CN114018978A - Method for quantifying micro-plastic in environment based on micro-combustion calorimetry - Google Patents
Method for quantifying micro-plastic in environment based on micro-combustion calorimetry Download PDFInfo
- Publication number
- CN114018978A CN114018978A CN202111175080.0A CN202111175080A CN114018978A CN 114018978 A CN114018978 A CN 114018978A CN 202111175080 A CN202111175080 A CN 202111175080A CN 114018978 A CN114018978 A CN 114018978A
- Authority
- CN
- China
- Prior art keywords
- micro
- sample
- combustion
- plastic
- pyrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 67
- 229920003023 plastic Polymers 0.000 title claims abstract description 61
- 239000004033 plastic Substances 0.000 title claims abstract description 61
- 238000007707 calorimetry Methods 0.000 title claims abstract description 27
- 238000000197 pyrolysis Methods 0.000 claims abstract description 78
- 239000007789 gas Substances 0.000 claims abstract description 52
- 230000007613 environmental effect Effects 0.000 claims abstract description 48
- 239000011261 inert gas Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000000523 sample Substances 0.000 claims description 149
- 229920000426 Microplastic Polymers 0.000 claims description 49
- 239000007787 solid Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000036284 oxygen consumption Effects 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 9
- 229910052734 helium Inorganic materials 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- 239000012472 biological sample Substances 0.000 claims description 8
- 235000013305 food Nutrition 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010828 animal waste Substances 0.000 claims description 4
- 239000002361 compost Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 210000000056 organ Anatomy 0.000 claims description 3
- 238000011002 quantification Methods 0.000 claims description 3
- 101100185402 Mus musculus Mug1 gene Proteins 0.000 claims description 2
- 210000002784 stomach Anatomy 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 21
- 238000004458 analytical method Methods 0.000 abstract description 11
- 238000005259 measurement Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 150000001413 amino acids Chemical class 0.000 abstract description 3
- 239000003864 humus Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 210000001557 animal structure Anatomy 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 210000003736 gastrointestinal content Anatomy 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000005143 pyrolysis gas chromatography mass spectroscopy Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012418 validation experiment Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/22—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The method for quantifying the micro-plastic in the environment based on the micro-combustion calorimetry uses the existing micro-combustion calorimeter or the pyrolysis combustion flow calorimeter for detection, can simply and reliably measure the content of the micro-plastic in an environment sample, greatly reduces the time required by each analysis compared with the prior known method, and can also realize automation; when a micro combustion calorimeter or a pyrolysis combustion flow calorimeter is used for heating a sample to be detected, the sample to be detected does not contact with oxygen, the sample to be detected is pyrolyzed at a specified heating rate in an inert gas atmosphere, and the generated pyrolysis gas is combusted at a constant temperature, so that the influence on a detection result due to the oxidation of organic matters or inorganic matters such as humus, sugar, amino acid and the like in an environmental sample can be avoided, the pretreatment step of the environmental sample can be omitted, and the detection time is shortened under the condition of ensuring the accuracy of the measurement result.
Description
Technical Field
The invention relates to the technical field of detection of micro-plastic content, in particular to a micro-plastic quantification method in an environment based on a micro combustion calorimetry.
Background
The micro plastic is plastic particles or fibers with the particle size of less than 5mm, has strong adsorption capacity on persistent organic pollutants such as polychlorinated biphenyls (PCBs), Polycyclic Aromatic Hydrocarbons (PAHs) and the like in the environment and heavy metals, is easy to be mistakenly eaten by organisms with different nutritional levels in the environment, and threatens human health once entering a food chain. At present, the micro plastic is widely applied to personal care products, medical products and other industrial products as a product additive, so that the micro plastic enters the environment and causes primary micro plastic pollution. The primary micro plastic entering the environment is continuously broken and degraded through physical, chemical and biological actions, and secondary micro plastic pollution is generated. At present, micro-plastic pollution has become an environmental problem of common concern to governments, scholars and the public of all countries.
At present, no unified method exists for quantitative analysis of the micro-plastics, and the quantitative analysis is generally carried out from the aspects of quantity concentration and mass concentration of the micro-plastics.
