WO2017121344A1 - 一种高浓度有机物样品的预处理方法及对重金属含量的测量方法 - Google Patents

一种高浓度有机物样品的预处理方法及对重金属含量的测量方法 Download PDF

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WO2017121344A1
WO2017121344A1 PCT/CN2017/070943 CN2017070943W WO2017121344A1 WO 2017121344 A1 WO2017121344 A1 WO 2017121344A1 CN 2017070943 W CN2017070943 W CN 2017070943W WO 2017121344 A1 WO2017121344 A1 WO 2017121344A1
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sample
solution
acid
organic matter
digestion
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WO2017121344A9 (zh
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刘文涛
刘哲龙
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刘文涛
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4022—Concentrating samples by thermal techniques; Phase changes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4022—Concentrating samples by thermal techniques; Phase changes
    • G01N2001/4027—Concentrating samples by thermal techniques; Phase changes evaporation leaving a concentrated sample

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  • the invention belongs to the technical field of heavy metal detection, in particular to a pretreatment method capable of removing most organic substances in a sample containing (a large amount) of organic substances, and the sample containing (large amount) of organic substances pretreated by the present invention is more than the existing sample.
  • the pretreatment method treats samples containing (large amounts) of organic matter, and the measured (heavy metal) results are (in theory) more accurate.
  • a pretreatment method for an organic sample such as a wet digestion method, a dry ashing method, a dissolution method, and the like, wherein the wet digestion method is classified into sulfuric acid-nitric acid-perchloric acid digestion according to the addition of different acids.
  • the wet digestion method is also the most commonly used sample pretreatment method for pretreatment of high concentration organic matter samples.
  • the purpose of the sample pretreatment method is to remove the interfering (organic matter) substances and concentrate the components to be tested to be less or even undisturbed. If the existing sample pretreatment method has the ability to remove or digest most of the organic matter in the high concentration organic sample, the existing sample pretreatment method is to remove the interfering substance and concentrate the measured component to make it Sample pretreatment methods that are less susceptible or even undisturbed are (in theory) more favorable for the results of heavy metals measured by existing analytical methods.
  • the existing sample pretreatment method does not have the ability to remove or digest most of the organic matter in the high concentration organic sample, only a small portion of the organic matter in the sample can be removed or digested, and the existing sample pretreatment method is not one.
  • a sample pretreatment method that removes interfering substances and concentrates the measured components to be less susceptible or even undisturbed is (in theory) not conducive to more accurate measurement of existing heavy metal results. Therefore, is the existing sample pretreatment method capable of removing most of the organic matter in the high concentration organic matter sample? The ability to remove or digest will involve more accurate results of heavy metal measurements measured by existing analytical methods and is the focus of this discussion.
  • the present invention is to investigate whether the existing pretreatment method has the ability to remove or digest most of the organic matter in a high concentration organic sample by discussing the blood sample pretreatment method in the existing blood Pb standard analysis method. If the existing sample pretreatment method has the ability to remove or digest most of the organic matter in the blood sample, it can be inferred that the existing pretreatment method has the ability to remove or digest most of the organic matter in the high concentration organic sample. There will be more accurate results for heavy metals measured using existing analytical methods, so it is not meaningful to discuss existing pretreatment methods or measurements for high concentration organic samples.
  • the existing sample pretreatment method does not have the ability to remove or digest most of the organic matter in the blood sample, it can be inferred that the existing pretreatment method may not have the ability to remove or digest most of the organic matter in the high concentration organic sample.
  • the ability to do this without using the existing analytical methods to measure heavy metal results is more accurate, so study a method of pretreatment that has the ability to remove or digest most of the organic matter in the blood sample, in addition to facilitating the measurement of heavy metals in blood samples. Accuracy is of great significance, and it is also beneficial to remove or digest most of the organic matter in high-concentration organic matter samples, which is more accurate and more important for measuring heavy metals in high-concentration organic matter samples.
  • the question is whether the existing pretreatment method for blood Pb samples has the ability to remove or digest most of the organic matter in the blood sample.
  • Xingwang Company smashed the canteen and dormitory.
  • Xingwang Company smashed the canteen and dormitory.
  • the company's main business is recycled lead.
  • the enterprise said: The company has not yet put into production, there is no possibility of pollution, and various environmental protection measures are implemented step by step. But the villagers do not believe because of doubt or to prevent possible lead poisoning in the future. Why is the factory not put into production, nor can it be polluted, and the factory is beaten? Because there were two incidents of lead poisoning in children in Xiangyang County, in 2010, more than 200 children in a village near Zhimin Community in Shuyang County exceeded the standard.
  • Non-standard analysis methods are usually published in various journals, magazines, books, etc., without the scientifically certified analysis methods of experts from relevant national departments.
  • Non-standard analytical methods usually only have certain academic value and reference value, but they are less comparable and less authoritative.
  • the standard analysis method is divided into the national standard analysis method and the industry standard analysis method in China.
  • the standard analysis method is an in-depth study by experts of relevant state departments, and multiple laboratory scientific argument analysis methods have good comparability. , accuracy and authority, only the standard analysis method is the legal arbitration method for environmental pollution disputes.
  • the above analysis method belongs to the industry (standard) analysis method and does not belong to the national standard analysis method.
  • the industry (standard) analysis method is equivalent to the national standard analysis method, and therefore can also be used as a statutory arbitration method for environmental pollution disputes.
  • As a statutory arbitration method for environmental pollution disputes it will involve the interests of villagers, children, and enterprises in the blood lead pollution incident, as well as the dismissal of officials, etc., which is a very serious legal issue, which requires the results of the measurement to be More accurate and reliable is worthy of scrutiny, the question is whether the standard analysis method of blood Pb measured in China has (more) accurately inferred the ability of children's blood Pb to exceed the standard?
  • the standard of Pb in children's blood is that the Pb content in the blood sample is less than 100 ⁇ g/L.
  • the Pb content in the blood sample is more than 100 ⁇ g/L, and the Pb exceeds the standard, that is, the Pb of the child exceeds the standard.
  • the sample is pretreated by taking 50 ⁇ L of the earlobe blood sample or venous blood sample, placing it in a 10 mL beaker containing 4 mL of water, and adding 50 ⁇ g of chlorinated high mercury solution. Then, 1 mL of 1+9 hydrochloric acid was used, and the blood sample was diluted 100 times, and then directly measured by a differential potentiometric dissolution method. Obviously this is a sample pretreatment method (also known as simple dilution method) in which the blood sample is simply diluted (100 times). This simple diluted sample pretreatment method does not theoretically have the ability to remove interfering substances.
  • this analysis method Pb below 0.9 ⁇ g / L concentration, can not measure the Pb elution peak, only when it is equal to or greater than 0.9 ⁇ g / L, only the dissolution peak of Pb can be measured, we use only one equals Or greater than 0.9 ⁇ g / L, can only measure the standard analytical method of Pb elution peak, to measure the concentration of 1 ⁇ g / L (Pb) of the sample, but also take into account a lot of organic interference, reagent blanks and other interference, theoretically achieved The possibility of accurately measuring 1 ⁇ g/L of Pb is small or impossible.
  • the WS/T 21-1996 differential potentiometric stripping method for measuring lead in blood samples for measuring Pb in blood samples has serious defects in theory. Theoretically, it does not have a relatively accurate ability to infer whether children's blood Pb exceeds the standard. If we adopt the technical solution of the differential potential dissolution determination method of lead in blood of WS/T 21-1996, artificial blood lead pollution event may occur.
  • the sample was pretreated by taking 40 ⁇ L of the blood sample with a micro-pump and placing it in a lid with 0.32 mL of Triton X-100 solution. In the tube, shake it thoroughly, then add 40 ⁇ L of 1% (V/V) nitric acid solution to mix, dilute the blood sample by 10 times, and then measure with a graphite furnace atomic absorption spectrometer. This is obviously a blood sample.
  • a simple dilution (10 times) sample pretreatment method also does not have the ability to remove interfering substances and concentrate the components to be tested to be less susceptible or even undisturbed.
  • this simple dilution of the sample pretreatment method is also not conducive to the more accurate measurement of Pb in blood samples by graphite furnace atomic absorption spectrometry of WS/T 20-1996 lead in blood. Due to this simple dilution of the sample pretreatment method, it is impossible to eliminate the interference of the reagent blank relatively high, a large amount of organic matter, salt, etc., so in the actual measurement, a large number of experimental results show that the same sample Different analysts and different analytical instruments often have large differences in measurement results. Therefore, analysts generally report that this analysis method is difficult to master, and the factors affecting it are too many, and the measurement results are also very unsatisfactory. Therefore, we use a sample pretreatment method with premature defects in the sample, and a standard analysis method with many problems in the actual measurement to delineate whether the blood Pb of the child in the blood lead pollution event exceeds the standard, which is debatable.
  • the sample is pretreated by taking 0.15 mL of blood, adding 0.6 mL of 5% (V/V) nitric acid solution, and centrifuging. 10 ⁇ g of the supernatant was directly measured by a graphite furnace atomic absorption spectrometer.
  • the sample pretreatment method is still a simple dilution of the sample pretreatment method, the result or phenomenon measured by the graphite furnace atomic absorption spectrometry method of the lead in blood in WS/T 20-1996 due to the measurement results and phenomena in the actual measurement. Basically the same, so we will not explain in detail.
  • Beads are first mixed with nitric acid and sulfuric acid, and heated slowly by electric heating plate, sand bath, aluminum block or graphite block heater. After a large amount of foam is dispersed, the temperature is appropriately increased, and a large amount of organic components are removed to make the solution clear. Add a small amount of perchloric acid, continue to heat until white smoke, the sample is white crystal, let cool and dissolve in water and dilute to a certain volume.”
