CN108680726A - Measure the DGT enrichment films and preparation method thereof of Paddy Soil Solutions biological effectiveness Hg (II) - Google Patents
Measure the DGT enrichment films and preparation method thereof of Paddy Soil Solutions biological effectiveness Hg (II) Download PDFInfo
- Publication number
- CN108680726A CN108680726A CN201810430812.8A CN201810430812A CN108680726A CN 108680726 A CN108680726 A CN 108680726A CN 201810430812 A CN201810430812 A CN 201810430812A CN 108680726 A CN108680726 A CN 108680726A
- Authority
- CN
- China
- Prior art keywords
- dgt
- film
- enriched
- paddy soil
- enrichment
- 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.)
- Granted
Links
Classifications
-
- 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
- G01N33/24—Earth materials
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Analytical Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Remote Sensing (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of DGT of measurement Paddy Soil Solutions biological effectiveness Hg (II) to be enriched with film and preparation method thereof, and material includes：The bond material for adsorbing Hg (II) is the nanometer sulfydryl metal bi hydroxide of modification, backing material is modified agar gel, dispersant is ethyl alcohol, above-mentioned material is proportionally required be placed in 80 DEG C of ultra-pure waters and mixes well glass board slot that rear implantation temperature is 60 DEG C until sealing, it keeps flat and is cooled to 25 DEG C of taking-ups of temperature, the DGT films of enrichment Hg (II) are made.The enrichment membrane material of the present invention can efficiently, quickly be enriched with Hg (II), and it can be completely dissolved in 30min after 5ml concentrated hydrochloric acids or 1M nitric acid is added, the DGT enrichment film resolutions for overcoming previous absorption Hg (II) are incomplete, laboratory prepare it is complicated, it is weak to Hg (II) absorption property, purchase is difficult the shortcomings of.
Description
Technical field
The present invention relates to a kind of assay method of bivalent mercury biologically effective state in Paddy Soil Solutions, more particularly to one kind has
It is molten that the diffusion thin film technique for the enrichment film that the effect mercuric bond material nanometer SH-MMHs of state makes is measured to paddy soil
Effective mercuric method in liquid.
Background technology
Paddy soil heavy metal pollution has the characteristics that concealment, chronicity, non-degradable and irreversibility, excessive
Heavy metal not only influences growth, the yield and quality of crop, can also be absorbed by crops and pass through food chain once entering paddy soil
It is detrimental to health with biological amplification.Rice be more than the staple food of sixty percent Chinese, and now rice heavy metal pollution
Increasingly emerge.Environmental protection administration estimate, the whole nation every year because the grain of heavy metal pollution is up to 12,000,000 tons, caused by directly pass through
Ji loss is more than 20,000,000,000 yuan.Such as in China, rice yield accounts for 12 of rice total output about 81% regional rice production areas acquisition samples
Product are detected, it is found that the Rice Samples total mercury content that Guangdong, Jiangxi, Hubei, Hunan, Guizhou and Jiangsu share 11% is more than state
20 μ g/kg as defined in family's limitation.Therefore, rice field heavy metal pollution becomes the potential killer for jeopardizing grain security, accelerates contaminated
The repair in rice field is very urgent.
Numerous results of study show only not can be shown that with total metals occurrence status of the element in paddy soil,
The validity of transfer ability and plant absorption, can not accurate evaluation paddy soil heavy metal Potential environmental risk and human body
Health risk.From the viewpoint of soil chemistry, it includes not only water-soluble state, sour solvent, chelating state and ADSORPTION STATE, but also should include
It can be released to certain forms that plant available utilizes in a short time, such as certain labile organics, the mine of certain easy-weatherings
States of matter etc..These forms are influenced by the property of the physics of soil, chemistry, biology and are in dynamic equilibrium, exactly this dynamic
Balance determines the biological effectiveness of heavy metal element in paddy soil.Therefore the migration of mercury is largely in paddy soil
Depending on its occurrence patterns, and determine that it is absorbed and utilized in its toxic degree and biology, i.e. biological effectiveness.
DGT (diffusive gradients in thin films, diffusion thin film technique) is that the nearly more than ten years are quick
Method of the one kind to grow up for water body, deposit and soil available (unstable state) heavy metal in-situ enrichment.It leads
To pass through the diffusion barrier to passing through specific thicknesses in specific time with Fick (Fick) First Law of Diffusion for its theoretical foundation
Various metals ion carry out measurement calculating and obtain accurate various ion concentrations simultaneously.Traditional form with other
Analytical technology is compared, which can effectively measure heavy metal biological available state in nature, can preferably reflect organism
The content of beary metal absorbed.And DGT measure the mercuric application aspect of Paddy Soil Solutions biologically effective state also in rise
Step section, there is presently no commercially produced product, only a small number of domestic and international researchers have carried out preliminary exploratory development.We will
DGT technologies are applied to measure the mercuric content of Paddy Soil Solutions biologically effective state to be a new breakthrough, and use is received
Rice SH-MMHs does enrichment film, can very clear up completely, overcomes traditional DGT adsorbed films dissolving not exclusively, prepared by laboratory
Complexity, it is weak to Hg (II) absorption property the shortcomings of, be conducive to the popularization and use of DGT large area at home.
Invention content
It is the diffusion thin film technique measurement rice field for being enriched with film present invention aims at providing a kind of with nanometer SH-MMHs
Mercuric method in soil can solve existing DGT technologies resolution not exclusively, and laboratory prepares complexity, is adsorbed to Hg (II)
The shortcomings of performance is weak, difficult without commercialization purchase.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：It is mercuric in a kind of in-site detecting Paddy Soil Solutions
Method, material group become：Bivalent mercury bond material nanometer SH-MMHs, improved agar gel, ethyl alcohol.Above-mentioned material is placed in
Mixing in ultra-pure water is heated, high silica glass tablet slot is added, DGT enrichment films are made in sealing postcooling to 25 DEG C of taking-ups.
The nanometer sulfydryl metal bi hydroxide is prepared as follows：By 0.3g metal bis hydroxide,
15mL methanol and 5mL (3- mercaptopropyis) trimethoxy silane (CAS 4420-74-0) are added in 200mL toluene solutions,
Reaction 6h is vigorously stirred under logical condition of nitrogen gas.Milli-Q water is used after then taking out 3-4 times, freeze and freeze in general refrigerator
For 24 hours, after freeze-dryer freeze-drying is gone to after, 200 mesh sieve is crossed, a nanometer thiol resin is obtained.
The preparation method of the modified agarose is：5g top pure grade agaroses are dissolved in 50ml ultra-pure waters, are heated
So that it is melted completely to 80 DEG C, then progressively cool to 60 DEG C, 10ml dichlroroethanols are added dropwise under agitation, stirring 3 is small
When, acetone extract is used after cooling, then modified agarose is made with ultrapure water elution.
It measures the mercuric DGT of Paddy Soil Solutions biologically effective state and is enriched with film, preparation methods steps are as follows：
(1) by nanometer sulfydryl metal bi hydroxide (SH-MMHs), modified agar gel, ethyl alcohol be placed in 80 DEG C it is ultrapure
In water, above-mentioned material is mixed well.
(2) the high-boron-silicon glass board slot (added with certain thickness gasket) that implantation temperature is 60 DEG C is until sealing, keeps flat cooling
To 25 DEG C of taking-ups of temperature, it is put into ultra-pure water and stores for use.
Advantages of the present invention and helpfulness：
(1) the SH-MMHs film productions that the present invention uses are very simple, and more traditional DGT technologies are molten using polyacrylamide
It is easy to operate for liquid, it is easier to store.It need to only be impregnated and be stored with ultra-pure water after completing, no longer need to carry out aquation
(replacing 4-5 water).
(2) SH-MMHs materials of the invention can efficiently, quickly adsorb available state bivalent mercury, and 5ml ultrapure hydrochloric acids are added
Or 1M nitric acid is dissolved as rapidly clear solution in 30 minutes, is conducive to upper various instruments and is tested, it is not necessary to consider resin particle
Dissolving not exclusively generates Matrix effects and influences measurement result.
