CN103384823A - Device and process for passive sampling - Google Patents

Device and process for passive sampling Download PDF

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Publication number
CN103384823A
CN103384823A CN2011800667908A CN201180066790A CN103384823A CN 103384823 A CN103384823 A CN 103384823A CN 2011800667908 A CN2011800667908 A CN 2011800667908A CN 201180066790 A CN201180066790 A CN 201180066790A CN 103384823 A CN103384823 A CN 103384823A
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Prior art keywords
pim
film
equipment
solution
aquo system
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Inventor
S·D·科列夫
R·W·凯特罗尔
V·佩蒂格罗夫
C·陈
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University of Melbourne
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University of Melbourne
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Priority claimed from AU2010905321A external-priority patent/AU2010905321A0/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/301—Polyvinylchloride
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4005—Concentrating samples by transferring a selected component through a membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/087—Single membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/10—Devices for withdrawing samples in the liquid or fluent state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/10—Specific supply elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/06—Submerged-type; Immersion type
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1813—Specific cations in water, e.g. heavy metals

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Dispersion Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention generally relates to the field of monitoring or analysing an aqueous system (both water or sediment) for analytes and in particular to processes and devices for sampling and analysing the concentration or levels of specific analytes or solutes in an aqueous system such as a natural water system (e.g., rivers, ponds, etc.) or industrial effluent streams. The analytes or solutes may or may not be pollutants of said aqueous systems. The sampling device comprises a polymer inclusion membrane or a composite polymer inclusion membrane.

Description

The equipment and the method that are used for passive sampling
Technical field
The present invention relates in general to monitoring or analyzes the field of the analyte in Aquo System (water or sediment), and relate in particular to for taking a sample and analyzing specific analyte or the concentration of solute or the method and apparatus of grade in Aquo System (such as natural aquatic system (such as river, pond etc.), perhaps Industry Waste current).Described analyte or solute can be or can not be the pollutant of described Aquo System.Described sampling equipment comprises that polymkeric substance comprises film or composition polymer comprises film.
Background technology
At present, it is important all the more that the sampling technique in environmental analysis is just becoming, because the existence of some chemical substance in environment (comprising air, earth and water) may produce adverse influence to organism (comprising the mankind).Passive sampling refers to over a long time take a sample in (for example from several days to many months), is simply a kind of and allows cheaply the technology of a large amount of chemical substances being taken a sample in many places.It can also determine the analyte mean concentration in time of bioavailable, the concentration that fluctuates at any time at occurring in nature due to them and/or accidental pollution, and this is for adopting spot sampling to realize.The method also allows picked-up and the accumulation of chemical substance in organism (for example metal and organic contaminant) are studied.
Now developed the passive sampler of the sampling of many number of chemical materials for water (being mainly metal and organism class).In some sampler in them, sampling method is based on passive dialysis, and wherein analyte diffuses through semi permeable hydrophilic porous film and enters and receive in aqueous solution, until reach balance.For the analysis that receives phase, this passive sampler need not complicated pre-treatment step.Yet passive dialysis has by the determined limited selectivity of the hole dimension of film.The method does not have the pre-concentration ability, and the pre-concentration ability is vital for the detection of trace level pollutant usually.By chelating resin introduce is received water or with supported liquid membrane (SLM) replace the hydrophilic film of porous and in the moisture reception mutually interpolation suitable peel off reagent (stripping reagent) (for example complexing agent), these defectives are overcome to a certain extent.SLM is that the organic solution of described extractant is deposited in described fenestra by capillary force through the macropore hydrophobic membrane (film liquid phase) of the organic solution dipping of extractant.A kind of passive sampler with principle of similitude work is diffusive gradients in thin-films (DGT) sampler.This sampler comprises gel layer, and described gel layer contains the compound of bound analyte strongly.This gel layer is separated by propene hydrate acid amides diffusion gel and aqueous environment.In the situation of DGT and chelating resin equipment, before the analysis to measure of the analyte of pre-concentration, need series of preprocessing step (for example extraction, desorb).These routine analyzers need laboratory environment and can not implement at the scene.The analysis of moisture reception phase is directly carried out usually in based on the passive sampler of SLM.Yet due to the leaching in mutually at aqueous environment and container of film liquid phase, the life-span of SLM is limited.
The present invention seeks to overcome some deficiency at least of known sampling equipment and method.
Summary of the invention
The invention provides by use polymkeric substance as amberplex comprise film (PIM), with equipment and the method for the passive sampling that is contained in analyte in aqueous systems or solute, described polymkeric substance comprises film can be effectively and optionally extractive analysis thing or solute from described Aquo System usually.
Correspondingly, in one aspect, the invention provides the equipment for the passive sampling of Aquo System, wherein said passive sampling equipment comprises that polymkeric substance comprises film (PIM) or composition polymer comprises film.
In embodiment, the equipment that is used for the passive sampling of Aquo System comprises in one:
(i) container;
(ii) thief hole; With
(iii) film, described film is that polymkeric substance comprises film (PIM) or composition polymer comprises film (PIM);
Wherein
(a) described container comprises reception solution and is equipped with described thief hole, receive solution or remove reception solution from described container to allow to add in described container, and
(b) described film is fluid between solution and Aquo System and is communicated with receiving.
In one embodiment, described film is attached to described container.
In one embodiment, described film is that polymkeric substance comprises film.
In another embodiment, described film is compound-PIM, wherein said compound-feature of PIM is with non-PIM polymeric layer.
Further, the invention provides a kind of method of the passive sampling for Aquo System, comprise described passive sampling equipment is submerged to step in described Aquo System, wherein said passive sampling equipment comprises that polymkeric substance comprises film or composition polymer comprises film.
Further, the invention provides a kind of method of the passive sampling for Aquo System, comprise and carry current to pass the step of passive sampler, wherein said passive sampling equipment comprises that polymkeric substance comprises film (PIM) or composition polymer comprises film, and described current and then contact with described PIM or compound PIM.