  • This is a wet digestion method specifically for blood sample or urine sample pretreatment, In theory, there is a method to remove interfering substances, concentrate the components to be tested, and make them less susceptible to or even undisturbed. But why has China not used this professional sample pretreatment method in the past few decades? Because of the blood sample pretreated by wet digestion, the interference is too large, resulting in a very unsatisfactory measurement of heavy metals.
  • the sample is now dried in a crucible and then Transfer the crucible to a high temperature furnace (muffle furnace) at 700-800 ° C (Pb should be controlled below 400 ° C) for about 12 h, so that the organic components are completely destroyed, the sample is grayish white powder, and then dissolved with dilute acid and injected.”
  • a sample pretreatment method with the ability to remove interfering substances and concentrate the components to be tested to be less susceptible or even undisturbed.
  • the pretreatment method of this sample theoretically has a low reagent blank and a small interference, but the experimental results show that the operation of turning the blood sample into an off-white powder is difficult to control, and often becomes charred carbonization, which is charred and carbonized.
  • the microwave digestion method adopts a sample pretreatment method of high temperature, high pressure and strong acid medium, and is a blood sample to be digested ( Or soil, high concentration of organic matter samples), add appropriate amount of nitric acid (acid can also use other commonly used strong oxidizing acids such as sulfuric acid, hydrochloric acid), together in a closed tank, high temperature, high pressure, strong acid medium by microwave heating
  • the pretreatment method of lower digestion which adopts high temperature, high pressure and strong acid medium, has strong digestion ability, is simple and fast, and greatly improves work efficiency, and is widely used in soil, high concentration organic matter and the like.
  • the pretreatment method of the sample is to pretreat the blood sample by a simple dilution method with serious defects under the premise that there is no way, which is why only one of the existing standard analysis methods can be used.
  • the organic matter is cleaved into organic matter with a smaller molecular weight, but the possibility of cracking into an inorganic salt is not high. These unfavorable factors will cause the existing pretreatment method to be unfavorable for digesting the larger molecular weight organic matter in the blood sample into inorganic matter.
  • the pretreated sample will contain a relatively high concentration of organic matter of a larger or smaller molecule, which will cause serious interference to the measurement, and the measurement of the heavy metal result is unsatisfactory. Obviously, we have a problem in the technical route of destroying or digesting the larger molecular weight organic matter in the blood sample into an inorganic salt.
  • the technical route of the present invention is that if we cannot measure the larger molecular weight (normal temperature is liquid or solid) in the blood sample. Organic matter is destroyed or digested, but we can take advantage of the larger molecular weight organic matter in the blood sample, which is liquid at higher temperatures, and is a liquid or solid physical property at room temperature (room temperature or 0 ° C), which is common in chemical industrial production.
  • a method similar to fractional distillation in which a large molecular weight solid or liquid organic substance in a blood sample is precipitated from a blood sample by a heating condition and left in a sample solution, and then the sample is cooled to a normal temperature, and then an appropriate amount of water is boiled.
  • the (solid or liquid) organic matter precipitated from the blood sample is sufficiently or further separated or separated from the solution (water). Since the organic matter is insoluble in the solution (water), the larger molecular weight organic substance floats in a solid form. The surface of the solution, the smaller molecule The amount of liquid organic matter will form oil beads and float on the surface layer of the solution.
  • the technical solution adopted by the present invention has the ability to remove most of the organic matter in the blood sample. Therefore, the technical solution of the present invention is to remove the interference substance and concentrate the measured component.
  • a sample pretreatment method that makes it less susceptible to even interference, which will be very important for us to more accurately measure Pb in high blood samples or heavy metals in high concentration organic samples.
  • a pretreatment method for a high concentration organic matter sample which is characterized in that it is a separation and digestion method, specifically, adding an acid solution to the sample and uniformly mixing to obtain a pretreatment Mixing liquid, the volume of the acid solution is 0.5-100 times of the sample volume, heating and boiling, controlling the heating temperature to prevent the sample from being carbonized by burning; the preliminary digestion is completed by heating the boiling water and the acid, and after the water is completely evaporated, Continue to digest by heating to boil acid to acid fumes.
  • the heating is stopped, and the second digestion is completed; in the sample of the two-step digestion process
  • the organic matter is precipitated from the sample and remains in the sample solution, cooled, and water or acid solution is added to continue boiling.
  • the volume of the water or acid solution is 0.5-100 times the volume of the sample; then cooled to room temperature, and the organic matter precipitated in the sample is
  • the solid or liquid form floats on the surface of the solution, and then subjected to solid-liquid separation or liquid-liquid separation to obtain a separated and digested solution.
  • the present invention provides a pretreatment method capable of removing most of the organic matter in a (large amount) organic sample, and the (large amount) organic matter sample pretreated by the present invention is more than the existing sample.
  • the pretreatment method treats samples containing (large amounts) of organic matter, and the measured (heavy metal) results are (in theory) more accurate.
  • the following two digestion methods can be used for pretreatment of blood samples: one is to separate first, and the liquid or solid organic matter in the pretreated sample is first separated from the (water) solution, and then the existing microwave digestion method or wet digestion is used. The method is further digested by the pretreatment such as the method, and the first separation is followed by the existing digestion and other measures, and the advantage is that the efficiency of digestion can be improved.
  • the invention adopts the second method, and the sample is placed in a glass test tube and an appropriate amount of the acid solution is uniformly mixed to obtain a pretreatment mixture;
  • the acid solution is a nitric acid, hydrochloric acid, sulfuric acid or perchloric acid having a mass concentration of 0.1-100%. , acetic acid, phosphoric acid, hydrofluoric acid or a mixed acid thereof.
  • Glass tubes are recommended for separate vessels. Heating can be alcohol lamps, aluminum or graphite block heaters, microwaves, etc.
  • Heating and boiling using the process of heating boiling water and acid to complete the preliminary digestion, after the water is completely evaporated, and then using the heating to boil the acid to acid fumes to continue digestion, when the volume of the mixture to be tested is 1-5 times the volume of the sample
  • the heating is stopped, and the second digestion is completed.
  • the organic matter in the sample is precipitated from the sample and remains in the sample solution, cooled, and water or an acid solution is added to continue boiling, at this time, the water or the acid solution.
  • the volume is 2-100 times the volume of the sample; then cooled to room temperature, the organic matter precipitated from the sample floats on the surface of the solution in solid or liquid form, and then subjected to solid-liquid separation or liquid (organic) solution (solution) separation. , the solution after separation and digestion is obtained.
  • the pretreatment mixture is heated and boiled, and the preliminary digestion and the second digestion are completed, cooling, adding water or an acid solution to continue boiling, repeating the preliminary digestion and the second digestion process, either once or repeatedly. Multiple times, to increase the efficiency of converting a relatively large molecular weight solid or liquid organic material in a blood sample into a liquid organic material in a pretreated solution.
  • the appropriate amount of ultrapure water is added after cooling, and the purpose of boiling is to thoroughly mix the heavy metals and organic substances in the digested sample with the aqueous solution again, and the sample to be heated is cooled to room temperature (room temperature or 0 ° C), from the pre-
  • room temperature room temperature or 0 ° C
  • the large molecular weight solid or liquid organic matter precipitated in the sample is floated on the surface of the solution in the form of solid or liquid organic matter, and then solid-liquid separation and liquid-liquid separation are performed, and the organic matter is separated from the solution to realize blood.
  • the purpose of separating a large amount of organic matter from the solution in the sample is to indirectly achieve the purpose of digesting most of the organic matter in the blood sample.
  • the method for digesting while separating, re-digesting or separating the above is called a separation and digestion method.
  • This separation and digestion method theoretically has the ability to remove interfering substances and concentrate the components to be tested to be less susceptible or even undisturbed.
  • a pretreatment method such as microwave digestion
  • the blood sample is pretreated by using a suitable temperature, a suitable pressure, acid addition or no acid, and then a large amount of liquid is obtained by standing or centrifuging. Separation of the organic matter from the solution is also within the scope of the infringement of the present invention as long as the (large amount) of the organic substance is separated from the solution.
  • the problem is whether the larger molecular weight solid or liquid organic matter in the blood sample can be separated by the separation and digestion method of the present invention.
  • the separation method of the larger molecular weight solid or liquid organic substance in the blood sample, the separation and digestion method of the present invention specifically takes 1.5 mL of the blood sample in a glass test tube (about 25 mL), and adds 3 mL of a nitric acid solution having a mass concentration of 1:1.
  • the blood sample is further subjected to a certain degree of digestion while being separated; the sample to be heated is boiled When the remaining 2mL or so, the distance between the alcohol lamp and the heated glass test tube is appropriately controlled to continue the digestion of the blood sample.
  • the sample to be pretreated and digested remains about 1 mL, the heating is stopped, and the sample is prevented from being dried and carbonized.
  • the sample to be pretreated and digested remains about 1 mL, the heating is stopped, and the sample is prevented from being dried and carbonized.
  • Add an appropriate amount of 1:1 nitric acid solution to the sample and heat the boiling process. It can be one or more times.
  • After the sample to be pretreated is cooled, add about 5 mL of ultrapure water and continue to boil for about 2 minutes. The purpose is to digest. The heavy metals, organic matter, etc.
  • the liquid organic matter in the pretreatment sample will continue to float on the surface of the solution in the form of solid or liquid organic matter, and the liquid organic matter can be sucked out by the suction pipe to achieve the purpose of separation, as for the solid organic matter floating on the surface layer of the solution.
  • the pretreatment of the blood sample usually only separates the solid organic matter, and the solid organic matter (fat) floating on the surface layer of the solution proves that the separation and digestion method of the present invention can take larger molecules in the blood sample.
  • the molecular weight (solid) organic matter is separated from the solution, and the concentration of a large amount of large molecular weight organic matter in the blood sample is greatly reduced, thereby achieving the purpose of separating a large amount of organic matter from the solution in the blood sample, and indirectly realizing digestion of most of the organic matter in the blood sample. The purpose of this will be more accurate in the results of existing analytical methods for measuring heavy metals.