(3) the method for the present invention measures the mercuric content of available state in paddy soil using DGT in-situ techniques, simulates water
The process of rice organism-absorbing available mercury, this provides technology branch to the Forms Transformation mechanism study of mercury in parsing paddy system
Support provides new technology for evaluation paddy soil mercury pollution risk, is the pass for realizing paddy soil mercuric pollution treatment and grain security
Key is conducive to the promotion and application of DGT technologies at home.
Description of the drawings
Fig. 1 is that SH-MMHs DGT measure the pH ranges adapted to, the DGT suitable for solution of the pH value within the scope of 3-9,
Bivalent mercury can be effectively enriched with.
Fig. 2 is the adsorbance of available mercury and the correlation of adsorption time.DGT is enriched with mercuric content and is exposed with DGT
Time has fabulous linear relationship, shows that DGT can effectively be enriched with bivalent mercury, and linear with the time.
Fig. 3 is that 5 kinds of resin glues adsorb mercuric comparative study.Newly developed material SH-MMHs can purchase with other
Resin (Chelex-100, SH-SBA, Spheron-Thiol, the 3-Mercaptopropyl Functionalized arrived
Silica Gel (3-MFSG) are compared mercuric adsorbance, and finding new research and development material, it adsorbs mercuric amount than it
His material is good, illustrates that newly developed resin material (SH-MMHs) can be enriched with bivalent mercury completely.
Fig. 4 is to cut open bivalent mercury concentration in Wanshan Mountain paddy soil that the method for the present invention is measured by SH-MMHs DGT
Face figure.
Specific implementation mode
The method of the present invention is described below by specific embodiment.Unless stated otherwise, technology used in the present invention
Means are method known in those skilled in the art.
The invention discloses a kind of mercuric method of available state in in-site detecting Paddy Soil Solutions, which is enriched with film
Material is made of available mercury sorbing material nanometer SH-MMHs, improved agar gel, dispersant ethyl alcohol.
One, material preparation：
(1) nano material SH-MMHs：By 0.3g metal bis hydroxide, 15mL methanol and 5mL (3- mercaptopropyis) three
Methoxy silane (CAS 4420-74-0) is added in 200mL toluene solutions, and reaction 6h is vigorously stirred under logical condition of nitrogen gas.
With milli-Q water 3-4 time after then taking out, in general refrigerator freezing freeze for 24 hours, after go to freeze-dryer and be freeze-dried
Afterwards, 200 mesh sieve is crossed, a nanometer thiol resin is obtained.
(2) modified agarose：5g top pure grade agaroses are dissolved in 50ml ultra-pure waters, being heated to 80 DEG C makes it melt completely
Change, then progressively cool to 60 DEG C, 10ml dichlroroethanols are added dropwise under agitation, stir 3 hours, is extracted with acetone after cooling
It takes, then modified agarose is made with ultrapure water elution.
Two, DGT enrichments membrane preparation method is：
(1) 0.2g nanometers of sulfydryl metal bi hydroxide (SH-MMHs), 0.2g are modified agar gel, 50 μ L ethyl alcohol
It is placed in 80 DEG C of 10ml ultra-pure waters, above-mentioned material is mixed well.
(2) the high-boron-silicon glass board slot (added with 0.5mm hassocks piece) that implantation temperature is 60 DEG C is until sealing, keeps flat and be cooled to
25 DEG C of temperature is straight to be caused to take out after forming a film, and is put into ultra-pure water (Milli-Q, 18.2M Ω cm) and is stored for future use.
Three, the assembling and use of DGT devices：
(1) material assembles：Mercury enrichment film, diffusion barrier, dialyser containing SH-MMHs are sequentially overlapped and are assembled into DGT devices.
Mercury enrichment film thickness is 0.5mm, diffusion barrier 0.75mm, dialyser 0.13mm used in the present invention.
The diffusion membrane preparation method is：Thickness is the Ago-Gel of the 1.5wt% of 0.8mm, and preparation method is：Fine jade
Lipolysaccharide solution is heated to 80 DEG C, fully dissolves, must not generate bubble, then pour into glass guide channel, and the thickness of slot is 0.8mm, lid
Upper tabletting, natural cooling.Dialyser is the semipermeable membrane with dialyzing, and exclusion molecular weight is less than or equal to 11000.