In one embodiment, above-mentioned two aspects include detecting step.
Description of drawings
Fig. 1 is the schematic diagram according to the passive sampler of film base of the present invention (membrane-based);
Fig. 2 is the schematic diagram according to the passive sampler of Zn of the present invention (II);
Fig. 3 is in solution externally, in 0 (◆), and 100 μ g L -1(■) He 500 μ g L -1In the situation of Zn () (II) concentration, transient state Zn (II) concentration in described reception solution;
Fig. 4 is for adopting the calibration curve of Electrothermal Atomic Absorption spectroscopic methodology (ET-AAS);
Fig. 5 is that emissive porwer is to described sample (50 μ g L -1Zn (II)) with the volume ratio of reagent (p-taq, the pH7.5 of 160 μ Μ in the Tris-HCl damping fluid of the SDS of 0.19M and 0.45M) solution;
Fig. 6 is the calibration curve of the fluorescence measurement of Zn in deionized water (II);
Fig. 7 is the calibration curve of the fluorescence measurement of Zn (II) in the HCl of 0.1M solution;
Fig. 8 is in solution (PIM:40%D2EHPA/60%PVC (m/m)) externally, at 0 μ gL -1(o), 25 μ g L -1(●), 50 μ g L -1(▲), 75 μ g L -1(◆) and 100 μ g L -1In the situation of Zn (■) (II) concentration, transient state Zn (II) concentration in described reception solution;
The mean speed that Fig. 9 extracts for the Zn (II) that compares with time weight average external volume Zn (II) concentration in described passive sampler.
Figure 10 is that the sampling of 4,8 and 10 days is for the calibration curve of passive sampler;
Figure 11 a is the photo according to the passive sampler of film base of the present invention;
Figure 11 b is the parts of described passive sampler by the photo of assembling sequence:
(a) stainless steel frame, (b) are with teflon (Teflon) piece of received well and sample tap, square PIM, (d) Gore-tex that (c) is cut into length of side 2.5cm TMPacking ring, (e) sheet polytetrafluoroethylene gasket, (f) stainless steel packing ring, (g) stainless steel packing ring and bolt, and (h) stopper of sample tap;
Figure 12 is for describing the NH as time (h) function 4 +Concentration (mgL -1) curve map;
Figure 13 is used for NH according to the present invention 4 +The schematic diagram of the passive sampler of film base of sampling;
Figure 14 is used for NH according to the present invention 4 +The picture of the passive sampler of film base of sampling;
Figure 15 is the gas that is used for the ammonia monitoring-diverging flow Injection Analysis (GD-FIA) system (reagent: 2M NaOH; Cresol red/thymol blue is as indicator; PP, peristaltic pump (flow velocity 1mL min -1); IV, introduction valve (sample 200mL); MC mixes coil pipe (50cm is long); GDU, gas-diffusion unit (poly tetrafluoroethylene); L, spectrophotometer flow cell (580nm); W, refuse) schematic diagram;
Figure 16 is for describing the NH as time (h) function 4 +Concentration (mgL -1) curve map;
Figure 17 is for describing NH 4 +Concentration (receiving in solution) is to NH 4 +Concentration (in feedstock solution) (is mgL -1) curve map;
Figure 18 is the schematic diagram according to the passive sampler of flow type of the present invention;
Figure 19 is the picture of the passive sampler of flow type (the right) of improved stainless steel packing ring of the present invention (left side) and assembling;
Figure 20 is the schematic diagram of the passive sampling system of flow type of the present invention, comprises pump, source analyte and refuse storage.
Embodiment
In whole instructions and appending claims, except as otherwise noted, word " comprises (comprise) " and should be understood as that such as the variant of " comprising (comprises) " and " comprising (comprising) " and hinted the integral body that comprises statement or the group in step or integral body or step, but do not get rid of the group in any other integral body or step or integral body or step.
In this manual to quoting of publication (or be derived from its information) or any known things formerly arbitrarily, be not and should be considered to be and admit or approval or any type of suggestion, namely formerly publication (or be derived from its information) or any known things have formed the part of the common practise in this area that this instructions relates to.
The present invention is based on following discovery: use PIM effectively (and usually optionally) extraction may be present in analyte and solute in the industrial logistics of for example natural Aquo System (comprising water and sediment) or discharging, wherein said PIM is characterised in that to have immobilized extractant (such as quaternary ammonium salt), and therefore described PIM can be the film of the passive sampling of effective described analyte for moisture (for example water) system and solute.
The character of PIM
Polymkeric substance comprises film and is well known in the art, and can be called as " polymeric liquid ", " gel liquid ", " polymeric plasticiser ", " fixed position carrier " or " solvent polymeric membrane ".PIM, for example than supported liquid membrane (SLMs), major advantage be their stability.In addition, be different from bulk liquid membrane (BLMs), PIMs does not have the feature of low interface surface area and quality transmission rate usually.There is not the problem of emulsion breakage in PIMs yet, and the emulsion breakage tends to endanger emulsion liquid membrane (ELMs).
Usually the solution that contains analyte/solute extractant (for example quaternary ammonium salt), plastifier/modifier (optional) and base polymer according to PIMs of the present invention by mixing (preparation) is prepared from.Usually with an organic solvent (such as ethers (for example THF, ether)) and chlorinated solvent (for example methylene chloride) promote this process for preparation, and described organic solvent and chlorinated solvent are removed (for example by air dry or in a vacuum) usually during film forms.
Will be understood that, " extraction " mentioned herein and " reextraction " process comprise needs or target analytes/solute enters or leaves the controlled transfer of film.This procedure division promotes by carrier (being called as in this article " extractant "), and described carrier is to be fixed on analyte in PIM/solute complexing agent or ion exchanger in itself.
In one embodiment, described extractant consists of the 5-40%m/m of described PIM, consists of in another embodiment the 10%-30%m/m of described PIM and consist of the 15-25%m/m of described PIM in further embodiment.