Quantitative concentration analysis is generally performed using microscopic visualization or spectroscopy based on the resulting microplastic filtrate or solid sample from the environment, the type of polymer in the microplastic is determined by specific spectral structural features, and the number, size and geometry of the microplastic particles in a volume or area is determined by visual methods to calculate the sample quantitative concentration. The disadvantages of both of these methods are that the mass content of the micro-plastic in the environmental sample cannot be determined, and that the detection time of these methods depends strongly on the nature of the environmental matrix, since several long and time-consuming sample preparation steps are required to reduce the organic and inorganic components in the environmental matrix in order to obtain meaningful results, which take days or even weeks. Particle identification after particle acquisition can be automated, but the selection of an analytical record for a representative sample or sample fraction is still time consuming, typically requiring several hours for each measurement to process and analyze the data.
Thermal analysis is a known mass concentration analysis method, which uses a combination of pyrolysis gas chromatography-mass spectrometry to detect the content of specific thermal decomposition products of microplastic particles or synthetic polymers to determine the mass concentration of the microplastic itself. Although the method cannot directly detect the quantity, size and geometric shape of the micro-plastic, screens with different pore diameters can be used in the sampling and sample preparation processes, so that the micro-plastic particles with different size grades can be quantitatively analyzed. The existing thermal analysis method for the micro-plastics in the environmental sample has the main defects that detection instruments such as a thermogravimetric analyzer (TGA), a pyrolysis gas chromatography-mass spectrometer (Pyr-GC-MS) and the like have high purchase cost, the instruments are difficult to operate, a plurality of time-consuming pretreatment needs to be carried out on the sample, and the rapid determination of the content of the micro-plastics in the environmental sample is not facilitated.
In addition, the development of micro-plastics is also performed by elemental analysis of carbon, nitrogen, oxygen and sulfur in environmental samples, but prior separation of organic matter in the samples is required and automated measurement of the samples is hardly possible.
Under the background, the conventional detection methods all have certain defects and shortcomings, and because no standardized environmental sample sampling, preparation and detection procedures exist, a detection method which safely and quickly meets the detection requirement on the micro-plastics in the environmental sample is needed, the approach and the popularity of the micro-plastics to the environment are systematically and reliably recorded, and the micro-plastic pollution is propagated and restrained in the shortest time.
It is therefore an object of the present invention to provide a method which allows the quantitative determination of the mass concentration of a micro-plastic in an environment, which reduces the time and costs required compared to previously known methods, and which can be automated.
Micro combustion calorimetry, also known as pyrolysis combustion flow calorimetry, is a method of measuring the heat release rate of a sample in milligrams that enables the rate of heat release to be obtained by controlling the pyrolysis in an inert gas stream and subjecting the pyrolysis product to high temperature oxidative combustion, the oxygen concentration and the flow rate of the combustion gases enabling the determination of the amount of oxygen lost during combustion. So far, the method is only used for research and development of refractory materials and fireproof materials, and the invention provides that the content of the micro-nano materials in an environmental sample is determined by determining the heat release rate of pyrolysis gas detected by heating the environmental sample in a certain temperature interval.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the method for quantifying the micro-plastic in the environment based on the micro-combustion calorimetry, which has the advantages of simple determination method, short determination time and high working efficiency.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for quantifying micro-plastics in an environment based on micro-combustion calorimetry comprises the following steps:
step S1, obtaining a solid part in the environmental sample to obtain a sample to be detected;
step S2, heating the sample to be measured in inert gas atmosphere to obtain pyrolysis gas containing micro-plastics;
step S3, burning the pyrolysis gas in an oxygen-containing atmosphere, measuring the amount of oxygen consumed in the process of burning the pyrolysis gas, and calculating to obtain the total heat release amount in the process of burning the pyrolysis gas;
and step S4, determining the content of the micro plastic in the environmental sample through the total heat release.
Further, the environmental sample in the step S1 is selected from a water sample, an air sample or a solid sample; the weight of the sample to be measured is 1 mug-1 kg.
Further, the solid sample in step S1 is selected from soil, food, intermediate product of food, compost, sludge, sediment, biological sample or animal waste.
Further, the biological sample in step S1 is selected from an animal or a plant, an organ of an animal, a tissue of a plant, or a sample of animal stomach content.
Further, the inert gas in the step S2 is nitrogen, argon or helium.
Further, in the step S2, the sample to be measured is placed in a micro combustion calorimeter or a pyrolysis combustion flow calorimeter, and the sample to be measured is heated in an inert gas atmosphere to obtain a pyrolysis gas containing micro plastic.
Further, in the step S2, the sample to be measured is placed in a micro combustion calorimeter or a pyrolysis combustion flow calorimeter, and the sample to be measured is heated under the inert gas atmosphere condition that the heating rate is 1 to 100 ℃/min and the inert gas flow rate is 100 to 200ml/min, so that the sample to be measured is pyrolyzed, and the pyrolysis gas containing the micro plastic is obtained.