  • the separation and digestion method of the present patent is a method for pretreating a blood sample with the ability to remove interfering substances (organic matter, salt) and concentrate the component to be tested to be less susceptible or even undisturbed. (Theoretically) This will facilitate the existing analytical methods to more accurately infer whether the child's blood Pb is over-labeled.
  • the problem is that the blood sample is pretreated by the separation and digestion method of the present invention, and the existing analytical method is used to measure the blood sample. Pb, can you have a more accurate estimate of whether children's blood Pb exceeds the standard?
  • An experiment for measuring Pb in a blood sample; measuring the blood sample (Pb) pretreated by the separation and digestion method in Example 1, comprises the following steps: firstly washing the electrolytic cell, taking about 20 mL of acidic ultrapure water or other clean acidic water, washing the electrolytic cell several times by stirring, and after washing the electrolytic cell, using an electronic balance to call the electrolytic cell Re-record the weight of the electrolytic cell.
  • the liquid sample prepared by the separation and digestion method described in Example 1 has been separated from the liquid or solid bulk organic matter, and the analytical method adopted by the present invention is not used because the separated solid bulk or liquid organic oil is insoluble in the acidic solution.
  • the measurement causes interference, so the separation or separation of the liquid or solid bulk organic matter in the solution can be measured.
  • the easiest way is to use a pipette to suck out the liquid organic matter. It should be noted that sometimes the blood sample is pretreated and no obvious liquid organic matter can be observed, so this step can be omitted. If you want to simply filter the solid block organic oil in the solution, the simplest method is to fold a funnel into a funnel, place a small hole in the bottom of the filter funnel, and place the paper funnel above the electrolytic cell. The blood samples pretreated by the separation and digestion method described in Example 1 were all poured into a paper funnel, and the solid block-like organic matter was left in the paper funnel, and the digested solution leaked into the electrolytic cell through the small hole of the paper funnel.
  • all the blood samples pretreated by the separation and digestion method described in Embodiment 1 can be transferred to the electrolytic cell, and the glass test tube is washed twice with a small amount of ultrapure water, and Transfer the rinsed solution to the electrolytic cell. It is necessary to pay attention to the two rinses plus the digested solution. The total weight added is less than 15g. Then add the appropriate amount of ultrapure water to control the weight of the electrolytic cell to 15g. This is equivalent to diluting the digested blood sample to 15 mL, which is 10 times diluted. We can continue to measure by either filtering or not filtering the solid block organic oil in the solution.
  • Zn-ion reagents if a very high Zn dissolution peak or a full-scale Zn dissolution peak can be measured in the measured dissolution spectrum, we It is considered that the amount of the reagent to which Zn ions are added is appropriate, and if there is no high Zn elution peak or a full-scale Zn elution peak, an appropriate amount of the Zn ion reagent is continuously added.
  • the blood sample pretreated by the separation and digestion method of the present invention can be directly measured, and the stable repeated Pb elution peak can be measured, and the stable repeated Pb elution peak can be measured, and it is possible to accurately measure the Pb (concentration in the bleeding sample). ).
  • After adding 60 ⁇ L of 4 mg/l Pb standard solution to the sample to be tested it is necessary to add 60 ⁇ L of 4 mg/l Pb standard solution to the sample to be tested, which is equivalent to adding 16 ⁇ g/L of Pb to the sample to be tested.
  • the dissolution spectrum is shown in Figure 2-2.
  • the Pb elution peak is obviously increased.
  • the peak heights of the Pb dissolution peaks are 16.90 and 16.53, respectively.
  • the formula for calculating the concentration according to the anodic stripping voltammetry is:
  • h spiked before - a high value represents a peak eluted before the spiked.
  • V standard - that is the volume of standard solution was added.
  • C mark - indicates the concentration of the standard solution.
  • V sample represents the volume of the sample.
  • the calculated concentration was 7.61 ⁇ g/L.
  • the amount of the standard addition is required to be controlled within 3 times of the concentration of the sample to be tested.
  • adding 60 ⁇ L of 4 mg/l Pb standard solution to the sample to be tested is equivalent to adding 16 ⁇ g/L of Pb to the sample to be tested, and the amount of spiked is within 3 times.
  • the recovery rate continue After adding 4 mg/l of Pb standard solution to the test sample, 100 ⁇ L of the Pb standard solution was continued, and the scanning dissolution was continued.
  • the dissolution spectrum was shown in Fig. 2-3, and the Pb elution peak continued to increase.
  • the same continuous measurement of Pb dissolution peak height was 36.65 and 35.60, respectively.
  • the calculated concentration was 22.96 ⁇ g/L. Then calculate the formula according to the recovery rate:
  • the calculated recovery was 95.9%. With good recovery, it can be inferred that the Pb in the blood sample measured by the analytical conditions of the analytical method of the present invention is accurate, and a good recovery rate can be inferred, and the measurement result is accurate.
  • the abscissa is the voltage unit is volt (V)
  • the ordinate is the peak current, expressed by the peak height value, due to the following dissolution spectrum and
  • the abscissa and the ordinate of Fig. 2-1 are exactly the same, and therefore the abscissa and the ordinate are not described in detail in the following elution spectrum, and it is hereby explained.
  • the reagent blank test using the existing washing method, the electrolytic cell is washed clean, the reagent blank sample pretreated with the same conditions as the blood sample is adjusted to a volume of 15 mL, and then transferred to the electrolytic cell, and 300 ⁇ L of 5% ZnCl is added.
  • the solution and instrument parameters were the same as in Example 2.
  • the enrichment time was 60 seconds.
  • the measurement was started, and the dissolution was carried out.
  • the dissolution spectrum is shown in Figure 3-1. A high Zn dissolution peak appeared. This is the concentration of 300 ⁇ L added to the sample to be tested.
  • the peak heights of the two consecutive Pb elution peaks were 4.81 and 5.03, respectively.
  • the concentration of the reagent blank 20 ⁇ L of the 2 mg/l Pb standard solution was added to the sample to be measured, and the measurement was continued. Scanning and elution, the dissolution spectrum is shown in Fig. 3-2, and the Pb elution peak is obviously increased. The peak heights of the Pb dissolution peaks are also measured continuously for 14.75 and 14.90, respectively.
  • the concentration of the reagent blank was calculated to be 1.33 ⁇ g/L according to the formula for calculating the concentration by anodic stripping voltammetry.
  • the Pb in the reagent blank was 1.36 ⁇ g/L
  • the Pb in the reagent blank was 1.33 ⁇ g/L.
  • the content of Pb in the blood sample was more than 5 times larger than the reagent blank. A relatively low value is more accurate for the measurement results. Because the Pb7.61 ⁇ g/L in the blood sample pretreated by the separation and digestion method measured in this experiment is verified by the recovery rate, the Pb 7.61 ⁇ g/L in the blood sample pretreated by the separation and digestion method is accurate, and the reagent is subtracted. A blank of 1.33 ⁇ g/L, multiplied by a multiple of 10 times the dilution, it can be inferred that the Pb in the blood sample is 62.8 ⁇ g/L.
  • an analytical method has a relatively accurate ability to infer or measure 62.8 ⁇ g/L, theoretically, it should have a more accurate ability to infer 100 ⁇ g/L Pb. Therefore, the analytical method adopted by the present invention theoretically has a more accurate ability to infer whether the child's blood Pb exceeds the standard. It should be noted that we use the blood sample measured by the analytical conditions of the analytical method of the present invention. If the blood sample pretreated by the separation and digestion method of the present invention is repeatedly measured, the inner wall, the stir bar and the electrode of the electrolytic cell will adhere to a large amount of pale yellow solid.
  • the analytical method of the present invention is compared with the existing standard analytical method, 1) in terms of pretreatment of the sample: the present invention adopts a sample pretreatment method having separation (organic matter) and digestion ability, which is a kind It has a technical solution to remove (most of the organic matter) interfering substances and to concentrate the components to be tested, which is less subject to undisturbed sample pretreatment.
  • the existing blood sample pretreatment method adopts a simple dilution sample pretreatment method, which is a technical scheme for diluting the interfering substance and diluting the sample pretreatment of the sample.
  • the present invention employs a measurement method that is close to no interference
  • the existing analysis method employs a measurement method in which a large amount of organic matter is present.
  • the analytical method of the present invention is theoretically more accurate than the blood Pb results measured by the existing standard analytical methods.
  • This is also the first time in the world to measure Pb in blood samples.
  • the pretreatment of the sample uses a sample with the removal of (most organic matter) interfering substances, which concentrates the measured components to make them less susceptible or even undisturbed.
  • the treatment method measuring the Pb in the blood sample by measuring the measurement method without any interference, is very important for more accurate measurement of Pb in the blood sample at home and abroad.
  • the pretreated blood sample is fixed to 10mL, equivalent Dilute the sample 5 times, if the Pb in the blood sample is 100 ⁇ g / L, so theoretically the Pb concentration in the blood sample is 20 ⁇ g / L, because the pretreatment method of the present invention is a kind of removal of interference substances, the concentration is A pretreatment method that measures the components to make them less susceptible to or even undisturbed.
  • the separation and digestion method of the present invention is a sample pretreatment method having the ability to remove interference (organic matter) and concentrate the measured component to be less susceptible or even undisturbed, (theoretically) is advantageous.
  • the heavy metal results measured by existing analytical methods are more accurate.
  • the separation and digestion method of the present invention is only more accurate for the results of heavy metals measured by the existing analytical methods, it will be very important to more accurately infer whether the blood Pb of the child exceeds the standard at home and abroad, due to the separation of the present invention.
  • the digestion method is not only suitable for the pretreatment of blood samples, but also theoretically suitable for the pretreatment of samples containing high concentrations of organic matter.