In one embodiment, described PIM is suitable for use in for monitoring ammonia and (is expressed as NH 3And NH 4 +) passive sampler in, described extractant is DNNSA or its salt (for example potassium or sodium salt) and the 10-30% that can consist of whole compositions (%m/m) of described PIM.
In one embodiment, described DNNSA is utilized as the solution that is dissolved in the 0.2M-0.5M in organic solvent (such as heptane).This solution can consist of about 40-15%m/m that total PIM forms.As selection, the DNNSA(that can adopt purifying wherein heptane is removed) or the salt of DNNNSA.
In one embodiment, described PIM is suitable for use in the passive sampler for monitoring zinc (II), and described extractant is the 30-50%(for example about 40% of D2EHPA and total composition (%m/m) that can consist of described PIM).
Listed suitable extractant and the example of typical target analytes/solute in table 1:
(all abbreviations all exist the example of table 1:PIM carrier (extractant) target solute typical with it GlossaryIn explain).
Figure BDA00003614173000061
In one embodiment, passive sampling equipment of the present invention can be used for heavy metal (for example Hg (II), Zn (II), Cu (Il), Cd (II), Pb (II), U (VI), Cr (VI)); Poisonous inorganic ions and nutrients (ammonium (NH for example 4 +), prussiate (CN -), thiocyanate (SCN -), arsenate (AsO 4 3-), arsenite (AsO 2 -) or (AsO 3 3-), phosphate (PO 4 3-) and nitrate (NO 3 -)); And little organic ion (for example some pesticides or herbicide are such as the sampling of 2,4-dichlorophenoxyacetic acid (2,4-D) and Simanex (simazine)).
According to the present invention, described PIM can be by forming for described film provides the base polymer of physical strength of being fit to arbitrarily.
In one embodiment, described polymkeric substance be selected from poly-(vinyl chloride) (PVC), cellulose triacetate (CTA), three butyric acid celluloses (CTB), PVDF and PVDF multipolymer or their suitable derivant.
In one embodiment, described polymkeric substance is a kind of in PVC, CTA or their derivant.
In one embodiment, described polymkeric substance is PVC.
In one embodiment, described polymkeric substance consists of about 40-80%m/m of described PIM.Consist of in another embodiment about 50-75%m/m of described PIM, further consisting of about 77-75%m/m of described PIM in embodiment, and consist of about 70%m/m of described PIM in further embodiment.
For example, when analyte was Zn (II), described polymkeric substance can be to consist of about 50-70% (m/m) that total PIM forms and the PVC of 60% (m/m) preferably approximately.
In one embodiment, described analyte is that ammonia (is expressed as NH 3And NH 4 +), described polymkeric substance can also be to consist of about 50-70% (m/m) that total PIM forms and the PVC of 60% (m/m) preferably approximately.
Described polymkeric substance can also comprise plastifier or modifier.The effect of described plastifier is to infiltrate between polymer molecule, and with himself the described polymkeric substance of polar group " neutralization " polar group or only increase between described polymer molecule distance also so reduce intermolecular intensity of force.Correspondingly, described plastifier can be the organic compound that is fit to arbitrarily that can function as described above.The organic compound that is fit to comprises that those comprise the compound of the hydrophobic alkyl main chain of the polar group with one or more height solvations.The effect of described modifier is the solubleness of chemical substance in described film liquid phase that increases extraction.
In one embodiment, described plastifier/modifier selects free 2-nitrobenzophenone octyl ether (2-NPOE), dibutyl-butylphosphonate (DBBP), the 1-group of alcohol, 1-heptanol, 1-octanol, 1 nonyl alcohol, 1-decyl alcohol, DODECANOL, 1-, 1-tetradecanol, o-nitrobenzophenone amyl ether (oNPPE), tributyl phosphate (TBP), dioctyl phthalate (DOP), terephthalic acid (TPA) two (2-ethyl hexyl) ester (DDTP), di-n-octyl sebacate (DOS) and tricresyl phosphate (2-ethyl hexyl) ester (T2EHP) composition.
In one embodiment, described plastifier is selected from TBP, 2-NPOE, 1-tetradecanol and DODECANOL, 1-.
In one embodiment, described plastifier/modifier consists of about 0-40%m/m of described PIM, preferably approximately 0-30%m/m and more preferably about 0-15%m/m.
In one embodiment, the PIM that is used for Zn (II) sampling does not comprise independent plastifier/modifier, because D2EHPA also can be used as plastifier.
In another embodiment, (be expressed as NH for ammonia 3And NH 4 +) passive sampling, described PIM comprises as the DODECANOL, 1-of modifier or 1-tetradecanol.About this embodiment, described modifier can consist of the 0-30% that total PIM forms.
The technician is understandable that, PIMs of the present invention also can include other compositions that help extraction process.For example, described PIM can comprise see Table 1 except for example D2EHPA() the preparation solvent of extractant, plastifier/modifier and base polymer, antiseptic (for example, being used for suppressing film pollutes), antioxidant (be used for improve stability), hole reagent (pore-foaming agent), ferromagnetic particle and residual quantity.