Further, in the step S3, the pyrolysis gas is delivered to a separate combustion chamber through the inert gas, the pyrolysis gas is combusted at a temperature of 900 ℃ in the combustion chamber under an oxygen-containing atmosphere, curves of oxygen consumption amounts in solid and gas combustion processes are respectively drawn, the amount of oxygen consumed in the combustion process of the pyrolysis gas is measured, and a total heat release amount in the combustion process of the pyrolysis gas is calculated.
Further, the inert gas used in step S3 is nitrogen, argon or helium.
Further, the method for determining the content of the micro plastic in the environmental sample through the total heat release in the step S4 is as follows: and dividing the total heat release quantity by the absolute mass difference to obtain a total heat release rate, and comparing the total heat release rate and the combustion specific heat of the measured sample with a standard curve to determine the content of the micro-plastic.
The invention has the beneficial effects that: the method for quantifying the micro-plastic in the environment based on the micro-combustion calorimetry can accurately and selectively measure the content of the micro-plastic in an environment sample, and compared with the existing measuring method, the method provided by the invention has the advantages that the analysis quality is higher; the method has the advantages that the existing micro combustion calorimeter or pyrolysis combustion flow calorimeter is used for detection, the content of the micro plastic in an environmental sample can be simply and reliably measured, compared with the previously known method, the time required by each analysis is greatly reduced, and the automation can be realized; when a micro combustion calorimeter or a pyrolysis combustion flow calorimeter is used for heating a sample to be detected, the sample to be detected does not contact with oxygen, the sample to be detected is pyrolyzed at a specified heating rate in an inert gas atmosphere, and the generated pyrolysis gas is combusted at a constant temperature, so that the influence on a detection result due to the oxidation of organic matters or inorganic matters such as humus, sugar, amino acid and the like in an environmental sample can be avoided, the pretreatment step of the environmental sample can be omitted, and the detection time is shortened under the condition of ensuring the accuracy of the measurement result.
The invention relates to a detection principle of a method for quantifying micro-plastics in an environment based on a micro-combustion calorimetry method, which comprises the following steps: the content of the micro-plastics in the environmental sample is determined by detecting the total heat release of the pyrolysis gas and converting by using the typical specific heat of combustion of different polymers in the micro-plastics; the determination of the total heat release rate is determined by the amount of oxygen consumed by the pyrolysis gases in the combustion chamber, and the amount of oxygen entering and exiting the combustion chamber is determined by sensors in the oxygen supply line and the exhaust line to infer the consumption of oxygen and to infer the release of heat. Given that 1kg of oxygen is consumed for 13.1MJ of heat, the characteristic heat of combustion for typical types of micro-plastics, such as PE, PP, PS or various suspensions, is about 40MJ/kg, but the characteristic specific heat of combustion for other components in the environment in the temperature window of detection is only 1-2MJ/kg, enabling the micro-plastic content to be determined based on the total heat release rate.
Drawings
FIG. 1 is a thermogravimetric analysis (TGA) result of a non-micro plastic environmental sample in example 1 of the present invention.
FIG. 2 is a thermogravimetric analysis (TGA) result of three samples of the microplastic polymeric material of example 1 of this invention.
FIG. 3 is a graph of the results of 3 repetitions of the Heat Release Rate (HRR) for a non-micro plastic environmental sample (total sample amount about 5 mg) in example 1 of the present invention.
FIG. 4 is a graph of the Heat Release Rate (HRR) results for three microplastic polymeric materials (sample total about 5 mg) in example 1 of the present invention.
FIG. 5 is a graph of the Heat Release Rate (HRR) results for 3 replicates of a non-micro plastic environmental sample (total sample amount about 5 mg) with 1% PE added in example 1 of the invention.
FIG. 6 is a graph of the Heat Release Rate (HRR) results for 3 replicates of a non-micro plastic environmental sample (total sample amount about 5 mg) with 3% PE added in example 1 of the invention.
FIG. 7 is a graph of the results of 3 repetitions of the Heat Release Rate (HRR) for a non-micro plastic environmental sample (total sample amount about 5 mg) with 5% PE added in example 1 of the present invention.
FIG. 8 is a graph of the results of 3 repetitions of the Heat Release Rate (HRR) for a non-micro plastic environmental sample (total sample amount about 5 mg) with 1% PE and 1% PS added in example 1 of the present invention.