  • the pretreatment of the separation and digestion method of the high concentration organic matter sample is basically the same as the pretreatment process of the separation and digestion method of the blood sample. If we can separate the solid or liquid organic matter in the high concentration organic sample, it will also greatly reduce the interference caused by the organic matter on the measurement of the existing analytical methods. (Theoretically) it is also beneficial to the existing analytical methods. Heavy metal results are more accurate. Although the separation and digestion method of the present invention is only more accurate for the measurement of heavy metals in the existing analytical methods, it is also very important for more accurate measurement of heavy metals in high-concentration organic samples at home and abroad. The significance of its significance is exactly the same as the inference of Pb in children's blood.
  • the separation and digestion method of the present invention is a general sample pretreatment method which has evolved from the existing wet digestion method, the acid used in the digestion sample, the amount of acid used, the amount of the digested sample, and the like are substantially the same. And all are heated by boiling, there are temperatures or processes of heating boiling water and acid, there are temperatures or processes of heating acid boiled acid fumes, although many of the same, but the wet digestion and separation digestion is still There is a clear difference.
  • the People’s Health Publishing House published and published the manual “Methods for Analysis of Toxic Substances in Biomaterials” edited by Yan Xianlin.
  • the method is: "a blood sample or a urine sample (plus a few glass beads) is first mixed with nitric acid and sulfuric acid, and heated slowly by a hot plate, a sand bath, an aluminum block or a graphite block heater. After a large amount of foam is dispersed, the temperature is appropriately increased.
  • the separation and digestion method of the present invention is a temperature or a process of boiling boiled water and acid by heating, using a temperature or a process of boiling acid to boil acid, and the sample to be pretreated is 1-5 times the sample volume (1 ml remaining here) Left and right solution), stop heating, after the sample to be pretreated is cooled, add about 5mL of ultrapure water and continue to boil for about 2 minutes, the purpose is to thoroughly mix the heavy metals, organic matter and the like in the digested sample with the aqueous solution, in the blood sample. Larger molecular weight or smaller organic matter will float in the form of liquid organic oil beads.
  • the sample to be heated is cooled to room temperature (room temperature or 0 ° C), and the liquid organic matter in the sample is pretreated.
  • the form of liquid organic matter continues to float on the surface of the solution, and the liquid organic matter can be sucked out by the suction pipe to achieve the purpose of separation.
  • the filter paper can be folded into a funnel, and a small hole is made at the bottom of the funnel through the solution.
  • the solid organic matter is separated from the solution by filtration through a small orifice. It can be seen from the pretreatment method of the present invention that the main purpose is to separate, the second is to achieve a certain degree of digestive function, and there is a separation process.
  • the separation and digestion methods have many similarities with the wet digestion method, since the purpose of the separation digestion method and the wet digestion method are significantly different, the separation digestion method and the wet method digestion method belong to two distinct common pretreatment methods. Because the existing wet digestion method pretreats the high concentration organic matter sample, it does not have the ability to remove the interference (organic matter), and concentrates the measured component to be less or even undisturbed, so it is theoretically disadvantageous to the existing one. The analytical method is more accurate for measuring heavy metals in high concentration organic samples.
  • the separation and digestion method of the present invention pretreats the high concentration organic matter sample, has the ability to remove the interference (organic matter) substance, and concentrates the measured component to be less or even undisturbed, which is theoretically disadvantageous to the existing analytical method. It is more accurate to measure heavy metals in high-concentration organic samples, which will be of great significance for more accurate measurement of heavy metals in high-concentration organic samples at home and abroad.

Abstract

一种高浓度有机物样品的预处理方法及对重金属含量的测量方法，预处理方法为分离消化法，是将样品加入酸或酸性溶液均匀，此时酸或酸性溶液的体积是样品体积的2-100倍，加热煮沸，控制加热温度以防烧干将样品碳化；利用加热煮沸水和酸的温度或过程，还有利用加热煮沸酸的冒酸烟雾的温度或过程，将血样品中较大分子量的固体或液态的有机物转变成液态的有机物留存在预处理的溶液中，加热完成，稍微冷却，加入酸溶液继续煮沸，此时酸溶液的体积是样品体积的2-100倍；然后冷却至室温，油脂凝固，固液分离或油水分离后得到消化后的溶液。相比现有技术这样的方法能够大大的降低样品中较大分子量有机物的浓度，提高浓度测量的准确度。

Description

一种高浓度有机物样品的预处理方法及对重金属含量的测量方法 技术领域
本发明属于重金属检测技术领域，特别涉及一种能将含有(大量)有机物样品中大部分的有机物除去的预处理方法，采用本发明预处理的含有(大量)有机物样品，比采用现有的样品预处理方法处理含有(大量)有机物样品，测量的(重金属)结果(理论上)更准确。
背景技术
国内外测量含有(大量)有机物的样品中的重金属的含量有几十年的历史，什么样品含有(大量)的有机物？例如血、奶油、膏状的化妆品、牛奶、生物材料、含有动物植物油的食品、药品等等，这些样品的共同特点是样品中含有(大量)有机物，以下我们将含有(大量)有机物的血、奶油、膏状的化妆品、牛奶、生物材料、含有动物植物油的食品、药品等样品称为高浓度有机物样品。本领域的技术人员知道，现有的分析方法是不能直接测量高浓度有机物样品中的重金属，必须将高浓度有机物样品中的待测重金属元素转入溶液中再测量。
常用的样品预处理方法，在1994年5月，人民卫生出版社出版发行，缐引林主编的《生物材料中有毒物质分析方法手册》中，针对不同的分析方法，给出了很多关于高浓度有机物样品的预处理方法，例如湿法消化法、干法灰化法、溶解法等等样品预处理方法，其中湿法消化法，根据加入不同的酸，分为硫酸—硝酸—高氯酸消化法、硝酸—高氯酸消化法、过氧化氢—硝酸法等等。其中湿法消化法也是目前预处理高浓度有机物样品，最常用的样品预处理方法，我们将以上的预处理方法称为现有的样品预处理方法。从专业的角度来讲样品预处理方法的目的，是为了除去干扰(有机物)物质，浓集了被测组分，使之少受甚至不受干扰。假如现有的样品预处理方法具备将高浓度有机物样品中大部分的有机物除去或消化的能力，现有的样品预处理方法就是一种具备除去干扰物质，浓集了被测组分，使之少受甚至不受干扰能力的样品预处理方法，(理论上)有利于现有的分析方法测量的重金属结果更准确。假如现有的样品预处理方法不具备将高浓度有机物样品中大部分的有机物除去或消化的能力，仅能将样品中很小部分的有机物除去或消化，现有的样品预处理方法就不是一种具备除去干扰物质，浓集了被测组分，使之少受甚至不受干扰能力的样品预处理方法，(理论上)不有利于现有的测量的重金属结果更准确。因此现有的样品预处理方法是否具备将高浓度有机物样品中大部分的有机物除 去或消化的能力，将涉及到现有的分析方法测量的重金属结果能否更准确，也是本发明讨论的重点。本发明是通过对现有的测量血Pb标准分析方法中的血样品预处理方法的讨论，来推断现有的预处理方法是否具备将高浓度有机物样品中大部分的有机物除去或消化能力的，假如现有的样品预处理方法具备将血样品中大部分的有机物除去或消化的能力，就可以推断现有的预处理方法具备将高浓度有机物样品中大部分的有机物除去或消化的能力，这将有利用现有的分析方法测量的重金属结果更准确，因此再讨论现有的关于高浓度有机物样品的预处理方法或测量没有任何意义。假如现有的样品预处理方法不具备将血样品中大部分的有机物除去或消化的能力，同样可以推断现有的预处理方法有可能不具备将高浓度有机物样品中大部分的有机物除去或消化的能力，这将不利用现有的分析方法测量的重金属结果更准确，因此研究一种具备血样品中大部分的有机物除去或消化的能力预处理方法，除了有利于测量血样品中的重金属更准确具有重要的意义，同时也有利于将高浓度有机物样品中大部分的有机物除去或消化，有利于测量高浓度有机物样品中的重金属更准确，同样具有非常重要的意义。问题是现有的关于血Pb样品预处理方法，是否具备将血样品中大部分的有机物除去或消化的能力？
问题的引出，过去的几年中，我国每年都会发生一起或数起关于血Pb污染的事件，例如2009年，陕西省凤翔县长青镇东岭集团冶炼公司环评范围内两个村庄的731名儿童接受权威血铅检测后，确认615人血铅超标，其中166人属于中度或重度铅中毒。还有2012年2月17日，广东韶关市仁化县董塘镇部分群众先后发现有血铅超标情况，共有103名群众到医院进行血铅检查，14周岁以下的未成年人有94人，发现64人超标，其中有2人属于轻度中毒。2010年2月24日，湖南嘉禾县250名儿童血铅超标等等。每次发生血铅污染事件，都会引起社会、国内外的媒体的广泛关注，这也给我国造成了极大的负面的影响，其共同之处，多是儿童血铅超标。由于每次发生关于血铅污染的事件，都会给政府带来极大的压力，官员的免职等等，在湖南衡东县300余名儿童血铅超标事件中，就有4名官员被免职(网上即可搜到)。因此百姓谈“铅”色变。2014年8月在江西弋阳县港口镇，就发生一起离奇的打砸事件。是由南方周末记者鲍小东南方周末实习生杨国要发自：江西戈阳，题目《超标阴影下的中国小镇样本血铅死结》2014年8月，在江西省弋阳县港口镇，发生了一起离奇的打砸事件，8月11日上午和下午发生了两起打砸事件。上午约10时，港口镇一百余名村民冲进弋阳县兴旺实业有限公司(以下简称兴旺公司)生活区，砸了食堂、宿舍。下午约2时，村民们又聚集到兴旺公司生产区， 打砸生产设备和办公用品。该公司主营业务为再生铅。企业方称：企业还未投产，不可能有污染，而各项环保措施都在按部就班执行。但村民不相信，因为怀疑或为了防止未来可能出现的铅中毒。为什么企业还未投产，也不可能有污染，工厂就被打砸？因为弋阳县发生过两起儿童铅中毒事件，在2010年，弋阳县志敏小区附近的一个村庄有二百多名儿童铅超标，其中铅中度中毒儿童有六十多名，铅中毒严重的儿童有七名。在2012年弋阳县潮水岩村三十多名孩子也存在不同程度的血铅超标。这给村民造成不止一次痛苦的回忆。而最近打砸事件的开端(8月11日打砸事件)，是村民从网络上查询得知，铅会致人中毒，于是提议各家带儿童去检验。检验的结果令村民们很吃惊。发现镇上一百多个儿童血铅超标。虽然在弋阳县发生了多起血铅污染事件，但许多现象无法给出合理的解释。例如上述的两起血Pb超标事件发生后，对河水、自来水等样品中的Pb进行了检测，未发现Pb超标的现象，因此对导致血Pb污染事件的污染源没有找到。对于血铅污染事件的发生，有两种可能，一种是确实发生铅污染，导致儿童血铅超标。还有一种可能，根本就没有发生铅污染事件，导致儿童血铅超标的原因，有可能是现有的测量血Pb的标准分析方法存在问题，为什么这么说？因为在(江西省弋阳县)2010年的大规模铅超标事件中，弋阳县疾病控制中心曾在弋阳县城、偏僻农村等地选了几个点，对儿童进行血铅检验，竟发现即使在偏僻农村也有儿童血铅含量超过100微克/升的现象，这种现象同样无法给出合理的解释。为了避免造成人为的铅污染事件的发生，因此研究一种能更准确的测量血铅的分析方法具有非常重要的意义。
作为分析方法分为非标准的分析方法和标准的分析方法两种。非标准的分析方法通常是发表在各种期刊、杂志、书籍等，没有经过国家有关部门的专家经过科学的认证的分析方法。非标准的分析方法，通常仅具有一定的学术价值和参考价值，但可比性较差，不具权威性等缺点。标准分析方法，在我国分为国家标准分析方法和行业的标准分析方法，标准分析方法是经过国家有关部门的专家经过深入研究，多个实验室科学的论证的分析方法，具有较好的可比性、准确性和权威性，只有标准分析方法是环境污染纠纷法定的仲裁方法。
Pb这种重金属元素，比较活泼，无处不在，因此在我们的实验室分析中，Pb非常容易沾污。为了防止测量血样品中的Pb出现重大的失误，我国特在2006年01月09日发布了卫生部关于印发《血铅临床检验技术规范》的通知(卫医发[2006]10号)在通知中，对实验室的基本条件，样品的采集，样品的预处理，检测的方法，实验室室内质量 控制等等都有详细的技术要求，并对测量血样品中Pb的分析方法进行了严格的限定，目的就是为了防止测量的过程中出现Pb沾污的问题。我国目前测量血Pb的标准分析方法有以下3种：
Figure PCTCN2017070943-appb-000001
以上的分析方法属于行业(标准)分析方法，不属于国家标准分析方法，但行业(标准)分析方法与国家标准分析方法等效，因此也可作为环境污染纠纷法定的仲裁方法。作为一种环境污染纠纷法定的仲裁方法，将涉及到血铅污染事件中的村民、儿童、企业的利益，还有官员的免职等等非常严肃法律层面的问题，这就要求测量的结果必须(较为)准确可靠值得推敲，问题是我国测量的血Pb的标准分析方法是否具备(较为)准确推断儿童血Pb超标的能力？在我国卫生部相关指导意见中，儿童血Pb的标准，是血样品中Pb含量小于100μg/L为正常，血样品中Pb含量大于100μg/L为Pb超标，即儿童血Pb超标。
在WS/T 21—1996血中铅的微分电位溶出测定方法中，样品的预处理是，取耳垂血样或静脉血样50μL，置于盛有4mL水的10mL烧杯中，加入氯化高汞溶液50μg，再1+9盐酸1.0mL，血样品稀释了100倍，再用微分电位溶出测定方法直接测量。显然这是一种将血样品进行了简单稀释(100倍)的样品预处理方法(也可称为简单稀释法)，这种简单稀释的样品预处理方法，理论上不具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力。因此这种简单稀释的样品预处理方法，将不利于WS/T 21—1996血中铅的微分电位溶出测定方法测量血样品中的Pb更准确。我们继续讨论，假如被测样品中的Pb就是100μg/L，采用简单稀释100倍的样品预处理方法后，理论上样品中的Pb浓度仅为1μg/L，而WS/T 21—1996血中铅的微分电位溶出测定方法，最低检测浓度仅为0.9μg/L，最低检测浓度为0.9μg/L是什么意义？就是说这种分析方法，低于0.9μg/L浓度的Pb，不能测量出Pb溶出峰，只有等于或大于0.9μg/L时，才仅仅能测量出Pb的溶出峰，我们用一种只有等于或大于0.9μg/L，才仅仅能测量出Pb溶出峰的标准分析方法，去测量浓度为1μg/L(Pb)的样品，还要考虑到大量有机物干扰，试剂空白等干扰，理论上实现较为准确的测量1μg/L的Pb的可能性很小或不可能。显然WS/T 21—1996血中铅的微分电位溶出测定方法测量血样品中Pb的技术方案，理论上存在严重的缺陷，理 论上就不具备较为准确的推断儿童血Pb是否超标的能力。假如我们采用WS/T 21—1996血中铅的微分电位溶出测定方法的技术方案，就有可能发生人为的血铅污染事件。
在WS/T 20—1996血中铅的石墨炉原子吸收光谱测定方法中，样品的预处理是，用微量取液器抽取血样40μL，置于盛有0.32mL Triton X-100溶液的带盖离心管中，充分振摇，然后加入40μL1％(V/V)的硝酸溶液混匀，将血样品稀释了10倍，再用石墨炉原子吸收光仪器测量，这显然还是一种将血样品进行了简单稀释(10倍)的样品预处理方法，同样不具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力。显然这种简单稀释的样品预处理方法，同样不利于WS/T 20—1996血中铅的石墨炉原子吸收光谱测定方法测量血样品中的Pb更准确。由于这种简单稀释的样品预处理方法，无法消除试剂空白相对过高，大量的有机物、盐等对测量的结果造成的干扰，因此在实际的测量中，大量的实验的结果表明，同一个样品，不同的分析人员，不同的分析仪器，测量的结果常常相差很大，因此分析技术人员普遍反映，这种分析方法很难掌握，影响的因素太多，测量的结果也很不理想。因此我们用一种样品的预处理存在明显缺陷的样品预处理方法，在实际的测量中又存在很多问题的标准分析方法，去推断血铅污染事件中的儿童血Pb是否超标，值得商榷。
在WS/T 174—1999血中铅、镉的石墨炉原子吸收光谱测定方法中，样品的预处理方法是，取0.15mL血，加0.6mL5％(V/V)的硝酸溶液混匀，离心取上清液10ug直接用(石墨炉原子吸收光谱仪)测量。显然样品预处理方法还是一种简单稀释的样品预处理方法，由于在实际的测量中测量的结果与现象与WS/T 20—1996血中铅的石墨炉原子吸收光谱测定方法测量的结果或现象基本相同，因此我们不再进行详细的解释。
通过以上的讨论，尤其是WS/T 21—1996血中铅的微分电位溶出测定方法测量血样品中Pb的技术方案，理论上就不具备推断血铅污染事件中的儿童血Pb是否超标能力。还有三种标准分析方法中都是采用了简单稀释的样品预处理的方法，显然都不是具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰能力的样品预处理方法。属于一种非常不专业的样品预处理的方法，这将不利于现有的标准分析方法更准确的推断血铅污染事件中的儿童血Pb是否超标。为什么现有的标准分析方法中不采用一中具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰能力的更为专业的样品预处理方法？还有现有的血样品预处理方法中，是否有具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的更为专业的关于血样品预处理的方法？答案是，有。在1994年5月，人民卫 生出版社出版发行，缐引林主编的《生物材料中有毒物质分析方法手册》中，就有专门针对血样或尿样样品预处理的方法，其方法是“血样或尿样(加几粒玻璃珠)先用硝酸、硫酸混合，用电热板、沙浴、铝块或石墨块加热器徐徐加热，待大量的泡沫驱散后，再适当提高温度，将大量的有机成分除去，使溶液变清，再加少量的高氯酸，继续加热至冒白烟，样品呈白色结晶，放冷后用水溶解并稀释至一定体积。”这是一种专门针对血样或尿样预处理的湿法消化法，理论上讲具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力预处理的方法，但为什么我国在过去的几十年没有采用这种专业的样品预处理方法？因为采用湿法消化法预处理的血样品，干扰太大，导致测量的重金属结果很不理想。
除了以上采用湿法消化法预处理，从道理上讲血样品的预处理也可以采用干法灰化法，在1994年5月，人民卫生出版社出版发行，缐引林主编的《生物材料中有毒物质分析方法手册》中，“对部分不易挥发的重金属元素的分析时可以采用干法灰化预处理(Pb理论上400℃以下不挥发)，现将样品放在坩埚内烘干，然后将坩埚转移至高温炉(马弗炉)内700-800℃(Pb要控制在400℃以下)烘烤12h左右，使有机成分完全破坏，样品成灰白色粉末，再用稀酸溶解后进样。”这显然也是一种具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰能力的样品预处理方法。这种样品的预处理方法，理论上试剂空白很低，干扰小，但实验的结果表明，将血样品变成灰白色粉末的操作较难掌控，常常变成烧焦碳化，这种烧焦碳化的物质很难溶于酸性的溶液，因此干法灰化的样品预处理方法无法采用。除了以上的两种样品预处理方法，还有一种科技含量高，自动化程度高的微波消化法，微波消化法采取了高温、高压、强酸介质的样品预处理方法，是将需要消化的血样品(或土壤、高浓度有机物样品)，加适量的硝酸(酸也可采用其它常用的硫酸、盐酸等强氧化性酸)，一起放在密闭罐体中，通过微波加热产生高温、高压、在强酸介质下消化的预处理方法，这种预处理方法，由于采用了高温、高压、强酸介质，消化的能力非常强，简单快速，工作效率大大的提高，被广泛的应用在土壤、高浓度有机物等样品的预处理中，并且有二十年以上的使用经验，技术非常成熟，也是一种具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力的样品预处理方法。从道理上讲，如果能预处理土壤、高浓度有机物等样品中的重金属，似乎预处理血样品中的Pb应该不会存在问题，但实验的结果表明，测量血Pb的结果同样很不理想，仍然存在严重的干扰问题，这也是为什么微波消化法同样没有被采用的原因。由于到目前为止， 国内外还没有一种具备除去血样品中干扰物质(有机物)，浓集被测组分，使之少受甚至不受干扰能力的样品预处理方法，这导致现有的标准分析方法中关于血样品的预处理方法，是在没有办法的办法的前提下，只能采取一种存在严重缺陷的简单稀释的方法预处理血样品，这也是为什么现有的标准分析方法中，只能采用一种存在严重缺陷的简单稀释的样品预处理方法的最主要的原因。因此目前国内外如何更好的预处理血样品中的Pb是世界性的难题。
通过以上的讨论，我们采用理论上具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰能力的湿法消化法或微波消化法预处理血样品，测量的重金属结果都不理想，为什么？因为血是一种粘稠度较高的介乎与固态与液态之间的一种物质，类似于胶体物质，血主要成分是有机物，水、盐和重金属等等(这与高浓度有机物样品的成分非常相似)。其有机物主要分为两类，一类是分子量较小的有机物，单独存在时，常温(室温)下是液态；还有一类是较大分子量的有机物，例如蛋白质，(油)脂等等，单独存在时，常温下是固态。从我们学过的知识可知，要想将较大分子的有机物破坏有一种可能，就是通过裂解(反应)，什么是裂解(反应)？在石油工业常见，就是通过高温(700-1000℃)、高压(40以上的大气压)等特殊条件，将较大分子量的有机物裂解成不同(较小)分子量的有机物的反应，由于实验室条件，很难达到工业所需的高温、高压等条件，因此将血样品中大部分的较大分子量的有机物裂解成分子量较小的有机物的可能性大大降低，还有裂解理论上仅能将较大分子量的有机物裂解成分子量更小的有机物，但是裂解成无机物盐的可能性不大，这些不利的因素，将导致现有的预处理方法不利于将血样品中较大分子量的有机物消化成无机物，预处理的样品中就会含有较高浓度的较大或较小分子的有机物，就会对测量造成严重的干扰，发生测量的重金属结果很不理想的现象发生。显然我们想将血样品中较大分子量的有机物破坏或消化成无机物盐的技术路线存在问题，本发明的技术路线是，如果我们不能将血样品中较大分子量(常温是液态或固态)的有机物破坏或消化，但我们可以利用血样品中较大分子量的有机物，在较高的温度下，是液态，在常温(室温或0℃)是液态或固态的物理特性，采取化学工业生产中常见的与分馏相似的方法，通过加热等条件，将血样品中较大分子量的固态或液态的有机物从血样品中析出并留存在样品溶液中，再将样品冷却至常温，再加适量的水煮沸，将从血样品中析出的(固态或液态)有机物充分或进一步的与溶液(水)分层或分离，由于有机物不溶于溶液(水)，较大分子量的有机物就会以固态的形式漂浮在溶液的表面，较小分子 量的液态有机物就会形成油珠也漂浮于溶液的表层，通过固液分离，液(有机物)液(溶液)分离，就能将血样品中大部分的有机物除去，间接的实现将血样品中大部分的有机物消化的目的，由于本发明采用的技术方案，具备将血样品中大部分的有机物除去的能力，因此本发明的技术方案，是一种具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰能力的样品预处理方法，这将对我们更准确的测量血样品中的Pb或高浓度有机物样品中的重金属具有非常重要的意义。
发明内容
本发明为了解决现有技术中的不足，提供了如下技术方案，一种高浓度有机物样品的预处理方法，其特征在于，为分离消化法，具体为在样品中加入酸溶液混合均匀得到预处理混合液，此时酸溶液的体积是样品体积的0.5-100倍，加热煮沸，控制加热温度以防烧干将样品碳化；利用加热煮沸水和酸的过程完成初步消化，待水完全蒸发后，再利用加热煮沸酸至冒酸性烟雾的过程继续消化，当待测混合液的体积为样品体积的0.5-10倍时，停止加热，此时完成二次消化；在两步消化过程的同时样品中的有机物从样品中析出并存留在样品溶液中，冷却，加入水或酸溶液继续煮沸，此时水或酸溶液的体积是样品体积的0.5-100倍；然后冷却至室温，样品中析出的有机物以固态或液态的形式漂浮在溶液的表面，再进行固液分离或液液分离，得到分离消化后的溶液。
与现有技术相比，本发明提供一种能将含有(大量)有机物样品中大部分的有机物除去的预处理方法，采用本发明预处理的含有(大量)有机物样品，比采用现有的样品预处理方法处理含有(大量)有机物样品，测量的(重金属)结果(理论上)更准确。
附图说明
图2-1，2-2，2-3 实施例2中的溶出谱图；
图3-1，3-2      实施例3中的溶出谱图。
具体实施方式
预处理血样品可以采用以下的两种消化方法：一种是先分离，将预处理样品中的液态或固态的有机物先与(水)溶液分离，再采用现有的微波消化法或湿法消化法等预处理进一步消化，这种先分离再采用现有的消化等措施方法，优点是可以提高消化的效率等。还有一种是在分离的同时，利用加热煮沸水和酸的温度或过程，还有利用加热煮沸酸的冒酸烟雾的温度或过程进行消化，这个消化的过程可以是一次或多次对血样品进 行消化。这种分离的同时进行消化的方法，虽然比微波消化法消化的效率低，但通常已经能够满足测量的技术要求，因此也是最常用的一种消化方式。
本发明采用第二种，将样品置于玻璃试管中加适量的酸溶液混合均匀，得到预处理混合液；所述酸溶液为质量浓度为0.1-100％的硝酸、盐酸、硫酸、高氯酸、醋酸、磷酸、氢氟酸或其混合酸。分离的器皿建议采用玻璃试管，加热方式可以是酒精灯、铝块或石墨块加热器、微波等等。加热煮沸，利用加热煮沸水和酸的过程完成初步消化，待水完全蒸发后，再利用加热煮沸酸至冒酸性烟雾的过程继续消化，当待测混合液的体积为样品体积的1-5倍时，停止加热，此时完成二次消化，在两步消化过程的同时样品中的有机物从样品中析出并存留在样品溶液中，冷却，加入水或酸溶液继续煮沸，此时水或酸溶液的体积是样品体积的2-100倍；然后冷却至室温，从样品中析出的有机物以固态或液态的形式漂浮在溶液的表面，再进行固液分离或液(有机物)液(溶液)分离，，得到分离消化后的溶液。为了进一步提高分离的效率，将预处理混合液加热煮沸，完成初步消化和二次消化，冷却，加入水或酸溶液继续煮沸，重复初步消化和二次消化过程，可以是一次，也可以是反复多次，来提高将血样品中较大分子量的固态或液态的有机物转变成液态的有机物留存在预处理的溶液中的效率。停止加热后，冷却后再加入适量的超纯水继续煮沸的目的是将消化样品中的重金属、有机物等再次与水溶液充分混匀，待加热的样品冷却至常温(室温或0℃)，从预处理样品中析出的较大分子量的固态或液态的有机物，就会以固态或液态有机物的形式漂浮于溶液的表面，再进行固液分离及液液分离，将有机物与溶液分离，就可以实现血样品中大量有机物与溶液分离的目的，间接的实现将血样品中大部分的有机物消化的目的。
本发明将上述分离再消化或分离的同时进行消化的方法叫作分离消化法。这种分离消化法，理论上具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力。需要说明的是，若采用微波消化法等预处理方法，利用合适的温度、合适的压力、加酸或不加酸等条件，预处理血样品，再通过静置或离心等方法将大量的液态有机物与溶液分离，只要是以(大量的)有机物与溶液分离为目预处理方法也在属本发明侵权的范围。问题是采用本发明的分离消化法，能否将血样品中的较大分子量的固态或液态有机物分离？
实施例1
血样品中的较大分子量的固态或液态有机物分离实验，本发明的分离消化法具体为，取1.5mL的血样品于(25mL左右)玻璃试管中，加3mL质量浓度为1:1的硝酸溶液混匀，加入数粒玻璃珠，用酒精灯加热至煮沸，适当控制酒精灯与加热玻璃试管的距离，使消化的样品徐徐加热，待大量的泡沫驱散后，再适当提高温度加热煮沸，利用加热煮沸水和酸的温度，将血样品中较大分子量的固态或液态的有机物从血样品中析出并留存在预处理的溶液中，在分离的同时也对血样品进行一定程度的消化，同时也可以将预处理样品中的水蒸发掉，完成初步消化；再利用加热煮沸硝酸冒红棕色烟雾的温度或过程，进一步将血样品中较大分子量的固态或液态的有机物从血样品中析出并留存在预处理的溶液中，在分离的同时也进一步对血样品进行一定程度的消化；待加热煮沸样品剩余2mL左右时，适当控制酒精灯与加热玻璃试管的距离继续对血样品进行消化，待预处理消化的样品剩余1mL左右时，停止加热，要防止样品烧干碳化，需要说明的是，在血样品中加适量的1:1的硝酸溶液，加热煮沸的过程，可以是一次或多次，待预处理的样品冷却后，再加5mL左右超纯水继续煮沸2分钟左右，目的是将消化的样品中的重金属、有机物等与水溶液充分混匀，血样品中析出的较大分子量或较小的有机物，就会以液态有机物油珠的形式漂浮于溶液中，待加热的样品冷却至常温(室温或0℃)，预处理样品中液态的有机物，就会以固态或液态有机物的形式继续漂浮于溶液的表面，液态的有机物可以用吸管吸出，达到分离的目的，至于漂浮在溶液表层的固态有机物可以采用滤纸折成漏斗，在漏斗的底部扎一个小孔，通过溶液通过小孔的过滤，将固态的有机物与溶液的分离。需要说明的是，对血样品的预处理，通常只能分离出固态的有机物，这些漂浮在溶液的表层的固态有机物(油脂)，证明了本发明的分离消化法可以将血样品中较大分子分子量(固态)有机物与溶液分离，血样品中大量的较大分子量的有机物浓度将大大的降低，实现血样品中大量有机物与溶液分离的目的，间接的实现将血样品中大部分的有机物消化的目的，这将有利于现有的分析方法测量重金属的结果更准确。因此本专利的分离消化法是一种具备除去干扰物质(有机物、盐)，浓集被测组分，使之少受甚至不受干扰能力的关于血样品的预处理的方法。(理论上)这将有利于现有的分析方法更准确的推断儿童血Pb是否超标具，问题是采用本发明的分离消化法预处理血样品，再采用现有的分析方法测量血样品中的Pb，能否具备更准确的推断儿童血Pb是否超标？
实施例2
测量血样品中Pb的实验；对实施例1中经分离消化法预处理的血样品(Pb)的测量， 包括以下步骤：首先洗涤电解池，是取酸性的超纯水或其它洁净的酸性水20mL左右，通过搅拌的方式对电解池进行多次洗涤，电解池洗涤干净后，用电子天平对电解池称重记录电解池重量。实施例1所述分离消化法预处理的血样品中已将液态或固态块状的有机物分离，由于分离出的固态块状的或液态有机物油不溶于酸性溶液，不会对本发明采用的分析方法的测量造成干扰，因此将溶液中的液态或固态块状的有机物分离或分离均可进行测量。假如要想将液态的有机物分离，最简单的方法是用吸管将液态有机物吸出即可，需要说明的是，有时预处理血样品，不能观察到明显的液态有机物，因此这个步骤可省略。假如要想对溶液中的固态块状的有机物油脂进行简单过滤，最简单的方法，用滤纸折成一个漏斗，在滤纸漏斗的底部扎一个小孔，将纸漏斗至于电解池的上方，将玻璃试管中采用实施例1所述分离消化法预处理的血样品全部倒在纸漏斗中，固态块状的有机物留在纸漏斗中，消化的溶液通过纸漏斗的小孔漏到电解池中，用少量的纯水冲洗玻璃试管，再将玻璃试管中冲洗的溶液通过纸漏斗转移到电解池中，用少量的超纯水冲洗玻璃试管2次，并将冲洗的溶液转移到电解池中，需要注意的是冲洗两次再加上消化的溶液，总增加的重量要小于15g，这时再加适量的超纯水将电解池增加的重量控制在15g，这相当于将消化的血样品定容到15mL，即稀释10倍。假如不想对溶液中的固态块状的有机物油脂进行过滤，可以将实施例1所述分离消化法预处理的血样品全部转移到电解池中，用少量的超纯水冲洗玻璃试管2次，并将冲洗的溶液转移到电解池中，需要注意的是冲洗两次再加上消化的溶液，总增加的重量要小于15g，这时再加适量的超纯水将电解池增加的重量控制在15g，这相当于将消化的血样品定容到15mL，即稀释10倍。我们可以采用对溶液中固态块状的有机物油脂过滤或不过滤中的任意一种继续测量。由于实施例1中，在消化的样品中加入了3mL 1:1的硝酸，虽然消化样品需要消耗一定的硝酸，加热煮沸也会消耗一定的酸，但是定容至15mL的被测样品的中的pH＝1，酸度非常强，按照现有的阳极溶出伏安法的分析条件，必须采用强碱先粗调pH，再用氨水细调PH＝4-5最佳，再采用分析的仪器测量样品。
本发明中采用了一种经验的分析条件，没有采用强碱和氨水回调pH，而是在样品中加入300μL浓度为5％的ZnCl溶液，采用了一种强酸的(pH＝1)介质，再用分析仪器直接测量定容的血样品，这种分析条件减少了由强碱和氨水带来的试剂空白，使分析的条件变得更为简单，实现了在强酸的介质下直接测量被测样品中的Pb。加Zn离子试剂的经验是，在测量的溶出谱图中，如果能测量出很高的Zn溶出峰或满刻度的Zn溶出峰，我们 就认为加入Zn离子的试剂量合适，如果没有很高的Zn溶出峰或满刻度的Zn溶出峰则继续加入适量的Zn离子试剂。
仪器主要参数设置：灵敏度为8，清洗时间QT＝30秒，富集时间FT＝50s，静置时间JT＝6s，扫描时间ST＝6s；富集电压为负1.2V，起始电压为负1.3V，扫描终止电压为负0.05V，开始测量，扫描溶出，溶出谱图见图2-1，出现较高的Zn溶出峰，这是在被测样品中加入300μL浓度为5％的ZnCl溶液造成的，连续测量2次Pb溶出峰的峰高分别为5.23和5.54，能连续测量出稳定重复的Pb溶出峰，说明采用了经验的分析条件，可以实现在强酸的介质(PH＝1)下，直接测量采用本发明的分离消化法预处理的血样品，并且能测量出稳定重复的Pb溶出峰，能测量出稳定重复的Pb溶出峰，就有可能能较为准确的测量出血样品中Pb(浓度)。在被测样品中加4mg/l的Pb标准溶液60μL后，需要说明的是在被测样品中加入4mg/l的Pb标准溶液60μL，相当于在被测样品中加入了16μg/L的Pb，继续测量扫描溶出，溶出谱图见图2-2，Pb溶出峰明显的增高，连续测量2次Pb溶出峰峰高分别为16.90和16.53，按照阳极溶出伏安法计算浓度的公式：
Figure PCTCN2017070943-appb-000002
h加标前—表示加标前的溶出峰峰高值。
h加标后—表示加标后的溶出峰峰高值。
V标—表示加入标准溶液的体积。
C标—表示标准溶液的浓度。
V样—表示样品的体积。
计算浓度为7.61μg/L。下面我们采用现有的分析方法通常采用的样品加标回收率的方法判断测量的结果是否正确，加标的量要求控制在被测样品浓度的3倍内。在以上的实验中，在被测样品中加入4mg/l的Pb标准溶液60μL，相当于在被测样品中加入了16μg/L的Pb，加标的量在3倍以内，为了计算回收率，继续在被测样品中加4mg/l的Pb标准溶液100μL后继续测量扫描溶出，溶出谱图见图2-3，Pb溶出峰继续增高，同样连续测量2次Pb溶出峰峰高分别为36.65和35.60，计算浓度为22.96μg/L。再按照回收率计算公式：
Figure PCTCN2017070943-appb-000003
计算回收率为95.9％。良好的回收率，可以推断，采用本发明分析方法的分析条件测量的血样品中的Pb是准确的，良好的回收率可以推断，测量的结果准确。
需要说明的是，从测量的溶出谱图，图2-1可以看出，横坐标是电压单位是伏(V)，纵坐标是峰电流，用峰高值表示，由于以下的溶出谱图与图2-1的横坐标与纵坐标的表示方法完全相同，因此在以下的溶出谱图中不再详细的标识横坐标与纵坐标，特此说明。
实施例3
试剂空白实验，采用现有的洗涤方法，将电解池洗涤干净，采取与血样品相同的条件预处理的试剂空白样品定容到15mL，再转移到电解池中，加入300μL浓度为5％的ZnCl溶液，仪器参数同实施例2，富集时间为60秒，开始测量，扫描溶出，溶出谱图见图3-1，出现了较高的Zn溶出峰，这是在被测样品中加入300μL浓度为5％的ZnCl溶液造成的，连续测量2次Pb溶出峰的峰高分别为4.81和5.03.为了计算试剂空白的浓度，在被测样品中加2mg/l的Pb标准溶液20μL后，继续测量扫描溶出，溶出谱图见图3-2，Pb溶出峰明显的增高，同样连续测量2次Pb溶出峰峰高分别为14.75和14.90。按照阳极溶出伏安法计算浓度的公式，计算试剂空白的浓度为1.33μg/L。