According to the present invention, described film can be also a kind of compound PIM, with the performance of further improvement based on the separation of PIM.For example, a kind of compound PIM is characterized as to have the non-PIM polymeric layer that adheres to (such as Nafion
Figure BDA00003614173000081
Or microporous film layers (for example cellulose acetate or three acetic acid)) PIM.Preferably, the non-PIM polymeric layer of this compound substance will be exposed to (described PIM is exposed to and receives in solution) in outside Aquo System.Expectation being set can greatly reducing any leaching of described PIM liquid phase in described Aquo System like this, thus the stability of described PIM layer improved.Simultaneously, described non-PIM polymeric layer can provide mechanical protection for described PIM layer.The loss of PIM liquid phase depends primarily on ionic strength and the pH value of the aqueous solution that contacts with described film.By: (1) prevents dissociate (described extractant negative ion is usually more soluble in water than its corresponding neutral molecule) of extractant; (2) so-called " salting-out effect " (reducing the solubleness of organic compound in aqueous solution), high ionic strength and low pH value make the leaching of acidic extractant (for example D2EHPA) be down to minimum or even substantially eliminate the leaching of acidic extractant (for example D2EHPA).In the passive sampler that provides, described reception solution preferably has little volume (being several milliliters) and usually has high acidity.These conditions will almost be eliminated the leaching of described acidic extractant in described reception solution.Described outside Aquo System (such as river, pond etc.) has much bigger volume and relatively high pH value (being 6.5-9.0).These conditions will promote the leaching of described acidic extractant, and therefore expectation makes this unnecessary process minimize or almost eliminate this unnecessary process by the introducing of non-PIM polymeric layer.The added advantage of using compound PIM film can be higher to the control degree of the speed of the membrane mass transfer of solute (such as ammonia).Pass
Figure BDA00003614173000091
It is relative high and more be difficult to control comparing with PIM with the transfer rate of dialysis membrane.For some passive sampling was used, it may be too high.The PIM layer that has controlled thickness and composition by introducing can be handled the permeability of whole composite membrane to be suitable for corresponding passive sampling demand.
Passive sampler and sampling method
Fig. 1 shows a kind of embodiment of the equipment for passive sampling.This figure has drawn housing (1) (or container), described housing (1) limits the recess (2) for described reception solution, described recess has the opening (3) that tunicle (4) covers, described film (4) is that polymkeric substance comprises film or composition polymer comprises film, wherein said film comprises the inside surface (5) that can contact with described reception solution and the outside surface (6) that can contact with described Aquo System (described Aquo System can be water or sediment), thereby described film is communicated with described reception solution and the equal fluid of Aquo System.Described housing or container also comprise for adding described reception solution to described recess or container or removing the sample tap (7) of described reception solution from described recess or container.As shown in fig. 1, described sample tap can extend from described housing.Described film can be attached to described housing by water-tight equipment.In one embodiment, described water-tight equipment can comprise at least one packing ring.Described at least one packing ring can comprise polymeric material.
Described sampling process comprises makes equipment contact with Aquo System, thereby described PIM or compound PIM are exposed in Aquo System to be taken a sample (for example water or sediment).This process can comprise simply with in the described Aquo System of described equipment immersion.This equipment is called as " immersion (dip-in) " passive sampling equipment in this article.The sample procedure of selecting as for the election, the present invention has also considered " flow type " sampling equipment, wherein said equipment is transformed into the liquid that allows described PIM or compound PIM to contact from Aquo System to be taken a sample (for example water) and flows.
In one embodiment, this transformation can comprise the adding device compartment, described unit compartment is connected to described housing or container and surrounds the outside surface of described PIM and can hold liquid stream from described Aquo System (for example water), thereby makes the side of described PIM be exposed to described reception fluid and opposite side is exposed to described liquid stream.This unit compartment can be described as the flow type unit and can be combined with described housing, so that flow through the outside surface of described film from the liquid of described Aquo System.
Correspondingly, further in, the invention provides a kind of equipment of the passive sampling of flow type for Aquo System, this equipment comprises:
(i) contain the container that receives solution;
The unit compartment that (ii) contains described Aquo System;
(iii) thief hole, described thief hole is assembled to described container, and receive solution or remove reception solution from described container to allow to add in described container,
Wherein:
(a) described unit compartment is connected to described container, by film, described reception solution and described Aquo System are separated thus, described film is that polymkeric substance comprises film (PIM) or compound PIM, described film is communicated with described reception solution fluid by its inside surface and also is communicated with described Aquo System fluid by its outside surface, and
(b) described unit compartment includes an inlet and an outlet, and contacts with the outside surface of described PIM or compound PIM from the liquid stream of described Aquo System allowing.
The invention provides a kind of passive sampling method of novelty, the method comprises to be measured and need not described passive sampler is taken out from described Aquo System the intermittence of the pollutant of for example a kind of pre-concentration.For example, this by will be of the present invention equipment immerse in described Aquo System and realize, described Aquo System can be the sediment of natural current (such as river, pond, well etc.), industrial current (such as evaporation tank, industrial waste water or effluent streams etc.) or Aquo System.Therefore, when the average pollutant levels that can only provide between whole sampling date, it will be feasible to passive sampling classification that same passive sampling equipment collection analysis thing/solute of providing or the Delta Time mean concentration (incremental time averaged concentrations) (" Dynamic sampling ") of pollutant are provided.Therefore, this new method will produce the management of more in time tackling for example contamination accident.
Passive sampling equipment permission mean concentration to target contaminant during whole deployment of using is at present assessed.In most of the cases, this information only can obtain after described sampler is transported back the assay laboratory.Usually also need to carry out complicated analysis pre-service (for example extraction, desorb) before pollutant monitoring.Sampling equipment of the present invention has significant advantage in this respect, and namely they are the low-cost reusable passive sampler that adopted spe membrane.Be different from existing passive sampler, sampling equipment of the present invention not only can be realized traditional passive sampling but also can realize " Dynamic sampling ".
In described sampling process, described analyte/solute is collected in and receives in water (" reception solution "), and described analyte/solute can be measured by intermittent measurement or after disposing end.Preferably, described reception solution is the aqueous acid solution of dilution, but it can be also the solution of suitable salt.Passive sampler of the present invention is easy to use and by selecting the chemical composition of suitable spe membrane and suitable described reception aqueous solution, can be adapted to different pollutants.
Except the chemical composition that changes described reception solution, form by changing described film, can control the film quality transfer rate of target chemical matter.This will allow to select to the expectation concentration of the duration of sample period and target chemical matter and stark suitable speed.Like this, can avoid relating to the saturated situation of reception solution with target chemical matter.