FIG. 9 is a graph of the results of 3 repetitions of the Heat Release Rate (HRR) for a non-micro plastic environmental sample (total sample amount about 5 mg) with 3% PE and 3% PS added in example 1 of the present invention.
FIG. 10 is a graph of the results of 3 repetitions of the Heat Release Rate (HRR) for a non-micro plastic environmental sample (total sample amount about 5 mg) with 5% PE and 5% PS added in example 1 of the present invention.
FIG. 11 is a graph of THE effective heat of combustion (THE) in accordance with THE invention in example 1 plotted against THE weight of THE micro-plastic in a sample of a non-micro-plastic environment.
FIG. 12 is a graph of THE effective heat of combustion (THE) versus PE weight in a non-micro plastic environmental sample in example 1 of THE present invention.
Detailed Description
The following examples may help one skilled in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The invention relates to a method for quantifying micro-plastics in an environment based on micro-combustion calorimetry, wherein an environment sample is selected from a water sample, an air sample or a solid sample; the solid sample is selected from soil, food intermediate products, compost, sludge, sediment, biological samples or animal waste and the like, but the solid sample is not limited to the above, and can also be sand, sand and the like, and the solid sample is selected in various ways according to actual needs; the biological sample is selected from the group consisting of an animal, a plant, an organ of an animal, a tissue of a plant, a content sample of an animal stomach, and the like, but is not limited thereto, and may be animal blood, and the like.
The invention relates to a method for quantifying micro-plastic in an environment based on a micro-combustion calorimetry, which comprises the following steps: the use of a micro-combustion calorimeter or a suitable pyrolysis combustion flow calorimeter suitable for the purpose is required to obtain the pyrolysis gas; determining the heat of combustion of the pyrolysis gas by means of a pyrolysis combustion flow calorimeter or a suitable micro combustion calorimeter; micro combustion calorimeter and pyrolysis combustion flow calorimeter in the present invention are represented by a device operating according to the same measurement principle, which device can be represented by either of these terms; the device of the invention can rapidly pyrolyze the solid sample under the inert gas atmosphere in the non-combustion test, and then carry out high-temperature oxidation (combustion) on the volatile pyrolysis gas to respectively draw curves of oxygen consumption in the solid-state and gas-state combustion processes so as to obtain the total heat release. It is to be noted that the combustion of the pyrolysis gases takes place in a separate combustion chamber.
The invention relates to a method for quantifying micro-plastics in an environment based on micro-combustion calorimetry, wherein the heating rate is selected, and the heating rate is generally between 1 ℃/min and 100 ℃/min, such as 1 ℃/min, 5 ℃/min, 10 ℃/min or 20 ℃/min or higher. The heating rate is increased, so that the accuracy of specific heat output can be effectively improved.
The invention relates to a method for quantifying micro-plastics in an environment based on micro-combustion calorimetry, wherein the measurement range of the micro-combustion calorimeter or a pyrolysis combustion flow calorimeter on the total heat release rate can be set between 100 and 300 ℃, namely the corresponding temperature window is 100, 150, 200, 250 or as high as 300 degrees, when the heating rate is 60 ℃/min to 100 ℃/min, the total heat release rate of the pyrolysis of a single micro-plastic type cannot be expanded to a significantly wider range, and if an expected micro-plastic type, such as PE, PP or PS, corresponding detection temperature ranges can be selected, such as 300 to 600 ℃, 350 to 550 ℃ and 350 to 500 ℃. This function can be effectively applied to specific detection scenarios of known micro-plastic types, such as specific industrial wastewater pollutant discharge points or water treatment quality detection in industrial production. It should be noted, however, that depending on the heating rate used, pyrolysis of the microplastic may also begin at a lower temperature. A heating rate significantly lower than 60 ℃/min, for example a heating rate of 30 ℃/min or 15 ℃/min, can achieve pyrolysis of olefins at temperatures around 200 ℃. In this context, the detection temperature range may also be selected to be a lower temperature including a temperature range of 200 to 450 ℃, a temperature range of 250 to 450 ℃, or a temperature range of 275 to 500 ℃; it is to be construed that the temperature interval in the meaning of the present invention is a closed range between two fixed temperatures, which is a continuous range.
According to the method for quantifying the micro-plastic in the environment based on the micro-combustion calorimetry, the detected mass of the sample to be detected can be between 1 mu g and 1kg, specifically between 1mg and 10g, or increased to the mass between 1mg and 30 mg.
The invention relates to a method for quantifying micro-plastic in an environment based on micro-combustion calorimetry, wherein the used inert gas can be nitrogen, argon or helium, but not limited to the nitrogen, argon or helium, and can also be neon and the like.
The invention relates to a method for quantifying micro-plastic in an environment based on micro-combustion calorimetry, which comprises the following steps:
1. obtaining a solid part in an environment sample, and weighing the solid part of the environment sample to be detected to obtain a sample to be detected, wherein the weight of the sample to be detected is 1 mu g-1 kg; the environmental sample is selected from a water sample, an air sample or a solid sample; wherein the solid sample is selected from soil, food, intermediate product of food, compost, sludge, sediment, biological sample or animal waste, etc.; the biological sample is selected from animal or plant, animal organ, plant tissue or animal gastric content sample, etc.;
2. heating the sample to be measured at a required heating rate selected from the heating rates of 1-200 ℃/min to pyrolyze the weighed sample to be measured; during heating and pyrolysis, the sample was not exposed to oxygen. Pyrolyzing a particle part in 100-200 ml/min inert gas, such as inert carrier gas flow of nitrogen, argon or helium;
3. conveying the formed pyrolysis gas to a separate combustion chamber by means of an inert gas;
4. the pyrolysis gas entering the combustion chamber is immediately combusted (simultaneously with pyrolysis);
5. measuring the heat release rate in the combustion process of the pyrolysis gas, wherein the total heat of the combustion of the pyrolysis gas released by continuous heating in a limited temperature interval is the total heat release, and the temperature interval is determined according to a specific pyrolysis temperature interval of the micro plastic;
6. re-weighing the weight of the crucible containing residues that may remain incompletely pyrolyzed to obtain an absolute mass difference before and after pyrolysis;
7. and dividing the total heat release quantity by the absolute mass difference to obtain a total heat release rate, and comparing the total heat release rate and the combustion specific heat of the measured sample with a standard curve to determine the content of the micro-plastic.
Example 1
A method for quantifying micro-plastics in an environment based on micro-combustion calorimetry comprises the following steps:
step S1, weighing the particle part of the environmental sample to be detected to obtain a sample to be detected, wherein the weight of the sample to be detected is 5 mg;
step S2, placing the sample to be tested into a micro combustion calorimeter or a pyrolysis combustion flow calorimeter, heating the sample to be tested under the inert gas atmosphere condition that the heating rate is 60 ℃/min and the inert gas flow rate is 200ml/min, so that the sample to be tested is pyrolyzed, and obtaining pyrolysis gas containing micro plastic; the inert gas is nitrogen;
step S3, conveying the pyrolysis gas to an independent combustion chamber through inert gas, combusting the pyrolysis gas at the temperature of 900 ℃ in the combustion chamber under the oxygen-containing atmosphere condition, respectively drawing curves of oxygen consumption in solid-state and gas-state combustion processes, measuring the oxygen consumption in the process of combusting the pyrolysis gas, and calculating to obtain the total heat release in the process of combusting the pyrolysis gas; the inert gas is nitrogen;
step S4, determining the content of the micro-plastic in the environmental sample through the total heat release; the method for determining the content of the micro-plastic in the environmental sample through the total heat release comprises the following steps: and dividing the total heat release quantity by the absolute mass difference to obtain a total heat release rate, and comparing the total heat release rate and the combustion specific heat of the measured sample with a standard curve to determine the content of the micro-plastic.
Verification experiment I: carrying out gravimetric analysis on the sample by using thermogravimetric analysis, and verifying the reliability of the result; the specific experimental groups are shown in table 1 below; thermogravimetric analysis (TGA) results are shown in fig. 1-2;
TABLE 1
| |
1 | 2 | 3 | 4 |
| Non-micro plastic solid sample | 5mg | |||
| PE | 5mg | |||
| PS | 5mg | |||
| PP | 5mg |
And (5) verifying an experiment II: performing heat release rate analysis on the sample by using the heat release rate analysis, and verifying the reliability of the result; the specific experimental groups are shown in table 2 below; heat Release Rate (HRR) results are shown in fig. 3-4;
TABLE 2
| |
1 | 2 | 3 | 4 |
| Non-micro plastic solid sample | 5mg | |||
| PE | 5mg | |||
| PS | 5mg | |||
| PP | 5mg |
And (3) a third verification experiment: performing heat release rate analysis on the sample by using the heat release rate analysis, and verifying the reliability of the result; the specific experimental groups are shown in table 3 below;
TABLE 3
| Unit: mg of | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Non-micro plastic |
5 | 4.95 | 4.85 | 4.75 | 4.90 | 4.70 | 4.60 |
| PE | 0.05 | 0.15 | 0.25 | 0.05 | 0.15 | 0.25 | |
| PS | 0.05 | 0.15 | 0.15 |
Heat Release Rate (HRR) results are shown in fig. 5-10; THE graph of THE correlation of THE effective heat of combustion (THE) with THE weight of THE micro plastic in THE non-micro plastic environmental sample is shown in FIG. 11, and THE graph of THE correlation of THE effective heat of combustion (THE) with THE weight of THE PE in THE non-micro plastic environmental sample is shown in FIG. 12.
