CN108918644A - Method that is a kind of while measuring 19 kinds of constituent contents in feces of livestock and poultry - Google Patents
Method that is a kind of while measuring 19 kinds of constituent contents in feces of livestock and poultry Download PDFInfo
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Abstract
The present invention relates to a kind of methods for measuring 19 kinds of elements in feces of livestock and poultry simultaneously, mainly include the following steps that：(1) sample pre-treatments；(2) icp ms running parameter is optimized；(3) Dynamic Reaction Cell analysis condition is established；(4) with the content of 19 kinds of elements in Dynamic Reaction Cell-icp ms measurement sample solution；(5) interpretation of result.Sample of the present invention uses nitrate acid and hydrofluoric acid-hydrogen peroxide Acid system, by clear up in advance-micro-wave digestion-catches up with acid and clears up sample, by choosing suitable isotope, correction equation and DRC technology etc. to reduce mass spectrum interference, it is online that scandium and rhodium inner mark solution is added to reduce sample matrices interference, this method is fast and convenient, the range of linearity is wide, and detection limit is low, and accuracy is good and precision is high.
Description
Technical field
The invention belongs to environmental analysis technical fields, are related to side that is a kind of while measuring 19 kinds of constituent contents in feces of livestock and poultry
Method is measured in feces of livestock and poultry more particularly, to a kind of using Dynamic Reaction Cell-icp ms simultaneously
The method of Na, Mg, P, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Ba, Pb and Hg constituent content.Sample is suitable
Use range：Feces of livestock and poultry and with feces of livestock and poultry be raw material made of organic fertilizer.
Background technique
Feces of livestock and poultry is a kind of good organic fertilizer raw material, rich in organic matter, nutrient (N, P, K) necessary to plant growth,
The substances such as mineral element, organic acid and carbohydrate, but also contain some harmful substances, such as toxic toxic heavy metal element.The nineties
Since, in order to enhance the disease resistance of livestock and poultry, promote its fast-growth, and pursue economic interests maximization, it is universal in feed
The microelements such as a large amount of copper, zinc, arsenic are added.And livestock and poultry are low to microelement utilization rate, generally 10%-20%, it is big absolutely
Part microelement is excreted with excrement, causes contents of heavy metal elements in excrement higher, if copper, Zn content are up to several
Hundred to thousands of mg/kg.A large amount of harmful heavy metal not only constitutes a threat to soil environment and plant growth in feces of livestock and poultry, may be used also
To be enriched in crop, it is detrimental to health eventually by food chain.
There is element determination common methods in environmental sample：Ultraviolet spectrophotometry (UV), atomic absorption spectrography (AAS) (AAS),
Inductively coupled plasma body method (ICP) and inductively coupled plasma mass spectrometry (ICP-MS) etc..UV and AAS can only be measured every time
A kind of element, cumbersome, time-consuming, inefficiency；Although ICP can measure multiple element simultaneously, detection limit is higher, is not suitable for
The measurement of low Determination of trace element contents.Although ICP-MS has, high sensitivity, analysis speed is fast, the range of linearity is wide, is suitable for a variety of
The advantages of detection of element, but some elements, especially low quality number element ICP-MS analysis test process in vulnerable to compared with
For serious mass spectrum (such as multi atom molecular ion, isobary), and then influence the accuracy of measurement result.As ArC,
HClO etc. pairs52Cr、53Cr disturbs；Kr,ArAr,Ar2H、ArCl、BrH、ArCa、CCl2Deng pair77Se、78Se、80Se、82Se also has serious mass spectrum to interfere, simultaneously because Se ionization energy with higher (9.75eV), ionizes in argon plasma
Degree is lower, therefore its sensitivity is poor, these make the Accurate Determining of Cr and Se in environmental sample usually become problem.
In conclusion establishing, a kind of speed is easy, accurately can sensitively measure the analysis side of feces of livestock and poultry multiple element simultaneously
Method, be highly desirable with it is significant.Currently, still lack it is a kind of can measure simultaneously beneficial element in feces of livestock and poultry (such as P, K,
Se etc.) and poisonous and harmful element (such as Cr, As, Cd, Hg, Pb) detection method.As far as we know, a kind of same with DRC-ICP-MS
When measurement feces of livestock and poultry in the methods of 19 kinds of constituent contents there is not been reported.
Summary of the invention
The technical problem to be solved in the present invention is that overcoming cannot measure in feces of livestock and poultry simultaneously in the prior art beneficial to mine
Prime element (P, K, Mg, Ca, Mn, Fe, Cu, Zn, Se) and toxic heavy metal element (Cr, As, Cd, Hg, Pb), to provide one kind
Accuracy is good, high sensitivity and the method that can measure simultaneously 19 kinds of constituent contents in feces of livestock and poultry.
In order to solve the above-mentioned technical problem,
The present invention provides a kind of methods for measuring 19 kinds of constituent contents in feces of livestock and poultry simultaneously, include the following steps：
(1) sample preparation：It takes suitable feces of livestock and poultry sample to be placed in freeze drier to be freeze-dried, by the sample after freeze-drying
Product are placed in pulverizer and crush, and cross nylon mesh, finally sample is fitted into polytetrafluoroethylene (PTFE) valve bag, spare；
(2) sample pre-treatments：Weighing step, (1) nitric acid, hydrofluoric acid and gold dollar is added in micro-wave diminishing pot in sample obtained
Plain standard solution is placed in graphite resolution instrument and clears up in advance, after pre- resolution finishes cooling, hydrogen peroxide is added, covers micro-wave digestion
Cover is simultaneously tightened, and is put into microwave dissolver after standing 30min and is carried out micro-wave digestion, and micro-wave digestion opens lid after finishing cooling
Micro-wave diminishing pot is returned in graphite resolution instrument again and carries out catching up with acid, washed Specimen eliminating liquid with ultrapure water after catching up with acid by son
It is to be measured into plastics volumetric flask；
(3) with 19 kinds of constituent contents to be measured in Dynamic Reaction Cell-inductively coupled plasma mass spectrometry measurement digestion solution.
Moreover, the pre- resolution is specially：It weighs as the sample that is prepared described in 0.1-0.3g in micro-wave diminishing pot, adds
Enter the nitric acid (HNO of 5.0mL mass fraction 65%3), the hydrofluoric acid (HF) of 0.5mL mass fraction 40% and 100 μ L 1000mg/L
Golden (Au) solution；Graphite resolution instrument is cleared up in advance is specially：95 DEG C are warming up to, 30min is kept；Pre- resolution finishes, and sample solution is cold
But the hydrogen peroxide of 1.0mL mass fraction 30% is added afterwards.
Moreover, the pre- resolution is specially：Step (2) in sample clear up program in advance and be：45min rises to 100 DEG C from room temperature,
45min is kept, reaction is excessively acutely overflowed when slower temperature program purpose is to prevent sample from heating；
Or step (2) in, micro-wave digestion program is：6min rises to 120 DEG C from room temperature, keeps 3min；4min rises from 120 DEG C
To 160 DEG C, 4min is kept；4min rises to 195 DEG C from 160 DEG C, keeps 30min；
Or step (2) in, catch up with the sour program to be：10min rises to 100 DEG C from room temperature, 100 DEG C of holding 50min.
The acid-specific is caught up with to be moreover, described：Graphite digestion device is warming up to 95 DEG C, keeps 30min.
Moreover, step (3) further includes examination criteria blank solution and at least five kinds of various concentration gradients before detecting digestion solution
19 kinds of elemental standards working solutions, and draw canonical plotting according to testing result；Standard blank solution is volume fraction 5%
Nitric acid solution.
Moreover, 19 kinds of elemental standards working solution concentrations：Cr, Co, Ni, As, Se, Sr, Cd, Ba and Pb are 0.5-50
μ g/L, Hg are 0.1-10 μ g/L, and Mn, Fe, Cu and Zn are 50-1000 μ g/L, and Na, Mg, P, K and Ca are 0.2-10mg/L, simultaneously
100 μ L 1000mg/LAu solution are added.
Moreover, being corrected using internal standard to Instrument measuring process in step (3), the interior scandium (Sc) for being designated as 1mg/L
With rhodium (Rh) solution of 50 μ g/L；
Moreover, elemental analysis condition to be measured in step (3)：Under argon gas (Ar) mode standard, Na, Mg, P, K, Ca, Mn,
The mass number that Fe, Co, Ni, Cu, Zn, As, Sr, Cd, Ba, Pb and Hg choose is respectively 21,24,31,39,44,55,57,59,
60,63,66,75,88,114,137,202 and 208, wherein As, Cd and Ba are measured using correction equation；Cr and Se is anti-in dynamic
It answers and is measured under the DRC mode of pond.
Moreover, the correction equation of described step (3) As, Cd and Ba be respectively I (75As)=I (m/z75) -3.127 × I
(77ArCl-(0.873×82Se))、I(114Cd)=I (m/z114) -0.026826 × I (118Sn) and I (138Ba)=I (m/
z138)-0.000901×139La-0.002838×140Ce。
Moreover, the foundation of Dynamic Reaction Cell (DRC) analysis condition of step (3) Cr and Se, mainly passes through optimization
DRC job parameter and CH4Reaction gas flow velocity and quadrupole rod low quality intercept voltage (RPq) value to realize.CH4, purity is greater than
99.999%, flowing rate range is 0.1-1.0mL/min, luffing 0.1mL/min；RPq value optimization range is 0.45-0.80,
Luffing 0.05 chooses corresponding CH finally according to optimum signal-noise ratio (S/M)4Flow velocity and RPq value.
Technical solution of the present invention has the following advantages that：
(1) it is crushed after sample is freeze-dried, sieving, the uniformity of sample is effectively guaranteed；
(2) sample uses HNO3-HF-H2O2Acid system resolution, the system can make feces of livestock and poultry sample adequately be disappeared
Solution, while introducing less reagent interference, and dosage is few adds Au solution that can preferably prevent in sample Hg when clearing up in advance and catching up with acid
Loss, and mitigate its ICP-MS analysis test process in memory effect；
(3) the avoidable sample of pre- resolution reacts excessively violent in micro-wave digestion, improves safety when micro-wave digestion,
And extend the service life of micro-wave diminishing pot；Acid is caught up with to be conducive to mitigate corruption of the acidity to ICP-MS sampling system (such as sample introduction cone)
Erosion；
(4) mass spectrum is effectively inhibited by aggregate measures such as the suitable isotope of selection, correction equation and DRC technologies to do
It disturbs, especially DRC analysis condition is generated according to the element to be measured (Cr and Se) of actual sample solution and its certain content of addition
Optimum signal-noise ratio, and online be added Sc and Rh inner mark solution with reduce sample matrices interference；
(5) this method it is fast and convenient, it is accurate it is sensitive, dynamic linear response range is wide, accuracy is good, can once measure livestock and poultry simultaneously
Excrement and its with Na, Mg in organic fertilizer sample made of raw material, P, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr,
Cd, Ba, Pb and Hg content.
(6) sample of the present invention uses nitrate acid and hydrofluoric acid-hydrogen peroxide Acid system, by clear up in advance-micro-wave digestion-catches up with acid
Sample is cleared up, by choosing suitable isotope, correction equation and DRC technology etc. to reduce mass spectrum interference, scandium is added online
With rhodium inner mark solution with reduce sample matrices interference, this method is fast and convenient, and the range of linearity is wide, and detection limit is low, accuracy it is good with
Precision is high.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.In addition, below
Technical characteristic involved in described different embodiments of the present invention as long as they do not conflict with each other can be mutual
In conjunction with.
19 kinds of constituent contents in a kind of Dynamic Reaction Cell-inductively coupled plasma mass spectrometry measurement feces of livestock and poultry, it is special
Sign is that key step includes：
(1) sample preparation：It takes suitable feces of livestock and poultry sample to be placed in freeze drier to be freeze-dried, by the sample after freeze-drying
Product are placed in pulverizer and crush, and cross nylon mesh, finally sample is fitted into polytetrafluoroethylene (PTFE) valve bag, spare；
(2) sample pre-treatments：Weighing step, (1) nitric acid, hydrofluoric acid and gold dollar is added in micro-wave diminishing pot in sample obtained
Plain standard solution is placed in graphite resolution instrument and clears up in advance, after pre- resolution finishes cooling, hydrogen peroxide is added, covers micro-wave digestion
Cover is simultaneously tightened, and is put into microwave dissolver after standing 30min and is carried out micro-wave digestion, and micro-wave digestion opens lid after finishing cooling
Micro-wave diminishing pot is returned in graphite resolution instrument again and carries out catching up with acid, washed Specimen eliminating liquid with ultrapure water after catching up with acid by son
It is to be measured into plastics volumetric flask；
(3) the optimization of icp ms running parameter：With tuning liquid Optimization Work parameter；
(4) the foundation of Dynamic Reaction Cell analysis condition：Using methane as reaction gas, optimize Dynamic Reaction Cell with the solution containing selenium
Running parameter；A sample solution is chosen as matrix, chromium and selenium is added and is added in the sample solution as matrix, by optimizing first
Alkane flow velocity and quadrupole rod low quality interception voltage value are to inhibit the mass spectrum of chromium and selenium to interfere；
(5) the foundation of elemental analysis condition to be measured：By selecting suitable elemental isotope, correction equation and DRC technology etc.
The mass spectrum interference that aggregate measures generate in test process to inhibit instrument to analyze, and suitable internal standard element is introduced to reduce sample
Product Matrix effects, and then guarantee the accuracy of test result；
(6) configuration standard solution：Volume fraction is used to dilute elemental standards stock solution to be measured step by step for 5% nitric acid solution
In 50mL plastics volumetric flask, make Cr, Co, Ni, As, Se, Sr, Cd, Ba and Pb standard working solution 0.5-50 μ g/L, Hg mark
Quasi- working solution is that 0.1-10 μ g/L, Mn, Fe, Cu and Zn standard working solution is 50-1000 μ g/L, Na, Mg, P, K and Ca mark
Quasi- working solution is 0.2-10mg/L, while certain density Au standard solution is added；The nitric acid solution for being 5% with volume fraction
Sc and Rh stock solution is diluted step by step, and making Sc and Rh inner mark solution ultimate density is respectively 1mg/L and 50 μ g/L；
(7) standard curve is drawn：It is (6) configured using the nitric acid solution that volume fraction is 5% as standard solution blank and step
Standard working solution, (3) the online Sc and Rh inner mark solution that step is added and (6) configures arrives what (5) step was established using step
DRC-ICP-MS operating condition draws the standard curve of element to be measured；
(8) sample measures：According to step (7) elemental standards curve test condition to be measured, determination step (1) testing sample solution.
(9) interpretation of result：Member to be measured in sample is calculated according to the densimeter for weighing weight and detecting sample solution of sample
The content of element：
W is constituent content to be measured in sample, is suitable for Na, Mg, P, K and Ca, unit %；C is to be measured in sample solution
Elemental mass concentration, unit mg/L；C0Elemental mass concentration to be measured in the blank solution of position, unit mg/L；V is sample constant volume
Volume, unit mL；M is that sample weighs quality, unit g；
W' be sample in constituent content to be measured, be suitable for Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Ba, Pb and
Hg, unit mg/kg；C' is mass concentration in sample solution, and unit is μ g/L；C'0Element quality to be measured in the blank solution of position
Concentration, unit are μ g/L；V is sample constant volume, unit mL；M is that sample weighs quality, unit g.
Step (2) in sample clear up program in advance and be：45min rises to 100 DEG C from room temperature, keeps 45min, slower heating journey
Reaction when being to prevent sample from heating of the preface and table of contents is excessively acutely overflowed.
Step (2) in, micro-wave digestion program is：6min rises to 120 DEG C from room temperature, keeps 3min；4min rises to from 120 DEG C
160 DEG C, keep 4min；4min rises to 195 DEG C from 160 DEG C, keeps 30min.
Step (2) in, catch up with the sour program to be：10min rises to 100 DEG C from room temperature, 100 DEG C of holding 50min.
Running parameter after optimization is：Purity of argon is greater than 99.999%, and it is first that tuning liquid contains Mg, In, U, Ce and Ba etc.
Element, concentration are 10 μ g/L, and tuning instrument makes In signal strength be greater than 20000cp/ppb, instrument oxide yield (CeO+/Ce+)<
1.5%, double charge yield (Ba++/Ba+)<2%, ICP-MS running parameter is：ICP RF Power 1190W, NEB 0.86mL/
Min, Lens Voltage 5.50V, Analog Stage Voltage-2200V, Pulse Stage Voltage 1100V.
Step (4) in CH4Purity is greater than 99.999%, optimizes DRC job parameter, DRC job parameter with 10 μ g/L selenium solutions
For：DRC Mode NEB 0.90mL/min, DRC Mode CPV-20V, DRC Mode QRO-5.5V, DRC Mode CRO-
0.5V；Use a sample digestion solution for matrix, the Cr and Se for adding 20 μ g/L are added in Specimen eliminating liquid as matrix, CH4Stream
Fast optimization range is 0-1mL/min, and amplitude 0.1mL/min, RPq optimization range is 0.45-0.80, and amplitude 0.05 is chosen best
Signal-to-noise ratio come establish DRC measurement Cr and Se analysis condition.
Step (5) in, Na, Mg, P, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Cd, Ba, Hg and Pb ICP-MS mark
Measurement in quasi-mode (argon gas), the mass number of selection is respectively 23,24,31,39,43,55,57,59,60,63,66,75,88,
114,138,202 and 207, wherein As, Cd and Ba use correction equation, respectively I (75As)=I (m/z75) -3.127 × I
(77ArCl-(0.873×82Se))、I(114Cd)=I (m/z114) -0.026826 × I (118Sn) and I (138Ba)=I (m/
z138)-0.000901×139La-0.002838×140Ce；Cr and Se are to CH4It is measured for the DRC mode of reaction gas；Na,Mg,
P, K and Ca with45Sc is internal standard, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Ba, Hg and Pb with103Rh is internal standard.
Step (6) in 100 μ L 1000mg/LAu standard solution are also added in elemental standard solution to be measured.
In following embodiments：
Instrument and equipment：Icp ms (Perkinelmer, DRC-e), microwave dissolver (CEM,
MARS6), graphite resolution instrument (Shanghai strives forward conspicuous scientific instrument, XMX-40C), ultrapure water machine (Millipore, Milli-Q
Intergral 5), freeze drier (BIOCOOL, pilot-8E), pulverizer (Tianjin Stettlen, FW80)；All vessel are equal
The soaked overnight in 20% nitric acid, with distilled water repeated flushing six times, finally with ultrapure water it is clean after dry.
Reagent：Nitric acid, hydrofluoric acid, hydrogen peroxide are excellent pure grade or more.
Embodiment 1
(1) preparation and resolution of sample
1) sample preparation：The fresh feces of livestock and poultry sample about 200g or so that acquisition is come, is placed in freeze drier and freezes
Dry, the sample after freeze-drying is placed in pulverizer again to be crushed, and crosses the nylon mesh in the aperture 0.25mm, finally fills the sample prepared
Enter in polytetrafluoroethylene (PTFE) valve bag, it is spare.
2) Specimen eliminating：Weigh the sample prepared about 0.2g (four are accurate to after decimal point) in micro-wave diminishing pot,
The HNO of 5.0mL mass fraction 65% is added3, 0.5mL mass fraction 40% HF and 100 μ L 1000mg/LAu solution.It stands
0.5h is placed in graphite resolution instrument to be cleared up in advance, and pre- program of clearing up is to keep 30min after being warming up to 95 DEG C.Pre- resolution finishes, sample
The hydrogen peroxide that 1.0mL mass fraction 30% is added after product solution is cooling, covers micro-wave diminishing pot lid and tightens, and stands
Micro-wave diminishing pot is put into microwave dissolver after 0.5h and carries out micro-wave digestion, micro-wave digestion program be with 20min to 190 DEG C,
Keep 20min.Micro-wave digestion finishes, and opens lid after sample solution is cooling, and micro-wave diminishing pot is returned to graphite resolution instrument again
In carry out catching up with acid, catch up with sour program be 95 DEG C after keep 30min.After catching up with acid, Specimen eliminating liquid is washed till 50mL with ultrapure water
It is to be measured in plastics volumetric flask.Blank test is done simultaneously.
(2) optimization of ICP-MS running parameter
Optimize ICP-MS running parameter with the tuning liquid that 10 μ g/L contain Mg, In, U, Ce, Ba element, such as ICP RF
Power, NEB, Lens Voltage, Analog Stage Voltage, Pulse Stage Voltage make instrument keep one
A higher sensitivity, while possessing a lower oxide yield and double charge yield, i.e., In intensity is greater than 20000cps/
Ppb, CeO+/Ce+<2%, Ba++/Ba+<2%.ICP-MS running parameter is：ICP RF Power 1190W, NEB 0.86mL/
Min, Lens Voltage 5.50V, Analog Stage Voltage-2200V, Pulse Stage Voltage 1100V.
(1) establishment of elemental analysis condition to be measured
Element to be measured is reduced by selecting many kinds of measures such as suitable elemental isotope, correction equation and DRC technology
Mass spectrum interference, and introduce suitable internal standard element to reduce the Matrix effects of sample, it is specific as follows：
1) under Ar mode standard, measure Na, Mg, P, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Cd, Ba, Pb and
Hg element, the mass number chosen is respectively 21,24,31,39,44,55,57,59,60,63,66,75,88,114,137,202
With 208, wherein As, Cd and Ba are measured using correction equation, correction equation be respectively I (75As)=I (m/z75) -3.127
×I(77ArCl-(0.873×82Se))、I(114Cd)=I (m/z114) -0.026826 × I (118Sn) and I (138Ba)=I (m/
z138)-0.000901×139La-0.002838×140Ce。
2) in CH4Under dynamic response pool mode, Cr and Se is measured：The optimization of DRC job parameter：With CH4For reaction gas, use
Solution containing 10 μ g/L Se optimizes DRC job parameter, as DRC Mode NEB, DRC Mode CPV, DRC Mode QRO and
DRC Mode CRO makes Se under DRC mode keep a higher sensitivity, i.e. Se intensity is greater than 10000cps/ppb.DRC work
It is as parameter：DRC Mode NEB 0.90mL/min, DRC Mode CPV-20V, DRC Mode QRO-5.5V, DRC Mode
CRO-0.5V；2. the foundation of the DRC analysis condition of Cr and Se：A sample solution is chosen as matrix (M), adds the Cr of 20 μ g/L
(S) is added as matrix in the sample solution with Se, adjusts CH4Flow velocity and quadrupole rod low quality intercept voltage (RPq) value, CH4Stream
Fast optimization range is 0-1mL/min, and amplitude 0.1mL/min, RPq optimization range is 0.45-0.80, amplitude 0.05.Final basis
Corresponding CH when optimal signal-to-noise ratio (S/M)4The DRC analytical test strip part of flow velocity and RPq value as Cr and Se.
The DRC analytical test strip part of table 1 Cr and Se
(4) preparation of standard solution：Volume fraction is used to dilute elemental standards deposit to be measured step by step for 5% nitric acid solution
Liquid makes Cr, Co, Ni, As, Se, Sr, Cd, Ba and Pb standard working solution 0.5-50 μ g/L, Hg in 50mL plastics volumetric flask
Standard working solution is that 0.1-10 μ g/L, Mn, Fe, Cu and Zn standard working solution is 50-1000 μ g/L, Na, Mg, P, K and Ca
Standard working solution is 0.2-10mg/L, while the Au solution of 100 μ L1000mg/L is added；The nitric acid for being 5% with volume fraction
Solution dilutes Sc and Rh stock solution step by step, and making Sc and Rh inner mark solution ultimate density is respectively 1mg/L and 50 μ g/L.
(5) standard curve is drawn：Matched using the nitric acid solution that volume fraction is 5% as standard solution blank and step 6)
The standard working solution set, the online Sc and Rh inner mark solution that step 6) configuration is added, the DRC- established using step 3-5)
ICP-MS operating condition draws the standard curve of element to be measured.
(6) sample measures：It is calculated according to the densimeter for weighing weight and detecting sample solution of sample to be measured in sample
The content of element：
W is element (Na, Mg, P, K, Ca) content to be measured in sample, unit %；C is first quality to be measured in sample solution
Measure concentration, unit mg/L；C0Elemental mass concentration to be measured in the blank solution of position, unit mg/L；V is sample constant volume,
Unit is mL；M is that sample weighs quality, unit g.
W' is element (Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Ba, Pb, Hg) content to be measured in sample, single
Position is mg/kg；C' is mass concentration in sample solution, and unit is μ g/L；C'0Elemental mass concentration to be measured in the blank solution of position,
Unit is μ g/L；V is sample constant volume, unit mL；M is that sample weighs quality, unit g.
Interpretation of result：
As known from Table 2,19 kinds of element related coefficients illustrate that it is linear good between 0.9990 and 0.9999；From table 3
It is found that 19 kinds of element recovery rates are 91%-109% in sample, relative standard deviation (RSD) is 1.3%-8.7%.
Due in organic fertilizer P and K content generally with K2O and P2O5Meter, P the and K concentration obtained by this analysis method can be with
It is converted to K2O and P2O5, i.e. W (K2O)=1.077 × W (K), W (P2O5)=2.292 × W (P) after conversion and then can refer to correlation
Standard judges K in organic fertilizer2O and P2O5Whether nutrient content is up to standard.
2 method detection limit of table, quantitative limit, calibration curve equation and its related coefficient
Remarks：Detection limit weighs quality 0.2g, constant volume 50mL meter with sample.
As known from Table 3, nutrient content and beneficial Mineral Elements Content are compared with horn of plenty in feces of livestock and poultry, and content is mostly several hundred
To thousands of mg/kg；But poisonous and harmful heavy metallic content is also higher in feces of livestock and poultry, in addition to Hg, in mg/kg or more, is worth
It draws attention.
3 sample measurement result of table and its rate of recovery
*：Na, Mg, P, K, Ca sample measurements, add value and measurement total value unit are %.
Comparative example 1
This comparative example 1 provides method that is a kind of while measuring 19 kinds of constituent contents in feces of livestock and poultry, the difference is that,
The fresh feces of livestock and poultry sample that acquisition comes is dried in ventilating and cooling place, Acid system is added without Au solution, other concrete operations
With examples detailed above 1, Hg measured value is 0.029mg/kg, RSD 11.6% in sample.
Comparative example 2
This comparative example 2 provides method that is a kind of while measuring 19 kinds of constituent contents in feces of livestock and poultry, and concrete operations are same
Above-described embodiment 1, the difference is that, in the DRC analysis of Cr and Se, CH4The flow velocity of gas is 0.6mL/min, and RPq is
0.75.The results show that the detection of Cr is limited to 0.018mg/kg, Cr measured value is 0.98, relative standard deviation 5.5%.
In conjunction with table 1-3 and above-mentioned comparative example 1 and 2 it is found that the present invention measures 19 kinds of constituent contents in feces of livestock and poultry simultaneously
Method, the range of linearity is wide, detection limit is low, accuracy and precision are good, meets requirement of experiment.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments, and it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of method for measuring 19 kinds of elements in feces of livestock and poultry simultaneously, which is characterized in that include the following steps：
(1) sample preparation：It takes suitable feces of livestock and poultry sample to be placed in freeze drier to be freeze-dried, the sample after freeze-drying is set
It is crushed in pulverizer, crosses nylon mesh, finally sample is fitted into polytetrafluoroethylene (PTFE) valve bag, it is spare；
(2) sample pre-treatments：Weighing step, (1) nitric acid, hydrofluoric acid and gold element mark is added in micro-wave diminishing pot in sample obtained
Quasi- solution is placed in graphite resolution instrument and clears up in advance, after pre- resolution finishes cooling, hydrogen peroxide is added, covers micro-wave digestion cover
Son is simultaneously tightened, and is put into microwave dissolver after standing 30min and is carried out micro-wave digestion, and micro-wave digestion opens lid after finishing cooling,
Micro-wave diminishing pot is returned in graphite resolution instrument again and carries out catching up with acid, caught up with and Specimen eliminating liquid is washed till modeling with ultrapure water after acid
Expect in volumetric flask, it is to be measured；
(3) with 19 kinds of constituent contents to be measured in Dynamic Reaction Cell-inductively coupled plasma mass spectrometry measurement digestion solution.
2. the method according to claim 1, wherein the pre- resolution is specially：It weighs as described in 0.1-0.3g
Nitric acid (the HNO of 5.0mL mass fraction 65% is added in micro-wave diminishing pot in the sample prepared3), 0.5mL mass fraction
40% hydrofluoric acid (HF) and golden (Au) solution of 100 μ L 1000mg/L；Graphite resolution instrument is cleared up in advance is specially：95 DEG C are warming up to,
Keep 30min；Pre- resolution finishes, and the hydrogen peroxide of 1.0mL mass fraction 30% is added after sample solution is cooling.
3. the method according to claim 1, wherein the pre- resolution is specially：Step (2) clear up in advance by middle sample
Program is：45min rises to 100 DEG C from room temperature, keeps 45min, and slower temperature program purpose is anti-when being to prevent sample from heating
It excessively should acutely overflow；
Or step (2) in, micro-wave digestion program is：6min rises to 120 DEG C from room temperature, keeps 3min；4min rises to 160 from 120 DEG C
DEG C, keep 4min；4min rises to 195 DEG C from 160 DEG C, keeps 30min；
Or step (2) in, catch up with the sour program to be：10min rises to 100 DEG C from room temperature, 100 DEG C of holding 50min.
4. according to the method described in claim 3, it is characterized in that, described catch up with the acid-specific to be：Graphite digestion device is warming up to 95 DEG C,
Keep 30min.
5. the method according to claim 1, wherein step (3) further includes examination criteria before detecting digestion solution
19 kinds of elemental standards working solutions of blank solution and at least five kinds of various concentration gradients, and it is bent to draw standard according to testing result
Line chart；Standard blank solution is the nitric acid solution of volume fraction 5%.
6. according to the method described in claim 5, it is characterized in that, 19 kinds of elemental standards working solution concentrations：Cr,Co,
Ni, As, Se, Sr, Cd, Ba and Pb are 0.5-50 μ g/L, and Hg is 0.1-10 μ g/L, and Mn, Fe, Cu and Zn are 50-1000 μ g/L,
Na, Mg, P, K and Ca are 0.2-10mg/L, while 100 μ L 1000mg/LAu solution are added.
7. the method according to claim 1, wherein being carried out using internal standard to Instrument measuring process in step (3)
Correction, rhodium (Rh) solution of the interior scandium (Sc) and 50 μ g/L for being designated as 1mg/L.
8. the method according to claim 1, wherein elemental analysis condition to be measured in step (3)：At argon gas (Ar)
Under mode standard, the mass number that Na, Mg, P, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Cd, Ba, Pb and Hg choose is distinguished
It is 21,24,31,39,44,55,57,59,60,63,66,75,88,114,137,202 and 208, wherein As, Cd and Ba use school
Positive equation measurement；Cr and Se is measured under Dynamic Reaction Cell DRC mode.
9. the method according to claim 1, wherein the correction equation of the step (3) As, Cd and Ba is difference
For I (75As)=I (m/z75) -3.127 × I (77ArCl-(0.873×82Se))、I(114Cd)=I (m/z114) -0.026826
×I(118Sn) and I (138Ba)=I (m/z138) -0.000901 ×139La-0.002838×140Ce。
10. the method according to claim 1, wherein the Dynamic Reaction Cell (DRC) of the step (3) Cr and Se
The foundation of analysis condition mainly passes through optimization DRC job parameter and CH4Reaction gas flow velocity and the interception of quadrupole rod low quality
Voltage (RPq) value is realized.CH4, for purity greater than 99.999%, flowing rate range is 0.1-1.0mL/min, luffing 0.1mL/
min；RPq value optimization range is 0.45-0.80, and luffing 0.05 chooses corresponding CH finally according to optimum signal-noise ratio (S/M)4Stream
Speed and RPq value.
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