CN106323689B - Trace polar organic pollutant trap with water quality monitoring as guide - Google Patents
Trace polar organic pollutant trap with water quality monitoring as guide Download PDFInfo
- Publication number
- CN106323689B CN106323689B CN201610692412.5A CN201610692412A CN106323689B CN 106323689 B CN106323689 B CN 106323689B CN 201610692412 A CN201610692412 A CN 201610692412A CN 106323689 B CN106323689 B CN 106323689B
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- polar organic
- solid phase
- phase extraction
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
-
- 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
- G01N1/34—Purifying; Cleaning
Abstract
The invention relates to an accumulative sampling device which takes a composite characteristic adsorbent as an accepting phase and can be used for monitoring the concentration of polar organic pollutants in water. The device is based on synthetic polymeric membrane material and mixed mode solid phase extraction adsorbent, arranges compound adsorbent in between two-layer polymeric membrane, constitutes a sandwich structure's sample thief, can enrich multiple polarity organic pollutant in aquatic simultaneously. Aiming at the difference of polar organic pollutants in water, the invention selects five characteristic solid phase extraction adsorbents to form a mixed mode adsorbent, and simultaneously has the reversed phase adsorption effect with enlarged polarity range, the weak anion exchange effect and the weak cation exchange effect, and has the broad spectrum adsorption effect on the polar organic pollutants in the water; meanwhile, the polymer permeable membrane with a specific pore diameter range is selected as the outer membrane, so that free passing of water, free dissolved compounds and colloidal compounds can be guaranteed, adsorption balance time is shortened, and the polymer permeable membrane can be used as a balance sampler for monitoring trace organic pollutants in water and biological simulation sampling.
Description
Technical Field
The invention relates to a capturing device for enriching and monitoring polar organic pollutants in water by taking a composite characteristic adsorbent as a receiving phase, which only allows the polar organic pollutants in two forms of a free dissolved state, a colloidal state and the like to enter a trap and be adsorbed due to the limitation of the aperture of an external polymer membrane, really reflects the biological effective state concentration of the polar organic pollutants in the water, can be used for simulating biological monitoring, evaluating the ecological toxicological effect of the polar pollutants, screening 'priority control pollutants' and reasonably managing the use and discharge of the polar pollutants.
Background
The invention relates to a capturing device for enriching and monitoring polar organic pollutants in water by taking a composite characteristic adsorbent as a receiving phase, which only allows the polar organic pollutants in two forms of a free dissolved state, a colloidal state and the like to enter a trap and be adsorbed due to the limitation of the aperture of an external polymer membrane, really reflects the biological effective state concentration of the polar organic pollutants in the water, can be used for simulating biological monitoring, evaluating the ecological toxicological effect of the polar pollutants, screening 'priority control pollutants' and reasonably managing the use and discharge of the polar pollutants.
Active sampling technique
The active sampling technology is the most common technology for collecting and extracting pollutant residues in water, and is applied to the sample collection process and can finish the sample collection work by external power. Liquid-liquid extraction and solid-phase extraction are two typical types of active sampling methods. The concentration of pollutants collected by liquid-liquid extraction is the total concentration of chemicals in a sample, the compounds in bioavailable and bioavailable forms in the environment cannot be accurately distinguished, and the consumption of organic solvents is high. In order to overcome the drawbacks of liquid-liquid extraction, researchers have developed solid-phase extraction methods, including solid-phase extraction trays, which involve passing a water sample through a cylindrical container containing a polymer material by suction filtration or pumping.
When the active sampling technology is used for sample collection and extraction, if a water body sample is turbid, the sample generally passes through the adsorbent filler after being filtered by the glass fiber filter membrane, so that the filtering time is long. In addition, the loss of contaminants during storage of the sample due to volatilization, adsorption of the reservoir walls, and chemical degradation is a problem with the target contaminants. Moreover, the concentration of the pollutants obtained by the active sampling method can only reflect the pollutant condition at the sampling moment, and the sampling mode is easily influenced by the pulse input of the pollutants. Moreover, trace analysis and biotoxicity testing studies require the collection and handling of large volumes of sample, which is time and labor intensive. Although some researchers adopt a large-volume solid phase extraction sampling system, the problem that the solid phase extraction method is inevitable still exists, and the large-volume sampling system is more time-consuming and labor-consuming when a plurality of sampling points need to be distributed, and the investment cost is high.