The results of the validation experiment in example 1 confirm that pyrolysis gas is generated by the decomposition of the microplastic, and also verify the reliability of the process of the present invention.
Example 2
A method for quantifying micro-plastics in an environment based on micro-combustion calorimetry comprises the following steps:
step S1, obtaining a solid part in the environment sample, and weighing a particle part of the environment sample to be detected to obtain a sample to be detected, wherein the weight of the sample to be detected is 100 g; 99 g of clean soil and 1 g of PE are contained in a sample to be detected;
step S2, placing the sample to be tested into a micro combustion calorimeter or a pyrolysis combustion flow calorimeter, heating the sample to be tested under the inert gas atmosphere condition that the heating rate is 100 ℃/min and the inert gas flow rate is 100ml/min, so that the sample to be tested is pyrolyzed, and obtaining pyrolysis gas containing micro plastic; the inert gas is argon;
step S3, conveying the pyrolysis gas to an independent combustion chamber through inert gas, combusting the pyrolysis gas at the temperature of 900 ℃ in the combustion chamber under the oxygen-containing atmosphere condition, respectively drawing curves of oxygen consumption in solid-state and gas-state combustion processes, measuring the oxygen consumption in the process of combusting the pyrolysis gas, and calculating to obtain the total heat release in the process of combusting the pyrolysis gas; the inert gas is argon;
step S4, determining the content of the micro-plastic in the environmental sample through the total heat release; the method for determining the content of the micro-plastic in the environmental sample through the total heat release comprises the following steps: and dividing the total heat release quantity by the absolute mass difference to obtain a total heat release rate, and comparing the total heat release rate and the combustion specific heat of the measured sample with a standard curve to determine the content of the micro-plastic.
The experiment of this example was repeated ten times and the PE content of the sample was measured to be between 0.995 g and 0.998 g.
Example 3
A method for quantifying micro-plastics in an environment based on micro-combustion calorimetry comprises the following steps:
step S1, obtaining a solid part in the environment sample, and weighing a particle part of the environment sample to be detected to obtain a sample to be detected, wherein the weight of the sample to be detected is 200 g; 198 g of clean soil and 2 g of PS exist in a sample to be detected;
step S2, placing the sample to be tested into a micro combustion calorimeter or a pyrolysis combustion flow calorimeter, heating the sample to be tested under the inert gas atmosphere condition that the heating rate is 1 ℃/min and the inert gas flow rate is 150ml/min, so that the sample to be tested is pyrolyzed, and obtaining pyrolysis gas containing micro plastic; the inert gas is helium;
step S3, conveying the pyrolysis gas to an independent combustion chamber through inert gas, combusting the pyrolysis gas at the temperature of 900 ℃ in the combustion chamber under the oxygen-containing atmosphere condition, respectively drawing curves of oxygen consumption in solid-state and gas-state combustion processes, measuring the oxygen consumption in the process of combusting the pyrolysis gas, and calculating to obtain the total heat release in the process of combusting the pyrolysis gas; the inert gas is helium;
step S4, determining the content of the micro-plastic in the environmental sample through the total heat release; the method for determining the content of the micro-plastic in the environmental sample through the total heat release comprises the following steps: and dividing the total heat release quantity by the absolute mass difference to obtain a total heat release rate, and comparing the total heat release rate and the combustion specific heat of the measured sample with a standard curve to determine the content of the micro-plastic.
The experiment of the embodiment is repeated ten times, and the PS content of the sample to be tested is measured to be 1.992 g-1.997 g.
