Application scheme of detecting heavy metals in goat milk

Introduction

Goat milk is an important drink in daily life, but in addition to containing calcium and other elements that are beneficial to the human body, it may also contain heavy metal elements such As AS, Pb, Hg and Cd. Especially in the case of frequent safety accidents in dairy products in recent years, the heavy metal content in goat milk has become an important index of dairy product inspection.

The determination of heavy metals in goat milk by atomic absorption spectrometry is sensitive, efficient and accurate. According to the different types and concentrations of metals to be measured, atomic absorption spectra such as graphite furnace, flame and hydride generation should be selected in the experiment, and appropriate pretreatment means should be combined, in which digestion equipment, improvers, digestion reagents and digestion temperature directly affect the accuracy of the determination results. The application, improvement and innovation of atomic absorption spectrometry will certainly drive the supervision of food safety and the improvement of relevant testing standards. Atomic fluorescence spectrometry for the determination of heavy metals As, Hg, Pb, Sb and Se in goat milk has the advantages of sensitivity, efficiency and accuracy. Atomic absorption spectrometer combined with graphite furnace and atomic fluorescence photometer can meet the requirement of detecting heavy metals in goat milk.

Experimental principles of atomic absorption spectrometer

When the electromagnetic radiation radiated from the light source with the characteristic wavelength of the element to be measured passes through the sample vapor generated by the atomization system such as flame or electric heat, it is absorbed by the ground state atoms of the element to be measured in the vapor. Under certain test conditions, the relationship between the absorbance value and the concentration of the element to be measured in the sample conforms to the light absorption law. The digested sample is directly inhaled into the flame, and the atoms formed in the flame absorb the characteristic electromagnetic radiation. The absorbance of the measured sample is compared with that of the standard solution to determine the concentration of the measured element in the sample.

Experimental principle of atomic fluorescence photometer

The pre-treated test liquid enters the atomic fluorescence photometer, and under the reduction of potassium borohydride under acidic conditions, hydrogen arsenide, hydrogen bismuth, hydrogen antimonide, hydrogen selenide gas and mercury atoms are formed. The hydrides form ground state atoms in the argon-hydrogen flame, and the ground state atoms and mercury atoms are excited by the light emitted by the elemental lamp to produce atomic fluorescence. The atomic fluorescence intensity is proportional to the element content in the test solution within a certain range.

Requirements for water and solution preparation for determination of goat milk

When using atomic absorption spectrometry for major analysis, the water used should meet the specifications of secondary water in GB/T6682; For trace analysis, the water used should conform to CB/T 6682 Grade I water specifications. Inorganic acid is a common reagent, it often contains trace metal elements, should be strictly checked before use.

The formulated solution shall meet the following requirements:

a) Suitable solvents should be selected, the prepared solution should not precipitate insoluble matter, and the solution should be stored in a clean and suitable container.
b) The reagents used to prepare the standard solution shall be substances with high purity, accurate composition and chemical formula, and stable properties.
c) The mass concentration of the standard storage solution – generally 1mg/mL, some elements of the standard solution need to add a small amount of inorganic acid, in order to facilitate the preservation of a few days or longer, different elements of its preservation time is different. Store in teflon or polyethylene containers.

Detection basis

Pollutant limits implement the provisions of the “National Food Safety Standard Food Pollutant Limits” (GB2762-2017), The detection methods refer to the Determination of total Arsenic and inorganic Arsenic in Food of National Food Safety Standards (GB5009.9-2014) and the determination of total mercury and organic mercury in Food of National Food Safety Standards (GB5009.17-2014).

Instruments and reagents required

AA-1800H atomic absorption spectrometer (equipped with hollow cathode lamps such as Cu, Cd, Pb, Zn, Ni, Fe, Mn, etc.);
Hydrochloric acid; GR, nitric acid; GR, standard solution required for each element (method certification requires a standard substance starting with GBW or a standard solution starting with GSB); Acetylene gas (99.0%);
AFS-680 atomic fluorescence photometer (hollow cathode lamps such As AS, Hg, Pb, Sb, Se, etc.)
Nitric acid (GR), hydrochloric acid (GR), potassium borohydride (GR), sodium hydroxide (GR), thiourea (AR). Potassium dichromate (AR). Hydroxylamine hydrochloride (AR). Potassium permanganate (AR). Standard liquid required for each element (standard material starting with GBW or standard solution starting with GSB for method certification) High purity argon (99.99%).

Take measuring mercury, for example

Sample pretreatment

Weigh 1.0g~4.0g(accurate to 0.001g) milk or dairy products, place them in a conical bottle of digestion device, add glass beads and 30mL nitric acid, 10mL sulfuric acid for milk, 5mL sulfuric acid for dairy products, and turn the conical bottle to prevent local carbonization. After installing the condensing tube, heat it on low fire and do blank test at the same time.

After the sample is treated, in the acidic medium, arsenic and mercury in the sample are reduced by potassium borohydride (KBH4) into volatile components of arsenic and mercury, which are brought into the atomizer by the carrier gas (argon) and atomized in the hydrogen flame. Under the irradiation of a special hollow cathode lamp, the ground state atoms are excited to a high energy state. When deactivation returns to the ground state, fluorescence of characteristic wavelength is emitted. Its fluorescence intensity is proportional to the element content, and it is more quantitative than the standard series.

Instrument debugging, adjust the instrument to the best working state according to the instruction manual, photomultiplier negative high voltage :240V; Mercury hollow cathode lamp current :30mA; Atomizer temperature :300C; Carrier gas flow rate :500 mL/min; Shielding gas flow rate :1000 mL/ min.

Interference and elimination

The elements that react with potassium borohydride to form hydride in acidic medium will interfere with each other, and the interference can be basically eliminated by adding thiourea + antiblood acid solution. Higher than a certain concentration of copper and other transition metal elements may interfere with the determination, adding thiourea + asthenic acid solution can eliminate most of the interference. Physical interference elimination, the selection of double-layer structure quartz tube atomizer, the inner and outer two layers are argon, the outside form a protective layer to isolate the air, so that the ground state atoms of the element to be measured do not collide with oxygen and nitrogen in the air, reduce the influence of fluorescence quenching on the determination.
Standard solution concentration:100ug/mL Constant volume:100mL
ID Standard liquid added volume(mL) Standard Series concentration (ug/L) Fluorescence value (IF) remark
Standard curve drawing original record table
1   0.000 0.000  
2   0.200 350.419  
3   0.400 642.898  
4   0.600 949.686  
5   0.800 1233.224  
6   1.000 1.000  
a=24.358          b=1524.398           r=0.9996
Detection limit record table
Sample type: Analysis time :2023.03.09
ID Blank fluorescence value Slope b Instrument detection limit Method detection limit
1 17.393      1524.398      0.0076ug/L      0.012ug/L
2 11.379
3 11.325
4 13.718
5 14.473
6 13.348
7 12.993
8 3.698
9 11.536
10 8.570
11 6.421
Recovery record
ID concentration( ug/L ) Constant volume (mL) Measured value (ug/L) Recovery rate (%)
Sample 1 0.450 100 0.465  
Sample 2 0.450 100 0.408  
Sample 1 plus standard solution   100 0.571 106
Sample 2 plus standard solution   100 0.514 106
Recovery rate =(measured content after marking - content to be measured)/ added scalar *100%
National standard of arsenic and mercury concentration limits in dairy products
ID category Pollutant item Concentration limit mg/kg
1 Raw milk, pasteuria milk, sterilized milkMixed milk, fermented milk Hg 0.01
2 As 0.1
3 Milk powder Hg By milk source control
4 As 0.5

Instrument parameters

AFS-680 atomic fluorescence photometer

application scheme of detecting heavy metals in goat milk 1

1. Product introduction

AFS-680 series reduces the excitation Angle of light source and PMT on the basis of the original model, which not only increases the intensity of the received fluorescence signal, but also reduces the background interference, thereby improving the sensitivity of the instrument. The front door of the instrument adopts the semi-transparent corrosion-resistant ABS magnetic structure to avoid the interference of external air, and at the same time, the chemical reaction of the test process can be observed online. When a split-channel signal control module is added to the circuit, no interchannel interference can be guaranteed even if the concentration of the two elements measured in the sample is very different. It is especially suitable for the testing department with large sample quantity and dual channel simultaneous measurement. The innovative software and hardware design ensures the accuracy, safety and ease-of-use of sample analysis, and the maintenance of the instrument is simple and convenient.

2. Instrument characteristics

* Two channels and two elements can be measured at the same time, suitable for trace analysis of arsenic, mercury, selenium, tin, lead, bismuth, antimony, tellurium, germanium, cadmium, zinc, gold and other 12 elements in the sample.
* Hollow core cathode lamp adopts new pulse modulation/constant current drive power supply mode.
* Intermittent flow injection device is adopted. (The sample blank is introduced alternately to avoid cross-contamination of the sample and ensure the measurement accuracy). The carrier gas stabilizing device can not only eliminate the bubbles generated by potassium borohydride online, but also reduce the diffusion effect between reagents and improve the stability of the instrument. Hollow cathode lamp using coding technology, the instrument automatically identifies the hollow cathode lamp, and can monitor the working state and service life of the hollow cathode lamp. The high efficiency gusher flow two-stage chemical gas-liquid reaction separation device is used, the chemical reaction is more complete, the gas-liquid separation effect is better, especially suitable for rock, ore, soil and other complex samples determination.
* With a new type of throttle gas path design, the gas source can be controlled and closed at any time, saving the amount of argon gas and reducing the operating cost of the instrument. The instrument circuit adopts the strong and weak current separation and the latest high concentration module, the steady flow separation gas path generation device, and the new throttle type gas path design, which can control the gas source at any time, save the amount of argon gas and reduce the operating cost of the instrument.
* Using closed quartz atomizer. The instrument uses low temperature furnace atomizer.
* With external filter argon hydrogen flame real-time observation window, can directly observe the flame state in real time.

3. Product characteristics

Instrument function
 
* Single channel, double channel simultaneous detection function.
* Single point, two points, multi-point establish standard curve function.
* With single point, two point standard curve correction function.
* With double channel independent curve correction, double channel independent dilution function.
* Automatic dilution of high concentration samples.
* With continuous flow injection and intermittent injection and other comprehensive injection mode control function.
* With real-time observation test process, on-line adjustment of atomizer three-dimensional parameters.
* With pressure self-balancing liquid waste removal function, no additional pump discharge is required.
* With small background deduction function.
* Friendly software interface, recommend the best instrument test conditions, test data graphical display and playback, statistics and query, a variety of graphics, data page saving, output, backup and printing functions. The floating measurement window increases the amount of information that can be displayed (fluorescence intensity, blank values, etc.).
* Instrument self-test and outage warning protection function.
* It has the function of seamless docking with liquid phase and online digestion unit to realize the morphological analysis of arsenic, mercury, selenium and other elements.

Interference and elimination method
 
(1) Fe, Al, Mg, Ca, K, Na, Cu, Pb, Li, Rb, Cs, Mn, W, Mo, V, Sr, Ti, Sn, Ba, Ti, Cd, Co, Ni, Cr, Ge, Ga, In do not interfere with the determination.
(2) Can form hydride elements As, Sb, Bi is not greater than 500μg/mL generally do not interfere with the determination.
(3) Au<5μg/mL,Ag<25μg/mLwithout interference assay.
(4) When elements such as Au, Ag, Pt and Pd have interference, thiourea can be added to eliminate the interference of precious metals, and the concentration of KBH4 or iron salt can also reduce the interference of the above elements.

Hydride generation system
 
The multifunctional reaction module is adopted, which highly integrates hydrogenation reaction, gas-liquid separation, waste liquid removal and other functions in one. The large number of bubbles produced during testing for inorganic arsenic greatly affects the test results. The multifunctional reaction module can effectively reduce the bubble, simplify the pipeline, reduce the fault point, and directly insert and remove the loading and unloading, which brings convenience to the operation and maintenance of the instrument.
 
Sampling system
 
Using the continuous flow injection method with patented technology, the double peristaltic pump injection greatly improves the test efficiency, which is three times the efficiency of the traditional injection method. It takes just 30 seconds to test a sample three times.