Passive sampling technique
Passive is a relatively active way of performing sample collection and contaminant extraction in a passive manner, i.e., without the need for external power or energy. The passive sampling technology is completely based on the process that a chemical substance automatically diffuses from high chemical potential or high escape degree to low chemical potential or low escape degree, and a target pollutant can automatically enter an organic phase along chemical potential difference through passive diffusion. Compared with the active sampling technology, the passive sampling technology is closer to the enrichment mode of pollutants in the biological organism.
Passive sampling techniques have been developed for many years, and currently, passive sampling techniques for organic pollutants in water environments mainly include, but are not limited to, semi-permeable membrane sampling devices (SPMD), solid-phase microextraction devices (SPME), solid-phase extraction trays (ED), polyethylene sampling devices (PEDs), polyoxymethylene sampling devices (POM), and the like. SPMD is formed by filling materials such as triolein in the middle of a semi-permeable membrane made of low-density polyethylene (LDPE), organic pollutants in a water body can be adsorbed by lipid in the membrane through the semi-permeable membrane, and SPMD has been successfully used for measuring hydrophobic organic matters in a water environment and simulating a biological enrichment process for measuring aquatic organisms. SPME sampling usually achieves the distribution balance of target pollutants on a water phase and a SPME phase as soon as possible by stirring, thereby achieving the extraction process of the target pollutants. These passive samplers are widely used to simulate biology to predict the bioaccumulation behavior and bioavailability of hydrophobic organic contaminants in environmental media.
The enrichment phase in the passive sampling technology and the device is a high molecular organic phase, the polarity is generally weaker, and the extraction process is basically completed by the principle of 'similar compatibility', so the passive sampling technologies are mainly suitable for the determination of hydrophobic organic pollutants and are not suitable for polar or hydrophilic organic pollutants, and although researchers are reported to be used for the determination of polar organic pollutants, the effect is not ideal. In recent years, research on drugs and personal care products is more and more focused, and sampling technologies (such as a polar organic pollutant accumulation sampler, POCIS) for these polar organic pollutants are more and more concerned and are generally used for monitoring estrogen, antibiotic and non-antibiotic drugs in water environment. The polar organic pollutant accumulation sampling technology has strong binding force on polar organic pollutants, and can well solve the problems of overlong sampling enrichment time, insufficient enrichment amount and the like when other passive sampling technologies are used for collecting and extracting the polar organic pollutants.
The microporous hydrophilic membrane used in the traditional POCIS technology is generally a polyether sulfone material with the pore diameter of 0.1 micrometer, and in the using process, the problem that the pore diameter of 0.1 micrometer is small, the resistance of a target object when the target object passes through an outer membrane and is extracted by an inner enrichment phase is high, so that the extraction rate is low, after the target object is exposed for 28 days, the target object is still in a linear enrichment stage in a sampler and does not reach the distribution balance, and a series of problems of large deviation, long time consumption and the like are caused in the subsequent application process in practical application. The pore size of 0.1 micron only allows the free soluble polar organic pollutants to enter the sampler but cannot collect the colloidal polar organic pollutants, and the colloidal state in the natural water body is an important existing form of the polar organic pollutants and also has biological effectiveness. In addition, due to the fact that the sampling is carried out in a natural water body for a long time, a biological sedimentation phenomenon easily occurs, the aperture of a polymer membrane on the outer layer of the sampler is blocked by biomass, the sampling rate is influenced, and the sampling cannot be carried out normally. The adsorbent used by the traditional POCIS sampler is mainly an Oasis HLB adsorbent, and the reversed-phase adsorption principle is applied to collect polar and non-polar organic pollutants in a water body. At present, no report exists on a passive sampling technology for polar organic pollutants developed by a mixed adsorption mode (reverse phase adsorption and ion exchange adsorption) mechanism.
Disclosure of Invention
The principle of the invention (economic and efficient polar organic pollutant accumulation sampling technology) is as follows: by selecting the hydrophilic polymer permeable membrane with a proper aperture range as the outer wrapping membrane and combining a specific composite adsorbent as an enrichment phase, the enrichment and extraction of the sampler on broad-spectrum polar organic pollutants in a water environment are ensured, the sample collection time is greatly shortened, the enrichment amount and the analysis sensitivity are improved, the biofouling phenomenon of the sampler is effectively avoided, the sampling cost is reduced, and further the simulation of biological monitoring and the ecological risk evaluation can be efficiently realized.