From the experimental results of the above embodiments 1 to 3, it can be known that the method for quantifying the micro-plastic in the environment based on the micro combustion calorimetry can accurately and selectively measure the content of the micro-plastic in the environmental sample, and compared with the existing measuring method, the method of the present invention has higher analysis quality; the method has the advantages that the existing micro combustion calorimeter or pyrolysis combustion flow calorimeter is used for detection, the content of the micro plastic in an environmental sample can be simply and reliably measured, compared with the previously known method, the time required by each analysis is greatly reduced, and the automation can be realized; when a micro combustion calorimeter or a pyrolysis combustion flow calorimeter is used for heating a sample to be detected, the sample to be detected does not contact with oxygen, the sample to be detected is pyrolyzed at a specified heating rate in an inert gas atmosphere, and the generated pyrolysis gas is combusted at a constant temperature, so that the influence on a detection result due to the oxidation of organic matters or inorganic matters such as humus, sugar, amino acid and the like in an environmental sample can be avoided, the pretreatment step of the environmental sample can be omitted, and the detection time is shortened under the condition of ensuring the accuracy of the measurement result.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for quantifying micro-plastics in an environment based on micro-combustion calorimetry is characterized by comprising the following steps:
step S1, obtaining a solid part in the environmental sample to obtain a sample to be detected;
step S2, heating the sample to be measured in inert gas atmosphere to obtain pyrolysis gas containing micro-plastics;
step S3, burning the pyrolysis gas in an oxygen-containing atmosphere, measuring the amount of oxygen consumed in the process of burning the pyrolysis gas, and calculating to obtain the total heat release amount in the process of burning the pyrolysis gas;
and step S4, determining the content of the micro plastic in the environmental sample through the total heat release.
2. The method according to claim 1, wherein the environmental sample in step S1 is selected from water sample, air sample or solid sample; the weight of the sample to be measured is 1 mug-1 kg.
3. The method according to claim 2, wherein the solid sample in step S1 is selected from soil, food intermediate, compost, sludge, sediment, biological sample or animal waste.
4. The method according to claim 3, wherein the biological sample in step S1 is selected from the group consisting of an animal or a plant, an organ of an animal, a tissue of a plant, and a content sample of an animal stomach.
5. The method for micro plastic quantification in micro combustion calorimetry based environment according to claim 1, wherein the inert gas in step S2 is nitrogen, argon or helium.
6. The method for the quantitative determination of the micro plastic in the environment based on the micro combustion calorimetry as claimed in claim 1, wherein the sample to be measured is placed into a micro combustion calorimeter or a pyrolysis combustion flow calorimeter in step S2, and the sample to be measured is heated in an inert gas atmosphere to obtain the pyrolysis gas containing the micro plastic.
7. The method for quantifying the micro plastic in the environment based on the micro combustion calorimetry as claimed in claim 6, wherein in step S2, the sample to be measured is placed into a micro combustion calorimeter or a pyrolysis combustion flow calorimeter, and the sample to be measured is heated under the inert gas atmosphere conditions that the heating rate is 1-100 ℃/min and the inert gas flow rate is 100-200 ml/min, so that the sample to be measured is pyrolyzed to obtain the pyrolysis gas containing the micro plastic.
8. The method according to claim 1, wherein in step S3, the pyrolysis gas is delivered to a separate combustion chamber through inert gas, the pyrolysis gas is combusted under the conditions of 900 ℃ temperature in the combustion chamber and oxygen-containing atmosphere, the oxygen consumption during solid-state and gaseous combustion is plotted respectively, the oxygen consumption during combustion of the pyrolysis gas is measured, and the total heat release during combustion of the pyrolysis gas is calculated.
9. The method for micro plastic quantification in micro combustion calorimetry based environment according to claim 8, wherein the inert gas used in step S3 is nitrogen, argon or helium.
