SYSTEM AND METHOD FOR PRESERVATION, TRANSPORT, AND ANALYSIS OF WATER SAMPLES
20170322127 · 2017-11-09
Assignee
Inventors
- Emily Hanhauser (Brookline, MA, US)
- Michael Bono (Somerville, MA, US)
- Anastasios John Hart (Waban, MA)
- Rohit Karnik (Cambridge, MA, US)
- Xiaoyuan Ren (Cambridge, MA, US)
- Chintan Vaishnav (Belmont, MA, US)
Cpc classification
B01J20/264
PERFORMING OPERATIONS; TRANSPORTING
B01L2300/0627
PERFORMING OPERATIONS; TRANSPORTING
B01L2200/0631
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3425
PERFORMING OPERATIONS; TRANSPORTING
B01L2300/12
PERFORMING OPERATIONS; TRANSPORTING
B01L2200/185
PERFORMING OPERATIONS; TRANSPORTING
B01D15/1892
PERFORMING OPERATIONS; TRANSPORTING
C12Q1/6806
CHEMISTRY; METALLURGY
B01L2300/069
PERFORMING OPERATIONS; TRANSPORTING
B01L3/5023
PERFORMING OPERATIONS; TRANSPORTING
B01J2220/00
PERFORMING OPERATIONS; TRANSPORTING
B01J20/2805
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A device for collecting contaminants from water samples is provided. The device includes a solid sorbent that collects and stores the contaminants from water samples. The solid sorbent is configured to allow for the preservation of the stored contaminants. The concentrations of the contaminants in the water samples are determined via analysis of the solid sorbent or via elution of the stored contaminants from the sorbent and analysis of the eluate solution.
Claims
1. A device for collecting and releasing contaminants from water samples comprising: at least one solid sorbent that is capable of adsorbing target contaminants, preserving the target contaminants for extended periods of time, and releasing the target contaminants for subsequent analysis; means for supporting or containing the at least one solid sorbent and facilitating rapid adsorption of the contaminants; and a package for storing the at least one solid sorbent with adsorbed contaminants.
2. The device in claim 1, wherein the macroscopic surface to volume ratio of the at least one solid sorbent is greater than 10 per mm, not including sorbent pore area.
3. The device in claim 1, wherein the at least one solid sorbent is separated after contaminant adsorption.
4. The device in claim 1, wherein the at least one solid sorbent comprises particles that are contained within a mesh or porous material.
5. The device in claim 1, wherein the at least one solid sorbent comprises particles that are coated on a mesh, wire, brush, or fabric.
6. The device in claim 1, wherein the at least one solid sorbent is fabricated so that it remains intact during analysis and assumes the desired geometry during adsorption, storage, and release of contaminants without the need for additional device geometry aside from the at least one sorbent and packaging.
7. The device in claim 1, wherein the containment means is a foldable vessel.
8. The device in claim 1, wherein the at least one solid sorbent comprises multiple kinds of sorbents that adsorb different classes of contaminants.
9. The device in claim 1 further comprising at least one pH sensor, a salinity sensor, a turbidity meter, or a chromogenic sensor.
10. The device in claim 1 further comprising one or more additional reagents for controlled release into the fluid sample during contaminant adsorption, so as to enhance contaminant adsorption.
11. The device in claim 1, wherein the at least one solid sorbent is in the form of a porous composite with another material that provides mechanical support or other desired mechanical properties.
12. A device for collecting and releasing contaminants from fluid samples comprising: at least one solid sorbent that adsorbs and releases target contaminants, means for supporting or containing the at least one solid sorbent and facilitating rapid adsorption of the contaminants; and a package for storing the at least one solid sorbent with adsorbed contaminants.
13. The device in claim 12, wherein the at least one solid sorbent comprises xerogel.
14. The device in claim 13, wherein the xerogel comprises an iron oxide matrix.
15. The device in claim 12, wherein the at one least solid sorbent material comprises ion-exchange resin.
16. The device in claim 15, wherein the ion-exchange resin comprises a copolymer incorporating polystyrene and divinylbenzene.
17. The device in claim 13, wherein at least one solid sorbent material is cellulose, either untreated or with modification to enhance adsorption or desorption.