(2) inflated with nitrogen：Assembled device is put into the container equipped with ultra-pure water (Milli-Q, 18.2M Ω cm), to
Institute is oxygenous in inflated with nitrogen removal DGT devices in water, simulates paddy soil anaerobic environment.
(3) DGT devices are placed：The DGT devices for nitrogen of substituting the bad for the good are sealed, set-point is transported to, device is inserted perpendicularly into rice field
In soil, a week is placed.
(4) DGT devices are fetched：After device is taken out, device is rinsed well with ultra-pure water (Milli-Q, 18.2M Ω cm)
Surface adhesion soil is put into a small amount of ultra-pure water and preserves, and is put into 4 DEG C of refrigeration in refrigerator, takes back laboratory.
(5) DGT films are sliced：DGT devices are taken out, permeable membrane, the diffusion barrier on surface are opened, mercury enrichment film is pressed into paddy soil
Vertical direction is cut into the thin slice of 1cm width with Teflon blades, is respectively put into different high-boron-silicon glass pipes.
(6) bivalent mercury is extracted：In high-boron-silicon glass pipe be added 5mL 12N ultrapure hydrochloric acids, be completely dissolved in 30 minutes for
Transparency liquid after a small amount of ultrapure water tube wall is added, adds 0.5% chlorination bromine solutions, finally adds to quarter with ultra-pure water
Line 25mL is spent, it can examination with computer after placing 12 hours.
(7) divalent sclera remodeling：The solution that 200 microlitres are taken out from each high-boron-silicon glass pipe, is surveyed using Cold Atomic Fluorescent Mercury
Mercury instrument (TeKran 2500) measures the concentration of mercury in extracting solution, and calculation formula is：
Wherein, D is that (25 DEG C are 8.81 × 10 to diffusion coefficient of the inorganic mercury ion in diffusion layer-6cm2/ s), be and temperature
Related constant；M is secure bond glue fixed mercury ion total amount within the unit interval；T is that DGT devices are immersed in aqueous solution or heavy
Time (86400S) in product object；A is absorption glue exposed area (0.14cm2/ segment)；△ g are thickness of diffusion layer
(0.138cm)；CDGTIt is the concentration of mercury ion in Paddy Soil Solutions, unit is μ g/L.
(8) field test, Fig. 4 are two in the Wanshan Mountain paddy soil for measuring the method for the present invention by SH-MMHs DGT
The sectional view of valence mercury concentration, the paddy soil pore water bivalent mercury concentration profile figure measured with conventional centrifugal method are compared, and are sent out
Result consistent statistically (t inspections, the p that existing two methods measure>0.05), illustrate that SH-MMHs DGT technologies can have
Effectiveness is in measuring available mercury in Paddy Soil Solutions.
1 eluent of table is to being enriched with the mercuric eluting rate of glue
Claims (9)
1. a kind of DGT measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, it is characterised in that：Contain available state Hg
(II) the nanometer sulfydryl metal bi hydroxide that bond material is modified.
2. the DGT according to claim 1 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：Further include modified agar gel, dispersant.
3. the DGT according to claim 2 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：Nanometer sulfydryl metal bi hydroxide, modified agar gel, dispersant that available state Hg (II) bond material is modified are set
It forms a film after being mixed well in 80 DEG C of ultra-pure waters, the DGT enrichment films of enrichment Hg (II) is made.
4. the DGT according to claim 1 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：The nanometer sulfydryl metal bi hydroxide of the modification is prepared as follows：By metal bi hydroxide, dispersant
(3- mercaptopropyis) trimethoxy silane is added in 200mL toluene solutions, and reaction 3- is vigorously stirred under logical condition of nitrogen gas
10h, uses milli-Q water 3-4 times after taking-up, icing 20-30h is freezed in general refrigerator, goes to freeze-dryer freeze-drying
Afterwards, sieving；
Metal bi hydroxide：Dispersant：(3- mercaptopropyis) trimethoxy silane weight ratio=0.3-1g：10-20：3-
10。
5. the DGT according to claim 2 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：The metal bi hydroxide is magnesium-aluminium, magnesium-iron, zinc-aluminium, zinc-iron, calcium-aluminium, calcium-iron, in nickel-aluminum, Ni-Fe
The molar ratio of one or more combination, divalent metal and trivalent metal cation is 2:1, electric core balance it is used it is cloudy from
Son is nitrate anion or chlorion.
6. the DGT according to claim 1 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：The preparation method of the modification agar gel is：Top pure grade agarose is dissolved in ultra-pure water, mass fraction 5-
20%, being heated to 80 DEG C makes it melt completely, then progressively cools to 60 DEG C, and volume fraction 10- is added dropwise under agitation
30% dichlroroethanol stirs 3 hours, acetone extract is used after cooling, then modified agarose is made with ultrapure water elution.
7. the DGT according to claim 1 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：Modified nanometer sulfydryl metal bi hydroxide：Modified agar gel：The total amount ratio of dispersant is：1:1-3：0.1-1.
8. the DGT according to claim 1 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：Preparation method is：Nanometer sulfydryl metal bi hydroxide (SH-MMHs), modified agar gel, dispersant are placed in 80 DEG C
In ultra-pure water, above-mentioned material is mixed well, the glass board slot that implantation temperature is 60 DEG C keeps flat until sealing and is cooled to temperature 25
DEG C take out, be made enrichment Hg (II) DGT films.
9. the DGT according to claim 1 for measuring Paddy Soil Solutions biological effectiveness Hg (II) is enriched with film, feature exists
In：The described DGT enrichment film ultrapure hydrochloric acids or salpeter solution elution, enrichment film are completely dissolved by acid, eluting rate up to 95 ±
0.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810430812.8A CN108680726B (en) | 2018-05-08 | 2018-05-08 | DGT enrichment membrane for determining bioavailability Hg (II) of paddy field soil solution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810430812.8A CN108680726B (en) | 2018-05-08 | 2018-05-08 | DGT enrichment membrane for determining bioavailability Hg (II) of paddy field soil solution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108680726A true CN108680726A (en) | 2018-10-19 |
| CN108680726B CN108680726B (en) | 2020-06-26 |
Family
ID=63803030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810430812.8A Active CN108680726B (en) | 2018-05-08 | 2018-05-08 | DGT enrichment membrane for determining bioavailability Hg (II) of paddy field soil solution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108680726B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892244A (en) * | 2021-01-15 | 2021-06-04 | 南开大学 | Biochar modified film for DGT device, DGT device and manufacturing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102507388A (en) * | 2011-10-24 | 2012-06-20 | 河海大学 | Improved phosphorus fixing film used in DGT (diffusive gradients in thin films) measurement and preparation method thereof |
| CN103743655A (en) * | 2014-02-13 | 2014-04-23 | 中国科学院南京地理与湖泊研究所 | Method for determining inorganic arsenic in soil or water body based on diffusive gradients in thin-films technique |
| CN104043409A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院南京地理与湖泊研究所 | Immobilized membrane for synchronously enriching phosphor and ferrum and preparation method thereof |
| CN104198405A (en) * | 2014-08-11 | 2014-12-10 | 渤海大学 | Method for determining bio-available phosphorus in soil |
| CN106290785A (en) * | 2016-07-29 | 2017-01-04 | 农业部环境保护科研监测所 | A kind of method using DGT technology separation soil heavy metals of different forms |
| CN106568689A (en) * | 2016-10-17 | 2017-04-19 | 农业部环境保护科研监测所 | Total-dissociation DGT combined film for determination of soil available phosphorus and preparation method thereof |
-
2018
- 2018-05-08 CN CN201810430812.8A patent/CN108680726B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102507388A (en) * | 2011-10-24 | 2012-06-20 | 河海大学 | Improved phosphorus fixing film used in DGT (diffusive gradients in thin films) measurement and preparation method thereof |
| CN104043409A (en) * | 2013-03-12 | 2014-09-17 | 中国科学院南京地理与湖泊研究所 | Immobilized membrane for synchronously enriching phosphor and ferrum and preparation method thereof |
| CN103743655A (en) * | 2014-02-13 | 2014-04-23 | 中国科学院南京地理与湖泊研究所 | Method for determining inorganic arsenic in soil or water body based on diffusive gradients in thin-films technique |
| CN104198405A (en) * | 2014-08-11 | 2014-12-10 | 渤海大学 | Method for determining bio-available phosphorus in soil |