Thereby the extractant in described reception solution should be able to described analyte complexing or by with film in the analyte exchange described analyte of stripping from film.For example, due to corresponding complex compound in described film dissociate and described film in these two kinds of ions and the ion-exchange between the H+ in described reception solution, the Zn in the D2EHPA/PVC film 2+And UO 2 2+Can be entered acid solution by reextraction.As the SCN at described coating solution interface -With NO 3 -The result of the ion-exchange between negative ion, thiocyanate radical negative ion (SCN -) can pass through NaNO 3Stripped from tri-n-octyl methyl ammonium chloride (Aliquat336)/PVC film.Similarly, be extracted the ammonium cation that enters the DNNSA/PVC film, on the one hand as NH 4 +With H +Or on the other hand as NH 4 +With other kation (K for example +) between the result of interface ion exchange, can be entered in the solution of acid or salt (for example KCl) by reextraction.
The analysis of reception solution-monitoring
From described Aquo System transfer move up into analyte described reception solution or solute concentration can by known in the art quantitatively or quilitative method obtain.This can relate to the use of analytical approach, such as DPASV differential pulse anodic stripping voltammetry, atomic absorption spectrometry, spectrophotometry and/or fluorometry.Be understandable that, in the equipment of mentioning in this article, described reception solution can be realized by described thief hole in the sampling of its arbitrfary point.Described reception solution can be analyzed through the analytical approach that is fit in the laboratory, such as these above-mentioned methods or by the hand-held analyzer on-the site analysis.The example of this equipment is the analyser that utilizes Flow Analysis Technique, ion-selective electrode or paper substrate microfluid.
Now will conduct further description the present invention with following non-limiting example with reference to the accompanying drawings.It should be understood, however, that following specific descriptions of the present invention are not in order to replace the ubiquity of the preamble description of this invention.
Embodiment
1.Zn passive sampling (II)
Purpose is in order to study the use for the PIM in the passive sampler of Zn (II) being taken a sample at natural water.The sampling equipment that comprises PIM is designed, manufactured and is transformed into and allow to carry out this research in resulting solution and natural water.
Experiment
Reagent
Use business extractant D2EHPA(Sigma-aldrich (Sigma-Aldrich) by the former state received), the PVC(high molecular) (Selectophore, Fluka, Switzerland), THF (AR, Chem-Supply, Australian) and lauryl sodium sulfate (SDS) (Scharlau Chemie, Australia).
From 100mgL -1Zn (II) (ZnCl 2, Unilab, Australia) and liquid storage preparation 0-100 μ gL -1The aqueous solution of zinc (II).When needed, respectively from 1000 μ gL -1And 100mgL -1Zn (II) liquid storage preparation 0-125 μ gL -1Zn (II) aqueous solution and in the 0.1M HCl (Scharlau Chemie, Australia) 0-10000 μ gL -1Zn (II) solution.
The concentrated acid (Scharlau Chemie, Australia) of the supply by suitable dilution makes the reception solution of 0.1M HCl.
The damping fluid that is used for anodic stripping voltammetry: make by being dissolved in 56.8g acetic acid (Chem-Supply, Australia) and 32.8g sodium acetate trihydrate (Chem-Supply, Australia) in water and demarcating to 1L the solution that the pH value is the acetate buffer of 4.3 1.42M.
Preparation p-tosyl-8-aminoquinoline (p-taq) is as fluorescent reagent: the method that the people (1962) such as the method for preparation and Billman describe is similar.In ice-water-bath with the 0.86g(6 mM) the 8-aminoquinoline by stirring and dissolving the 10ml pyridine in being placed in the 25ml conical flask.With surpassing time of 2 hours with the 1.14g(6 mM) the p-paratoluensulfonyl chloride marginally joins in omnidistance this solution that stirs at every turn.Then under vigorous stirring, reaction mixture is poured in the cold water of 40ml.Separate out pink solid, filter and wash with water, then use ethyl alcohol recrystallization.Obtain like this p-taq product, this product shows as linen acicular crystal (1.24g, 69%).
Preparation p-taq reagent: at 60/40(v/v) ethanol-water mixture in the liquid storage of preparation p-taq, and be heated to 50 ℃ during working solution to guarantee dissolving fully in preparation.
By be dissolved in appropriate SDS in water and stirring until all solids has all dissolved to prepare the SDS liquid storage of 0.4M.
By be dissolved in appropriate solid Tris (Chem-Supply, Australia) in water and titration until reach the pH value of expectation, with the liquid storage of preparation Tris-HCl damping fluid.
Mix the work reagent solution of preparation p-taq with the SDS of 450mL and the Tris-HCl of 450mL by the p-taq solution with the 100ml deposit.PH7.5, the potpourri that forms with the Tris-HCl that obtains by the SDS of p-taq, the 0.19M of 160 μ Μ and 0.45M.
All use deionized water (Synergy 185, France for 18.2 Μ Ω cm, Millipore) in the preparation of all solution.
Device
All glasswares are all at 10% HNO 3Soaked at least 24 hours in (Scharlau Chemie, Australia), and before use with deionized water washing three times.
Use hydrology pump (water feature pump) (AQUAP333L, Watermaster, White International company limited, Australia) to make the main body solution circulation circulation of Zn (II).
Using electrochemical analyser (797VA Computrace, Metrohm, Switzerland) to carry out anodic stripping voltammetry measures.
Using polarization Zeeman atomic absorption spectrophotometer (Model Z-2000, Hitachi (Hitachi), Japan) to carry out atomic absorption spectrometry (AAS) measures.
Use fluorescent spectrograph (Gary Eclipse, Varian company) to carry out fluorescence spectral measuring.
The design of " immersion " passive sampler
The schematic diagram of " immersion " passive sampler (Fig. 2 is also referring to the picture of Figure 11 a) is similar to the universal design shown in Fig. 1.Figure 11 b shows the parts (unassembled) of described passive sampling equipment.It comprises as main body source phase (bulk source phase) (being Aquo System) and the inner PIM that receives the barrier between solution.This reception solution is accommodated in the groove of a 10ml (" container "), described groove cuts out in the teflon piece of diameter 50mm, with sample port at an angle (" thief hole ") as shown in the figure, take a sample with the intermittence that allows to carry out as a part of studying.Described PIM is arranged on the notch of described groove, and is fixed and be tightened until fastening by other teflon and stainless steel packing ring.