4. Technical index

Sample atomization
 
* Atomizer: hydrogenated shielding atomizer
* Carrier gas/shielding gas: Argon

Sample preparation and introduction
 
* Steam: The use of new intermittent flow without residual steam reaction system, reaction efficiency is higher
* Hydride generator: The use of high-efficiency gusher two-stage chemical gas-liquid reaction separation device, chemical reaction is more complete, gas-liquid separation effect is better, especially suitable for rock, ore, soil and other complex sample determination
* Peristaltic pump: 6-channel peristaltic pump, with two pressure adjustable clamp, software speed regulation
* Exhaust system: With pressure self-balancing liquid waste removal function, no additional pump discharge
 
Optical system
 
* Optical design: Short focal length, non-dispersive, integrated closed optical design
* Double channel: Double channel and two elements can be measured simultaneously
* Light source: hollow cathode lamp using coding technology, the instrument automatically identifies the hollow cathode lamp, and can monitor the working status and service life of the hollow cathode lamp
* Detector: imported photomultiplier tube
* Linear range: greater than three orders of magnitude

Element detection performance
 
* Detection limit (D.L.):As, Se, Pb, Bi, Sb, Te, Sn < 0.01μg/L
Hg, Cd < 0.001μg/L
Ge < 0.05μg/L
Zn < 1.0μg/L
Au < 3.0μg/L
* Precision (RSD):≤ 0.7%. Linear range: greater than three orders of magnitude

Data processing system:

* Can be switched offline/offline at will. Open single/multiple Windows. Single/multi-database option. Management sample correction to further improve measurement accuracy. Unlimited report formatting, measurement data can be switched to EXCEL for modification. Measurement data can be shared through LANtion. Measurement data can be shared through LAN

5. Standard configuration

* 1 host computer
* 2 high strength hollow cathode lamps
* Hydride shielded atomizer 1 set

About us 

Shanghai Macylab Instruments Co., LTD. (hereinafter referred to as Macy), is a high-tech enterprise with independent intellectual property rights, Macy’s entrepreneurial philosophy “science and technology – because you change”, and take this as the enterprise purpose, continuous exploration, bold innovation. Especially in the field of analytical testing instruments, we have continuously developed advanced products, making us a supplier of high-quality instrument resources.

Main spectral instruments: visible spectrophotometer, UV-visible spectrophotometer, atomic absorption spectrometer, atomic fluorescence photometer, ICP-AES, ICP-MS, life science instruments: Ultramicrospectrophotometer, automatic nucleic acid extraction instrument, at present, our products have been widely used in organic chemistry, inorganic chemistry, biochemistry, medicine, environmental protection, metallurgy, petroleum, agriculture and other fields. At the same time, with the rich experience accumulated in product mechanical structure, optical design, electrical application and software development, combined with the latest practical needs of the market, the company will launch a number of new analytical instruments in the near future.

Macy attaches great importance to the introduction and training of talents, the human factor is a core factor for the sustainable development of an enterprise, so Macy fully respects every employee, and truly “build a platform and realize yourself”. To this end, the company has established a strong training team to provide comprehensive training for in-service employees and help employees develop career plans, in order to develop the company and employees together. At the same time, the United States analysis to “family, dedication, learning” professional ethics to inspire employees, each of the United States analysis people are full of enthusiasm and professional skills, the United States presents every instrument, service every customer. The importance and respect for talents make all aspects of the company full of rigor and passion, the new design concept, the demanding requirements of high precision and high parameters, the continuous extension of the application range, all of which are perfectly presented in the advanced nature of our products; From the strict acceptance of raw materials, to the standard assembly line operation of each process flow, and then to the strict factory inspection of the quality inspection department, the harsh requirements of the company on all aspects of production have made the company establish a perfect process quality control system, and the quality of the instrument has been strongly reflected. Therefore, our products are well received by domestic and foreign users.

The headquarters and production base of Macy are located in Shanghai, the marketing center is located in Beijing, and the R & D base is set up in Shanghai, Beijing and Jiangsu. In order to make full use of the intellectual resources around the country, the United States has also carried out in-depth scientific research cooperation with some scientific research institutions at home and abroad, and constantly transform scientific research achievements into productive forces. In order to better serve our customers, Macy has 12 offices in China to customize application solutions that meet your needs and improve the added value of products. In the continuous service of domestic users at the same time, the United States analysis has also established a deep strategic cooperation relationship with more than 20 countries.

With the acceleration of Macy ‘s pace among the ranks of global brand instruments, Macy ‘s requirements for itself continue to improve, and we also hope to get care and support from all walks of life, let us work together to look forward. Technology will change because of you and me.

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