CN100372781C - Method for enriching and separating yellow substance from seawater - Google Patents
Method for enriching and separating yellow substance from seawater Download PDFInfo
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- CN100372781C CN100372781C CNB2005100453873A CN200510045387A CN100372781C CN 100372781 C CN100372781 C CN 100372781C CN B2005100453873 A CNB2005100453873 A CN B2005100453873A CN 200510045387 A CN200510045387 A CN 200510045387A CN 100372781 C CN100372781 C CN 100372781C
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Abstract
The present invention relates to a method for enriching and separating yellow substances from seawater. Macroporous resin is used as an adsorbing agent; after the seawater is filtered, the pH of the hydrochloric acid is regulated into acidity; a peristaltic pump is sampled and organic reagent is used for elution; through rotary evaporation or nitrogen gas purging eluan, the organic reagent is removed; the water solution of the yellow substances can be obtained after the ultra-pure water is dissolved, and the water solution is carried out for freeze drying to obtain dry powder of the yellow substances or is carried out for reseparation through gel columns to obtain yellow substance ingredients with different molecular weight ranges; the macroporous resin adopts LSA-20, XAD-8, etc. The eluant adopts the organic reagent with pure chromatogram, such as methyl alcohol and ethyl alcohol; gelatin adopts G-25 and G-50. Having the advantages of rich adsorption medium materials, selective CDOM adsorption, large adsorption quantity, high sampling speed, simple operation, easy control and high elution rate, the present invention can obtain a plurality of yellow substances from the seawater.
Description
Technical field
The present invention relates to a kind of from seawater the method for a large amount of enriching and separating yellow substances (CDOM).
Background technology
As coloured dissolved organic matter (chromophoric dissolved organic matter, CDOM) yellow substance, Kalle is referred to as Gelbstoff the earliest, is the important component part of dissolved organic matter (DOM), accounts for the 40%-60% of dissolved organic carbon in the water body; Its title is from its influence to water colour, and contribution reaches 85%-100% to yellow substance to water colour, can make water be yellow or brown.Yellow substance belongs to inert substance biologically, in the ocean, has good conservative property, thereby be considered to best tracer material in the ocean, be widely used in the evaluation of littoral water quality, pollution of the sea degree, and the division of ocean water body etc., many yellow substances that studies show that are requisite research factors in Marine ecosystems, optical remote sensing, the marine carbon circulating research.
Yellow substance content is very low in the seawater, and form complicated, as Qingdao immediate offshore area seawater yellow substance content only is 0.32mg/L, preparing yellow substance must separate its dissolved organic matter and inorganics with other, promptly use technology concentration and separation such as freeze-drying, chemical precipitation, solvent extraction, reverse osmosis, ultrafiltration, but the complicated operating process of these methods can not selective separation, and is unsuitable for a large amount of enriching and separating yellow substances from seawater.The method of at present the most frequently used separation water body yellow substance is the column chromatography technology with the non-ionic type solid adsorbent.Utilize non-ionic type solid adsorbent such as aluminum oxide, carbon 18, silica gel all can adsorb yellow substance, but their adsorptive capacity is few, last sample speed is slow, eluting rate is low, obviously can not satisfy the demand of a large amount of enriching and separating yellow substances from seawater.
Summary of the invention
The object of the invention be to provide a kind of can be from the very low seawater of yellow substance content the method for a large amount of enriching and separating yellow substances, promptly a kind of from seawater the method for enriching and separating yellow substance.
Method of the present invention is will handle clean macroporous resin earlier with pack into the glass column of wash clean of wet method, uses the aqueous hydrochloric acid of PH=2.3 ± 0.4 to wash post then, and keeps acid state standby; The glass fiber filter of seawater with 0.22 μ m filtered, transfer its PH=2.3 ± 0.4 with analytically pure hydrochloric acid again, use the peristaltic pump upper prop then, last sample speed 4.0 ~ 8.0ml/min; Behind the end of the sample, earlier wash post with the aqueous hydrochloric acid of PH=2.3 ± O.4, so that remove residual seawater in the post, retain (checking) with ultrapure washing post no chlorion to the post again with silver nitrate solution, obtain the yellow substance elutriant with certain eluent wash-out at last; The yellow substance elutriant is concentrated into earlier dried with rotary evaporation or nitrogen purging, obtains the aqueous solution of yellow substance again with the ultrapure water dissolving, this aqueous solution freeze-drying obtains yellow substance dry powder.
Above-mentioned yellow substance is the mixture of a class complexity, molecular weight difference between heterogeneity is bigger, its optical characteristics of the composition of different molecular weight ranges and the effect in water body thereof also are different, composition as macromolecule has stronger melts combine ability, is the important component that the water body weight metallics is removed in complexing.Therefore to really further investigate the physicochemical property of yellow substance and the vital role in environment thereof, be necessary the yellow substance that is enriched to is separated again.Therefore, the above-mentioned yellow substance aqueous solution is separated with dress post gel again, use the ultrapure water wash-out, get final product the yellow substance elutriant of Fractional Collections different molecular weight ranges, and, then obtain the yellow substance dry powder of different molecular weight ranges respectively with these elutriant vacuum-freeze-drys.
Above-mentioned macroporous resin is selected model specification LSA-20 for use, LSA-10 (the blue deep friendship in Xi'an is changed sorbing material limited liability company and produced), any macroporous resin among the XAD-8, four kinds of XAD-2 (production of U.S. Rhom and Hass); Above-mentioned eluent is selected chromatographically pure methyl alcohol, ethanol or acetone for use; Above-mentioned gel is selected commercially available general G-25 or G-50 gel for use.
The present invention has the following advantages: the adsorption medium abundant raw material, the macroporous resin energy selective adsorption yellow substance of selecting for use, and adsorptive capacity is big, last sample speed is fast, dress posts etc. are simple to operate easy to control, and eluting rate height, eluent are easily removed, can avoid the influence of eluent as far as possible, and from seawater, obtain a large amount of yellow substances the enrichment composition.Also separate again, thereby obtain the yellow substance composition of different molecular weight ranges from the angle of molecular size.
Embodiment
This method basic step is: 1, pre-treatment macroporous resin: use earlier NaOH, HCl solution washing resin respectively for several times, ultrapure water is washed till PH neutrality then, again macroporous resin is placed in the apparatus,Soxhlet's and handled 1-3 days, handle clean resin immersion and be stored in the methyl alcohol with analytically pure acetonitrile or methyl alcohol.
2, resin dress post: select the glass column of corresponding size for use according to applied sample amount, wash with 10% salpeter solution, and rinse well with ultrapure water.Conventional wet method is adorned post with resin, cleans remaining methyl alcohol in the post with ultrapure water then, uses the HCl solution of PH=2.3 ± 0.4 to wash post again, and it is standby promptly to keep pillar to be in acid state.
3, seawater filters with the glass fiber filter of 0.22 μ m, transfers pH=2.3 ± 0.4 with analytical pure HCl again, then with sample on the peristaltic pump; Control is gone up sample speed at 4.0 ~ 8.0ml/min according to dress post amount of resin.
4, wash post with the HCl aqueous solution of pH=2.3 ± 0.4 earlier behind the end of the sample, remove seawater remaining in the post, use ultrapure washing post again, being washed till out post water does not have chlorion outflow (checking with silver nitrate solution).
5, eluent uses methyl alcohol, ethanol or acetone, be eluted to elutriant colourless till.
6, elutriant uses rotary evaporation or nitrogen purging to be concentrated into dried down at 45 ℃ ± 5 ℃.
7, concentrate the yellow substance that obtains with the ultrapure water dissolving, obtain its aqueous solution, aqueous solution vacuum-freeze-dry is got yellow substance dry powder.
8, Gel Treatment and dress post: at first wash gel, topple over and repeatedly go out the water surface composition that floats; To boil gel abundant to its swelling for boiling water again, with gel slurry method dress post, washes post 30min with the NaOH solution of 0.1M again, is washed till neutrality with ultrapure water at last; Cross gel column with concentrating the yellow substance aqueous solution that obtains, use the ultrapure water wash-out again, collect the yellow substance composition of different molecular weight ranges respectively.With the each several part aqueous solution freeze-drying of collecting, getting molecular weight ranges is greater than 10000Da then, and 1000 ~ 5000Da is less than the yellow substance dry powder of 1000Da.Describe with following specific embodiment.
