to reduce nitrification risk of water in municipal water supplies. Yet
further, the present ion provides a nitrification risk factor that allows municipal water
supply ors to assess whether nitrification is likely to happen in their system.
The present invention allows a substantially direct estimation of the free ammonia
species present in a water sample, so as to substantially eliminate the need to overshoot the
monochloramine part of the curve to generate knowledge of whether and how much free
ammonia was present in the water sample before addition of the chlorine (or chlorine
containing species). Such ability to directly te free ammonia present in potable water
provides a significant advance over existing methodologies to inline treat water supplies in
secondary disinfection regimes.
In particular, the present invention allows inline direct estimation of the free
a content of a water supply in situ by use of ORP dose response curves generated for a
plurality of free ammonia concentrations, loramine, di- and tri- chloramine
concentrations, pHs, and temperatures of nce in water supplies, including but not limited
to municipal water supplies and well water. The various dose response curves can then be used
in an inline s whereby a water sample is automatically pulled from the water supply and
chlorine (or a chlorine-containing material) is ed therewith in the presence of an ORP
electrode. The resulting ORP electrode response upon addition of the chlorine-containing
material is then compared to the corresponding ORP dose response curve, so as to provide an
estimation of the amount of free ammonia t in the water supply.
In some non-limiting embodiments, the present invention allows a water supply
operator to detect the real—time condition of a water supply in relation to the amount of free
ammonia present. This, in turn, provides an improvement in the ability to substantially maintain
the amount of free ammonia in a water supply to the optimum range of greater than 0 mg/L to
about 0.1 mg/L.
In particular, free ammonia in chloraminated systems cannot readily be ined
by traditional total a methods. Traditional metric s for ammonia such as
the phenate, salicylate, and the other methods, suffer to various degrees from interference due
to monochloramine, dichloramine, or organic mines. The level of interference in these
s depends on the chloramine concentration, the form of the organic chloramines present
and the unique characteristics of the method being used. This means that chloramine level must
also be determined so that the value can be subtracted out of the free ammonia detection results.
Should the real time ORP measurements indicate that the amount of free ammonia
present is above the desired range, chlorine (or chlorine-containing materials) can be added
using known methods. If the chlorine residual concentration needs to be increased or “boosted”
to maintain a safe disinfectant level throughout the der of the distribution system,
chlorine can be added. Either of these additions can be done at elevated water tanks, storage
reservoirs, entrances to consecutive systems, or at selected points in low residual or
troublesome sections in a distribution . Feeding chlorine (or chlorine—containing
al) and ammonia (or ammonia-containing al) in the specified ratio forms
onal chloramines, thereby providing the necessary secondary disinfection to ensure safe
and good tasting water for consumers. Such feeding can be conducted using automatic methods
that provide inline treatment.
The chlorine (or chlorine—containing al) addition levels can be determined by
standard volumetric on calculations. When the water is present in a storage container,
such as a water tank, the calculations are conducted to apply the chlorine (or ne-
containing material) in batch form. When the chlorine (or chlorine-containing material) is
added to a water pipe while the water is flowing therein, process control addition processes can
be used. For example, a pipe with 1000 liters per minute of flow would need 1 g/min of chlorine
addition to achieve a residual disinfectant raise of 1 mg/l.
Alternatively, should the real time ORP measurements indicate that free ammonia is
not detectable, it will then be apparent that the chloramination disinfection regime has moved
from monochloramine to di- or trichloramine region, or even past the chlorine breakpoint
region.
To generate an ORP ement of the water sample, from which the disinfectant
composition of the potable water supply can be determined, the water sample to be tested is
placed in the presence of an ORP sensor, such as an ORP electrode. The oxidant, that is, the
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chlorine (or chlorine-containing material) is added to the water sample, where the t has
a known tration. The ORP measurement device provides a se that is measured in
olts, and it is this dose response relationship that is plotted to generate data from which
the al materials of interest and amounts thereof can be derived.
Testing of water supply using ORP involves, for example, introducing an oxidant
into the sample in a known volume and following the change in electro-chemical potential
resulting from the oxidant addition. The ORP measurement tus will follow the
electrochemical potential signal generated from the oxidant addition. In regard to chlorine as
the oxidant, the stoichiometry of the chloramine reaction states that one part of chlorine reacts
with one—part ammonia on a molar basis (or 5:1 ratio on a weight basis).
ORP electrodes and attendant reporting componentry are available from a wide
variety of suppliers, for example, Myron L Company’s 720 Series of measurement devices.
er, unlike with other ORP methodologies, the robust methodology herein
substantially does not require ORP electrodes to be precisely maintained to ensure that results
provide accurate estimations of disinfectant composition of a municipal water supply. In this
regard, baseline ORP measurements can be taken as the treated water (that is, water that has
one primary disinfection) leaves the treatment facility. ORP measurements can be taken
at one or more locations in the water distribution network (that is, at a water storage tank, etc.),
and those results compared to the results at the water treatment plant to obtain an estimation of
whether the water sample, and, therefore, the water supply that is evaluated downstream from
the water treatment facility maintains suitable ection efficacy. In short, the pH,
temperature, and dissolved salt content of the water will not change markedly from the point
that the water leaves the treatment plant until it reaches the consumer. Indeed, if these
characteristics of the water did change, the water system could be experiencing significant
failure that would go beyond the need to estimate disinfectant composition. Thus, the inventors
have found that reliable ORP measurements can be obtained within a single water system as
described .
While ORP electrodes may te buildup of residue and/or memory effects over
time, those effects will be gradual. Therefore, comparison of results from hour to hour or day
to day or week to week or even month to month have been found by the inventors to be fairly
le. Moreover, any measurements that are affected by changes in the ORP odes over
time can also be measured and disinfectant composition estimations adjusted in relation thereto.
This means that the ORP measurement device can either remain in the field for use and/or be
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deployed for an extended time period within a municipal water system distribution network
ntially without maintenance.
The inventors herein have further determined, in some non-limiting embodiments,
that valuable ation about the disinfectant composition of a water supply that is
downstream from a water treatment facility can be obtained by estimating the presence (or
absence) of chemicals relevant to ection, as opposed to generating precise measurements
of such als. Notably, potable water analysis has traditionally been directed toward
g the actual chemical makeup, including amounts, in order to comply with regulatory
requirements, as well as to provide safe water to consumers. The inventors herein have
fied a way to ensure that water that is compliant and safe in relation to sanitization level
when it leaves the water treatment facility and remains so as it travels through the water
distribution network on its way to the consumer, namely by using ORP to estimate the
disinfection level of the potable water. Such estimation provides “good enough” ation
about disinfectant composition, and the simplicity of the methodology herein relative to other
methods of measurement used historically, enables cost effective real time measurement of
disinfectant composition. Moreover, the use of ORP is highly suitable for estimation of the
disinfectant composition of chloraminated systems as described in detail .
In certain non-limiting embodiments, the present invention is used to measure
chloramination levels and/or free ammonia levels of potable water, that is water intended for
ingestion by humans. Yet further, the present invention consists essentially of measuring the
chloramination levels andfor free ammonia levels of potable water. Still further, the present
invention is substantially not used to measure the levels of free chlorine in potable water.
Additionally, the robust methodology herein allows comparison of results from
different water supplies to be compared in an “apples to apples” framework, such that the
disinfectant composition of different water ent ns or scenarios can be evaluated
both within a single pal water system (e.g., different locations ream from the
water treatment plant) or among different municipal water systems (e.g., different cities in a
tory jurisdiction). Widespread deployment of ORP to estimate disinfectant composition
of a water system may serve to improve the evaluation of e water quality generally. Such
improvements are enhanced by use of the inventive ORP methodology in water systems as
discussed in more detail after.
Referring to addition of chlorine (or other oxidants) to the water sample
results in a change in millivolts, as measured by a properly configured ORP electrode. In the chlorine on regime is presented in relation to evaluating and, in some non—limiting
embodiments, ing the chloramination and/or free a levels of e water. In the
section denoted “A”, addition of chlorine will be in the form of salt ion and combination
of ne with organic materials in the water. As such, the section denoted “A” will e
substantially no disinfection efficacy because the chlorine is not available to provide
disinfecting activity. Practically speaking, in a secondary disinfection regime, at least some
chlorine should be present in the water sample because of an addition in the water treatment
plant, that is, in the primary ection regime. Accordingly, ORP measurements in the
present invention will be with reference to points later in the plot after “A.”
In accordance with a desired secondary disinfection regime, detection of free
ammonia in relation to generation of a suitable disinfection activity with no foul tasting di— and
trichloramine ion will be relevant primarily in the point just to the left of the point
marked “X.” This can be termed as the “sweet spot” for chloraminated disinfection systems,
that is, where the optimum stoichiometry of ne to ammonia of substantially equal to 1:1
molar ratio is obtained. At this point, there will be substantially no free ammonia present—and,
thus, substantially no nitrification potential— and substantially all monochloramine species
will exist as the chloramination disinfecting species. When a old level of additional
chlorine containing material is added, the dichloramine and, at higher chlorine concentrations,
trichloramines (collectively denoted “C”) will become the predominant chloraminated species.
While these materials have some ecting capabilities, they are sour smelling and tasting,
and, thus, signal to consumers that their e water is not high quality. Free ammonia will
be absent to the right of the section denoted “B.”
Moreover, since monochloramine requires significantly less chlorine to generate, the
presence of di- and trichloramines signify that the water system operators are using more
chlorine than necessary to achieve disinfection composition. Thus, the present invention also
ly allows water system operators to manage the amount of chlorine they are using in
secondary disinfection regimes. When the amount of ne reaches the “breakpoint,” that is,
where the chlorine is no longer combined with ammonia, chlorine will be present in the water
sample substantially as free chlorine, C12 (denoted as “D”). As would be recognized, free
chlorine is largely undesirable in modern water treatment systems because of the propensity of
undesirable chlorinated nds to be ped. Moreover, the presence of free chlorine
in a secondary disinfection regime also signifies that a great excess of chlorine is present in the
water . Again, the ability to readily detect the presence of chlorine in a water sample
extracted from a water supply using ORP greatly simplifies management of chlorine addition
and use in secondary disinfection regimes.
In accordance with the detection regime of the t invention, the disinfectant
composition represented by monochloramine present in the water sample, and, thus, in the
water supply at the point where the water sample is taken, can be determined by evaluating the
slope of the curve generated by plotting the onship—that is, the dose response—between
added chlorine and ORP measurement, as presented in millivolts. The change from
monochloramine to dichloramine will be apparent when there is a change in the slope of the
curve, as denoted by “X” on At that point, the added chlorine will combine with the
monochloramine to create di- and trichloramines. Thus, measured chlorine residual will
decrease, and the ORP ement will change because the redox reaction is changing. It is
this change that allows determination of the disinfectant composition of the water sample, and,
thus, the water supply at the location from which it was extracted.
The free ammonia level can also be generated from the ORP curves generated for a
water . The point just before this slope change at X will comprise only a small amount
of ammonia (more than 0 mg/L) and less than about 0.1 mg/L.
Moreover, the pH, temperature, and dissolved salts are unlikely to change markedly
from hour to hour or day to day or week to week within the same municipal water . Thus,
any pH, temperature and dissolved salt effects between and among measurements are likely to
be very small, or at least small enough to not substantially reduce the accuracy of the
measurements within the time scales relevant to ensuring disinfectant composition of a
municipal water supply. y, the recognition that pH, temperature, and dissolved salt
s, while highly influential to laboratory use of ORP, do not practically affect the viability
of ORP in evaluating municipal water supplies or in well water in real time, or substantially in
real time, represents a marked improvement in potable water quality evaluation. In the present
invention, pH and ature can be measured concurrently with an ORP measurement,
however, such pH and temperature measurements are typically used to confirm that the water
sample has consistent qualities to a first water sample obtained from the same water source.