18. The device in claim 13, wherein the at least one solid sorbent is incorporated into modules which can be removed from a sampling geometry after adsorption of the contaminant.
19. A method of collecting and releasing contaminants from water samples comprising: providing a water sampling device having at least one solid sorbent; exposing the device to a sample of water; allowing the at least one solid sorbent to adsorb one or more contaminants from the water; removing the device from contact with the water; releasing the one or more contaminants from the at least one solid sorbent at a later time; and performing analysis on the released contaminants.
20. The method in claim 19, wherein the device is packaged for storage or transportation before the release step.
21. The method as in claim 19, wherein the device dries after the removal step and before the release step.
22. The method as in claim 19, wherein the duration between the removal step and the analysis step is at least 24 hours.
23. The method as in claim 19, wherein the duration between the removal step and the analysis step is at least 7 days.
24. The method as in claim 19, wherein the duration between the removal step and the analysis step is at least 30 days.
25. The method in claim 19, wherein the at least one solid sorbent comprises at least one of an ion exchange resin, xerogel, or cellulose.
26. The method in claim 19, wherein the at least one solid sorbent absorbs multivalent cations, organic molecules, arsenic, fluoride, chromium, multivalent anions, viruses, bacteria, protozoa, parasitic organisms, nucleic acids, and proteins.
27. The method of claim 19, wherein the device is stored in a package to prevent contamination.
28. The method in claim 19, wherein the one more contaminant is adsorbed by manually stirring the device in the sample.
29. The method in claim 19, wherein the one or more contaminants are adsorbed by flowing the sample through the device.
30. The method in claim 19, wherein the one or more contaminants are adsorbed by immersing the device in the sample.
31. The method in claim 19, wherein the one or more contaminants are released by flowing a release solution through the device.
32. The method in claim 19, wherein the one or more contaminants are released by immersing the device in a release solution.
33. The method of claim 19, wherein the one or more contaminants adsorption step requires less than 15 minutes.
34. The method of claim 19, wherein the one or more contaminants adsorption step requires less than 3 minutes.
35. The method of claim 19, wherein at least 80% of the one or more contaminants in the sample are adsorbed and released.
36. The method of claim 19, wherein the amount of target contaminants in the sample and the amount that is released is consistent.
37. The method in claim 19, wherein the device is transported to another location after adsorption for storage or analysis.
38. The method in claim 37, wherein the device is transported via the postal service or a commercial shipping service.
39. The method in claim 19, wherein the device is stored at the same location after adsorption for analysis at a later date.
40. The method in claim 19, wherein the device utilized is the device described in claim 1.
41. The method in claim 19, wherein the device utilized is the device described in claim 12.
42. A method of collecting and releasing contaminants from water samples comprising: providing a fluid sampling device containing at least one solid sorbent; exposing the device to a sample of fluid; allowing the at least one solid sorbent to adsorb one or more contaminants from the fluid, removing the device from the fluid; releasing the one or more contaminants from the at least one solid sorbent; and performing analysis on the one or more contaminants.
43. A method of collecting and releasing contaminants from water samples comprising: providing a fluid sampling device containing at least one solid sorbent; exposing the device to a sample of fluid; allowing the at least one solid sorbent to adsorb one or more contaminants from the fluid; removing the device from contact with the fluid; and performing direct analysis on the at least one solid sorbent to determine the one or more contaminants adsorbed on the at least one solid sorbent.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0023] The invention describes a water quality monitoring paradigm using sampling technology, materials, and system-level protocols to enable dry sample preservation of water samples to facilitate easy ambient-temperature shipping, storage, and rapid processing at centralized laboratories to greatly improve the ability to monitor the water quality. The ability to easily store and ship water samples has the potential to open a new paradigm in water quality management. Dry water sample preservation techniques described here are expected to facilitate easy shipping, storage, and rapid chemical and microbial analysis of water quality in centralized laboratories.
[0024] Several approaches can be conceived for dry preservation of water samples. Commercially available dried blood spot (DBS) sorbents already used for chemical and microbial analysis in human blood samples could be applied to water sample analysis. Custom-designed sorbents could also be used for this purpose. For example, membranes or porous media can be functionalized with positive charge using polyethyleneimine to bind negatively-charged bacteria when water is flushed through. In addition, high-surface-area inorganic morphologies such as silica or metal-oxide xerogels frequently present charged sites that may change charge with pH and redox conditions. Also, polymers containing stationary charged groups, such as ion exchange resins, can be used to adsorb positively or negatively charged species over a wide range of pH conditions. Water samples that are preserved in dry (or compact) state can then be analyzed using existing laboratory-based chemical and microbial analysis methods.
[0025] The key consideration in chemical preservation is to ensure a quantitative relationship between the concentration of analytes in original water sample and the laboratory results from the preserved sample. On one hand, strongly adsorbing sorbents may be used to facilitate concentration of the chemical during filtration across the sorbent. On the other hand, sorbents can provide a surface for chemicals to precipitate or crystallize out when water evaporates.
[0026] The water sample to be analyzed is flowed through or contacted by a porous sorbent, where the porosity and dimensions of the sorbent are designed to ensure adsorption of the analytes of interest. It is well-known that the amount of analyte that can be adsorbed will depend on the nature of the sorbent, total surface area of the sorbent, volume of weight of the sorbent, volume of the water sample, concentration of the analyte, pH, and any competing species in the water sample. A greater amount of sorbent or greater surface area of sorbent will result in greater amount of analyte adsorption. Furthermore, the diffusion and adsorption kinetics of the analyte will influence the amount adsorbed. Therefore, the porosity and dimensions (e.g. thickness or cross-section area) of the sorbent can be tuned to control the flow rate (for example, driven by gravity) and the sorbent surface area to achieve rapid adsorption. Examples of sorbents include cellulose (including filter paper) and surface modified cellulose (including cellulose nitrate and amidoximated cellulose), synthetic polymers such as polyamide, polyacrylamide and polyacrylonitrile, cation or anion ion exchange resins made of polystyrene-divinylbenzene or polyacrylic acid, chitin and chitosan, zeolites, mineral clays, lignin, xerogels with metal-oxide or silica backbone, activated carbon, carbon nanotubes, and composites of these materials.
[0027] As an explicit example of these sorbents,
[0028] In many cases, complete adsorption of the analyte or analytes of interest can be desirable, but in some cases partial adsorption can be sufficient provided that it is consistent and a calibration can be established to relate the analyte concentration in the water sample to the amount adsorbed. Furthermore, given that certain conditions such as pH can affect analyte adsorption, chemicals (e.g. buffer) may be added to the water sample or incorporated into the device or sorbent to facilitate adsorption. Additionally, sensors that measure pH, turbidity, conductivity or other parameters may be incorporated in the device to provide additional information for device operation and monitoring purposes. Other mechanisms that are known to promote adsorption of different species on surfaces can also be used; for example, it is well-known that charged species can be adsorbed on electrodes under the application of an electric potential, such as that used in capacitive deionization method for water desalination. In some cases, sorption in solids or liquids (which may be encapsulated in a matrix in the form of droplets) can be used instead of surface adsorption. For example, hydrophobic organic species in water can preferentially partition into oil or into some polymeric substances such as poly(dimethyl siloxane). Alternatively, adsorption (or sorption) may be achieved by immersing a sorbent material into a water sample, with or without stirring, for a sufficiently long period of time.
[0029] After adsorption is completed either by flowing the water sample through, by immersion, or any other means, the sorbent can be dried, or the residual water sample can be discarded, while retaining the desired analyte(s) on or in the sorbent. The sorbent may or may not be dried to remove water, stored, or transported to a different location. It is noted that the weight or volume of the sorbent (and any device the sorbent can be incorporated in) is less than that of the original water sample. By selecting materials with high adsorption capacities, the amount of sorbent needed for sampling is minimized. For example, commercial filter paper can adsorb 0.6 milligram (mg) copper per gram (g) of filter paper, as shown in
[0030] Alternatively, the analytes can be released into water or any liquid solution with controlled or known composition, so as to avoid interference with the analyte concentration measurement, such as deionized water, nitric, hydrochloric or sulfuric acid solution, or sodium hydroxide solution, with the desorbed analytes then quantified by use of methods such as ultraviolet/visible spectroscopy, flame atomic absorption spectroscopy (FAAS), ICP-OES, and ICP-MS. Examples of desorption methods include acidic pH dissolution of the sorbent (e.g. filter paper in nitric acid), acid pH elution (e.g. ion exchange resins in hydrochloric or nitric acid) or use of a pH where adsorption is no longer favorable (e.g. use of high-pH solutions such as sodium hydroxide to desorb anions from iron-oxide xerogels). For example, at least 80% of the amount of copper, lead or nickel adsorbed to ion exchange resins can be recovered from the sorbent after up to 4 months of dry storage at room temperature, as shown in
[0031] Similarly, dry or compact preservation of microbial contaminants can enable (1) direct culture of microbes for analysis and (2) nucleic acid (DNA/RNA) analysis. The process can involve concentration of the microbes by filtration or stirring and adsorption, or the use of cell lysis media to extract and adsorb nucleic acids or other biomolecules. For example, lysing the cells followed by filtering through a DNA-binding sorbent may be used to extract DNA and store it on the sorbent. The DNA can be released for analysis. Such sorbents and conditions to elute (remove) nucleic acids and other molecules are known, for example, for sorption and elution of DNA on silica.
[0032] Alternatively, bacteria can be captured using positively charged sorbents or filtered through a porous sorbent and the captured cells can be lysed (burst) before DNA analysis; for example, microbes could be captured in hydrogel matrices which facilitate their survival without allowing appreciable growth, such as methods that have been previously used for human cells. DBS cards and kits available for nucleic acid extraction and preservation may be adapted for analysis of water samples; for example, the FTA card marketed by GE Healthcare incorporates chemicals to lyse (burst) cells and bind their DNA, which can be preserved in dry state and is eluted upon exposing the card to water. Similarly, filtering or sorption may be used for preserving viable E. coli that can be cultured after dry or wet storage in a volume or weight that is smaller than that of the original sample. Preservatives may be added to the water sample or on the sorbent. For example, trehalose is a suitable preservative that retains high viability of E. coli after air-drying.
[0033] Materials for preservation of water samples can be integrated into cost-effective, easy-to-use devices that can be implemented for water monitoring paradigm in large-scale deployments.
[0034] Sorbents are molded into a geometry or contained in a device, whose geometry is optimized for fast contaminant absorption kinetics, for device operation time on the order of 10 minutes or less. Optimal geometries for rapid uptake may differ depending on the sorbent and so different geometries may be used for different sorbents. Additionally, any material used in the device must be compatible with the entire adsorb/store/release protocol. For example, kinetics of copper uptake on ion exchange resins contained in polypropylene tea bags are negatively affected by the particle size of ion exchange resin; however, the opening size of the polypropylene mesh does not affect the kinetics significantly with all copper adsorbed within 10 minutes, as shown in
[0035] These devices should include the capability for collection of a prescribed volume of water, and reuse for repeated collections without cross-contamination. This includes use of containers with set or marked volumes, and a disposable sorbent that may be removed from the container and shipped to a laboratory for analysis, with a new sorbent inserted for the next water sample. The sorbent can include filter paper, xerogels, polymers, or composites. Also, the sorbent can be of the form of a packed-bed cartridge containing sorbent granules, a cartridge containing the sorbent coated onto a monolithic structure such as a honeycomb for well-defined flow, a rigid wafer consisting of a porous matrix impregnated with sorbent particles, a rigid wafer consisting of a porous matrix coated with a conformal layer of sorbent, a membrane consisting of a flexible matrix (such as paper or fabric) coated with a layer of additional sorbent, or a membrane consisting of a flexible matrix (such as paper or fabric) impregnated with sorbent (as particles or a coating), where the shape of the flexible matrices may be maintained during sample collection and shipping via a rigid support around the edges of the flexible matrix.
[0036] The inventive device includes the active sorbent material, which takes up the contaminants from solution, and any supporting structure necessary for device operation and maximum interaction between the sorbent surface and sample solution. The device can include multiple sorbents, each specific for the uptake of a specific contaminant or class of contaminants (for example, cationic, anionic, and organic contaminants). The sorbents may be mixed together, or they may be modularly contained to allow for detachment of one type of sorbent and separate storage, transport, release, and/or analysis of each contaminant. All materials contained in the device are compatible with the entire sampling and preservation protocol.
[0037] The device is contained in clean packaging, such as an envelope or small thin box. When ready for use, the user removes the device from the packaging and applies the water sample to the device following an established protocol for the specified time. The device may then be blotted of excess water using clean absorbents and/or dried at room temperature, after which the device is deposited back in the original or specifically provided packaging for clean long term storage and/or transportation. Additionally, if the device does not need to be dried prior to storage and/or transportation, the device may be directly deposited in the appropriate packaging without drying or blotting.
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[0040] In some embodiments, the sorbent support has a rigid or flexible handle, a string, or other mechanism of holding that enables the sorbent to be immersed, stirred in, or exposed to the water, such that the fingers of the operator do not touch the sorbent or the water sample and cause contamination.
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[0043] The sorbent material can include coated structures, such as plastic meshes, porous strips, fabrics, cotton or synthetic fibers, porous monolithic structures or honeycombs. The materials to be coated may be in their desired form prior to being coated or be coated in bulk, allowing for manipulation of the coated material into the desired geometry after processing, such as a fibrous brush or woven mat.
[0044] Also, the sorbent materials can be formed into other high-surface-area structures. The sorbent material makes up the majority of the device, such that these devices may or may not have significant supporting material, unlike the other embodiments aforementioned. Sorbents, such as polymers or xerogels, may be formed into structures during synthesis or molded/formed into a structure after synthesis. Examples include sorbent polymer fibers or films that are woven into a mat or fabric, or cut into short sections and fused together at one end in a brush format; polymers or xerogels that are cast into a mesh mold during synthesis; and materials that are melted and extruded into different geometries through electrospinning or 3D printing. These high-surface-area structures can consist solely of the sorbent material, or of composite materials incorporating the sorbent and other materials (such as chitosan or other polymers) which confer flexibility, toughness, or other desired mechanical properties to the structure.
[0045] Application of the water sample to these devices may occur through processes such as 1) flow of solution through the device, 2) flow of solution over the device, 3) stirring the device within the water sample, or 4) static adsorption by placing the device within the solution or the solution within the device. Additional supporting equipment necessary to using the sorbent can be included with the original packaging. Examples include rigid outer supports for sorbent impregnated, coated or formed membranes, foldable flow-through application systems in a cup or box form for use of flow through or flow over geometries (such as membranes or meshes) and a handle or frame for materials to be rigidly supported while being stirred with water samples.
[0046] Moreover, the invention provides the capability for filtering and spatially defined deposition of chemical and bacterial contaminants from the prescribed volume of water may be achieved by use of different sorbents in the same device connected to a single or multiple water containers within the device. The amount of water sampled by each sorbent may be controlled by appropriate choice of resistance to fluid flow (pressure divided by fluid flow rate) for the fluid flow pathways corresponding to each sorbent. A single-use sample collection “card” can be used by the invention, which receives the filtered/deposited constituents and can be mailed by post or the like. Also, there should be a requirement for only simple text or graphical instructions, and offering visual confirmation of successful use, and ease of distribution and collection of the samples. The invention could be fabricated using environmentally sustainable materials, and using local manufacturing capacities.
[0047] In other embodiments of the invention, the inventive device can include at least one of a pH sensor, a salinity sensor, a turbidity meter, a chromogenic sensor, or other kinds of sensor. Moreover, the time frame when removing the inventive device from the water to the analysis can range from 7-30 days. In addition, it can take between 3 and 15 minutes for the sorbent to absorb one or more contaminants from the water.
[0048] The invention reduces the cost and time limitations imposed by traditional water quality monitoring, by stably preserving contaminations in a compact and/or dry form, which can be shipped to the advanced labs using the existing postal service structure and associated fees. Dry preservation enables the transport of samples from a range of distances to advanced laboratories, allowing more water sources can be accurately analyzed for complete contaminant arrays using standard analytical techniques, potentially increasing the monitoring capabilities and reach of centralized bodies. Additionally, analysis protocols developed with the dry preservation technology complement the existing standard analytical procedures, so that the dry sampling technology aids the existing system.
[0049] Although the present invention has been shown and described with respect to several preferred embodiments thereof, various changes, omissions and additions to the form and detail thereof, may be made therein, without departing from the spirit and scope of the invention.