Embodiment 1
At first, will handle clean LSA-20 resin wet method dress post, post footpath 1cm, resin dress post height 25cm, ultrapure washing post, the HCl aqueous solution of PH=2.3 ± 0.4 is washed post, promptly keeps acid state standby;
Get the 200L seawater sample,, transfer seawater pH=2.3 ± 0.4 with analytically pure HCl again with the glass fiber filter filtration of 0.22 μ m.Sample on the peristaltic pump, control flow velocity 4.0-6.0ml/min;
Wash-out: pH=2.3 ± 0.4HCl washes post, removes residual seawater in the post; Ultrapure washing post is removed remaining HCl in the post, check out post water not have a precipitation generation with AgNO3 solution till.Use at last the chromatographically pure methanol-eluted fractions to elutriant colourless till, obtain the methanol solution of yellow substance;
Concentrate: under 40 ℃ of conditions, the methanol solution that concentrates yellow substance is to doing with Rotary Evaporators, ultrapure water dissolve the aqueous solution of yellow substance;
Separate again: with the conventional slurry method dress of G-50 gel post, the aqueous solution of the above-mentioned yellow substance that obtains is added to the gel column top, use the ultrapure water wash-out, the fraction collection elutriant, obtain the yellow substance aqueous solution of different molecular weight ranges (greater than 10000Da, 1000 ~ 5000Da, less than 1000Da), with the each several part freeze-drying, promptly obtain the yellow substance dry powder of different molecular weight ranges respectively.
Embodiment 2
Handle clean XAD-8 resin wet method dress post, post footpath 1.6cm, resin dress post height 20cm, ultrapure washing post, the HCl aqueous solution of pH=2.0 is washed post, keeps acid state standby;
Get the 500L seawater sample, with the glass fiber filter filtration of 0.22 μ m, dense HCl transfers pH=2.0.Sample on the peristaltic pump, control flow velocity 6.0ml/min;
Wash-out: pH=2.0HCl washes post, removes residual seawater in the post; Ultrapure washing post is removed remaining HCl in the post, uses AgNO
3The solution check does not have till the precipitation generation; Use at last chromatogram alcohol ethanol elution to elutriant colourless till, obtain the ethanolic soln of yellow substance;
Concentrate: under 45 ℃ of conditions, the ethanolic soln that concentrates yellow substance is to doing with the nitrogen purging concentrating instrument, ultrapure water dissolve the aqueous solution of yellow substance;
Separate again: with the conventional slurry method dress of G-25 gel post, the aqueous solution of the above-mentioned yellow substance that obtains is added to the gel column top, use the ultrapure water wash-out, the fraction collection elutriant, obtain the yellow substance aqueous solution of different molecular weight ranges (greater than 10000Da, 1000 ~ 5000Da, less than 1000Da), with the each several part freeze-drying, promptly obtain the yellow substance dry powder of different molecular weight ranges respectively.
Embodiment 3
At first, will handle clean LSA-10 resin wet method dress post, post footpath 1cm, resin dress post height 25cm with ultrapure washing post, uses the HCl aqueous solution of PH=2.3 ± 0.4 to wash post again, promptly keeps acid state standby;
Seawater sample 200L with the glass fiber filter filtration of 0.22 μ m, transfers seawater pH=2.3 ± 0.4 with analytically pure HCl again.Sample on the peristaltic pump, control flow velocity 4.0-6.0ml/min;
Wash-out: pH=2.3 ± 0.4HCl washes post, removes residual seawater in the post; Use ultrapure washing post again, use AgNO
3Solution checks out post water not have till the precipitation generation.Use at last chromatogram alcohol methanol-eluted fractions to elutriant colourless till, obtain the methanol solution of yellow substance;
Concentrate: the methanol solution of 50 ℃ of concentrated yellow substances is to doing, again with ultrapure water dissolve the yellow substance aqueous solution, the last vacuum-freeze-dry aqueous solution gets yellow substance dry powder.Separate as need, method is the same again.
Embodiment 4
At first, will handle clean XAD-2 tree month fat wet method dress post, post footpath 1cm, resin dress post height 25cm, ultrapure washing post, the HCl aqueous solution of PH=2.3 ± 0.4 is washed post, promptly keeps acid state standby;
Seawater sample 200L with the glass fiber filter filtration of 0.22 μ m, transfers seawater pH=2.3 ± 0.4 with analytically pure HCl again.Sample on the peristaltic pump, control flow velocity 4.0-6.0ml/min;
Wash-out: pH=2.3 ± 0.4HCl washes post, removes residual seawater in the post; Use ultrapure washing post again, use AgNO
3Till when solution checks out post water not have the precipitation generation.Use at last chromatogram alcohol methanol-eluted fractions to elutriant colourless till, obtain the methanol solution of yellow substance;
Concentrate: the methanol solution of 45 ℃ of concentrated yellow substances is to doing, again with ultrapure water dissolve the yellow substance aqueous solution, the last vacuum-freeze-dry aqueous solution gets yellow substance dry powder.Separate as need, method is the same again.
Claims (5)
1. the method for an enriching and separating yellow substance from seawater is characterized in that will handling earlier clean macroporous resin with pack into the glass column of wash clean of wet method, uses the aqueous hydrochloric acid of PH=2.3 ± 0.4 to wash post then, and keeps acid state standby; The glass fiber filter of seawater with 0.22 μ m filtered, transfer its PH=2.3 ± 0.4 with analytically pure hydrochloric acid again, use the peristaltic pump upper prop then, last sample speed 4.0 ~ 8.0ml/min; Behind the end of the sample, earlier wash post,, retain with ultrapure washing post no chlorion to the post again so that remove the interior residual seawater of post with the aqueous hydrochloric acid of PH=2.3 ± 0.4, chlorion has or not to retain with silver nitrate solution to be checked, and obtains the yellow substance elutriant with certain eluent wash-out at last; The yellow substance elutriant is concentrated into earlier dried with rotary evaporation or nitrogen purging, obtains the aqueous solution of yellow substance again with the ultrapure water dissolving, this aqueous solution freeze-drying obtains yellow substance dry powder.
As right 1 require described a kind of from seawater the method for enriching and separating yellow substance, it is characterized in that with gel column it being separated again again after above-mentioned yellow substance dry powder is with the ultrapure water dissolving, use the ultrapure water wash-out, get final product the yellow substance elutriant of Fractional Collections different molecular weight ranges, and, then obtain the yellow substance dry powder of different molecular weight ranges respectively with these elutriant vacuum-freeze-drys.
As right 1 require described a kind of from seawater the method for enriching and separating yellow substance, it is characterized in that the macroporous resin of described adsorption medium is selected LSA-20 for use, LSA-10, XAD-8, any of four kinds of macroporous resins of XAD-2.
As right 1 require described a kind of from seawater the method for enriching and separating yellow substance, it is characterized in that described eluent select for use chromatographically pure methyl alcohol, ethanol, acetone any.
As right 2 require described a kind of from seawater the method for enriching and separating yellow substance, it is characterized in that above-mentioned gel selects G-25 or G-50 gel for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100453873A CN100372781C (en) | 2005-12-20 | 2005-12-20 | Method for enriching and separating yellow substance from seawater |
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| CNB2005100453873A CN100372781C (en) | 2005-12-20 | 2005-12-20 | Method for enriching and separating yellow substance from seawater |
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| CN1800039A CN1800039A (en) | 2006-07-12 |
| CN100372781C true CN100372781C (en) | 2008-03-05 |
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| CNB2005100453873A Expired - Fee Related CN100372781C (en) | 2005-12-20 | 2005-12-20 | Method for enriching and separating yellow substance from seawater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101726437B (en) * | 2009-12-01 | 2013-08-07 | 国家海洋环境监测中心 | On-line enrichment system of organic pollutants in water body |
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Non-Patent Citations (3)
| Title |
|---|
| 东太湖CDOM吸收光谱的影响因素与参数确定. 马荣华，戴锦芳，张运林.湖泊科学，第17卷第2期. 2005 * |
| 海水黄色物质研究进展. 张绪琴，张士魁，吴永森，夏达英.黄渤海海洋，第18卷第1期. 2000 * |
| 海洋腐植质的研究. 纪明侯，曹文达，韩丽君.海洋与湖沼，第13卷第4期. 1982 * |
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