For example, if a pH measurement of a first water sample is 7.1, but the subsequent water
sample taken from the same water source is 8.5, then it may be indicated that some type of
contamination occurred in the water source as it traveled through the water distribution system.
Wide variations in pH and temperature can also affect the estimation values, and are nt
to measure. Nonetheless, in most real use circumstances the pH and temperatures of the water
supply will not vary substantially between water sample measurements.
In r non-limiting embodiments, the present invention provides ologies
to estimate the level of al chlorine—containing material, in the water sample, and,
therefore, the water supply from which it is derived, where residual chlorine—containing
material comprises monochloramine, dichloramine, trichloramine, and, in some cases, free
chlorine. The chemical identities of these materials are provided by evaluating slope changes
in the curve resulting from plotting the relationship between added chlorine and ORP
measurements.
While the ORP methodology disclosed herein provides benefits when used
ndently, further utility is found when the invention is incorporated in an overall water
monitoring and treatment system, such as would be relevant with a municipal water supply
system or a well. In this , the improved chloramination and free ammonia measurement
system allows substantially real—time measurement of chloramination levels to enable water
system ors to better ensure that water is not just safe and compliant when it is initially
treated in a water treatment facility, but that it remains safe and ant when it is delivered
to consumers. Yet further, the system herein can allow baseline free ammonia levels to be
determined in well water, and e disinfection thereof. Whether used on municipal water
supplies or on well water, the methodology herein substantially reduces the likelihood that
nitrification of previously chloraminated water will occur, enabling improved measurement
and control of free ammonia levels in water. In sum, the various aspects of the present invention
allow water system operators to set and maintain consistent disinfectant levels in water
supplies, as well as allowing them to ntially eliminate costly and labor intensive manual
disinfectant testing and adjusting.
] In certain non—limiting ments, the present invention allows water system
operators to monitor and, therefore, treat and maintain, water quality substantially without an
attendant monitoring the concentrations of the feed source, namely chlorine and ammonia. This
allows the chlorine and ammonia to be stored in high concentrations for extended s
substantially t an attendant monitoring the concentration of the material. Operators are
able to add chlorine or ammonia to a water supply, for example, a water tank, and to determine
the appropriate additional level of chlorine or ammonia by examining the ORP dose response
readings. In this regard, the present invention further comprises a system to treat a water supply
comprising adding one or more of chlorine and a to the water supply and measuring
the ORP or using an ORP electrode, where the additional levels are directed by
observing the ORP electrode behavior.
In this regard, the ORP dose response curve of can be used to define the
addition of ne or ammonia to the water supply. y, the ORP or of the water
sample will allow the operator to know the effective disinfectant level of the water supply.
Addition of a chlorine or ammonia source to that sample will be in relation to the known dose
se behavior that is substantially independent of the concentration of the chlorine or
ammonia being added. To provide appropriate adjustment of the water supply, the operator
need only know the approximate volume of the water supply to which the multiple of the
ne or ammonia needs to be applied to generate approximately the same dose response for
the water supply. For example, a chlorine feed source added to a water sample of 1 L es
a dose response that indicates that 0.5 ml of chlorine needs to be added to generate an
appropriate level of monochloramination, and the total volume of water in the water supply,
such as in a water tank, is 500,000 L, the operator can add 0.5ml * 500,000L = 2.5 L of chlorine
to the water supply to obtain the desired level of disinfectant. This aspect of the present
invention presents a substantial improvement over prior art methods that require precise dosing
of a known concentration of chlorine to e an appropriate level of disinfection of a water
supply.