The invention selects the permeable membrane with larger pore diameter in the aspect of hydrophilic membrane, can effectively enrich and extract most polar organic pollutants distributed in true dissolved phase and water body colloid phase, improves the sampling rate, ensures that typical polar pollutants can reach enrichment balance within 2 weeks, and is convenient for calculating the concentration of pollutants in water.
In the invention, on the selection of the adsorbent of the enrichment phase, factors such as expansibility, application range, use cost and the like of a sampler are fully considered, and five solid phase extraction adsorbents are selected as receiving phases: polystyrene-divinylbenzene resin (suitable for adsorbing polar analytes such as antibiotics and the like which are not sufficiently reserved on C18 or C18 adsorbents), pyrrolidone-bonded polystyrene-divinylbenzene resin (on the basis of polystyrene/divinylbenzene resin, pyrrolidone is bonded, the surface polarity is enhanced, hydrophilic-lipophilic balance is achieved, and the solid-phase extraction adsorbent is suitable for extracting polar and non-polar substances), wherein anion exchange groups are modified on the pyrrolidone-bonded polystyrene-divinylbenzene resin (various acid and basic substances can be extracted without adjusting the pH value), the solid phase extraction adsorbent (which enhances the adsorption performance to weak alkaline substances) and the graphitized carbon black (which has strong adsorption to polar substances) are modified by cation exchange groups on the pyrrolidone-bonded polystyrene-divinylbenzene resin. In order to enable the sampler to adsorb various polar organic pollutants as much as possible in the one-time extraction process, the five filler adsorbents are mixed according to a certain proportion by a certain means, and the composite adsorbent has the reversed-phase adsorption effect with an enlarged polarity range, the weak anion exchange effect and the weak cation exchange effect at the same time, so that mixed-mode solid-phase extraction adsorption is realized, and compared with a single adsorption mode sampler, the composite adsorbent has better selectivity and extraction efficiency.
The invention (polar organic pollutant accumulation sampling technology and sampler) has the advantages that:
the sampling technical principle and the sampler are simple to manufacture, on the basis of later research, a hydrophilic polymer permeable membrane with a larger aperture is adopted, a composite characteristic adsorbent which is wide in application range, economical and feasible is selected, mixed-mode solid-phase extraction adsorption is realized, a passive sampling technology and a sampler can realize high-efficiency enrichment and extraction of various polar organic pollutants in a water environment, the sampler is low in manufacturing and using cost, wide in range of enrichment and extraction target pollutants, short in enrichment time, high in enrichment efficiency and high in analysis sensitivity, and biological sedimentation of the sampler is effectively avoided.
In the sampling technology, the target pollutants can quickly reach distribution balance in the sampler, and the sampler is used as a balance sampler, so that the environment concentration of the target pollutants in the tested water body can be calculated more conveniently.
Therefore, the sampling technology of the invention improves the conventional polar organic pollutant accumulation sampling technology, is more beneficial to monitoring polar organic pollutants in water environment, simulating biological monitoring and evaluating ecological risks, and has great scientific significance.
Drawings
FIG. 1 is a schematic view of a polar organic contaminant trap.
FIG. 2 is a schematic diagram showing the kinetics of sulfapyridine enrichment in a field exposure experiment of a sewage plant by using the polar organic pollutant catcher.
FIG. 3 is a schematic diagram showing the enrichment kinetics of sulfamethoxazole in a field exposure experiment of a polar organic pollutant trap in a certain sewage plant.
Fig. 4 is a schematic diagram showing the kinetics of ketoprofen enrichment of a polar organic pollutant trap in a field exposure experiment in a sewage plant.
FIG. 5 is a schematic diagram showing the enrichment kinetics of the polar organic pollutant trap on florfenicol in a field exposure experiment of a certain sewage plant.
FIG. 6 is a schematic diagram showing the kinetics of enrichments of ofloxacin by a polar organic pollutant catcher in a field exposure experiment of a certain sewage plant.
Detailed Description
For a better understanding of the present invention, reference is made to the accompanying drawings and examples, which are set forth to illustrate, but are not to be construed as the limit of the scope of the present invention.
