CN203053858U - Quantitative evaluation system for concentration of rare earth in water body based on ground reflection spectrum - Google Patents
Quantitative evaluation system for concentration of rare earth in water body based on ground reflection spectrum Download PDFInfo
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- CN203053858U CN203053858U CN2012207349151U CN201220734915U CN203053858U CN 203053858 U CN203053858 U CN 203053858U CN 2012207349151 U CN2012207349151 U CN 2012207349151U CN 201220734915 U CN201220734915 U CN 201220734915U CN 203053858 U CN203053858 U CN 203053858U
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Abstract
The utility model discloses a rare earth concentration ration evaluation system in water based on ground reflectance spectrum can realize the quick quantitative inversion of rare earth element concentration in the water based on ground reflectance spectrum data. The system of the utility model comprises a rare earth water sample collecting device, a surface feature spectrometer, an ICP-MS plasma mass spectrometer and a computer; the device comprises a rare earth water sample collecting device, a ground substance spectrometer, an ICP-MS plasma mass spectrometer and a data processing system, wherein the rare earth water sample collecting device is used for collecting rare earth water samples with different concentrations, the ground substance spectrometer is used for respectively carrying out ground reflection spectrum measurement on the collected rare earth water samples, analyzing and determining the characteristic absorption valley distribution characteristics with indicating significance on the rare earth concentration, and the ICP-MS plasma mass spectrometer is used for respectively carrying out rare earth element concentration test on the collected rare earth water samples; and the computer calculates the relative absorption depth of the characteristic absorption valley according to the obtained characteristic absorption valley distribution characteristics, establishes the correlation between the relative absorption depth of the characteristic absorption valley and the concentration of the rare earth element, and obtains a rare earth concentration quantitative evaluation model.
Description
Technical field
The utility model relates to rare earth element spectral signature research field, particularly relates to a kind of water body middle rare earth concentration quantitative evaluating system based on ground return spectrum.
Background technology
The ground return spectral measurement methods is a kind of quick, cheap, harmless technological means of obtaining sample wave spectrum feature.General and the material composition of spectral absorption characteristics has close ties, forefathers studies show that, kation such as the Fe relevant with processes such as electronic switch and transition, Ti, Cr, rare earth element has characteristic absorption at visible light-near-infrared band, and these to absorb parameters such as the position, shape, the degree of depth of features be that chemical characteristic by element determines.The correlation research that wave spectrum absorbs between feature and the chemical feature has obtained confirmation in fields such as pedology, mineralogy and vegetation sciences.The parameter of spectral absorption characteristics is wherein described---the spectral absorption degree of depth can be used as the parameter that a kind of qualitative assessment sample chemical is formed, and has been used in pedology, mineralogy and the vegetation study.But at present to the spectral signature of rare earth element and and its chemical characteristic between the correlative study of relation carry out seldom, document can be looked into mainly comprises the spectrum of having measured Eu, Nd, Sm rare earth oxide in the U.S. USGS wave spectrum storehouse; And for example EntonBedini has found that in spectral measurement one contains the wave spectrum of the carbonatite sample of rare earth oxide, because contain the Nd element, exists wave spectrum to absorb feature at visible light-near-infrared band 0.58 μ m, 0.74 μ m, 0.80 mu m waveband.
The ionic adsorption Rare Earth Mine is a kind of novel rare-earth ore deposit of finding first in China Jiangxi in 1969, this ore deposit have distribute wide, reserves are abundant, radioactivity is low, ree distribution pattern is complete, be rich in advantages such as middle heavy rare earth element, extensively be distributed in provinces such as the southern Jiangxi of China, Fujian, Hunan, Guangdong, Guangxi, wherein Jiangxi Province's portion maximum.Ion adsorption type rare earth ore middle rare earth element mainly is adsorbed in the clay mineral with ionic condition, generally adopts chemical leaching technology to extract.Ion adsorption type rare earth ore middle rare earth ion can be exchanged desorb by it running into the more active kation of chemical property (H+, NH4+ etc.), when ion adsorption type re is used the drip washing of salt electrolyte solution, rare earth ion will be exchanged, and is similar to ion exchange process.The extraction of rare earth element mainly is to add leaching agent such as salt to collect mother liquor in the mother liquor pond, therefore has the rare earth ion of variable concentrations in the different mother liquors pond.Because long-term underground infiltration and the unreasonable discharging of some mother liquor pond, mining area solution, the river of rare-earth mining area periphery also has certain density rare earth ion, so the utility model is gathered the water sample of different rare earth concentrations, measure and chemical analysis by wave spectrum, inquire into the wave spectrum feature of rare earth element in water body, and set up relation between wave spectrum feature and the rare earth element concentration, this research is significant for solution middle rare earth concentration fast inversion.
The utility model content
The utility model discloses a kind of water body middle rare earth concentration quantitative evaluating system based on ground return spectrum, can realize the fast quantification inverting of water body middle rare earth concentration of element based on the ground return spectroscopic data.The gained achievement can be used for quantitative-sxemiquantitative rapid evaluation that Rare Earth Mine periphery river middle rare earth pollutes, simultaneously good enlightenment effect has been played in the quantitative-sxemiquantitative research as weathering crust or rock middle rare earth concentration in other media, can also be provided theory and technical support to the aviation of rare-earth mineral and element and the mineral information extraction research of space flight high-spectrum remote-sensing in addition.
The technical solution of the utility model is:
A kind of water body middle rare earth concentration quantitative evaluating system based on ground return spectrum is characterized in that, comprises earth solution water sampling device, ground-object spectrum instrument, ICP-MS plasma mass spectrograph and computing machine; Described earth solution water sampling device is used for gathering the earth solution water sample of variable concentrations, described ground-object spectrum instrument is used for the earth solution water sample of the variable concentrations of gathering is carried out the ground return spectral measurement respectively, determine that for measured ground return spectral analysis rare earth concentration is had the characteristic absorption paddy distribution characteristics of indicative significance, described ICP-MS plasma mass spectrograph is used for the earth solution water sample of the variable concentrations of gathering is carried out the rare earth element concentration test respectively; Described computing machine calculates the relative absorption degree of depth of characteristic absorption paddy, and sets up the relative absorption degree of depth of characteristic absorption paddy and the correlationship between the rare earth element concentration according to the characteristic absorption paddy distribution characteristics that obtains, and draws rare earth concentration qualitative assessment model.
Described ground-object spectrum instrument is U.S. ASD FieldSpec3 series portable ground-object spectrum instrument.
Described ICP-MS plasma mass spectrograph is the X-series plasma mass spectrograph.
Described earth solution water sampling device comprises some containers that are used for collecting the earth solution water sample with suitable volume.
Technique effect of the present utility model:
The disclosed a kind of water body middle rare earth concentration quantitative evaluating system based on ground return spectrum of the utility model, proved that water body middle rare earth element has 6 characteristic absorption paddy at visible light-near infrared place, the relative absorption degree of depth and the rare earth total concentration of these 6 characteristic absorption paddy have the favorable linearity correlativity, therefore can realize the fast quantification inverting of water body middle rare earth concentration of element based on the ground return spectroscopic data.The utility model can be used for quantitative-sxemiquantitative rapid evaluation that Rare Earth Mine periphery river middle rare earth pollutes, simultaneously good enlightenment effect has been played in the quantitative-sxemiquantitative research as weathering crust or rock middle rare earth concentration in other media, this achievement in research can provide theory and technical support to the aviation of rare-earth mineral and element and the mineral information extraction research of space flight high-spectrum remote-sensing in addition.
Description of drawings
Fig. 1 is that the utility model is based on the structural representation of the water body middle rare earth concentration quantitative evaluating system of ground return spectrum.
Fig. 2 is the water body middle rare earth concentration quantitative evaluating method schematic flow sheet based on ground return spectrum of the present utility model.
Fig. 3 carries out the synoptic diagram of water sample reflectance spectrum test for the utility model uses the ground-object spectrum instrument.
Fig. 4 is 15 kinds of rare earth element concentrations of 10 water samples of ICP-MS plasma mass spectrograph test and the rare earth total concentration that calculates.
Fig. 5 is the reflectance spectrum comparison diagram (350-2500nm) of rare earth oxide, pure water, water sample D1.
Fig. 6 is the reflectance spectrum comparison diagram (350-1000nm) of rare earth oxide, water sample D1.
Fig. 7 is the reflected light spectrogram (350-900nm) of the water sample D1-D10 that measures.
Fig. 8 is 6 characteristic absorption paddy enlarged drawings of water sample D1-D10.
Fig. 9 is that water sample D1-D10 is in the relative absorption degree of depth of 6 characteristic absorption paddy.
Figure 10 absorbs the linear model of the degree of depth and rare earth total concentration relatively for 6 characteristic absorption paddy of water sample D1-D10.
Reference numeral lists as follows: 1-spectrometer probe, 2-light source, 3-water sample.
Embodiment
Below in conjunction with accompanying drawing embodiment of the present utility model is described in further detail.
As shown in Figure 1, be the structural representation of the utility model based on the water body middle rare earth concentration quantitative evaluating system of ground return spectrum.A kind of water body middle rare earth concentration quantitative evaluating system based on ground return spectrum comprises earth solution water sampling device, ground-object spectrum instrument, ICP-MS plasma mass spectrograph and computing machine; Earth solution water sampling device is used for gathering the earth solution water sample of variable concentrations, the ground-object spectrum instrument is used for the earth solution water sample of the variable concentrations of gathering is carried out the ground return spectral measurement respectively, determine that for measured ground return spectral analysis rare earth concentration is had the characteristic absorption paddy distribution characteristics of indicative significance, the ICP-MS plasma mass spectrograph is used for the earth solution water sample of the variable concentrations of gathering is carried out the rare earth element concentration test respectively; Computing machine calculates the relative absorption degree of depth of characteristic absorption paddy, and sets up the relative absorption degree of depth of characteristic absorption paddy and the correlationship between the rare earth element concentration according to the characteristic absorption paddy distribution characteristics that obtains, and draws rare earth concentration qualitative assessment model.
Wherein the ground-object spectrum instrument is U.S. ASD FieldSpec3 series portable ground-object spectrum instrument.FieldSpec3 series portable ground-object spectrum instrument is that U.S. ASD company is specially at the open-air reflective spectral measure product of geology, mineral products and soil surveying application and development.This instrument has high spectral resolution, high s/n ratio, high reliability, the characteristics of high duplication, can measure and observe reflection, transmission, radiancy (option) curve of spectrum in real time, the detection wavelength coverage of this instrument is 350～2500nm, and concrete technical parameter is as shown in the table.
As shown in Figure 2, be the water body middle rare earth concentration quantitative evaluating method schematic flow sheet based on ground return spectrum of the present utility model.A kind of water body middle rare earth concentration quantitative evaluating method based on ground return spectrum may further comprise the steps:
1) at first carries out the sample collection, gather the earth solution water sample of some variable concentrations;
2) use the ground-object spectrum instrument to carry out the ground return spectral measurement respectively based on the variable concentrations earth solution water sample of gathering then; Based on the reflectance spectrum of the variable concentrations earth solution water sample that measures, analyze and determine that rare earth concentration is had the characteristic absorption paddy distribution characteristics of indicative significance, calculate the relative absorption degree of depth of each characteristic absorption paddy of variable concentrations earth solution water sample;
3) use ICP-MS plasma mass spectrometer that the variable concentrations earth solution water sample of gathering is carried out rare earth concentration chemical analysis and rare earth element concentration test again; Calculate the rare earth total concentration of variable concentrations earth solution water sample respectively according to test result;
4) at last the relative absorption degree of depth and the rare earth total concentration of each characteristic absorption paddy of variable concentrations earth solution water sample are carried out linear regression analysis, set up the relative absorption degree of depth of characteristic absorption paddy and the correlationship between the rare earth total concentration, draw rare earth concentration qualitative assessment model.
Sample collection about step 1):
The sample collection is distributed in Jiangxi south 3 main mining area of ion adsorption type rare earth ore and mining area periphery, and water sample mainly is arranged in the river of mother liquor pond, mining area and mining area periphery pollution, and the utility model embodiment gathers the earth solution water sample of 10 variable concentrations.The vinyon bottle of 100ml is selected in the collection of water sample for use, and the water sample of gathering is used 0.45 μ m filter membrane suction filtration, before the water sampling, needs with water sample flushing sampling bottle 2,3 times.The water sample of gathering is in the refrigeration of 0-4 degree, so that spectrum test afterwards and chemical analysis.
About step 2) reflectance spectrum test:
Being illustrated in figure 3 as the utility model uses the ground-object spectrum instrument to carry out the synoptic diagram of water sample reflectance spectrum test.Test is carried out in the darkroom, during spectrum test, make 10 samples be in identical external environmental condition, at first prepares the measurement beaker of some 50ml capacity, and the liquor capacity of each different water samples that fall is 40ml during spectral measurement; The ground-object spectrum instrument is furnished with special light source and probe, with tripod spectrometer institute luminous intensity distribution source is fixed on the correct position that can shine the solution of surveying, and feasible probe solution that perpendicular alignmnet is surveyed; Under beaker, place a blank sheet of paper, retouch out the position of beaker on the blank sheet of paper, guarantee that each the measurement all is placed on same position with beaker, at 5 data of each sample measurement, is averaging the spectrum that obtains each sample for 5 data measuring.
Rare earth concentration test chemical about step 3):
The ICP-MS plasma mass spectrograph that the rare earth element concentration test is adopted is the X-series plasma mass spectrograph.Solubilised state REE concentration analysis process is as follows: with HDEHP and H2MEHP mixed extractant REE is extracted from aqueous solution earlier, and then REE back extraction from extractant is come out and be converted into nitrate with ultrapure HCl, measure with ICP-MS.The isotope that is used for each element of plasma mass spectrometry is
89Y,
139La,
140Ce,
141Pr,
146Nd,
147Sm,
151Eu,
157Gd,
159Tb,
163Dy,
165Ho,
167Er,
169T m,
173Yb,
175Lu.ICP-MS detects and is limited to
89Y0.022 μ g/l,
139La0.018 μ g/l,
140Ce0.028 μ g/l,
141Pr0.005 μ g/l,
146Nd0.076 μ g/l,
147Sm0.009 μ g/l,
151Eu0.002 μ g/l,
157Gd0.021 μ g/l,
159Tb0.002 μ g/l,
163Dy0.009 μ g/l,
165Ho0.003 μ g/l,
167Er0.005 μ g/l,
169Tm0.002 μ g/l,
173Yb0.003 μ g/l and
175Lu0.0005 μ g/l.The plasma mass spectrometry precision of heavy rare earth element and Y is 2%～3%, and light rare earth element then is about 5%.15 kinds of rare earth element concentration test results of 10 water samples have obtained the rare earth total concentration of 10 water samples as shown in Figure 4 according to test result calculations.
About step 2) the spectral signature analysis and the calculating of the relative absorption degree of depth of each characteristic absorption paddy:
The rare earth water sample mainly is the mixing of water body and rare earth element, in order to be analyzed with water body and rare earth element, the utility model has carried out the reflectance spectrum test to pure water and rare earth oxide, as shown in Figure 5, be rare earth oxide, pure water, the reflectance spectrum comparison diagram (350-2500nm) of water sample D1, choosing the reflectance spectrum of the highest D1 sample of rare earth concentration and the reflectance spectrum of pure water and rare earth oxide compares, the result shows that the rare earth water sample of collection has the spectral signature of pure water body on the whole, have high reflectance at visible light, but reflectivity descends sharply after short-wave infrared.Again the spectrum of water sample D1 and the spectrum of rare earth oxide are analyzed, as shown in Figure 6, reflectance spectrum comparison diagram (350-1000nm) for rare earth oxide, water sample D1, by with the spectral signature comparative analysis of rare earth oxide, show that the rare earth water sample presents the spectral signature of rare earth oxide simultaneously, have more tangible 6 characteristic absorption paddy at visible light-near infrared, size according to absorption intensity, 6 characteristic absorption paddy lay respectively at 574nm, 790nm, 736nm, 520nm, 861nm, the 443nm place.And find the reduction along with rare earth concentration, absorb paddy absorption feature and become more and more not obvious, back 5 water samples that begin from D6 particularly, 6 characteristic absorption paddy features become not easy to identify, as shown in Figure 7, the reflected light spectrogram (350-900nm) for the water sample D1-D10 that measures is followed successively by D1 from top to bottom, D2 ... .D10.
Absorb before paddy absorbs the degree of depth relatively in calculated characteristics, need go continuum to handle to the spectrum of the water sample of D1-D10, fundamental purpose be the influence of removing background, and the spectral reflectivity of removing after the continuum becomes relative reflectance.This step is mainly utilized continuum removed function realization in the ENVI remote sensing image processing software.In order to seek unity of standard, we choose 10nm as the wavelength interval of going continuum to handle, absorb paddy (574nm for 6 rare earth element characteristic then, 790nm, 736nm, 520nm, 861nm 443nm), calculates the relative absorption degree of depth of 10 water samples respectively, absorb the degree of depth=1-relative reflectance relatively, as shown in Figure 8,6 characteristic absorption paddy enlarged drawing for water sample D1-D10 is followed successively by D1 from top to bottom, D2 ... .D10.As can be drawn from Figure 8, the relative reflectance of the characteristic absorption paddy 861nm D1-D10 of place is respectively 0.96452,0.97818,0.98861,0.99037,0.99176,0.99809,0.99872,0.99955,0.99979,0.99998, then absorb the degree of depth relatively and be respectively 0.03548,0.02182,0.01139,0.00963,0.00824,0.00191,0.00128,0.00045,0.00021,0.00002.Similarly, can draw the relative absorption degree of depth that other several characteristic absorb paddy, concrete result of calculation as shown in Figure 9.
About step 4), use least square method that the relative absorption degree of depth and the rare earth total concentration at 6 characteristic absorption paddy places are carried out linear analogue.For two variablees---characteristic absorption paddy absorbs the degree of depth relatively and the rare earth total concentration is made as x and y respectively, at 6 characteristic absorption paddy, can be by the paired data (x1 of D1-D10, y1.x2, y2...x10, y10), according to the principle of least square, try to achieve straight-line equation Y=b X+a, and can be in the hope of coefficient R:
The result shows that both have good linear dependence, related coefficient square up to 96-97%, as shown in figure 10, absorb the linear model of the degree of depth and rare earth total concentration relatively for 6 characteristic absorption paddy of water sample D1-D10.For 6 characteristic absorption paddy (574nm, 790nm, 736nm, 520nm, 861nm, 443nm), the equation of least square linear simulation is respectively y=15.703x-0.0057, y=10.835x+0.0088, y=29.295x-0.2549, y=20.677x+0.0128, y=26.062x+0.0293, y=40.092x-0.016.The relative error of model is respectively 0.0511g/L, 0.0526g/L, 0.0588g/L, 0.0470g/L, 0.0538g/L, 0.0545g/L.
Should be pointed out that the above embodiment can make those skilled in the art more fully understand the utility model and create, create but limit the utility model never in any form.Therefore, although creating, the utility model of this instructions and embodiment has been described in detail,, it will be appreciated by those skilled in the art that still to create the utility model and make amendment or be equal to replacement; And all do not break away from technical scheme and the improvement thereof of the spirit and scope of the utility model creation, and it all is encompassed in the utility model and creates in the middle of the protection domain of patent.
Claims (4)
1. based on the water body middle rare earth concentration quantitative evaluating system of ground return spectrum, it is characterized in that, comprise earth solution water sampling device, ground-object spectrum instrument, ICP-MS plasma mass spectrograph and computing machine; Described earth solution water sampling device is used for gathering the earth solution water sample of variable concentrations, described ground-object spectrum instrument is used for the earth solution water sample of the variable concentrations of gathering is carried out the ground return spectral measurement respectively, determine that for measured ground return spectral analysis rare earth concentration is had the characteristic absorption paddy distribution characteristics of indicative significance, described ICP-MS plasma mass spectrograph is used for the earth solution water sample of the variable concentrations of gathering is carried out the rare earth element concentration test respectively; Described computing machine calculates the relative absorption degree of depth of characteristic absorption paddy, and sets up the relative absorption degree of depth of characteristic absorption paddy and the correlationship between the rare earth element concentration according to the characteristic absorption paddy distribution characteristics that obtains, and draws rare earth concentration qualitative assessment model.
2. the water body middle rare earth concentration quantitative evaluating system based on ground return spectrum according to claim 1 is characterized in that, described ground-object spectrum instrument is U.S. ASD FieldSpec3 series portable ground-object spectrum instrument.
3. the water body middle rare earth concentration quantitative evaluating system based on ground return spectrum according to claim 1 is characterized in that described ICP-MS plasma mass spectrograph is the X-series plasma mass spectrograph.
4. the water body middle rare earth concentration quantitative evaluating system based on ground return spectrum according to claim 1 is characterized in that, earth solution water sampling device comprises some containers that are used for collecting the earth solution water sample with suitable volume.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103076292A (en) * | 2012-12-27 | 2013-05-01 | 中国地质科学院矿产资源研究所 | System and method for quantitatively evaluating concentration of rare earth in water body based on ground reflection spectrum |
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Cited By (2)
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| CN103076292A (en) * | 2012-12-27 | 2013-05-01 | 中国地质科学院矿产资源研究所 | System and method for quantitatively evaluating concentration of rare earth in water body based on ground reflection spectrum |
| CN103076292B (en) * | 2012-12-27 | 2015-09-30 | 中国地质科学院矿产资源研究所 | System and method for quantitatively evaluating concentration of rare earth in water body based on ground reflection spectrum |
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