Referring to an exemplary configuration of a disinfectant management
system 200 in accordance with an implementation of the present invention is illustrated therein.
System 200 ses various aspects, including a plurality of sensors 205 configured to
generate at least ORP measurements. Other sensors 205 that can be used with the system 200
include sensors to generate pH measurements and/or temperature measurements. Additional
sensors can be included in the plurality of s 205, where such additional s can be
configured to provide measurements of free chlorine, total chlorine, and the like.
System 200 also es control module 210 configured with software and
hardware. The ation of the plurality of sensors 205 and control module 210 provides a
water quality assessment module 215.
As would be understood, the plurality of sensors 205 are in operational
communication with the hardware and software aspects of control module 210. In use, water
y assessment module 215 allows a water system operator to r, control, and
generate data about a water system under ment as a substantially integrated .
Water quality assessment module 215 can be operated on a wide variety of hardware
devices including, but not limited to, PCs, tablets, mobile devices, etc. Software ions,
which will include various algorithms associated with system 200 and the various components
therein configured with use therein, can be maintained in the cloud on a remote server, or they
can be operated using software that is natively installed on or used in conjunction with system
200. As such, le microprocessor and er controls are incorporated into system 200
herein to enable operation of system 200 in accordance with the inventive methodology herein.
WO 05952
In further non-limiting embodiments, system 200 can be configured to transmit real time data
to water system rs and/or technicians who may be remote from system 200 via cellular,
Wifi, Bluetooth® communication, or the like.
The integration of the various aspects associated with maintaining water quality in
accordance with the invention herein allows operators to program the various parameters
associated with maintaining a suitable disinfection level/composition of chloraminated water
supplies, free ammonia determination in water supplies, and, optionally, other water quality
characteristics. Still further, the integration of the various aspects herein allows an operator to
uously or periodically r and treat water quality data generated from water quality
assessment module 215.
] In use, a water sample (not shown) is collected via a sample line 220 from water
supply 225, which is in a water tank 240 in Sample line 220 is operationally engaged
with a pump (not shown) and water sample delivery means (not shown), for example, a pipe or
tube or hose to direct the water sample to the plurality of sensors 205, which in pertinent part
includes at least an ORP sensor (not shown) and, ally, a pH sensor (not shown) and a
temperature sensor (not shown). Water y assessment module 215 is configurable to
activate the pump (not shown) so as to provide a suitable volume of water sampled from water
supply 225. If the water sample is found to have a disinfectant level or free ammonia level
outside of a desired set point, control module 210 will provide ctions to at least one of
chlorine feed source 230 or ammonia feed source 235 to add suitable material so as to maintain
uniform and consistent water quality within water supply 225. While system 200 can be
utilized in any municipal water supply uration, illustrates a water supply 225
contained in a water e tank 240.
As shown in chlorine feed source 230 and ammonia feed source 235 are in
fluid communication with water supply 225 contained in water tank 240 via chlorine injection
line 245 and ammonia injection line 250, respectively. Chlorine feed source 230 and ammonia
feed source 235 are in operational communication with the respective injection lines 240 and
245 as shown by 255 and 260, respectively. Further, as shown in chlorine ion line
245 and ammonia injection line 250 each terminate in chlorine injection nozzle 265 and
ammonia ion nozzle 270, respectively. Alternatively, chlorine injection line 245 and
ammonia injection line 250 can be joined via a connection point (not shown) and the respective
chemical ion can be provided by a single chemical injection nozzle (not shown).
In use, the water quality assessment module 215 can be ured to monitor
disinfectant level of water supply 225 via periodic or substantially continuous collection of a
2017/040263
plurality of water samples (not shown) via sample line 220, where at least a portion of each
water sample is provided to one or more of the sensors (not shown) of the plurality of sensors
205. In some non—limiting embodiments, each water sample is evaluated by each of the sensors
in ity of sensors 205 in each water sampling event. Yet further, only some of the sensors
in plurality of sensors 205 are used in each water sampling event. For example, the disinfectant
level related sensors in plurality of sensors 205, namely ORP, pH, and temperature sensors (not
shown) can be used on an ongoing basis (that is, substantially continuously or ically),
and other sensors included in plurality of sensors 205 can be used less frequently.