| CN106290785A (en) * | 2016-07-29 | 2017-01-04 | 农业部环境保护科研监测所 | A kind of method using DGT technology separation soil heavy metals of different forms |
| CN106568689A (en) * | 2016-10-17 | 2017-04-19 | 农业部环境保护科研监测所 | Total-dissociation DGT combined film for determination of soil available phosphorus and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| H.DOCEKALOVA ETAL: "Application of diffusive gradient in thin films technique (DGT)", 《TALANTA》 * |
| 刘金铃等: "ＤＧＴ富集－乙基化ＧＣ－ＣＶＡＦＳ测定天然水体中的甲基汞", 《地球与环境》 * |
| 夏志勇等: "聚乙二醇和叶酸对层状双金属", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892244A (en) * | 2021-01-15 | 2021-06-04 | 南开大学 | Biochar modified film for DGT device, DGT device and manufacturing method thereof |
| CN112892244B (en) * | 2021-01-15 | 2022-02-15 | 南开大学 | Biochar modified film for DGT device, DGT device and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108680726B (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lagerström et al. | Automated on-line flow-injection ICP-MS determination of trace metals (Mn, Fe, Co, Ni, Cu and Zn) in open ocean seawater: Application to the GEOTRACES program | |
| Falk et al. | Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements | |
| Fischer et al. | Carbohydrate and amino acid composition of dissolved organic matter leached from soil | |
| Guo et al. | Ultrafiltration and its applications to sampling and characterisation of aquatic colloids | |
| Yang et al. | Graphene oxide as an efficient adsorbent of solid-phase extraction for online preconcentration of inorganic and organic mercurials in freshwater followed by HPLC-ICP-MS determination | |
| Miró et al. | Dynamic flow-through approaches for metal fractionation in environmentally relevant solid samples | |
| Rao et al. | Styrene–divinyl benzene copolymers: synthesis, characterization, and their role in inorganic trace analysis | |
| Ding et al. | Fractionation mechanisms of rare earth elements (REEs) in hydroponic wheat: an application for metal accumulation by plants | |
| Janssen et al. | Separation of monomethylmercury from estuarine sediments for mercury isotope analysis | |
| Li et al. | Magnetic metal-organic frameworks nanocomposites for negligible-depletion solid-phase extraction of freely dissolved polyaromatic hydrocarbons | |
| Persson et al. | Determination of Nd isotopes in water: A chemical separation technique for extracting Nd from seawater using a chelating resin | |
| CN105080519A (en) | Adsorption film capable of selectively fixing hexavalent chromium ions and preparation method thereof | |
| Pan et al. | In-situ measurement of free trace metal concentrations in a flooded paddy soil using the Donnan Membrane Technique | |
| Lemos et al. | Amberlite XAD-2 functionalized with Nitroso R salt: synthesis and application in an online system for preconcentration of cobalt | |
| Di Bonito et al. | Extraction and characterization of pore water from contaminated soils | |
| Song et al. | Recent developments in microextraction techniques for detection and speciation of heavy metals | |
| CN111060511B (en) | PO-DGT combined detection device and acquisition detection method for sediment nutrients | |
| CN108680726A (en) | Measure the DGT enrichment films and preparation method thereof of Paddy Soil Solutions biological effectiveness Hg (II) | |
| Romero et al. | Equilibrium sampling through membranes of freely dissolved copper concentrations with selective hollow fiber membranes and the spectrophotometric detection of a metal stripping agent | |
| CN103487432A (en) | Lead ion detection test paper, and preparation method and use method thereof | |
| Yao et al. | Development of a novel composite resin for dissolved divalent mercury measurement using diffusive gradients in thin films | |
| Morales-Muñoz et al. | A continuous approach for the determination of Cr (VI) in sediment and soil based on the coupling of microwave-assisted water extraction, preconcentration, derivatization and photometric detection | |
| CN105289541B (en) | A kind of adsorbed film of fixed fluorine ion and preparation method thereof | |
| CN108421280B (en) | Sulfhydrylation organic-inorganic hybrid monolithic column and preparation method and application thereof | |
| Li et al. | Effect of preservation on the δ13C value of dissolved inorganic carbon in different types of water samples |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |