CN102841062A - Method for selectively and quantitatively collecting and measuring chromium (VI) in aquatic environment - Google Patents
Method for selectively and quantitatively collecting and measuring chromium (VI) in aquatic environment Download PDFInfo
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- CN102841062A CN102841062A CN2012103043419A CN201210304341A CN102841062A CN 102841062 A CN102841062 A CN 102841062A CN 2012103043419 A CN2012103043419 A CN 2012103043419A CN 201210304341 A CN201210304341 A CN 201210304341A CN 102841062 A CN102841062 A CN 102841062A
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Abstract
A method for selectively and quantitatively collecting and measuring chromium (VI) in aquatic environment comprises the steps of: carrying out pretreatment with a dialysis membrane with molecular cut off of 2000-14000, pretreating a binder, placing a collecting device in the aquatic environment with the dialysis membrane downward, fixing the collecting device, standing for 1-120d, taking out the collecting device once or multiple times, taking out 30-80vol% of the binder, diluting to a certain volume with hydrochloric acid, measuring the accumulation volume of chromium (VI) in the binder, and calculating average concentration of chromium (VI) in water. The method has the advantages that the collecting device is simple, low in cost, convenient for collecting and pollution-free to the environment, so that the concentration of chromium (VI) can be more accurately measured; the concentration of free chromium (VI) in the binder solution is approximate to zero; and the change of an aquatic environment system within a period of time can be more comprehensively reflected.
Description
Technical field
The invention belongs to the environmental monitoring field, the method for chromium in the water environment (VI) is quantitatively gathered, measured to particularly a kind of selectivity.
Background technology
In the physical environment, the common form of chromium is chromium (III) and chromium (VI), and all there were significant differences because the valence state difference causes chemical property of the earth, biochemical property, the toxic level of chromium (III) and chromium (VI).Chromium (VI) exists with anionic form, has higher activity, and its solubleness is big, and plant and animal is all had very big harm, and carcinogenic effect is arranged behind the contacting skin, the concurrent attitude reaction that changes.And chromium (III) is one of micro elements needed by human; Its poor activity; Animals and plants are very low to the absorptivity of chromium (III), at inside of human body, and chromium (III) and the complexing of b-globulin; Be the indispensable element of globulin eubolism, bring out angiocardiopathy easily in case lack chromium (III) in the human body.Therefore; Chromium total amount in the detection of contamination is not enough to explain the extent of injury that pollutant causes environment and animals and plants, and science appraisal chromium is to the influence of environment; Must carry out chemical speciation, particularly will accurately measure the content of the extremely strong chromium of toxicity (VI).
At present, the measuring method of chromium (VI) mainly comprises AAS, atomic spectroscopy, mass spectroscopy, electrochemical methods, film balance diffusion technique.AAS, atomic spectroscopy, mass spectroscopy are not the original position samplings, but behind the spot sampling, will gather water sample and send the lab analysis measurement back to.Be in mobile equilibrium owing to gather the chemical form of chromium in the water sample; Along with the variation of water body pH and the existence of other component; Gather water sample during storing and handling, can take place physics, chemistry and biological aspect variation, be difficult to accurately analyze the content of chromium (VI).
Along with the development of economic society, environmental standard improves constantly, and chromium in the water environment (VI) needs enrichment just can be detected, and has further increased chromium (VI) and has analyzed difficulty.Electrochemical methods, film balance diffusion technique do not have enrichment function, can not measure chromium (VI) content that is lower than detectability.
Summary of the invention
The technical matters that the present invention will solve provides the method that chromium in the water environment (VI) quantitatively gathered, measured to a kind of selectivity, and this method is to sampling of chromium in the water environment (VI) original position and enrichment, and detection limit is low, can accurately measure chromium (VI) content in the water environment.
Technical solution of the present invention is:
The method of chromium in the water environment (VI) is quantitatively gathered, measured to a kind of selectivity, and its concrete steps are:
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane is immersed in the deionized water and boils, and whenever changes deionized water one time at a distance from 20min～30min, and the accumulation boiling time is 1h～3h;
2) pre-service of bond
Get liquid bond 20～50g; With 50 mL～100 mL deionized waters dilution, said bond is water-soluble polymeric quaternary ammonium salt or Gemini (Gemini) quaternary ammonium salt, processes bag filter with said dialysis membrane; The bond solution of dilution is put into bag filter; In deionized water, soak 72h～168h and carry out purifying, during purifying, every separated 12h～24h changes deionized water one time;
3) harvester is installed
The bond solution dilution of purifying to 0.005mol/L～0.050mol/L, and according to the harvester volumetric quantity harvester of packing into, is sealed harvester with said dialysis membrane, and said harvester material is teflon or polypropylene;
4) harvester is placed
The harvester that bond is housed is put in the water environment, and be 1 day～120 days standing time, and during placement, the harvester dialysis membrane is downward, then fixing harvester;
5) harvester takes out and detects
Once all take out or take out several times harvester, the bond of enrichment chromium (VI) in the harvester is taken out according to 30%～80% of cumulative volume, using mass percent concentration is 1%～2% hydrochloric acid constant volume, measures chromium (VI) semi-invariant in the bond;
6) concentration of chromium (VI) in the calculating water environment
When harvester once all takes out, according to formula I: C
b=MDg/DtA, the concentration of chromium (VI) is accomplished the quick calibrating of chromium (VI) in the water environment in the calculating water;
When sampling apparatus takes out several times, with the semi-invariant of chromium in the sampling apparatus (VI) time is mapped, according to formula II: C
b=α Dg/DA, the concentration of chromium (VI) is accomplished the long-term detection of chromium (VI) in the water environment in the calculating water;
In formula I and the formula II, C
bBe the concentration of chromium in the bulk solution (VI), M is chromium (VI) semi-invariant in the bond, and Dg is a dialysis membrane thickness; D is the coefficient of diffusion of chromium (VI) through dialysis membrane; T is diffusion time, and A is the dialysis membrane working area, and α is the slope of accumulation to time curve.
Said dialysis membrane is a CAM.
Said water-soluble polymeric quaternary ammonium salt is a kind of in poly quaternary ammonium salt, ethylidene polyamines and the chloropropylene oxide quaternary ammonium copolymer.
Said water-soluble Gemini (Gemini) quaternary ammonium salt is a kind of in the two lauryl amine polyoxyethylene ether quaternary ammonium salts of ethylene group, two lauryl amine polyoxyethylene ether three quaternary ammonium salts, the two lauryl amine polyoxyethylene ether bi-quaternary ammonium salt.
Said harvester comprises fixed head, on fixed head, is provided with the shell of band inside edge; Be provided with supporter in the enclosure; Between supporter top and shell inside edge, be installed with dialysis membrane, on supporter, be provided with the back taper groove, said groove and dialysis membrane surround and form the bond container cavity.
Said harvester volume is 2mL.
Fixedly during harvester, with the harvester suspension or be placed on the stilt and swim in the water.
Fixedly during harvester, harvester is placed in the bottom and is buried in sediment, the soil.
Said water environment is water or the water in the soil in water in the natural fresh, natural mineralized water, sewage, potable water, recycle-water, biosome, the sediment.
The present invention is a theoretical foundation with Fick first diffusion law; Dialysis membrane through can infiltrating ion will separate with water body the bond (water-soluble polymeric quaternary ammonium salt or Gemini (Gemini) quaternary ammonium salt) that chromium (VI) has a selective binding effect; Through dialysis membrane control ion exchange process; Chromium in the water body (VI) ion combines with bond through behind the dialysis membrane, makes chromium in the bond (VI) ion concentration approach zero, keeps the lasting concentration gradient of chromium (VI) ion between water body and bond solution; Make chromium (VI) ion in the water body constantly pass through the dialysis membrane enrichment in bond, realize quantitative collection chromium in the water environment (VI).And chromium (III) institute is electrically charged opposite with chromium (VI), can not combine with the kation bond, so can not enrichment in the kation bond, thereby realized selective enrichment to chromium (VI).
Bond is separated with tested water body by the dialysis membrane of Hou Du Wei ⊿ g, and the transmission of chromium (VI) ion is that the dialysis membrane of A carries out through area only.In time t, chromium (VI) ion is diffused into the diffusing capacity M that chromium (VI) is had a bond of selective binding and inrichment from bulk solution through dialysis membrane and can be expressed as:
M?=D·C
b·t·A/?Dg (1)
M can through quantitative analysis method (like AAS, ICP-MS) measure and to obtain, be expressed as so chromium (VI) concentration then can be quantitative in the bulk solution:
C
b?=M·Dg/D·t·A (2)
M, △ g, A, D, t are measurable amount, and through type (2) can calculate the concentration C of bulk solution
b
Its beneficial effect is:
(1) use the sampling of harvester original position, harvester is simple, and is with low cost, and it is convenient to gather, environmentally safe; The form original position of monitored material shifts from water environment and is fixed in the bond, the metamorphosis of having avoided sample transportation, storage and processing to cause, and detection limit is low, can more accurately measure chromium (VI) concentration;
(2) select for use water-soluble polymeric quaternary ammonium salt or Gemini (Gemini) quaternary ammonium salt as bond, its effect is firmly to combine with chromium (VI) through dialysis membrane, makes the concentration of free chromium (VI) in the inboard bond solution of dialysis membrane approach zero;
(3) selective measurement can by the water-soluble polymeric quaternary ammonium salt or Gemini (Gemini) quaternary ammonium salt combines and the content of the chromium (VI) of enrichment;
(4) harvester is positioned in the water environment system that a concentration constantly changes for a long time, can obtain system at this moment between the mean intensity value of chromium (VI) in the scope, react the variation of water environment system in a period of time more all sidedly.
Description of drawings
Fig. 1 is a harvester synoptic diagram of the present invention.
Among the figure: 1-fixed head, 2-shell, 3-supporter, 301-groove, 4-dialysis membrane, 5-bond container cavity.
Embodiment
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing the two lauryl amine polyoxyethylene ether bi-quaternary ammonium salts of 50g liquid bond; With 80mL deionized water dilution and put into said bag filter, in deionized water, soak the 168h purifying, every at a distance from deionized water of 24 h replacing;
3) harvester is installed
The bond of purifying is made into the two lauryl amine polyoxyethylene ether bi-quaternary ammonium salt solution of 0.020mol/L; Getting 3 materials is the harvester (as shown in Figure 1) of 2mL for the polypropylene volume; This harvester comprises fixed head 1; On fixed head 1, be provided with the shell 2 of band inside edge, in shell 2, be provided with supporter 3, between supporter 3 tops and shell 2 inside edges, be installed with dialysis membrane 4; On supporter 3, be provided with back taper groove 301, said groove 301 surrounds with dialysis membrane 4 and forms bond container cavity 5; With the two lauryl amine polyoxyethylene ether bi-quaternary ammonium salt solution of the 2mL0.020mol/L that packs in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be suspended on the stilt and swim in 24h in the industrial waste water;
5) harvester takes out and detects
3 harvesters are all taken out; Get enrichment chromium (VI) bond in the 1.0 mL harvesters; Using mass percent concentration is that 2% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, the semi-invariant that records chromium (VI) in three harvesters is respectively 3.64 μ g, 3.64 μ g and 3.94 μ g, and flat semi-invariant (M) is 3.74 μ g;
6) concentration of chromium (VI) in the calculating water environment
With D=5.33 * 10
-7Cm
2S
-1, A=3.14 cm
2, Dg=85mm=85 * 10
-4Cm, M=3.74 μ g, t=24 * 3600s substitution formula C
b=MDg/DtA tries to achieve the mean concentration C of chromium in the industrial waste water (VI)
b=0.2198 μ g/ml.
The concentration that adopts AAS directly to record chromium in the industrial waste water (VI) is 0.2347 μ g/ml.The mean concentration of the chromium (VI) that interior present embodiment of monitoring phase is measured and the ratio of chromium (VI) content that AAS recorded in the same period are 93.65%, show that the present invention can accurately measure the content of the chromium (VI) in the water body.
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing two lauryl amine polyoxyethylene ether three quaternary ammonium salts of 40g liquid bond; With 100mL deionized water dilution and put into said bag filter, in deionized water, soak the 168h purifying, whenever change a deionized water at a distance from 12h;
3) harvester is installed
The bond of purifying is made into two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of 0.050mol/L, and getting 12 materials is the harvester of 2ml for the polypropylene volume, and this harvester structure is with embodiment 1; With two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of the 2ml 0.050mol/L that packs in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be placed on the stilt and swim in the sanitary sewage;
5) harvester takes out and detects
Take out 3 harvesters every day (by 24h); Get enrichment chromium (VI) bond in the 0.8mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, and calculate in standing time the average accumulated amount (M) of chromium (VI) in the sanitary sewage, the average accumulated amount (M) of chromium (VI) is respectively 2.08 μ g, 3.94 μ g, 5.40 μ g and 7.30 μ g in 24h, 48h, 72h and the 96h harvester;
6) concentration of chromium (VI) in the calculating water environment
To mapping standing time (t), trying to achieve slope α is 0.0715, with D=5.33 * 10 with semi-invariant (M)
-7Cm
2S
-1, A=3.14 cm
2, Dg=8.5mm=85 * 10
-4Cm substitution C
b=α Dg/3600D A (3600 is chronomere's reduction coefficient, 1h=3600s, down with), try to achieve the concentration C of chromium in the sanitary sewage (VI)
b=0.101 μ g/ml.
The concentration that adopts AAS directly to record chromium in the sanitary sewage (VI) is 0.102 μ g/ml.The mean concentration of the chromium (VI) that interior present embodiment of monitoring phase is measured and the ratio of chromium (VI) content that AAS recorded in the same period are 99.01%.
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 30min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1), take by weighing 20g liquid bond poly quaternary ammonium salt, with 50mL deionized water dilution and put into said bag filter, in deionized water, soak the 120h purifying, every at a distance from deionized water of 24 h replacing;
3) harvester is installed
The bond of purifying is made into 0.050mol/L poly quaternary ammonium salt solution, and getting 12 materials is the harvester of 2ml for the teflon volume, and this harvester structure is with embodiment 1; With the 2ml0.050mol/L poly quaternary ammonium salt solution of packing in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be placed on the stilt and swim in the industrial waste water;
5) harvester takes out and detects
Take out 3 harvesters weekly; Get enrichment chromium (VI) bond in the 0.6mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 50mL; Utilize the chromium (VI) in the aas determination bond; And calculate in standing time the average accumulated amount (M) of chromium (VI) in the industrial waste water, experiment records around first week, second week, the 3rd week and that the average accumulated amount (M) of chromium (VI) is respectively 28.4 μ g, 48.5 μ g, 82.6 μ g and 110.8 μ g in the harvester;
6) concentration of chromium (VI) in the calculating water body
To mapping standing time (t), trying to achieve slope α is 4.27571, with D=5.33 * 10 with semi-invariant (M)
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85 * 10
-4Cm, α=4.27571 substitution C
b=α Dg/24 * 3600D A tries to achieve the mean concentration C of chromium in the industrial waste water (VI)
b=0.251 μ g/ml.
The concentration that adopts AAS directly to record chromium in the industrial waste water (VI) is 0.239 μ g/ml.The mean concentration of the chromium (VI) that interior present embodiment of monitoring phase is measured and the ratio of chromium (VI) content that AAS recorded in the same period are 105%.
Embodiment 4
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1), take by weighing 20g liquid bond poly quaternary ammonium salt, with 100mL deionized water dilution and put into said bag filter, in deionized water, soak the 96h purifying, every at a distance from deionized water of 16 h replacing;
3) harvester is installed
The bond of purifying is made into 0.050mol/L poly quaternary ammonium salt solution, and getting 12 materials is the harvester of 2ml for the teflon volume, and this harvester structure is with embodiment 1; With the 2ml0.050mol/L poly quaternary ammonium salt solution of packing in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be placed on the stilt and swim in the natural fresh environment;
5) harvester takes out and detects
Take out 3 harvesters weekly; Get enrichment chromium (VI) bond in the 1.6mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, and calculate in standing time the average accumulated amount (M) of chromium (VI) in the sanitary sewage, record around first week, second week, the 3rd week and that the average accumulated amount (M) of chromium (VI) is respectively 0.652 μ g, 1.364 μ g, 1.828 μ g and 2.580 μ g in the harvester;
6) concentration of chromium (VI) in the calculating water environment
To mapping standing time (t), trying to achieve slope α is 0.08926, with D=5.33 * 10 with semi-invariant (M)
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85 * 10
-4Cm substitution C
b=α Dg/24 * 3600D A tries to achieve the mean concentration C of chromium in the natural water (VI)
b=0.0052 μ g/ml.
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing 50g liquid bond ethylidene polyamines and chloropropylene oxide quaternary ammonium copolymer; With 100mL deionized water dilution and put into said bag filter, in deionized water, soak the 168h purifying, every at a distance from deionized water of 24 h replacing;
3) harvester is installed
The bond of purifying is made into 0.010mol/L ethylidene polyamines and chloropropylene oxide quaternary ammonium copolymer solution, and getting 12 materials is the harvester of 2ml for the teflon volume, and this harvester structure is with embodiment 1; With 2ml0.010mol/L ethylidene polyamines and the chloropropylene oxide quaternary ammonium copolymer solution of packing in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, bury in the soil (paddy field);
5) harvester takes out and detects
Take out 3 harvesters every month; Get enrichment chromium (VI) bond in the 1mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 25mL; Utilize the chromium (VI) in the aas determination bond, and calculate in standing time the average accumulated amount (M) of chromium (VI) in the sanitary sewage, the semi-invariant (M) of chromium (VI) is respectively 14.23 μ g, 30.88 μ g, 42.31 μ g and 58.61 μ g in 30 days, 60 days, 90 days, 120 days harvesters;
6) concentration of chromium (VI) in the calculating water environment
To mapping standing time (t), trying to achieve slope α is 0.4819, with D=5.33 * 10 with semi-invariant (M)
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85 * 10
-4Cm substitution C
b=α Dg/24 * 3600D A tries to achieve the mean concentration C of chromium in the holard (VI)
b=0.0283 μ g/ml.
Embodiment 6
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 1h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing the two lauryl amine polyoxyethylene ether quaternary ammonium salts of 20g liquid bond ethylene group; With 100mL deionized water dilution and put into said bag filter; In deionized water, soak the 168h purifying, whenever change a deionized water at a distance from 24 h;
3) harvester is installed
The bond of purifying is made into the two lauryl amine polyoxyethylene ether quaternary ammonium salts of 0.0050mol/L ethylene group, and getting 3 materials is the harvester of 2ml for the polypropylene volume, and this harvester structure is with embodiment 1; With the two lauryl amine polyoxyethylene ether quaternary ammonium salts of the 2ml0.0050mol/L ethylene group of packing in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be suspended on the stilt and swim in 24h in the recycle-water;
5) harvester takes out and detects
3 harvesters are all taken out; Get enrichment chromium (VI) bond in the 1.6mL harvester; Using mass percent concentration is that 1% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, the semi-invariant that records chromium (VI) in three harvesters is respectively 1.244,1.364 and 1.174 μ g, and average accumulated amount (M) is 1.26 μ g
6) concentration of chromium (VI) in the calculating water environment
With D=5.33 * 10
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85 * 10
-4Cm, t=24 * 3600s, M=1.26 μ g substitution formula C
b=MDg/DtA tries to achieve the mean concentration C of chromium in the recycle-water (VI)
b=0.074 μ g/ml.
Embodiment 7
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 30min, and the accumulation boiling time is 3h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing two lauryl amine polyoxyethylene ether three quaternary ammonium salts of 50g liquid bond; With 100mL deionized water dilution and put into said bag filter, in deionized water, soak the 96h purifying, every at a distance from deionized water of 16 h replacing;
3) harvester is installed
The bond of purifying is made into two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of 0.0050mol/L, and getting 12 materials is the harvester of 2ml for the polypropylene volume, and this harvester structure is with embodiment 1; With two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of the 2ml0.050mol/L that packs in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be placed on the stilt and swim in the potable water;
5) harvester takes out and detects
Take out 3 harvesters every day; Get enrichment chromium (VI) bond in the 1.5mL harvester; Using mass percent concentration is that 1% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond; And calculate in standing time the average accumulated amount (M) of chromium (VI) in the sanitary sewage, recorded first day, second day, the 3rd day and the 4th day harvester in the average accumulated amount (M) of chromium (VI) be respectively 0.235 μ g, 0.481 μ g, 0.637 μ g and 0.950 μ g;
6) concentration of chromium (VI) in the calculating water environment
To mapping standing time (t), trying to achieve slope α is 0.00959, with D=5.33 * 10 with semi-invariant (M)
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85
*10
-4Cm substitution formula C
b=α Dg/3600D A tries to achieve the mean concentration C of chromium in the potable water (VI)
b=0.0135 μ g/ml.
Embodiment 8
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 1h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing two lauryl amine polyoxyethylene ether three quaternary ammonium salts of 15g liquid bond; With 75mL deionized water dilution and put into said bag filter, in deionized water, soak the 168h purifying, every at a distance from deionized water of 24 h replacing;
3) harvester is installed
The bond of purifying is made into two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of 0.005mol/L, and getting 3 materials is the harvester of 2ml for the polypropylene volume, and this harvester structure is with embodiment 1; With two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of the 2ml0.005mol/L that packs in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be suspended on the stilt and swim in and put into natural water 24h;
5) harvester takes out and detects
3 harvesters are all taken out; Get enrichment chromium (VI) bond in the 1.6mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, the semi-invariant (M) that records chromium (VI) in three harvesters is respectively 0.72,0.62 and 0.56 μ g, and flat semi-invariant (M) mean value is 0.63 μ g;
6) concentration of chromium (VI) in the calculating water environment
With D=5.33 * 10
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85
* 10
-4Cm, t=24
*3600s, M=0.63 μ g substitution formula (2) C
b=MDg/DtA tries to achieve the mean concentration C of chromium in the natural water (VI)
b=0.037 μ g/ml.
Embodiment 9
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing 15g liquid bond poly quaternary ammonium salt; With 100mL deionized water dilution and put into said bag filter, in deionized water, soak the 168h purifying, every at a distance from deionized water of 24 h replacing;
3) harvester is installed
The bond of purifying is made into 0.010mol/L poly quaternary ammonium salt solution, and getting 12 materials is the harvester of 2ml for the polypropylene volume, and this harvester structure is with embodiment 1; With the 2ml0.010mol/L poly quaternary ammonium salt solution of packing in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The harvester dialysis membrane is downward, be placed on the stilt and swim in the sanitary sewage;
5) harvester takes out and detects
Take out 3 harvesters every day (by 24h); Get enrichment chromium (VI) bond in the 1mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, and calculate in standing time the average accumulated amount (M) of chromium (VI) in the sanitary sewage, the average accumulated amount (M) of chromium (VI) is respectively 0.452 μ g, 0.821 μ g, 1.35 μ g and 1.78 μ g in 24h, 48h, 72h and the 96h harvester;
6) concentration of chromium (VI) in the calculating water environment
With semi-invariant (M) do, with D=5.33 * 10 to mapping standing time (t), trying to achieve slope α
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85 * 10
-4Cm substitution C
b=α Dg/3600DA tries to achieve the mean concentration C of chromium in the natural mineralized water (VI)
b=0.0265 μ g/ml.
Embodiment 10
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane (CAM) is immersed in the deionized water and boils, and whenever changes primary water at a distance from 20min, and the accumulation boiling time is 2h;
2) pre-service of bond
Process bag filter with pretreated CAM in the step 1); Take by weighing two lauryl amine polyoxyethylene ether three quaternary ammonium salts of 30g liquid bond; With 100mL deionized water dilution and put into said bag filter, in deionized water, soak the 72h purifying, every at a distance from deionized water of 12 h replacing;
3) harvester is installed
The bond of purifying is made into two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of 0.005mol/L, and getting 3 materials is the harvester of 2ml for the polypropylene volume, and this harvester structure is with embodiment 1; With two lauryl amine polyoxyethylene ether three quaternary ammonium salt solutions of the 2ml0.005mol/L that packs in the harvester, harvester is sealed with pretreated CAM in the step 1);
4) harvester is placed
The 100g marine alga is used refiner homogenate, and slurry dilution is the marine alga dilution of 10000ml, and the harvester dialysis membrane is downward, is suspended on the stilt and swims in 24h in the marine alga dilution;
5) harvester takes out and detects
3 harvesters are all taken out; Get enrichment chromium (VI) bond in the 1mL harvester; Using mass percent concentration is that 2% hydrochloric acid is settled to 10mL; Utilize the chromium (VI) in the aas determination bond, the semi-invariant that records chromium (VI) in three harvesters is respectively 0.15,0.18 and 0.21 μ g, and flat semi-invariant (M) is 3.74 μ g;
6) concentration of chromium (VI) in the calculating water environment
With D=5.33 * 10
-7Cm
2S
-1, A=3.14cm
2, Dg=85mm=85 * 10
-4Cm, t=24 * 3600s, M=0.18 μ g substitution formula C
b=MDg/DtA tries to achieve the mean concentration C of chromium in the marine alga (VI)
b=1.058 mg/kg.
Claims (9)
1. the method for chromium in the water environment (VI) is quantitatively gathered, measured to a selectivity, it is characterized in that:
1) pre-service of dialysis membrane
With molecular cut off is that 2000～14000 dialysis membrane is immersed in the deionized water and boils, and whenever changes deionized water one time at a distance from 20min～30min, and the accumulation boiling time is 1h～3h;
2) pre-service of bond
Get liquid bond 20～50g; With 50 mL～100 mL deionized waters dilution, said bond is water-soluble polymeric quaternary ammonium salt or Gemini (Gemini) quaternary ammonium salt, processes bag filter with said dialysis membrane; The bond solution of dilution is put into bag filter; In deionized water, soak 72h～168h and carry out purifying, during purifying, every separated 12h～24h changes deionized water one time;
3) harvester is installed
The bond solution dilution of purifying to 0.005mol/L～0.050mol/L, and according to the harvester volumetric quantity harvester of packing into, is sealed harvester with said dialysis membrane, and said harvester material is teflon or polypropylene;
4) harvester is placed
The harvester that bond is housed is put in the water environment, and be 1 day～120 days standing time, and during placement, the harvester dialysis membrane is downward, then fixing harvester;
5) harvester takes out and detects
Once all take out or take out several times harvester, the bond of enrichment chromium (VI) in the harvester is taken out according to 30%～80% of cumulative volume, using mass percent concentration is 1%～2% hydrochloric acid constant volume, measures chromium (VI) semi-invariant in the bond;
6) concentration of chromium (VI) in the calculating water environment
When harvester once all takes out, according to formula I: C
b=MDg/DtA, the concentration of chromium (VI) is accomplished the quick calibrating of chromium (VI) in the water environment in the calculating water;
When sampling apparatus takes out several times, with the semi-invariant of chromium in the sampling apparatus (VI) time is mapped, according to formula II: C
b=α Dg/DA, the concentration of chromium (VI) is accomplished the long-term detection of chromium (VI) in the water environment in the calculating water;
In formula I and the formula II, C
bBe the concentration of chromium in the bulk solution (VI), M is chromium (VI) semi-invariant in the bond, and Dg is a dialysis membrane thickness; D is the coefficient of diffusion of chromium (VI) through dialysis membrane; T is diffusion time, and A is the dialysis membrane working area, and α is the slope of accumulation to time curve.
2. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1, it is characterized in that: said dialysis membrane is a CAM.
3. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1, it is characterized in that: said water-soluble polymeric quaternary ammonium salt is a kind of in poly quaternary ammonium salt, ethylidene polyamines and the chloropropylene oxide quaternary ammonium copolymer.
4. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1, it is characterized in that: said water-soluble Gemini (Gemini) quaternary ammonium salt is a kind of in the two lauryl amine polyoxyethylene ether quaternary ammonium salts of ethylene group, two lauryl amine polyoxyethylene ether three quaternary ammonium salts, the two lauryl amine polyoxyethylene ether bi-quaternary ammonium salt.
5. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1; It is characterized in that: said harvester, comprise fixed head, on fixed head, be provided with the shell of band inside edge; Be provided with supporter in the enclosure; Between supporter top and shell inside edge, be installed with dialysis membrane, on supporter, be provided with the back taper groove, said groove and dialysis membrane surround and form the bond container cavity.
6. quantitatively gather, measure the method for chromium in the water environment (VI) according to claim 1 or 5 described selectivity, it is characterized in that: said harvester volume is 2mL.
7. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1, it is characterized in that: fixedly during harvester, with the harvester suspension or be placed on the stilt and swim in the water.
8. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1, it is characterized in that: fixedly during harvester, harvester is placed in the bottom and is buried in sediment, the soil.
9. the method for chromium in the water environment (VI) is quantitatively gathered, measured to selectivity according to claim 1, it is characterized in that: said water environment is water or the water in the soil in water in the natural fresh, natural mineralized water, sewage, potable water, recycle-water, biosome, the sediment.
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