通过以上的实验，由于经过分离消化法预处理的血样品中Pb 7.61μg/L，试剂空白中的Pb为1.33μg/L，消化是血样品中Pb的含量大于试剂空白5倍以上，试剂空白相对较低有利于测量的结果更准确。由于本实验测量的经过分离消化法预处理的血样品中Pb7.61μg/L，是经过回收率验证的，因此分离消化法预处理的血样品中Pb 7.61μg/L是准确的，再扣除试剂空白1.33μg/L，再乘以稀释的倍数10倍，可以推断血样品中的Pb是62.8μg/L也是较为准确的。
假如一种分析方法具备较为准确的推断或测量62.8μg/L的能力，理论上也应该具备较为准确的推断100μg/L Pb的能力。因此本发明采用的分析方法理论上具备更准确的推断儿童血Pb是否超标的能力。需要说明的是，我们采用本发明分析方法的分析条件测量的血样品，如果反复测量本发明分离消化法预处理的血样品，电解池的内壁、搅拌子、电极将粘附大量的淡黄色固态油脂，这些粘附在玻璃试管的内壁、电解池内壁、搅拌子、电极的淡黄色固态油脂，就是我们采用本发明的分离消化法预处理血样品中分离出来的固态的油脂类物质造成的，这些粘附在电解池的内壁淡黄色固态油脂，也证明了本发明 的分离消化法预处理方法，确实可以将血样品中较大分了的有机物，从血样品中分离出来。由于现有的阳极溶出伏安法不仅仅可以测量Pb，还可以测量Cd和Cu，因此这种分析方法测量的Cd和Cu也在保护的范围。
通过以上的实验，本发明的分析方法与现有的标准分析方法相比，1)在样品的预处理方面：本发明采用具备分离(有机物)和消化能力的样品预处理方法，这是一种具备除去(大部分有机物)干扰物质，浓集被测组分，使之少受甚至不受干扰的样品预处理的技术方案。而现有的血样品预处理方法是采用简单稀释的样品预处理方法，这是一种稀释干扰物质，稀释了测组分的样品预处理的技术方案。2)在测量方法上：本发明采用了一种接近不存在任何干扰的测量方法，而现有的分析方法是采用了一种存在大量的有机物干扰的测量方法。从测量的技术方案可以看出，理论上本发明的分析方法比现有的标准分析方法测量的血Pb结果更准确。这也是世界上第一次测量血样品中的Pb，样品的预处理采用了一种具备除去(大部分有机物)干扰物质，浓集被测组分，使之少受甚至不受干扰的样品预处理方法，测量接近不存在任何干扰的测量方法测量血样品中的Pb，这将对国内外更准确的测量血样品中的Pb具有非常重要的意义。
以上是我们采用了一种新的分析方法的情况，以下我们在采用本发明的分离消化法预处理血样品的前提下，讨论现有的标准分析方法是否具备推断儿童血Pb是否超标能力。
假如我们采用WS/T 21—1996血中铅的微分电位溶出测定方法测量，假如我们采用1mL血样品的预处理方案，还是采用本发明的分离消化法预处理血样品后，将样品的调至pH＝4-5，定容至5mL，相当于样品将稀释5倍，假如血样品中的Pb就是100μg/L，这样理论上样品中的Pb浓度是20μg/L，由于本发明的预处理方法是一种具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力的预处理方法。理论上将有利于WS/T21—1996血中铅的微分电位溶出测定方法测量(20μg/L的Pb)的结果更准确，因此推断儿童血Pb是否超标能力大大的提高。
假如我们采用WS/T 20—1996血中铅的石墨炉原子吸收光谱测定方法测量，我们采用2mL血样品的预处理方案，分离消化血样品后，将预处理的血样品定容至10mL，相当于将样品稀释5倍，假如血样品中的Pb就是100μg/L，这样理论上血样品中的Pb浓度是20μg/L，由于本发明的预处理方法是一种具备除去干扰物质，浓集被测组分，使之少受甚至不受干扰的能力的预处理方法。理论上将有利于WS/T 20—1996中的石墨炉原子吸收光谱测定方法测量(20μg/L的Pb)的结果更准确，较为准确的推断儿童血Pb是 否超标能力将大大的提高，就有可能将较为准确的推断儿童血Pb是否超标变成现实。由于WS/T 174—1999血中铅、镉的石墨炉原子吸收光谱测定方法与WS/T 20—1996血中铅的石墨炉原子吸收光谱测定方法非常相似，假如我们同样采用2mL血样品的预处理方案，由于测量的结果或现象与采用WS/T 20—1996血中铅的石墨炉原子吸收光谱测定方法测量的结果或现象基本相同，因此我们不再对WS/T 174—1999血中铅、镉的石墨炉原子吸收光谱测定方法进行详细的解释。
综合以上，由于本发明的分离消化法是一种具备除去干扰(有机物)物质，浓集了被测组分，使之少受甚至不受干扰能力的样品预处理方法，(理论上)有利于现有的分析方法测量的重金属结果更准确。虽然本发明的分离消化法，仅仅是有利于现有的分析方法测量的重金属结果更准确，但这将对国内外更准确的推断儿童血Pb是否超标具有非常重要的意义，由于本发明的分离消化法不仅适合于血样品的预处理，理论上还适合于含有高浓度有机物样品的预处理，高浓度有机物样品的分离消化法的预处理与血样品的分离消化法的预处理过程基本相同，如果我们能将高浓度有机物样品中的固态或液态的有机物分离出，同样将大大的降低有机物对现有的分析方法的测量造成的干扰，(理论上)同样有利于现有的分析方法测量的重金属结果更准确。虽然本发明的分离消化法，仅仅是有利于现有的分析方法测量的重金属结果更准确，但这将对国内外能更准确的测量高浓度有机物样品中的重金属，同样具有非常重要的意义，其重要意义的道理与推断儿童血Pb的道理完全相同。
由于本发明的分离消化法是在现有的湿法消化法演变而来的一种通用的样品预处理的方法，因此消化样品采用的酸，使用酸的量、消化样品的量等等基本相同，且都是通过加热煮沸，都有加热煮沸水和酸的温度或过程，都有加热煮沸酸的冒酸烟雾的温度或过程，虽然很多相同之处，但是湿法消化法与分离消化法还是有明显的不同，在1994年5月，人民卫生出版社出版发行，缐引林主编的《生物材料中有毒物质分析方法手册》中，就有专门针对血样或尿样样品预处理的方法，其方法是“血样或尿样(加几粒玻璃珠)先用硝酸、硫酸混合，用电热板、沙浴、铝块或石墨块加热器徐徐加热，待大量的泡沫驱散后，再适当提高温度，将大量的有机成分除去，使溶液变清，再加少量的高氯酸，继续加热至冒白烟，样品呈白色结晶，放冷后用水溶解并稀释至一定体积。从关于血样或尿样湿法消化法中可以看出，用硝酸、硫酸混合加热煮沸的目的是消化，再加少量的高氯酸，继续加热至冒白烟，样品呈白色结晶(这里几乎没有溶液)，放冷后用水溶解并稀 释至一定体积的目的是最大限度的将血样品中的有机物消化或破坏成无机物，且将消化的样品全部溶解并稀释到一定体积的测量溶液中，这里没有分离的目的或分离的过程，只有消化的目的。而本发明的分离消化法是利用加热煮沸水和酸的温度或过程，利用加热煮沸酸的冒酸烟雾的温度或过程，待预处理消化的样品剩余1-5倍样品体积时(这里剩余1ml左右的溶液)，停止加热，待预处理的样品冷却后，再加5mL左右超纯水继续煮沸2分钟左右，目的是将消化的样品中的重金属、有机物等与水溶液充分混匀，血样品中较大分子量或较小的有机物，就会以液态有机物油珠的形式漂浮于溶液中，待加热的样品冷却至常温(室温或0℃)，预处理样品中液态的有机物，就会以固态或液态有机物的形式继续漂浮于溶液的表面，液态的有机物可以用吸管吸出，达到分离的目的，至于漂浮在溶液表层的固态有机物可以采用滤纸折成漏斗，在漏斗的底部扎一个小孔，通过溶液通过小孔的过滤，将固态的有机物与溶液的分离。从本发明的预处理方法可以看出，主要的目的是分离，次要是实现一定程度的消化功能，且有分离的过程。虽然分离消化法与湿法消化法有很多相同之处，由于分离消化法和湿法消化法的目的明显不同，因此分离消化法与湿法消化法属于两种明显不同的通用的预处理方法，由于现有的湿法消化法预处理高浓度有机物样品，不具备除去干扰(有机物)物质，浓集了被测组分，使之少受甚至不受干扰的能力，因此理论上不利于现有的分析方法测量高浓度有机物样品中的重金属更准确。而本发明的分离消化法预处理高浓度有机物样品，具备除去干扰(有机物)物质，浓集了被测组分，使之少受甚至不受干扰的能力，理论上不利于现有的分析方法测量高浓度有机物样品中的重金属更准确，这将对国内外更准确的测量高浓度有机物样品中的重金属具有非常重要的意义。

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  1. 一种高浓度有机物样品的预处理方法，其特征在于，为分离消化法，具体为在样品中加入酸溶液混合均匀得到预处理混合液，此时酸溶液的体积是样品体积的0.5-100倍，加热煮沸，控制加热温度以防烧干将样品碳化；利用加热煮沸水和酸的过程完成初步消化，待水完全蒸发后，再利用加热煮沸酸至冒酸性烟雾的过程继续消化，当待测混合液的体积为样品体积的0.5-10倍时，停止加热，此时完成二次消化；在两步消化过程的同时样品中的有机物从样品中析出并存留在样品溶液中，冷却，加入水或酸溶液继续煮沸，此时水或酸溶液的体积是样品体积的0.5-100倍；然后冷却至室温，样品中析出的有机物以固态或液态的形式漂浮在溶液的表面，再进行固液分离或液液分离，得到分离消化后的溶液。
  2. 根据权利要求1所述的一种高浓度有机物样品的预处理方法，其特征在于，将预处理混合液加热煮沸，完成初步消化和二次消化，冷却，加入水或酸溶液继续煮沸，重复初步消化和二次消化过程，反复多次，用于提高消化及分离效率。
  3. 根据权利要求1所述的一种高浓度有机物样品的预处理方法，其特征在于，所述酸溶液为质量浓度为0.1-100％的硝酸、盐酸、硫酸、高氯酸、醋酸、磷酸、氢氟酸或其混合酸。
  4. 一种测量高浓度有机物样品中重金属含量的方法，其特征在于，步骤为：
    1)采用权利要求1所述的分离消化法预处理待测样品，得到分离消化后的溶液；
    2)采用酸性水对电解池进行多次洗涤；洗涤干净后，将上述分离消化后的溶液加入到电解池中定容到样品体积的2-50倍，相当于将样品稀释2-50倍；
    3)在定容后的样品中加入Zn溶液混合均匀得到待测溶液，然后对待测溶液进行测量得到样品浓度；
    4)测量试剂空白浓度，将样品浓度减去试剂空白浓度，得到有机物样品中的重金属浓度。
  5. 根据权利要求4所述的一种测量高浓度有机物样品中重金属含量的方法，其特征在于，所述步骤3)中加入Zn溶液后待测溶液的质量浓度为1×10-10％-1％。
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