Experimental arrangement
Film preparation: the PVC of known quantity is added the D2EHPA of known quantity and the total film quality of THF(10mL/g) solution in and stir until dissolving.Then the solution with gained moves in the glass ring that is placed on glass plate with transfer pipet, and covers with a slice filter paper and surface plate, and standing two days until all solvent evaporates.Then it can be peeled off described glass ring after the HCl that drips several 0.1M on two sides of film and can obtain described film.
Preliminary experiment: assemble described passive sampler, 40%D2EHPA/PVC(m/m be set) PIMs, receiving solution is the HCl of the 0.1M of 10mL.These sampler are placed on respectively that to contain 10L concentration be 0,100 and 500 μ g L -1Zn (II) the bucket in.Take out the sample (with the HCl displacement of fresh 0.1M) of the reception solution of 0.5mL in cycle predetermined time, and be diluted to 10mL.Then with the sample of gained by the anodic stripping voltammetry analysis.
Zn 2+Extraction and back-extraction get and can describe by following reaction equation:
Figure BDA00003614173000151
Wherein, (HR) 2Refer to the dimerization form as the D2EHPA of cationite, and subscript (aq) and (org) refer to respectively material and be present in water and organic phase.
Anodic stripping voltammetry (ASV): Zn (II) sample of 5mL is joined in the 1.42M acetate buffer (pH4.3) of 5mL, and this potpourri is analyzed.
Also test and used other analytical approach in follow-up experiment.
Electrothermal Atomic Absorption spectroscopic methodology (ET-AAS): be injected into by Zn (II) sample with 30 μ L in the graphite furnace of spectrometer it is analyzed.
Fluorescent spectrometry: during beginning, Zn (II) sample of 1.5mL joined in the p-taq reagent of 1.5mL and adopt the excitation wavelength of 377nm, recording its emissive porwer at the 503nm place.Different parameters is studied, to optimize the sensitivity of measuring.
Calibration: assemble described passive sampler, 40%D2EHPA/PVC(m/m be set) PIMs, receiving solution is the HCl of the 0.1M of 10mL.These passive sampler are placed on respectively that to contain 10L concentration be 0,25,50,75 and 100 μ g L -1Zn (II) the bucket in.Take out the sample (with the HCl displacement of fresh 0.1M) that receives solution in cycle predetermined time.By taking a sample but not replacing, also outer body concentration is monitored.When causing concentration to reduce to surpass 3 μ g L owing to carrying out Zn (II) extraction by passive sampler -1The time, by adding a small amount of 100mg L -1Zn (II) solution, make described main body concentration keep stable.Solution will be received and external solution is all analyzed in duplicate by above-mentioned fluorescence method.
Result and discussion
Preliminary experiment
Within the sample period of 12 days, preliminary experiment has demonstrated the substantial pre-concentration (Fig. 3) of Zn (II) in described reception solution.
Analytical approach
Anodic stripping voltammetry (ASV)
Due to time-consuming characteristic (sampling rate～10h of the ASV of simulation tracing output combination -1), attempt developing other and be used for efficient and the repeatability that trace Zn (II) method for measuring is inclined to reduce analysis time and increased analysis.In addition, in the situation that ASV analyzes, must carry out Macrodilution to described reception solution, make described sample to be cushioned by acetate buffer with the acidity that reduces sample), and the required volume of this analysis (5mL) is provided.These a large amount of dilutions are extra pollution source.
Electrothermal Atomic Absorption spectroscopic methodology (ET-AAS)
ET-AAS is as a kind of analytical approach, due to its sensitivity with less than the use amount of the small sample volume of 100 μ L and tried out.Yet, for the Zn in water (II) standard items, find that the range of linearity is high to 2 μ g L -1Zn (II) (Fig. 4), this requires again primary sample is carried out the unnecessary high dilution of following pollution problem.
Fluorescence analysis
Reported into for adopting p-taq to measure the fluorescence analysis of the sensitive method of Zn (II) as reagent in Flow Injection Analysis, attempted as the batch quantity analysis method in the present invention's research.
The optimization of fluorescence analysis method
Based on containing 50 μ g L -1The standard items of Zn (II), tested different reagent: the ratio of sample volume, result is shown in Figure 5.
Fig. 5 shows, launches growth and surpasses p-taq, i.e. small size ratio.This fluorescent emission that gives the credit to Zn (Il)-p-taq complex compound is much bigger than the fluorescent emission of independent p-taq.Yet along with reagent: the ratio of sample volume increases, and the background fluorescence of p-taq also increases than the fluorescence of Zn (Il)-p-taq complex compound and uprises.Select 0.33 reagent: the ratio of sample volume (being 2.25mL sample+0.75mL reagent) is as the optimum value of this parameter.
Other parameter
Studied equally the Other Instruments parameter, such as exciting and launch slit width (keep equate), and photomultiplier (PMT) voltage (table 2).
Table 2: the impact of different instrument parameters on the emissive porwer of 50 μ g L-1 Zn (II) samples and 160 μ Μ p-taq reagent mixtures.
Figure BDA00003614173000171
Although high photomultiplier transit tube voltage and large slit width have provided maximum sensitivity, the tube voltage of decision selection 600V and the slit width of 10nm are as optimum value, needing to avoid the described sample of Macrodilution.
Fig. 6 shows the calibration curve of making under top condition.
The quality factor (Analytical figures of merit) of analyzing
At 10-200 μ g L -1In the concentration range of Zn (II), the calibration curve shown in Fig. 6 is linear.Detectability (being defined as the concentration corresponding to the emissive porwer of the standard deviation that is three times in blank sample) is 1 μ g L -1Draw 1.2% relative standard deviation (RSD) through five duplicate measurementss.Sampling rate is 60h -1
In order to measure Zn (II), make described analytical approach be suitable for the mensuration of Zn in acid solution (II)
Make described method be suitable for acid solution so that its mensuration that is used for 0.1M HCl reception solution Zn (II) is very important.Add by the p-taq liquid storage with 10mL in the Tris-HCl damping fluid (pH8.3) of 0.2M of the SDS of 0.4M of 450mL and 450mL, and demarcate to 1L with deionized water.Thereby the solution that contains 16 μ Μ p-taq in the Tris-HCl damping fluid (pH8.3) of the SDS that obtains at 0.19M and 0.09M.Described routine analyzer comprises that the reagent solution with the 16 μ Μ p-taq of 3ml adds in Zn (II) solution of 0.1M HCl of 0.1mL.Corresponding calibration curve shown in Fig. 7.
The quality factor of analyzing
Calibration curve shown in Fig. 7 is at the 400-10 that is dissolved in 0.1M HCl, 000g L -1Linear in the concentration range of Zn (II).Detection is limited to 120 μ g L -1The method is used to the mensuration of all later Zn (II) in acidity reception solution of passive sampler.
Passive sampler calibration
Be 0 to 100g L to Zn (II) concentration range -1External solution carry out passive sampling.Fig. 8 shows Zn (II) concentration of corresponding transient state in described reception solution.
In fact, about the flux that passes film of Zn (II) or transfer rate directly with the proportional relation of Zn (II) concentration (Fig. 9) of outside aqueous phase, the Zn of described outside aqueous phase (II) concentration kept stablizing in the whole sample period.
Sampling for 4 days, 8 days and 10 days is calibrated described passive sampler, and Figure 10 shows corresponding calibration curve.
The design of the passive sampler of flow type
Figure 18 and 19 shows the schematic diagram of the another kind of embodiment of passive sampler of the present invention, and wherein the unit compartment is tightly bonded to (being the parts replacement that the parts (f) in Figure 11 b are illustrated by (left side) in Figure 19) on former stainless steel packing ring.
The schematic diagram of the passive sampling system of flow type that comprises the passive sampler of described flow type has been shown in Figure 20 in addition.
The passive sampler experiment of flow type
Assembled the passive sampler of flow type system according to Figure 20, wherein the source is one bottle of solution that contains zinc (II), and described source is connected to described passive sampler, and refuse forms the single channel sampling system by pipe and peristaltic pump.PIMs used is comprised of 40%D2EHPA/60%PVC, and described reception comprises the HNO of 0.1M mutually 3Described pump is set to 0.16mL min -1Low flow velocity.Gather the sample (replacing with fresh solution) of described reception solution and zinc (II) is analyzed in cycle predetermined time.
For temperature experiment, the source bottle that will contain zinc (II) solution is placed in water bath with thermostatic control, and is connected to the external water chuck that contains described passive sampler.In the pH experiment, in order to keep stable ionic strength, prepare zinc (II) solution in 1.8mM sodium nitrate, and use nitric acid or NaOH described zinc (II) solution to be adjusted to the pH that needs.These source solution were changed once in every two days, to prevent because the carbon dioxide that absorbs in atmosphere causes obvious pH to change.
Be different from " immersion " system, the passive sampling system of the flow type that provides allows outside main body solution to keep stable pH value.Why this can realize, be because those may be discharged into refuse together with the acid that described film is passed in described reception mutually with any by the outer body solution of the passive sampler of described flow type.In addition, this method allows the concentration stabilize of the solute at main body solution externally/membrane interface place.Experiment shows, although zinc (II) is to extract lower than the speed in the situation of described immersion passive type sampling system.This may be owing to comparing with the flow rate that is produced by pump for fish pot (underwater fish tank pump) under water in the passive sampling of immersion experiment, and liquid wants the much lower less reason of total amount of the zinc (II) that is exposed to described film that makes to cause along the flow rate of described film.
2.NH 4 +Passive sampling
Research method/target
Development is based on the passive type ammonia sampler of film, and described sampler can be used to the sewage pollution in (a few days to a few weeks) detection sewer stormwater within the time cycle that extends.
By using dinonylnaphthalene sulfonic acid (DNNSA) as extractant, dodecanol as base polymer, comprises film (PIM) for the preparation of the polymkeric substance of extraction of ammonia as plastifier and PVC.Some of them PIM is with solution purified or original DNNSA(50 % m/m in heptane) preparation.Carry out purifying under evaporation by heptane under vacuum, to obtain the DNNSA of expectation concentration.
The PIMs preparation
Polymkeric substance (PVC), extractant (DNNSA) and plastifier (dodecanol) are dissolved in tetrahydrofuran.Then pour into potpourri in glass ring and evaporate.
The composition of the PIM that studies is shown in Table 3.
The composition of the PIM that table 3. is studied.
? A B C
Business DNNSA
40 a 30 b ?
Pure DNNSA ? ? l6 c
Dodecanol ? 10 24
PVC 60 60 60
DNNSA concentration (a) 0.4M; (b) and (c) O.3M
Pure in upper table please be changed into purifying.
When described film was used in the situation of pH＜7, described extraction process was the ion-exchange that comprises ammonium ion:
Figure BDA00003614173000201
Ammonia is also with NH when higher pH 3Form exist, can be extracted according to following stoichiometric equation formula:
Figure BDA00003614173000202
Wherein subscript m and aq refer to respectively film or water.
In order to imitate full-scale condition (constant pH), according to following chemical equation, at first PIM was immersed in the KCl solution of 1M about 24 hours, so that it is converted into the potassium form:
Figure BDA00003614173000203
Select K +Be based on the selectivity of PIM: Na +＜K +＜NH 4 +
NH 4 +/ NH 3Passive sampler
Figure 13 shows the schematic diagram of described passive sampling equipment, and Figure 14 illustrates the practical photograph of described equipment.Described container comprises the reception solution of 1M KCl (10mL).With described PIM fix in position and be exposed to described reception solution and feedstock solution (Aquo System), described feedstock solution is the ammonia source in this case at the front end of described sampler.Be equipped with the hole that can seal at the rear portion of described sampler, add or remove part after being used for before sampling, taking a sample or taking a sample to receive solution.