The polar organic pollutant catcher is used in field experiment in certain sewage plant in Shanghai, and is taken out for elution analysis after being set for 1 day, 3 days, 5 days, 7 days, 14 days, 21 days and 28 days. The invention can simultaneously enrich more than ten kinds of drug polar pollutants and can enrich organic matters which can not be enriched by adopting an active sampling method (solid phase extraction). As can be seen from the accumulated enrichment concentrations of five polar drugs with high detection rates, namely sulfapyridine, sulfamethoxazole, ketoprofen, florfenicol and ofloxacin, the five pollutants can reach enrichment balance within 4 weeks or even shorter time (see the attached figures 2, 3, 4, 5 and 6 in the specification for details).
The first embodiment is as follows: experiment of enrichment kinetics of polar organic pollutant trap on typical PPCPs drugs in water
Selecting a certain large-scale urban sewage treatment plant in Shanghai, arranging a point position in a water treatment process section, suspending the sampling device in water, and taking out for elution analysis after respectively placing for 1 day, 3 days, 5 days, 7 days, 14 days, 21 days and 28 days. The invention can simultaneously enrich more than ten kinds of drug polar pollutants and can enrich organic matters which can not be enriched by adopting an active sampling method (solid phase extraction). From the accumulated enrichment concentrations (fig. 2, 3, 4, 5 and 6) of five polar drugs with high detection rates, namely sulfapyridine, sulfamethoxazole, ketoprofen, florfenicol and ofloxacin, it can be seen that the five pollutants can reach enrichment balance within 4 weeks or even shorter time.
Example two: broad-spectrum adsorption verification experiment of polar organic pollutant catcher
Taking the polar organic pollutant catcher on the 28 th day in the first embodiment, analyzing the adsorbed polar organic pollutants, taking 5L of water sample on the 28 th day on site, transporting the water sample back to a laboratory, and then adopting a solid phase extraction method for enrichment, concentration and determination. And comparing the polar organic contaminants detected by the two methods. The comparison of the steps of the solid phase extraction and polar organic pollutant trap method and the comparison result of the difference of the screened pollutant types are shown in table 1.
TABLE 1 comparison of lists of pharmaceutical contaminants screened by different monitoring methods in a municipal wastewater treatment plant
As can be seen from the above table, the pretreatment process of the polar organic pollutant catcher sample is simpler, and more types of pollutants can be detected.
Claims (3)
1. A polar organic pollutant catcher in water environment is characterized in that: the device comprises two filter membranes, a composite characteristic adsorbent, two stainless steel compression rings and stainless steel fixing screws, wherein the adsorbent is placed between the two filter membranes, the filter membrane is placed between the two compression rings, the two compression rings and the two filter membranes are fixed together by the screws to form a multilayer composite sandwich structure, and the composite characteristic adsorbent is arranged at the central position of an inner ring of a stainless steel compression ring and cannot flow out from between the compression rings to be lost; the composite characteristic adsorbent is prepared by five solid phase extraction adsorbents, namely polystyrene-divinylbenzene resin, pyrrolidone bonded polystyrene-divinylbenzene resin, solid phase extraction adsorbent which is modified with anion exchange groups on the pyrrolidone bonded polystyrene-divinylbenzene resin, solid phase extraction adsorbent which is modified with cation exchange groups on the pyrrolidone bonded polystyrene-divinylbenzene resin and graphitized carbon black according to a proportion; wherein the filter membrane adopts a hydrophilic macromolecule permeable membrane with the aperture range of 0.45-1.0 μm.
2. The polar organic pollutant trap for use in an aqueous environment of claim 1 further comprising: the pressure ring is made of stainless steel.
3. The polar organic pollutant trap for use in an aqueous environment of claim 1 further comprising: the composite characteristic adsorbent is prepared by processing five solid phase extraction adsorbents, namely polystyrene-divinylbenzene resin, pyrrolidone-bonded polystyrene-divinylbenzene resin, solid phase extraction adsorbent with anion exchange groups modified on the pyrrolidone-bonded polystyrene-divinylbenzene resin, solid phase extraction adsorbent with cation exchange groups modified on the pyrrolidone-bonded polystyrene-divinylbenzene resin and graphitized carbon black to form mixed mode solid phase extraction adsorbent, and then proportionally configuring according to the property of the monitored target pollutant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610692412.5A CN106323689B (en) | 2016-08-22 | 2016-08-22 | Trace polar organic pollutant trap with water quality monitoring as guide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610692412.5A CN106323689B (en) | 2016-08-22 | 2016-08-22 | Trace polar organic pollutant trap with water quality monitoring as guide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106323689A CN106323689A (en) | 2017-01-11 |
| CN106323689B true CN106323689B (en) | 2020-02-21 |
Family
ID=57744679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610692412.5A Expired - Fee Related CN106323689B (en) | 2016-08-22 | 2016-08-22 | Trace polar organic pollutant trap with water quality monitoring as guide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106323689B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770300A (en) * | 2017-03-14 | 2017-05-31 | 常州市人居环境检测防治中心 | The device and monitoring method of underwater in-situ biological monitoring are carried out using various biologies |
| CN108760392A (en) * | 2018-07-16 | 2018-11-06 | 未名环境分子诊断（常熟）有限公司 | A kind of Passive sampler and the method for sampling for the acquisition of hydrophily organic pollution |
| CN109932462A (en) * | 2019-03-20 | 2019-06-25 | 河海大学 | Passive sampler and its method of sampling for polarity organic pollutant in water environment |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250681A (en) * | 1999-11-26 | 2000-04-19 | 清华大学 | Bipolar film and its preparing process |
| CN1301671A (en) * | 1999-12-30 | 2001-07-04 | 同济大学 | Purifying technology for micro polluted water source |
| CN1828290A (en) * | 2006-01-23 | 2006-09-06 | 同济大学 | Method for analyzing trace organic substance in water using on-line combined solid phase extraction and liquid chromatography |
| CN101013114A (en) * | 2007-02-05 | 2007-08-08 | 同济大学 | Extraction purifying measuring method of polycyclic aromatic hydrocarbons in soil |
| CN101027367A (en) * | 2004-03-15 | 2007-08-29 | 卡伯特公司 | Modified carbon products and their applications |
| CN101186416A (en) * | 2007-12-13 | 2008-05-28 | 同济大学 | Packaging stage-type film bioreactor device for treating sewage or micro-polluted raw water |
| CN101264427A (en) * | 2008-05-08 | 2008-09-17 | 南京奥特高科技有限公司 | Film material with ionic exchange performance and use thereof |
| CN101696066A (en) * | 2009-10-29 | 2010-04-21 | 同济大学 | Method for removing organic pollutants from water by drinking water enhanced treatment |
| CN101813677A (en) * | 2010-04-29 | 2010-08-25 | 同济大学 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
| CN102085490A (en) * | 2010-12-27 | 2011-06-08 | 天津博纳艾杰尔科技有限公司 | Solid-phase extraction mixed filler and solid-phase extraction column |
| CN102515419A (en) * | 2011-11-29 | 2012-06-27 | 同济大学 | Short-flow micro-polluted raw water treatment combined system integrated with adsorption, biological oxidation and membrane separation technologies |
| CN102735500A (en) * | 2011-04-02 | 2012-10-17 | 南开大学 | Passive sampling technology aiming at anionic polar organic pollutant in water |
| CN103272654A (en) * | 2013-06-27 | 2013-09-04 | 南京大学 | High specific surface area magnetic anion exchange resin, and preparation method and application of resin |
| CN103342408A (en) * | 2013-07-03 | 2013-10-09 | 同济大学 | Method for processing degradation-resistant organic pollutants in water |
| CN103563027A (en) * | 2011-03-23 | 2014-02-05 | 梅斯皮鲁斯股份有限公司 | Polarized electrode for flow-through capacitive deionization |
| CN103946364A (en) * | 2011-09-25 | 2014-07-23 | 赛拉诺斯股份有限公司 | Systems and methods for multi-analysis |
| CN104807777A (en) * | 2015-04-28 | 2015-07-29 | 中国食品发酵工业研究院 | Rapid detection method for areca-nut water content based on near infrared spectrum analysis technology |
| CN105115788A (en) * | 2015-08-21 | 2015-12-02 | 厦门大学 | Water body pollutant time-weighted mean concentration sampling device based on osmotic pump and solid-phase extraction |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9920170D0 (en) * | 1999-08-25 | 1999-10-27 | Univ Portsmouth | A passive sampling device |
| US6478961B2 (en) * | 2000-09-26 | 2002-11-12 | The United States Of America As Represented By The Secretary Of The Interior | Device for sequestration and concentration of polar organic chemicals from water |
| CN1834641A (en) * | 2006-04-14 | 2006-09-20 | 清华大学 | Sampling and monitoring method and device for polarity endocrine interferent in water environment |
| EP2111380B1 (en) * | 2007-01-19 | 2015-10-28 | The Purolite Company | Reduced fouling of reverse osmosis membranes |
| CN100559179C (en) * | 2008-04-22 | 2009-11-11 | 济南市供排水监测中心 | Organic Pollutants purification process in a kind of water |
| FR2934681B1 (en) * | 2008-07-29 | 2011-09-30 | Bastien Karkouche | DEVICE FOR CAPTURING BIOLOGICAL PARTICLES AND USE. |
| CN101858896B (en) * | 2010-06-17 | 2013-01-02 | 浙江大学 | Combination method of polymer carbon nanotube chromatographic column and ion chromatography single pump column switching technology |
| CN102502913A (en) * | 2011-11-03 | 2012-06-20 | 同济大学 | Method for removing anion pollutants from water |
| CN102489249A (en) * | 2011-11-25 | 2012-06-13 | 中国检验检疫科学研究院 | Composite solid-phase extraction column used in vegetable pesticide removing, and preparation method thereof |
| CN103869065B (en) * | 2014-03-28 | 2015-03-11 | 中国农业科学院油料作物研究所 | Aflatoxin M1 nano antibody immunosorbent, immunoaffinity column, preparation method and application thereof |
-
2016
- 2016-08-22 CN CN201610692412.5A patent/CN106323689B/en not_active Expired - Fee Related
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250681A (en) * | 1999-11-26 | 2000-04-19 | 清华大学 | Bipolar film and its preparing process |
| CN1301671A (en) * | 1999-12-30 | 2001-07-04 | 同济大学 | Purifying technology for micro polluted water source |
| CN101027367A (en) * | 2004-03-15 | 2007-08-29 | 卡伯特公司 | Modified carbon products and their applications |
| CN1828290A (en) * | 2006-01-23 | 2006-09-06 | 同济大学 | Method for analyzing trace organic substance in water using on-line combined solid phase extraction and liquid chromatography |
| CN101013114A (en) * | 2007-02-05 | 2007-08-08 | 同济大学 | Extraction purifying measuring method of polycyclic aromatic hydrocarbons in soil |
| CN101186416A (en) * | 2007-12-13 | 2008-05-28 | 同济大学 | Packaging stage-type film bioreactor device for treating sewage or micro-polluted raw water |
| CN101264427A (en) * | 2008-05-08 | 2008-09-17 | 南京奥特高科技有限公司 | Film material with ionic exchange performance and use thereof |
| CN101696066A (en) * | 2009-10-29 | 2010-04-21 | 同济大学 | Method for removing organic pollutants from water by drinking water enhanced treatment |
| CN101813677A (en) * | 2010-04-29 | 2010-08-25 | 同济大学 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
| CN102085490A (en) * | 2010-12-27 | 2011-06-08 | 天津博纳艾杰尔科技有限公司 | Solid-phase extraction mixed filler and solid-phase extraction column |
| CN103563027A (en) * | 2011-03-23 | 2014-02-05 | 梅斯皮鲁斯股份有限公司 | Polarized electrode for flow-through capacitive deionization |
| CN102735500A (en) * | 2011-04-02 | 2012-10-17 | 南开大学 | Passive sampling technology aiming at anionic polar organic pollutant in water |
| CN103946364A (en) * | 2011-09-25 | 2014-07-23 | 赛拉诺斯股份有限公司 | Systems and methods for multi-analysis |
| CN102515419A (en) * | 2011-11-29 | 2012-06-27 | 同济大学 | Short-flow micro-polluted raw water treatment combined system integrated with adsorption, biological oxidation and membrane separation technologies |
| CN103272654A (en) * | 2013-06-27 | 2013-09-04 | 南京大学 | High specific surface area magnetic anion exchange resin, and preparation method and application of resin |
| CN103342408A (en) * | 2013-07-03 | 2013-10-09 | 同济大学 | Method for processing degradation-resistant organic pollutants in water |
| CN104807777A (en) * | 2015-04-28 | 2015-07-29 | 中国食品发酵工业研究院 | Rapid detection method for areca-nut water content based on near infrared spectrum analysis technology |
| CN105115788A (en) * | 2015-08-21 | 2015-12-02 | 厦门大学 | Water body pollutant time-weighted mean concentration sampling device based on osmotic pump and solid-phase extraction |
Non-Patent Citations (3)
| Title |
|---|
| Effect of irrigation water quality on organic matter, Cd and Cu mobility in soils of Central Mexico;A Herre 等;《Water Science & Technology》;20040229;第50卷(第2期);第277-284页 * |
| 吹扫捕集-气相色谱-质谱法测定地下水中挥发性有机物;胡璟珂 等;《理化检验(化学分册)》;20090331;第45卷(第3期);第281-283页 * |
| 白酒中邻苯二甲酸酯检测方法的选择和优化;李春扬 等;《酿酒科技》;20130228(第2期);第93-97页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106323689A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Diffusive gradients in thin films: devices, materials and applications | |
| Kot et al. | Passive sampling for long-term monitoring of organic pollutants in water | |
| Schäfer et al. | Micropollutant sorption to membrane polymers: a review of mechanisms for estrogens | |
| Wang et al. | Fluorescent natural organic matter responsible for ultrafiltration membrane fouling: Fate, contributions and fouling mechanisms | |
| US9683921B2 (en) | Devices and methods for determination of bioavailability of pollutants | |
| CN106323689B (en) | Trace polar organic pollutant trap with water quality monitoring as guide | |
| Jin et al. | Influence of dissolved organic matter on estrone removal by NF membranes and the role of their structures | |
| CN1834641A (en) | Sampling and monitoring method and device for polarity endocrine interferent in water environment | |
| DE19710525C2 (en) | Passive diffusion collector for analytes contained in gases as well as methods for passive sampling and analysis | |
| US11726015B2 (en) | System and method for preservation, transport, and analysis of water samples | |
| Jin et al. | Removal of natural hormone estrone from secondary effluents using nanofiltration and reverse osmosis | |
| US9527059B2 (en) | Field sampling kit for chemical recovery, storage, and profiling, method of making and using the kit, and dynamic fabric phase sorptive extraction (DFPSE) medium | |
| Ndungu et al. | Comparison of copper speciation in estuarine water measured using analytical voltammetry and supported liquid membrane techniques | |
| CN1175922C (en) | Preparing process and application of composite biolipid/cellulose acetate membrane | |
| CN105115788B (en) | Water pollutant time weighted average concentration sampler based on osmotic pumps and Solid Phase Extraction | |
| CN110108809A (en) | A kind of measuring method of essence crudefiber crop drug | |
| Zhang et al. | Microplastics contributed much less than organic matter to the burial of polycyclic aromatic hydrocarbons by sediments in the past decades: a case study from an urban lake | |
| CN102901798B (en) | Method for determining content of bioavailable heavy metal in compost sample | |
| CN204855205U (en) | Water body pollution thing time weighted mean concentration sample thief based on infiltration pump and solid -phase extraction | |
| US9074972B2 (en) | Surrogate addition device and a method of analyte concentration | |
| DE10042074A1 (en) | Passive collector for extraction of dissolved organic compounds, useful for monitoring pesticides, comprises sorbent body placed inside membrane chamber | |
| Harrower | Passive sampling polar organic contaminants | |
| Liu et al. | Adsorption of CECs in the nanofiltration process | |
| Mukherjee et al. | Sampling and analysis of emerging pollutants in aquatic environment | |
| Li et al. | Passive Detection of Phosphorus in Agricultural Tile Waters Using Reactive Hybrid Anion Exchange Resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100015 room 711, 6 building, 24 Jiuxianqiao Road, Chaoyang District, Beijing. Applicant after: CHINA NATIONAL RESEARCH INSTITUTE OF FOOD & FERMENTATION INDUSTRIES Co.,Ltd. Applicant after: TONGJI University Address before: 100015 room 711, 6 building, 24 Jiuxianqiao Road, Chaoyang District, Beijing. Applicant before: CHINA NATIONAL Research Institute OF FOOD AND FERMENTATION INDUSTRIES Applicant before: Tongji University |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200221 Termination date: 20210822 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |