CN107702972A - Application of the titanium dioxide in the preceding processing of ELISA detection heavy metal in soil ion - Google Patents
Application of the titanium dioxide in the preceding processing of ELISA detection heavy metal in soil ion Download PDFInfo
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Abstract
The present invention discloses application of the titanium dioxide in the preceding processing of ELISA detection heavy metal in soil ion.The present invention is attached to the heavy metal ion progress Adsorption and desorption in soil extraction using titanium dioxide, and the heavy metal ion for being enriched with to obtain can be detected by immunological method.The heavy metal ion that first Application titanium dioxide of the present invention is extracted to diluted acid in liquid soil carries out adsorption and desorption operation, so as to the heavy metal ion in the soil below application colloid gold test paper detection two level；PH value wherein is adjusted with ammoniacal liquor, avoids highly acidity and influence of the high salinity after regulation pH to colloidal gold immuno-chromatography test paper strip, ensures the accuracy of detection.Compare sample pre-treatments and continuous mode that National Standard Method is up to more than ten hour, association colloid gold test paper of the present invention can complete the measure to heavy metal ion in pedotheque in 2h, detection time is substantially reduced, and it is simple without large-scale instrument and Specialty Experiment personnel, operating process.
Description
Technical field
The invention belongs to heavy metal analysis field, more particularly to titanium dioxide detects heavy metal in soil in ELISA
Application in the pre-treatment of ion.
Background technology
Soil is material conditions for the survival of mankind, is the valuable natural resources of the mankind.In recent years, with China cities and towns
Change, the quickening of process of industrialization, a large amount of productions of chemical fertilizer, agricultural chemicals are with using in addition, and China's soil pollution is more serious, especially
Heavy metal pollution.This forms potential threaten to environmental ecology and people's life security.
The premise repaired to soil is to understand the situation of heavy metal pollution of soil.Traditional heavy metal detection method is big
All there is degree of accuracy height, high sensitivity, good selective, but there is also many shortcomings：Such as big multi-method is required for large-scale
Instrument, expensive, analysis cost is high, and sample segment needs to carry out complicated pretreatment process, analysis time length etc., Wu Fajin
The continuous monitoring of row heavy metal and on-site measurement.In recent years, as heavy metal pollution problem becomes increasingly conspicuous, the inspection of traditional heavy metal
Survey method has been difficult to the requirement for meeting people, and easy, quick, efficient and suitable for execute-in-place heavy metal detection method turns into
The focus of people's research.
The content of the invention
The shortcomings that it is an object of the invention to overcome prior art and deficiency, there is provided titanium dioxide detects in ELISA
Application in the pre-treatment of heavy metal in soil ion.
The purpose of the present invention is achieved through the following technical solutions：Titanium dioxide detects heavy metal in soil in ELISA
Application in the pre-treatment of ion, it is attached to the heavy metal ion progress Adsorption and desorption in soil extraction using titanium dioxide
Operation, reaches the purpose of enrichment, then detected by immunological method.
Described soil extraction refers to the solution obtained with dilute acid soln extraction soil.
Application of the described titanium dioxide in the preceding processing of ELISA detection heavy metal in soil ion, is preferably wrapped
Containing following steps：
(1) soil is extracted with diluted acid, then removes insoluble substance, obtain solution I；
(2) pH value of solution I is adjusted with ammoniacal liquor, obtains solution II；
(3) add titanium dioxide in solution II to be adsorbed, for the heavy metal ion in adsorbent solution II；
(4) separation of solid and liquid, desorption agent is added in solids and carries out desorption, obtains solution III.
Described heavy metal ion is preferably at least one of cadmium ion, lead ion and copper ion.
Soil described in step (1) is preferably the soil that can cross 100 mesh sieves.
Soil described in step (1) is the soil below standard of soil environment quality two level.
Diluted acid described in step (1) refers to that concentration is less than 6mol/L acid solution；Preferred concentration is 0.5~4mol/L
Acid solution；More preferably 2~4mol/L acid solution.
Described diluted acid is at least one of hydrochloric acid solution, sulfuric acid solution and salpeter solution；Preferably hydrochloric acid solution, sulphur
The mixed acid solution that two kinds of solution in acid solution and salpeter solution are formed；One more preferably in sulfuric acid solution or salpeter solution
The mixed acid solution that kind and hydrochloric acid solution are formed.
The concrete operations that soil is extracted with diluted acid described in step (1) are preferably as follows：Every 0.2000 ± 0.0005g soil
4mL dilute acid solns are matched, vibrate 30s, extraction；Wherein：
1) when described heavy metal ion is cadmium ion, dilute acid soln be 2~4M hydrochloric acid and 2~4M sulfuric acid by volume
1:3 obtained dilute acid solns, the condition of extraction are：20min is reacted at 40~60 DEG C；
2) when described heavy metal ion is lead ion, dilute acid soln is 4M hydrochloric acid and 4M nitric acid by volume 1:1
The dilute acid soln arrived, the condition of extraction are：50~60min is reacted at 60~80 DEG C；
3) when described heavy metal ion is copper ion, dilute acid soln is 4M hydrochloric acid and 4M sulfuric acid by volume 1:3
The dilute acid soln arrived, the condition of extraction are：60min is reacted at 80 DEG C.
The mode of removal insoluble substance described in step (1) is preferably to centrifuge.
The condition of described centrifugation is preferably to centrifuge 10~20min in 8000rpm.
The volume of solution I described in step (1) is preferably that every 0.2000 ± 0.0005g soil is extracted with dilute acid soln
Afterwards, it is settled to 10mL with water.
Ammoniacal liquor described in step (2) is concentrated ammonia liquor, i.e., concentration is 22~25% ammoniacal liquor.
PH value described in step (2) is preferably 8~9；More preferably 8.5.
Titanium dioxide described in step (3) is the titanium dioxide that average grain diameter is 5-10nm.
The dosage of titanium dioxide described in step (3) is preferably per 50mL solution IIs proportioning 50mg titanium dioxide.
The mode of absorption described in step (3) is adsorbed for vibration.
The condition of described vibration absorption is preferably to vibrate 5~10min, stands 20min.
The mode of separation of solid and liquid described in step (4) is preferably to centrifuge.
The condition of described centrifugation is preferably to centrifuge 8min in 4000rpm.
Desorption agent described in step (4) is preferably EDETATE SODIUM.
The concentration of described EDETATE SODIUM is preferably 0.01~0.2M；More preferably 0.1~0.2M.
The mode of desorption described in step (4) is preferably to vibrate desorption.
The condition of described vibration desorption is preferably to vibrate at least 10min；Preferably 10~15min.
Heavy metal ion in described solution III can be detected directly by colloidal gold strip.
The present invention is had the following advantages relative to prior art and effect：
(1) first Application titanium dioxide of the present invention extracts the heavy metal ion solution in soil to diluted acid and carries out absorption reconciliation
Adsorption operations, so as to the heavy metal ion in the soil below application colloid gold test paper detection two level.
(2) present invention is enriched with titanium dioxide to the heavy metal ion in the diluted acid leaching liquor after regulation pH, is used
EDTA2Na solution heavy metal ions (such as cadmium ion) are eluted, and effectively prevent highly acidity and the high salt after regulation pH
Spend the influence to colloidal gold immuno-chromatography test paper strip.
(3) sample pre-treatments and continuous mode that National Standard Method is up to more than ten hour, association colloid gold examination of the present invention are compared
Paper can complete the measure to heavy metal ion in pedotheque (such as cadmium ion) in 2h, substantially reduce detection time, and
Without large-scale instrument and Specialty Experiment personnel, operating process is simple, is a kind of heavy metal detection method efficiently, quick, easy.
In addition, for the cadmium ion in pedotheque, this method is not only adapted to the detection of immunity colloidal gold test paper strip, can also be by not
It is disconnected to improve, as a kind of independent Sample Pretreatment Technique, the detection for other fast methods.
(4) present invention optimizes since the condition of diluted acid extraction soil, and the adsorption and desorption of optimization titanium dioxide
Condition, the liquid association colloid gold test paper containing soil heavy metal ion is detected obtained from, and the degree of accuracy can be with ICP
Match in excellence or beauty.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
1st, the collection and preparation of pedotheque
In June, 2015, soil sampling is carried out near Sheng Ke institutes of Ji'nan University.Soil sampling method and procedure reference《Soil
Earth environmental monitoring technology specification》Principle and method in (HJ/T 166-2004) are carried out.Sampling sites are 0-20cm top layer
Soil, carried out using snakelike sampling method, the soil of 10 sample points is mixed into a pedotheque, removes the stone in soil sample
And plant and animal residues, 1kg or so soil is taken in teflon seal bag using quartering.By pedotheque in 90 DEG C of drum
Dried in wind drying box, 0.25kg or so soil is taken using quartering, pulverized with agate rod, cross 2mm nylon mesh, mixed, after
Continuous grinding, crosses 0.154mm (100 mesh) test sieve, is saved backup at cool place is dried.
2nd, the measure of standard soil and collection in worksite pedotheque physicochemical property
Standard soil Gss-7 used herein comes from State center for standard matter, and field sample picks up from Ji'nan University's life
Earth's surface near institute of section, respectively to the base such as both pH, the content of organic matter, cation exchange capacity (CEC) and cadmium, lead, copper plasma full dose
This parameter is measured, and design parameter is determined by Guangzhou Institute of Analysis.
The basic parameter of standard soil and spot sampling soil is shown in Table 1.As seen from the table：Both pH are overall below 7,
And the pH of standard soil, the content of organic matter are less than spot sampling soil, cation exchange capacity (CEC) is higher than spot sampling soil；Adopt at scene
Cadmium ion content in sample soil has exceeded China《Standard of soil environment quality》Primary standard in (GB 15618-1995)
0.20mg·kg-1, lead ion content is less than《Standard of soil environment quality》In primary standard 35mgkg-1, and copper ion contains
Amount exceedes《Standard of soil environment quality》In secondary standard 100mgkg-1。
The basic parameter table of the soil of table 1
3rd, pedotheque is extracted
(1) process is tested
1) influence of the dilute acid concentration to heavy metal in soil recovery rate
0.2000 ± 0.0005g standard soils or on-site soil are weighed respectively in 50mL centrifuge tubes, sequentially add 0.5,
1st, 2,3,4M salpeter solution, hydrochloric acid solution, sulfuric acid solution or mixed acid solution 4mL, 30s is vibrated, is reacted under normal temperature
20min, then centrifuge 10min under 8000rpm rotating speeds, take supernatant, 10mL is settled to ultra-pure water, every group set three it is parallel
With one group of blank control.With the content of sampling Graphite Furnace Atomic Absorption instrument detection wherein cadmium, lead ion, with ICP, (atomic emission spectrum divides
Analysis) detection wherein copper ion content, 1. calculate recovery rate using formula：
2) reaction time extracts the influence of heavy metal in soil to diluted acid
0.2000 ± 0.0005g standard soils or on-site soil are weighed in 50mL centrifuge tubes, adds dilute acid soln 4mL,
30s is vibrated, reaction 10,20,30,40,50,60min at normal temperatures is distinguished, then centrifuges 10min under 8000rpm rotating speeds, take
Supernatant, 10mL is settled to secondary water, every group sets three parallel and one group of blank controls.Detected with sampling Graphite Furnace Atomic Absorption instrument
The wherein content of cadmium, lead ion, with the content of ICP detections wherein copper ion, recovery rate is 1. calculated using formula.
3) reaction temperature extracts the influence of heavy metal in soil to diluted acid
0.2000 ± 0.0005g standard soils or on-site soil are weighed in 50mL centrifuge tubes, adds dilute acid soln 4mL,
30s is vibrated, respectively at reacting 20min at 20,40,60,80 DEG C, then 10min is centrifuged under 8000rpm rotating speeds, takes supernatant,
10mL is settled to secondary water, every group sets three parallel and one group of blank controls.With sampling Graphite Furnace Atomic Absorption instrument detection wherein cadmium,
The content of lead ion, with the content of ICP detections wherein copper ion, recovery rate is 1. calculated using formula.
4) under the conditions of optimum extraction recovery rate checking
Using optimal diluted acid extracting condition, pedotheque is handled by step 1), every group set 6 it is parallel, draw
Recovery rate under the conditions of optimum extraction.
(2) result of the test
1) influence of the dilute acid concentration to heavy metal in soil recovery rate：
1. in standard soil, either extracted using a kind of acid, or extracted with mixed acid, the extraction of cadmium, lead, copper ion
Rate raises with the rise of dilute acid concentration, and increase trend increases and is gradually reduced with concentration；Or during more than finite concentration, extraction
Rate is slightly decreased, and e.g., the extraction to cadmium, the recovery rate of 3M nitric acid and 4M nitric acid is slightly below 2M nitric acid, but recovery rate still exists
90%.
With under concentration, three kinds of diluted acids are dust technology ＞ dilute sulfuric acid ＞ watery hydrochloric acid to the size order of the recovery rate of cadmium ion,
2M salpeter solution is up to 92% to the recovery rate of cadmium ion, hydrochloric acid (58%) and sulfuric acid solution (70%) far above 2M；Together
Under concentration, three kinds of diluted acids are watery hydrochloric acid ＞ dust technology ＞ dilute sulfuric acids to the size order of lead ion recovery rate, 4M hydrochloric acid solution
60% is up to the recovery rate of lead ion, nitric acid (57%) and sulfuric acid (8%) higher than 4M；Extraction of three kinds of diluted acids to copper ion
Rate is not high, and 4M nitric acid, hydrochloric acid, the recovery rate of sulfuric acid are respectively 9%, 11%, 9%.
3M hydrochloric acid, nitric acid presses concentration ratio 1:The dilute acid soln of 1 mixing to the recovery rate of cadmium ion apparently higher than other groups,
Up to 60%；4M hydrochloric acid, nitric acid presses concentration ratio 1:The dilute acid soln of 1 mixing is up to 60% to the recovery rate of lead ion, significantly high
Other two groups of mixing diluted acids under same concentration；The recovery rate of copper ion is still very low, and only up to 10%.Hydrochloric acid, sulfuric acid mix
Conjunction diluted acid is all higher to the recovery rate of cadmium ion, and 2M hydrochloric acid, sulfuric acid press concentration ratio 1:The recovery rate of the dilute acid soln of 3 mixing
Highest, up to 97%；3M hydrochloric acid, sulfuric acid presses concentration ratio 3:The dilute acid soln of 1 mixing reaches to the recovery rate highest of lead ion
30%；The recovery rate of copper ion is still very low, and only 11%.Sulfuric acid, the recovery rate to cadmium ion of nitric acid mixing diluted acid are dense with acid
The change of degree is little, and 0.5M sulfuric acid, nitric acid press concentration ratio 1:Sulphur of the recovery rate of the dilute acid soln of 1 mixing up to 63%, 4M
Acid, nitric acid press concentration ratio 1:The recovery rate highest of the dilute acid soln of 1 mixing, up to 71%；Sulfuric acid, nitric acid mixing diluted acid to lead from
Sub recovery rate is on a declining curve with concentration increase not as the height of other group of diluted acid, and after concentration is more than 2M, 2M sulfuric acid,
Nitric acid presses concentration ratio 1:The recovery rate highest of the dilute acid soln of 3 mixing, close to 20%；The recovery rate of heavy metal copper ion is still not
Height, 10% or so.
The above results are summarized, as shown in table 2：
Two groups of higher dilute acid solns of recovery rate in the standard soil of table 2
Salt sulphur represents hydrochloric acid and sulfuric acid in table, and sal prunella represents hydrochloric acid and nitric acid, similarly hereinafter
2. in spot sampling soil, either being extracted using a kind of acid, or extracted with mixed acid, cadmium, lead, copper ion
Recovery rate raises with the rise of dilute acid concentration, and increase trend increases and is gradually reduced with concentration；Or during more than finite concentration,
Recovery rate is slightly decreased.
4M nitric acid, hydrochloric acid, sulfuric acid is respectively 67% to the recovery rate of cadmium ion, 48%, 69%, 4M nitric acid, hydrochloric acid,
Sulfuric acid is respectively 45% to the recovery rate of lead ion, 33%, 12%, 4M nitric acid, hydrochloric acid, sulfuric acid is to the recovery rate point of copper ion
Wei 7.3%, 10.95%, 10.43%.
4M hydrochloric acid, 4M nitric acid by volume 3:The dilute acid soln of 1 mixing is significantly higher than same to the recovery rate highest of cadmium ion
Other two groups of mixing diluted acids under concentration, close to 60%；4M hydrochloric acid, 4M nitric acid by volume 1:The dilute acid soln of 1 mixing is to lead
The recovery rate highest of ion, the other two groups of mixing diluted acids being significantly higher than under same concentration, up to 50%；4M hydrochloric acid, 4M nitric acid press body
Product ratio 1:1 obtained mixing diluted acid is not high to the recovery rate of copper ion, is below 8%, three does not have significant difference.4M salt
Acid, 4M sulfuric acid by volume 1:The dilute acid soln of 3 mixing is significantly higher than other diluted acids under same concentration to the recovery rate of cadmium ion
Solution, up to 95%, comparatively, hydrochloric acid, sulfuric acid in the dilute acid soln that different volumes ratio mixes to lead, copper recovery rate not
Height, it is below 20%.3M sulfuric acid, 3M nitric acid by volume 3:The dilute acid soln of 1 mixing is significantly higher than with dense to the recovery rate of cadmium
Other lower mixing diluted acids of degree, up to 68%；Comparatively, heavy metal lead, the recovery rate of copper be not high, below 20%.
The above results are summarized, as shown in table 3：
Two groups of higher dilute acid solns of recovery rate in the sampling soil of table 3
2) reaction time extracts the influence of heavy metal in soil to diluted acid
Using result 1) in table 2 and the higher acid solution of recovery rate of table 3 react under normal temperature (20 DEG C) and carry out respectively
Extraction, it is as a result as follows：
1. in standard soil, extending with the reaction time, the recovery rate of three heavy metal species ions gradually rises.With regard to cadmium ion
Say, after 20min, 2M hydrochloric acid, sulfuric acid press concentration ratio 1:The dilute acid soln of 3 mixing does not have to the recovery rate of cadmium ion significantly to be carried
It is high；After 30min, 2M salpeter solution is not significantly increased to the recovery rate of cadmium ion, selects 20,30min respectively as both
Optimum reacting time.For lead ion, 4M hydrochloric acid solution does not change substantially to the recovery rate of lead ion after 40min
Become, concentration ratio 1 is pressed up to 65%, 4M hydrochloric acid, nitric acid:The dilute acid soln of 1 mixing extends to the recovery rate of lead ion with the reaction time
Increase always, up to 70% during 60min, it both is optimal reaction time to select 40,60min respectively.For copper ion, 4M
Hydrochloric acid, nitric acid press concentration ratio 1:The dilute acid soln of 3 mixing becomes larger to the recovery rate of copper ion with the increase in reaction time,
But variation tendency very little, recovery rate is only 15.2% when the reaction time is 60min；Recovery rate of the 4M hydrochloric acid solution to copper ion
Increase with the reaction time and become big, variation tendency also very little, recovery rate is only 14.1% when the reaction time is 60min.
2. in sampling soil, with the extension in reaction time, three heavy metal species cadmiums, lead, the recovery rate of copper gradually rise, but increase
Long amplitude tapers into.For cadmium ion, 4M hydrochloric acid, sulfuric acid press concentration ratio 1 during 20min:The dilute acid soln of 3 mixing is to cadmium
Recovery rate highest, and extend with the reaction time and conspicuousness change no longer occurs；4M hydrochloric acid, sulfuric acid press concentration ratio 1 during 40min:1 is mixed
The dilute acid soln of conjunction extends with the reaction time and conspicuousness change no longer occurs to the recovery rate highest of cadmium, select 20 respectively,
40min is both optimum extraction time.For lead ion, recovery rate of the 4M salpeter solution to lead ion during 60min
Highest, concentration ratio 1 is pressed up to 4M hydrochloric acid, nitric acid during 61%, 50min:The dilute acid soln of 1 mixing is reachable to the recovery rate of lead ion
61%, and no longer significantly increased with time lengthening, the optimum extraction time of 60min, 50min for both is selected respectively.For
For copper ion, its recovery rate is with the extension increasing degree unobvious in reaction time, and 4M hydrochloric acid, sulfuric acid press concentration ratio during 60min
1:3、1:The dilute acid soln of 1 mixing is below 20% to the recovery rate of copper.
3) reaction temperature extracts the influence of heavy metal in soil to diluted acid
Using result 1) in table 2 and the higher acid solution of recovery rate of table 3 carry out extraction 20min respectively, it is as a result as follows：
1. in standard soil, with the rise of reaction temperature, heavy metal cadmium, lead, the recovery rate of copper gradually rise.60℃
When, 2M nitric acid and 2M hydrochloric acid, 2M sulfuric acid by volume 1:The dilute acid soln of 3 mixing is higher to the recovery rate of cadmium ion, nearly
100%, significant changes no longer occur with the increase of reaction temperature, select 60 DEG C of optimum temperatures that cadmium ion is extracted for diluted acid；Lead
The ion extraction rate variation with temperature amplitude is little, at 80 DEG C, 4M hydrochloric acid and 4M hydrochloric acid, 4M nitric acid by volume 1:1 mixing
Dilute acid soln is to the recovery rate highest of lead, and respectively 67% and 72%, select 80 DEG C of optimum temperatures for being diluted acid extraction lead ion；
The recovery rate of copper ion is raised and increased sharply with temperature, at 80 DEG C, 4M hydrochloric acid, 4M sulfuric acid by volume 1:The diluted acid of 3 mixing
Recovery rate highest of the solution with 4M hydrochloric acid to copper ion, respectively 46% and 41%, select 80 DEG C to extract copper ion for diluted acid
Optimum temperature.
2. in sampling soil, with the rise of reaction temperature, the recovery rate of heavy metal gradually rises.For cadmium ion, 4M
Hydrochloric acid, 4M sulfuric acid by volume 1:To the recovery rate of cadmium after 40 DEG C significant changes just no longer occur for the dilute acid soln of 3 mixing；60
4M hydrochloric acid, sulfuric acid press concentration ratio 1 after DEG C:To the recovery rate of cadmium significant changes do not occur for the dilute acid soln of 1 mixing, select 40 respectively
DEG C, 60 DEG C be both optimum extraction temperature.For lead ion, 4M nitric acid and 4M hydrochloric acid, 4M nitric acid by volume 1:1 is mixed
The dilute acid soln of conjunction increases the recovery rate of lead always with the increase of temperature, selects 80 DEG C of optimum extraction temperature for both.Pin
For copper ion, its recovery rate with reaction temperature increase trend it is obvious that selection 80 DEG C be 4M hydrochloric acid, 4M sulfuric acid press volume
Than 1:3、1:The optimum extraction temperature of the dilute acid soln of 1 mixing.
4) under the conditions of optimum extraction recovery rate checking, as a result as shown in table 4：
1. for standard soil：
The dilute acid soln that 1mL 2M hydrochloric acid and 3mL 2M sulfuric acid are mixed to get, 30s is vibrated, soil is extracted at 60 DEG C
20min, the recovery rate of heavy metal cadmium is all more than 95%, and RSD ＜ 4%, reappearance is good, can replace National Standard Method.
The dilute acid soln that 2mL 4M hydrochloric acid and 2mL 4M nitric acid are mixed to get, 30s is vibrated, soil is extracted at 80 DEG C
60min, the recovery rate of heavy metal lead is all more than 70%, and RSD ＜ 4%, reappearance is good, can replace National Standard Method.
The dilute acid soln that 1mL 4M hydrochloric acid and 3mL 4M sulfuric acid are mixed to get, 30s is vibrated, soil is extracted at 80 DEG C
60min, the recovery rate of heavy metal copper is relatively low, and in 50% or so, RSD ＜ 5%, reappearance is good.
2. for sampling soil：
The dilute acid soln that 1mL 4M hydrochloric acid and 3mL 4M sulfuric acid are mixed to get, 30s is vibrated, 20min is reacted at 40 DEG C, weight
The recovery rate of cadmium metal is all more than 95%, and RSD ＜ 4%, reappearance is good, can replace National Standard Method.
The dilute acid soln that 2mL 4M hydrochloric acid and 2mL 4M nitric acid are mixed to get, 30s is vibrated, 50min is reacted at 60 DEG C, weight
The recovery rate of metallic lead is all more than 70%, and RSD ＜ 4%, reappearance is good, can replace National Standard Method.
The dilute acid soln that 1mL 4M hydrochloric acid and 3mL 4M sulfuric acid are mixed to get, 30s is vibrated, 60min is reacted at 80 DEG C, weight
The recovery rate of metallic copper is relatively low, and in 50% or so, RSD ＜ 5%, reappearance is good.
Pedotheque landfill rate under the conditions of the optimum extraction of table 4
4th, the recovery testu of diluted acid extraction
(1) micro-wave digestion condition of pedotheque is as shown in table 5, comprises the following steps that：
1) 0.2000 ± 0.0005g three parts of pedotheque is weighed in specimen cup, and 2mL is separately added into fume hood
HNO3, 2mL HF, 1mL HCl, gently shake up, ensure that sample is all immersed in acid solution, and do blank control.
2) six conjuncted micro-wave diminishing pots are installed, be put into microwave dissolver, set boosting program by table 5 and start.
3) after resolution terminates, six conjuncted counteracting tank natural coolings in fume hood is taken out, are then carried out under the conditions of 150 DEG C
Acid is caught up with, stops catching up with acid when solution residue soybean grain size (about 1mL).After natural cooling, acid solution is transferred to 25mL capacity
In bottle, ultra-pure water is settled to 25mL, with the content of sampling Graphite Furnace Atomic Absorption instrument detection wherein cadmium, lead ion, is detected wherein with ICP
The content of copper ion.
The microwave digestion method of the pedotheque of table 5
| Step | P(MPa) | T(min) | W(w) |
| 1 | 0.3 | 3 | 400 |
| 2 | 0.8 | 3 | 600 |
| 3 | 1.3 | 3 | 600 |
| 4 | 1.8 | 20 | 600 |
(2) optimal diluted acid extracting condition is selected, recovery testu is carried out to sample, verifies the feasible of diluted acid extraction
Property, formula is as follows：
The feasibility of diluted acid extraction is verified by the way of mark-on reclaims.As shown in Table 6, National Standard Method processing standard soil
Heavy metal cadmium, lead, the recovery of standard addition of copper are 97-104% in Gss-7, and the recovery of standard addition of diluted acid extraction is 92%-
102%；Heavy metal cadmium, lead, the recovery of standard addition of copper are 95-99% in National Standard Method processing sampling soil, and diluted acid extraction adds
The mark rate of recovery is 92%-98%.First and last, the rate of recovery of diluted acid extraction is slightly below National Standard Method, but all more than 90%, especially
It is the rate of recovery of heavy metal cadmium, and National Standard Method is suitable, reliable results, but the concentrated acid solution that National Standard Method uses influences on blank value
Larger and needs are completed to operate by large-scale instrument, and Comparatively speaking diluted acid extraction is simple and easy, easy to operate, can replace
National Standard Method.
The recovery of standard addition of the diluted acid extraction of table 6 and National Standard Method
The absorption and elution of the titanium dioxide heavy metal ion of embodiment 2
1st, the pretreatment of titanium dioxide
Titanium dioxide (rutile titania, hydrophilic and oleophilic type, 5-10nm, purity 99.8%, Guangzhou Chemical Reagent Factory) is used before use
5M nitric acid dousing 30min, then centrifuges 10min under 4000rpm, removes supernatant, washed with secondary water, until will be upper
Clear liquid is washed till neutrality, and sediment is filtered, and is then dried at 100 DEG C, and grinding sieving preserves standby at lucifuge drying
With.
2nd, nano-TiO2The absorption and elution of heavy metal ion
1) test procedure
(A) pH is to nano-TiO2The influence of adsorption rate
The μ gmL of 2mL 1 are added in 50mL color-comparison tube-1Cadmium ion standard liquid, then add 40mL diluted acids
Simulated solution (taking 4M hydrochloric acid 100mL, 4M sulfuric acid 300mL, 1L is settled to ultra-pure water) is extracted, with dense ammonia after fully mixing
Water (25%) and watery hydrochloric acid (2M) regulation to required acidity (pH is respectively 1.0,1.5,2.0,2.5,3.0,3.5,4.5,5.5,
6.5th, 7.5,8.5,9.5,10.5, each pH set 3 parallel and blank), ultra-pure water is settled to 50mL, adds 50mg nanometers
TiO2, 10min is vibrated, 20min is stood after centrifuging 8min under 4000rpm, pipettes supernatant (A), deposit is filled with secondary water
Point washing after, add 1mL eluant, eluents (0.1M EDTA2Na solution), vibrate 15min, stand 20min after under 4000rpm from
Heart 8min, pipette supernatant (B), the content of cadmium ion in (A) and (B) determined with ICP-AES, respectively by formula 3. with formula 4.
Calculate adsorption rate and/or the rate of recovery.Heavy metal lead, copper respectively refer to the method progress.
(B) nano-TiO is added2Duration of oscillation afterwards is to nano-TiO2The influence of adsorption rate
Test method basic synchronization is rapid (A), differs only in：Lead ion, cadmium ion, the pH of copper ion solution are adjusted respectively
For 8.5, vibrate 1 respectively, 5,10,15,20min, every group set 3 it is parallel.
(C) adsorbent mass is to nano-TiO2The influence of adsorption rate
Test method basic synchronization is rapid (A), differs only in：Lead ion, cadmium ion, the pH of copper ion solution are adjusted respectively
For 8.5, be separately added into 10,25,50,75,100mg nano-TiO2, every group sets 3 parallel and blank.
(D) selection of eluant strength
Test method basic synchronization is rapid (A), differs only in：Lead ion, cadmium ion, the pH of copper ion solution are adjusted respectively
For 8.5, be separately added into 1mL concentration be respectively 0.0001,0.001,0.01,0.1,0.2M EDTA2Na solution, every group sets 3
An individual parallel and blank.
(E) influence of the duration of oscillation added after eluant, eluent to elution effect
Test method basic synchronization is rapid (A), differs only in：Lead ion, cadmium ion, the pH of copper ion solution are adjusted respectively
For 8.5, add the EDTA2Na solution that 1mL concentration is 0.1M, vibrate 1 respectively, 5,10,15,20min, every group set 3 it is parallel
With a blank.
(F) influence of the eluant, eluent volume to cadmium ion elution efficiency
Test method basic synchronization is rapid (A), differs only in：The pH for adjusting cadmium-ion solution is 8.5, and fixed eluant is dense
Spend for 0.1M, be separately added into 0.5,0.75,1,1.5, nano-TiO of the 2mL EDTA2Na solution after absorption2In precipitation, shake
15min is swung, is centrifuged after standing 20min, every group sets 3 parallel and blank.Cadmium ion in (A) and (B) is determined with ICP-AES
Content, calculate under different volumes EDTA2Na to the rate of recovery of cadmium ion.
(G) nano-TiO2To the measure of cadmium ion static capacity
Test method basic synchronization is rapid (A), differs only in：The pH for adjusting cadmium-ion solution is 8.5.
2) result of the test
(A) pH is to nano-TiO2The influence of adsorption rate
Result of the test shows, nano-TiO2The adsorption rate of heavy metal cadmium, lead, copper etc. increases with the increase of pH value, when
When pH is respectively 4.0,7.5,8.5, the heavy metal ion such as lead, copper, cadmium substantially can be by nano-TiO2Absorption is (i.e. close completely
100%), to ensure that three heavy metal species ions can be by maximum adsorption simultaneously, it is 8.5 to select optimal absorption pH.
(B) duration of oscillation is to nano-TiO2The influence of adsorption rate
Result of the test shows, the nano-TiO when duration of oscillation increases to 5min2The adsorption rate of heavy metal ion has reached
Significant changes no longer occur after to more than 90%, 10min, basically reach complete absorption, most preferably shaking when selecting 10min to adsorb
Swing the time.
(C) adsorbent mass is to nano-TiO2The influence of adsorption rate
Result of the test shows, when sample liquid volume is 50mL, nano-TiO2Quality when being 50mg, the adsorption rate of three is most
Height, it is TiO to select 50mg2The best in quality of absorption.
(D) selection of eluant strength
Result of the test (table 7) shows that EDTA2Na concentration is higher, and the elution effect of heavy metal ion is better, 0.1M's
EDTA2Na to the eluting rate of three up to more than 97%, 0.2M EDTA2Na to not having when the eluting rate and 0.1M of three
Difference, select optimal wash-out concentrations of the 0.1M for EDTA2Na.
The rate of recovery (%) of heavy metal under the different EDTA2Na concentration of table 7
(E) influence of the duration of oscillation to elution effect
Result of the test shows, with the increase of duration of oscillation, heavy metal recovery rate gradually increases, when duration of oscillation increases to
Heavy metal recovery rate has reached nano-TiO after more than 90%, 15min during 10min2Do not have to the rate of recovery of three and significantly carry
Height, optimal duration of oscillation when selection 15min elutes for EDTA2Na.
(F) influence of the eluant, eluent volume to cadmium ion elution efficiency
Result of the test shows, with the increase of volume, EDTA2Na gradually increases the rate of recovery of cadmium ion, works as volume
For 1mL when, the rate of recovery is maximum, can substantially reclaim completely, optimal volume when selecting the 1mL to be eluted for EDTA2Na.Nanometer
TiO2Cadmium ion in 50mL diluted acid extraction simulated solution is adsorbed, can finally be determined by 1mL0.1M EDTA2Na solution
Amount elution, it is seen that nano-TiO250 times are up to the enrichment times of cadmium ion.
(G) nano-TiO2To the measure of cadmium ion static capacity
Static capacity be weigh adsorbent quality a key factor, it is determined that optimum condition under to cadmium ion
Adsorbed, the static capacity that cadmium ion is measured by atomic absorption spectrum is 7.9mgg-1。
The checking of the diluted acid extraction of embodiment 3-colloidal gold immuno-chromatography test paper strip
1st, the determination of colloidal gold immuno-chromatography test paper strip test limit
1) test method：With 0.1molL-1EDTA2Na solution be solvent, by 1gL-1Cadmium ion standard it is molten
Liquid is diluted to 150,300,600,900,1200 μ gL-1Isoconcentration：Take 80 μ L cadmium ion colloidal gold immune chromatography test strips
(having an area of bio tech ltd in Shenzhen three) is detected, and readings, observation result are simultaneously taken pictures immediately in 3-5min, and each concentration repeats
5 times, investigate the test limit of cadmium ion colloidal gold immune chromatography test strips.
2) result of the test：The lower limit of quantitation of colloidal gold immuno-chromatography test paper strip is defined herein：Naked eyes are lower can significant difference inspection
Survey line (T) is more of light color than control line (C), and concentration now is the lower limit of quantitation of test strips.It is test result indicates that dense with cadmium ion
The increase of degree, the color of T lines gradually become shallower as, 150 μ gL-1When T line colors it is substantially more shallow than C line color, 600 μ gL-1When T lines
It is wholly absent, the lower limit of quantitation for determining colloidal gold strip is 150 μ gL-1。
2nd, influence of the salinity to colloidal gold immuno-chromatography test paper strip
1) test method：600 μ gL are prepared by the method in step 1-1Cadmium ion sample solution, add sodium chloride consolidate
Body, it is configured to the sample solution of various salinity：5th, 10,20,30,40,50,60,70 ‰, entered with colloidal gold immuno-chromatography test paper strip
Row detection, 3-5min readings, observe result and take pictures, each concentration is repeated 5 times, and contrasts the change that test strips develop the color under different salinity
Change, investigate influence situation of the salinity to cadmium ion colloidal gold immune chromatography test strips.
2) result of the test：600μg·L-1Influence of the different salinity to colloidal gold strip is as follows under concentration of cadmium ions：Work as salt
The T lines for spending test strips when between 0-50 ‰ do not change significantly；When salinity is higher than 50 ‰, T line colors change, meat
Eye can substantially tell the difference of color, and now carrying out interpretation according to method before then easily causes false negative, so detection liquid
Salinity should control within 50 ‰.
3rd, the specificity of cadmium ion colloidal gold immune chromatography test strips
1) test method：50,150,300,600,1200 μ gL are prepared respectively by the method in step 1-1Cadmium, chromium, copper,
The sample solutions such as mercury, iron, lead, zinc, magnesium, manganese, calcium, are detected with colloid gold chromatographic test paper strip, 3-5min readings, observe result
And take pictures, each concentration is repeated 5 times.
2) result of the test：With the different heavy metal ion of cadmium ion colloidal gold ELISA test strip, 3-5min readings, observation knot
Fruit simultaneously contrasts.The result of table 8 shows that the result under each concentration of the non-cadmium ion of ELISA test strip is all feminine gender, non-false positive, vacation
Feminine gender, illustrate that the specificity of cadmium ion colloidal gold test strips is good.
Influence of the different metal ions of table 8 to colloidal gold strip
Note："-" is negative, "+" weakly positive, and " ++ " is positive
4th, cadmium ion colloidal gold immune chromatography test strips and the coincidence rate of ICP detections are tested
1) test method：Weigh respectively 0.2000 ± 0.0005g standard soil and the pedotheque of actual acquisition in
In 50mL centrifuge tubes, the hydrochloric acid that 1mL concentration is 4M and the sulfuric acid that 3mL concentration is 4M are added, 30s is vibrated, reacts 20min under normal temperature
After centrifuging 10min under 8000rpm, supernatant is taken, is then settled to 10mL with ultra-pure water, 4 DEG C save backup.According to foregoing side
The diluted acid leaching liquor that method is prepared, pH to 8.5 (A) is adjusted with ammoniacal liquor, take 5 respectively, 10,25,50mL sample liquid is in 50mL
In centrifuge tube, 50mg nano-TiOs are added2, 10min is vibrated, 20min is stood after centrifuging 8min under 4000rpm, adds
1mL0.1M EDTA2Na solution, 15min is vibrated, stands 20min after centrifuging 8min under 4000rpm, take supernatant (B),
B liquid is detected with colloidal gold strip and ICP respectively, compares the coincidence rate of two methods.
2) result of the test (table 9)：
Good using the result in colloidal gold strip detection soil and ICP testing result degrees of conformity, false positive is cloudy with vacation
Property rate be 0.Colloidal gold strip is to the lower limit of quantitation of cadmium ion in sample up to 150 μ gL-1, nano-TiO2To cadmium ion most
High enrichment times be 50 times, so colloidal gold strip to the test limit of cadmium ion in actual sample up to 3 μ gL-1, can meet
China《Poisonous and harmful substance is limited the quantity in pollution-free food aquatic products》In it is minimum limitation and《Standard of soil environment quality》Middle one-level
The testing requirements of Soil standard.
The coincidence rate contrast of 9 two kinds of detection methods of table
Note："-" is negative, "+" weakly positive, and " ++ " is positive
Comparative example 1
1) test method：Weigh respectively 0.2000 ± 0.0005g standard soil and the pedotheque of actual acquisition in
In 50mL centrifuge tubes, the hydrochloric acid that 1mL concentration is 4M and the sulfuric acid that 3mL concentration is 4M are added, 30s is vibrated, reacts 20min under normal temperature
After centrifuging 10min under 8000rpm, supernatant is taken, is then settled to 10mL with ultra-pure water, 4 DEG C save backup.According to foregoing side
The diluted acid leaching liquor that method is prepared, pH to 9.5 is adjusted with strong base solution (5M sodium hydroxide solutions, 5M potassium hydroxide solutions)
(A), take 5 respectively, 10,25,50mL sample liquid in 50mL centrifuge tubes, add 50mg nano-TiOs2, 10min is vibrated, is stood
20min adds 1mL0.3M EDTA2Na solution after centrifuging 8min under 4000rpm, vibrates 15min, stand 20min after
8min is centrifuged under 4000rpm, supernatant (B) is taken, B liquid is detected with colloidal gold strip and ICP respectively, compares two kinds of sides
The coincidence rate of method.
2) result of the test：
Detected using colloidal gold strip, inspection does not measure.ICP can be detected effectively, as a result identical with embodiment 3.It can be seen that
With 50mg nano-TiOs2When being enriched with, the detection of colloidal gold strip to the end can be disturbed with highly basic regulation pH value, without shadow
Ring ICP testing result.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. application of the titanium dioxide in the preceding processing of ELISA detection heavy metal in soil ion, it is characterised in that including
Following steps：The attached operation of Adsorption and desorption is carried out to the heavy metal ion in soil extraction using titanium dioxide, is enriched with.
2. titanium dioxide according to claim 1 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that comprise the following steps：
(1) soil is extracted with diluted acid, then removes insoluble substance, obtain solution I；
(2) pH value of solution I is adjusted with ammoniacal liquor, obtains solution II；
(3) add titanium dioxide in solution II to be adsorbed, for the heavy metal ion in adsorbent solution II；
(4) separation of solid and liquid, desorption agent is added in solids and carries out desorption, obtains solution III.
3. titanium dioxide according to claim 1 or 2 is in the preceding processing of ELISA detection heavy metal in soil ion
In application, it is characterised in that：Described heavy metal ion is at least one of cadmium ion, lead ion and copper ion.
4. titanium dioxide according to claim 2 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that：
Soil described in step (1) is the soil below standard of soil environment quality two level；
Diluted acid described in step (1) refers to that concentration is less than 6mol/L acid solution；
Suddenly the diluted acid described in (1) is at least one of hydrochloric acid solution, sulfuric acid solution and salpeter solution；
Ammoniacal liquor described in step (2) is the ammoniacal liquor that concentration is 22~25%；
PH value described in step (2) is 8~9；
Titanium dioxide described in step (3) is the titanium dioxide that average grain diameter is 5-10nm；
Desorption agent described in step (4) is EDETATE SODIUM.
5. titanium dioxide according to claim 4 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that：
Described diluted acid is the mixed acid solution that two kinds of solution in hydrochloric acid solution, sulfuric acid solution and salpeter solution are formed.
6. titanium dioxide according to claim 4 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that：The concentration of described EDETATE SODIUM is 0.01~0.2M.
7. titanium dioxide according to claim 2 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that：
The concrete operations that soil is extracted with diluted acid described in step (1) are as follows：Every 0.2000 ± 0.0005g soil matches 4mL
Dilute acid soln, vibrate 30s, extraction；Wherein：
1) when described heavy metal ion is cadmium ion, dilute acid soln is 2~4M hydrochloric acid and 2~4M sulfuric acid by volume 1:3
Obtained dilute acid soln, the condition of extraction are：20min is reacted at 40~60 DEG C；
2) when described heavy metal ion is lead ion, dilute acid soln is 4M hydrochloric acid and 4M nitric acid by volume 1:1 obtains
Dilute acid soln, the condition of extraction are：50~60min is reacted at 60~80 DEG C；
3) when described heavy metal ion is copper ion, dilute acid soln is 4M hydrochloric acid and 4M sulfuric acid by volume 1:3 obtain
Dilute acid soln, the condition of extraction are：60min is reacted at 80 DEG C.
8. titanium dioxide according to claim 2 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that：The volume of solution I described in step (1) is that every 0.2000 ± 0.0005g soil is soaked with dilute acid soln
After carrying, 10mL is settled to water；
The dosage of titanium dioxide described in step (3) is to match 50mg titanium dioxide per 50mL solution IIs.
9. titanium dioxide according to claim 2 is in the preceding processing of ELISA detection heavy metal in soil ion
Using, it is characterised in that：
The mode of absorption described in step (3) is adsorbed for vibration；
The mode of desorption described in step (4) is vibration desorption.
10. titanium dioxide according to claim 9 is in the preceding processing of ELISA detection heavy metal in soil ion
Application, it is characterised in that：
The condition of described vibration absorption is 5~10min of vibration, stands 20min；
The condition of described vibration desorption is vibration at least 10min.
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