Analyze
Developed a kind of gas one diverging flow Injection Analysis (GD-FIA) system with spectrophotomelric assay, be used for measuring (Figure 15) from charging and the ammonia that receives the sample of solution.Described sample (200 μ L) is injected in the NaOH logistics of 2M, and described NaOH logistics mixes with the NaOH logistics of another gang 2M, so that sample mixes fully with the NaOH solution of 2M.Under these conditions, all ammonia (NH 3And NH 4 +) be converted into NH 3, described NH 3The poly tetrafluoroethylene that diffuses through gas-diffusion (GD) unit enters in the reception logistics that contains acid base indicator cresol red and thymol blue.Continue to monitor with 580nm in spectrophotometer flow cell (spectrophotometric flow-through cell) and diffuse through by ammonia the pH that described film causes and change the change color that is caused.
The analysis quality factor of described GD-FIA system comprises:
-concentration range: 0.70-6.0mg L -1NH 4 +
-detectability: 0.4mg L -1NH 4 +
-repeatability: less than 1.7% (3.0mg L -1NH 4 +)
-sampling frequency: 30hr -1
Glossary
Figure BDA00003614173000211

Claims (20)

1. an equipment that is used for the passive sampling of Aquo System, is characterized in that, described passive sampling equipment comprises that polymkeric substance comprises film or composition polymer comprises film.
2. equipment that is used for the passive sampling of Aquo System comprises:
(i) container;
(ii) thief hole; With
(iii) film, described film is that polymkeric substance comprises film or composition polymer comprises film;
Wherein
(a) described container comprises and receives solution and be furnished with described thief hole, add or remove described reception solution from described container allowing, and
(b) described film is fluid with described reception solution and described Aquo System and is communicated with.
3. equipment that is used for the passive sampling of Aquo System comprises:
Housing, described housing limits the recess for described reception solution, and described recess has the opening that tunicle covers, and described film is that polymkeric substance comprises film or composition polymer comprises film;
Wherein, described film comprises the inside surface that can contact with described reception solution and the outside surface that can contact with described Aquo System, so that described film is communicated with described reception solution and the equal fluid of Aquo System.
4. equipment that is used for the passive sampling of flow type of Aquo System comprises:
(i) contain the container that receives solution;
The unit compartment that (ii) contains described water-based system;
(iii) thief hole, described thief hole is assembled to described container, adds or removes described reception solution from described container allowing;
Wherein:
(a) described unit compartment is connected to described container, described reception solution and Aquo System are separated by film thus, described film is that polymkeric substance comprises film (PIM) or compound PIM, described film is communicated with described reception solution fluid by its inside surface and is communicated with described Aquo System fluid by its outside surface, and
(b) described unit compartment includes an inlet and an outlet, and contacts with the outside surface of described PIM or compound PIM from the liquid stream of described Aquo System allowing.
5. method that is used for the passive sampling of Aquo System comprises passive sampling equipment is immersed in step in described Aquo System that wherein said passive sampling equipment comprises that polymkeric substance comprises film or composition polymer comprises film.
6. method that is used for the passive sampling of Aquo System, comprise and carry current by the step of passive sampling equipment, wherein said passive sampling equipment comprises that polymkeric substance comprises film (PIM) or composition polymer comprises film, and described current contact with described PIM or compound PIM thus.
7. according to claim 5 or 6 described methods, is characterized in that, described passive sampling equipment is the sampling equipment that limits as any one in claim 1 to 4.
8. the described equipment of any one or method in 7 according to claim 1, is characterized in that, form based on total PIM, described PIM comprises the polymkeric substance of about 40 to 80% (m/m).
9. the described equipment of any one or method in 8 according to claim 1, is characterized in that, form based on total PIM, described PIM comprises the extractant of about 5 to 40% (m/m).
10. the described equipment of any one or method in 9 according to claim 1, is characterized in that, form based on total PIM, described PIM comprises plastifier/modifier of about 0-30% (m/m).
11. equipment according to claim 8 or method is characterized in that, described polymkeric substance is PVC.
12. equipment according to claim 9 or method is characterized in that, described extractant is sulfonic acid or its salt, is preferably DNNSA or its salt.
13. equipment according to claim 9 or method is characterized in that, described extractant is alkyl phosphoric acid, is preferably D2EHPA or D2EHDTPA.
14. equipment according to claim 13 or method is characterized in that, described extractant is D2EHPA.
15. equipment according to claim 9 or method is characterized in that, described extractant is quaternary amine, is preferably Aliquat336.
16. any one is used for equipment or the method for the passive sampling of ammonia in 6 according to claim 1, it is characterized in that, form based on total PIM, described PIM comprises the PVC of about 50 to 70% (m/m); DNNSA (or its salt) with about 10 to 30% (m/m).
17. be used for zinc (II) passive sampling according to claim 1 to the 6 described equipment of any one or methods, it is characterized in that, form based on total PIM, described PIM comprises the PVC of about 50 to 70% (m/m); D2EHPA with about 30 to 50% (m/m).
18. the described equipment of any one or method in 17, is characterized in that according to claim 1, described PIM is compound PIM, is attached with non-PIM polymeric layer on wherein said PIM.
19. equipment according to claim 18 or method is characterized in that, described non-PIM polymeric layer is Nafion
Figure FDA00003614172900031
Or microporous film layers.
20. according to claim 18 or 19 described equipment or methods is characterized in that, described non-PIM polymeric layer is exposed in described Aquo System.
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CN112229806A (en) * 2020-10-10 2021-01-15 宜宾海丰和锐有限公司 Method for detecting mercury content in vinyl chloride monomer
CN112229806B (en) * 2020-10-10 2022-12-13 宜宾海丰和锐有限公司 Method for detecting mercury content in vinyl chloride monomer
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