A notable ement in system 200 over prior art systems is that real time or
substantially real—time ation about the disinfectant composition of water supply 225 can
be provided, or historical data can be generated, maintained, and evaluated. In addition, water
quality data from other s, such as manual samples, can be inputted into the system to
provide a comparison and archive of multiple measurement methods. This allows water system
operators and managers to collect data on the quality of the water within the system 200 for
any duration of time from minutes to years. Such data allows water system operators to evaluate
day to day operations, react to unexpected changes in water chemistry, and observe the effects
of treatment plant s on bution system water y.
In particular, chlorine feed source 230 and ammonia feed source 235 are each
independently configured to inject disinfectant materials into water supply 225. As noted,
control module 210 provides instructions for on of chlorine and/or ammonia via
operational communication 260 and 265, which can be wired or wireless. Water quality
assessment module 215 is accordingly configured to monitor the system via the plurality of
sensors 205 so as to provide pertinent information regarding at least the disinfectant level of
water supply 225 in system 200, including providing alarms or other signals to an operator, if
needed. In this regard, system 200 is configured to alert the user of any irregularities within the
system and produce an automated se, from an alert on the screen to system shut down,
in order to ensure safe operating conditions. System 200 further incorporates a drain 275 in
operational communication with water quality assessment module to allow removal of the
water sample after g thereof.
When the water supply 225 in need of monitoring is orated in a water tank
240, as shown in an active mixing module 280 can be included. Such an active mixing
module 260 can comprise, but is not limited to, a submersible mixing system that is usable for
use in storage tanks (as shown in and reservoirs (not shown). Optimally, active mixing
module 260 will rapidly and completely mix the disinfectant chemicals inserted via chemical
WO 05952
feed nozzle 250 and/or ammonia feed nozzle 255 into the entire volume of water supply 225
in tank 230 or reservoir (not shown) or well (not shown), enabling rapid homogenization and
maximum water quality stability and reliability. The methodologies and devices disclosed in
US Patent Nos. 5,934,877, 6,702,552, 151, 7,862,302, and 9,039,902, which are
incorporated by reference herein in their entireties, are suitable for use in some mixing aspects
of the invention.
A number of embodiments have been described but a person of skill understands
that still other embodiments are encompassed by this disclosure. It will be appreciated by those
skilled in the art that changes could be made to the embodiments described above without
departing from the broad inventive concepts thereof. It is understood, therefore, that this
disclosure and the inventive ts are not d to the particular embodiments disclosed,
but are intended to cover modifications within the spirit and scope of the inventive concepts
including as defined in the appended claims. Accordingly, the foregoing description of various
embodiments does not necessarily imply exclusion. For example, “some” embodiments or
“other” ments may e all or part of “some”, “other,” “further,” and “certain”
embodiments within the scope of this invention.
Claims (24)
1. A method of ining a disinfectant composition of a pal water supply from a water sample comprising: a. obtaining a water sample from a water source at a sampling location, wherein: i. the water sample is d from a water treatment facility; ii. a chlorine-containing material and an a containing material are present in the water source; and iii. the sampling location is located downstream from the water treatment facility; b. adding a chlorine—containing material to the water sample in the presence of an oxidation reduction potential (ORP) measurement device; c. generating a plurality of ORP ements during addition of the chlorine-containing material to the water ; d. estimating a concentration of one or more of free a, fully combined ammonia, monochloramine or a e of dichloramine and trichloramine in the water sample, wherein the estimation is derived from the relationship between the added chlorine material and the plurality of ORP measurements; and e. determining a disinfectant composition of the water source at the water sampling location based upon the concentration calculation.
2. The method of claim 1, wherein the concentration is estimated from monitoring the rate of change of ORP measurement in millivolts as a function of the amount of chlorine-containing material added to the water sample.
3. The method of claim 1, wherein the concentration is estimated by calculating a slope obtained by plotting the ORP of the water sample versus the amount of chlorine—containing al added to the water sample.
4. The method of claim 1, wherein the disinfectant composition is determined as a real-time measurement.
5. The method of claim 1, wherein the chlorine-containing al is added to the water sample in a known volume while generating the plurality of ORP measurements to determine the relationship between the added chlorine material and the plurality of ORP ements.
6. The method of claim 1, further comprising ing the ity of ORP measurements ed from the water sample located downstream from the water treatment facility to ORP measurements obtained from a water sample obtained at the water treatment facility to determine disinfection efficacy.
7. The method of claim 1, wherein the estimated provides the concentration of both free ammonia and loramine in the water sample.
8. The method of claim 1, further comprising, after determining the disinfectant composition of the water source, adding additional ne-containing materials and ammonia-containing materials to the water source to achieve a desired level of the disinfectant composition.
9. The method of claim 8, wherein an amount of the added chlorine— containing materials and ammonia-containing materials is independent of a concentration of the chlorine—containing materials and ammonia-containing materials.
10. The method of claim 1, n a volume of the water sample obtained from the water source is known.
11. A method of determining free ammonia composition of a water supply comprising: a. obtaining a water sample from a water supply at a sampling location; b. adding a chlorine—containing material to the water sample in the presence of an oxidation reduction potential (ORP) measurement device; c. generating a plurality of ORP measurements during addition of the chlorine-containing material to the water sample; and d. estimating a concentration of free ammonia in the water sample, wherein the estimation is derived from the relationship between the added chlorine material and the plurality of ORP measurements.
12. The method of claim 11, wherein a volume of the water sample ed from the water source is known.
13. The method of claim 11, n the water sample is derived from a water treatment facility and the sampling location is located downstream from the water treatment facility.
14. The method of claim 11, further sing ining a concentration of free ammonia in the water supply within a range of greater than 0 mg/L and less than about 0.1 mg/L.
15. The method of claim 11, wherein the method of determining free ammonia composition is substantially free of a reagent other than chlorine and ammonia- containing materials.
16. The method of claim 11, wherein the concentration of free ammonia is estimated from monitoring the rate of change of ORP measurement in millivolts as a function of the amount of chlorine-containing material added to the water sample.
17. The method of claim 11, further comprising adding onal chlorine- ning materials when the estimated ammonia tration is above a desired ammonia tration range .
18. A system for maintaining the disinfectant level of a potable water supply comprising: a. a water quality assessment module comprising: i. a plurality of sensors comprising at least an oxidation reduction potential sensor; and ii. a control module in operational engagement with the plurality of sensors; b. a water supply intended for delivery of potable water to a er; c. a water sampling device comprising a fluid ry means configured to provide a sample of water derived from the water supply to the water quality assessment module; d. a chlorine feed source and an ammonia feed source, wherein each of the sources are independently: i. in operational engagement with the water quality assessment module; and ii. in fluid communication with the water supply, n the system is configured to measure and adjust the mination level and the free ammonia levels of a potable water supply prior to delivery of the water supply to the consumer.
19. The system of claim 18, wherein the water quality assessment module is configured to provide information regarding at least a disinfectant level of the water supply.
20. The system of claim 18, wherein the water supply is maintained in a water storage tank.
21. The system of claim 20, wherein the water storage tank includes a mixing module.
22. The system of claim 18, wherein the water sampling device r comprises a pump.
23. The system of claim 18, wherein the volume of the sample of water provided by the delivery means is known.
24. The system of claim 18, n the plurality of sensors further comprise a pH sensor and a temperature sensor.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62/356,718 | 2016-06-30 |
Publications (1)
Publication Number | Publication Date |
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NZ749640A true NZ749640A (en) |
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