10. The method for the quantitative determination of the micro plastics in the environment based on the micro combustion calorimetry as claimed in claim 1, wherein the method for determining the content of the micro plastics in the environmental sample through the total heat release in the step S4 is as follows: and dividing the total heat release quantity by the absolute mass difference to obtain a total heat release rate, and comparing the total heat release rate and the combustion specific heat of the measured sample with a standard curve to determine the content of the micro-plastic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111175080.0A CN114018978A (en) | 2021-10-09 | 2021-10-09 | Method for quantifying micro-plastic in environment based on micro-combustion calorimetry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111175080.0A CN114018978A (en) | 2021-10-09 | 2021-10-09 | Method for quantifying micro-plastic in environment based on micro-combustion calorimetry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114018978A true CN114018978A (en) | 2022-02-08 |
Family
ID=80055569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111175080.0A Pending CN114018978A (en) | 2021-10-09 | 2021-10-09 | Method for quantifying micro-plastic in environment based on micro-combustion calorimetry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114018978A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200340935A1 (en) * | 2019-04-25 | 2020-10-29 | The United States of America, as represented by the administrator of the Federal Aviation Administra | Generating and Determining the Products of Premixed Combustion of Solid Materials in a Microscale Fire Calorimeter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104612841A (en) * | 2015-01-21 | 2015-05-13 | 哈尔滨工程大学 | Dual fuel engine combustion closed-loop control method based on analysis of heat release rate |
| CN106770455A (en) * | 2016-12-05 | 2017-05-31 | 西南科技大学 | A kind of new combustion heat determination method |
| CN108445144A (en) * | 2018-02-11 | 2018-08-24 | 江阴爱科森博顿聚合体有限公司 | A method of PE reclaimed materials carbon black contents are measured using combustion method |
| DE102019106806A1 (en) * | 2019-03-18 | 2020-09-24 | Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) | Method for determining the microplastic content in environmental samples |
-
2021
- 2021-10-09 CN CN202111175080.0A patent/CN114018978A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104612841A (en) * | 2015-01-21 | 2015-05-13 | 哈尔滨工程大学 | Dual fuel engine combustion closed-loop control method based on analysis of heat release rate |
| CN106770455A (en) * | 2016-12-05 | 2017-05-31 | 西南科技大学 | A kind of new combustion heat determination method |
| CN108445144A (en) * | 2018-02-11 | 2018-08-24 | 江阴爱科森博顿聚合体有限公司 | A method of PE reclaimed materials carbon black contents are measured using combustion method |
| DE102019106806A1 (en) * | 2019-03-18 | 2020-09-24 | Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) | Method for determining the microplastic content in environmental samples |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200340935A1 (en) * | 2019-04-25 | 2020-10-29 | The United States of America, as represented by the administrator of the Federal Aviation Administra | Generating and Determining the Products of Premixed Combustion of Solid Materials in a Microscale Fire Calorimeter |
| US11579103B2 (en) * | 2019-04-25 | 2023-02-14 | The United States of America, as represented by the Administrator of the Federal Aviation Administration | Generating and determining the products of premixed combustion of solid materials in a microscale fire calorimeter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dümichen et al. | Automated thermal extraction-desorption gas chromatography mass spectrometry: A multifunctional tool for comprehensive characterization of polymers and their degradation products | |
| Currie et al. | A critical evaluation of interlaboratory data on total, elemental, and isotopic carbon in the carbonaceous particle reference material, NIST SRM 1649a | |
| JP2010515038A (en) | Device and method for continuous measurement of tar concentration in a gas stream | |
| US5981290A (en) | Microscale combustion calorimeter | |
| WO2014064985A1 (en) | System for unified quantitative determination of various forms of carbon and nitrogen which employs calibration curves based on organic compounds | |
| Liu et al. | A fast chemical oxidation method for predicting the long-term mineralization of biochar in soils | |
| CN114018978A (en) | Method for quantifying micro-plastic in environment based on micro-combustion calorimetry | |
| CN112697200A (en) | Emergency monitoring method for unknown pollutants in burst water body polluted by water in water source area | |
| CN112540150A (en) | Sensor performance evaluation device, method and system | |
| CN111239276A (en) | Method for measuring organic matter content of soil and sludge | |
| CN116879207A (en) | Method for determining organic matters in soil | |
| US20050129578A1 (en) | Fast system for detecting detectible combustion products and method for making and using same | |
| CN109696374B (en) | Method and apparatus for determining the content of elements and/or compounds | |
| CN111443056B (en) | Method for measuring mercury content in copper concentrate | |
| CN115876544A (en) | Method for rapidly measuring sludge organic matter | |
| CN111855886A (en) | Method for rapidly and quantitatively detecting residual quantity of oil stains on metal film | |
| Murillo et al. | Polycyclic aromatic hydrocarbons in filterable PM2. 5 emissions generated from regulated stationary sources in the metropolitan area of Costa Rica | |
| CN114136832A (en) | Method for detecting concentration of micro-plastic in soil by thermogravimetric analysis and application | |
| Muzyka et al. | Chemometric analysis of air pollutants in raw and thermally treated coals–Low-emission fuel for domestic applications, with a reduced negative impact on air quality | |
| US11579103B2 (en) | Generating and determining the products of premixed combustion of solid materials in a microscale fire calorimeter | |
| CN108844995A (en) | A kind of coal spontaneous combustion adiabatic oxygenation experimental bench | |
| Michal | Combustion products of polymeric materials. 1—Test chamber CAB 4.5 | |
| Yu et al. | Electronic nose integrated with chemometrics for rapid identification of foodborne pathogen | |
| Zhang et al. | Methods and applications for quantitative assessment of uncertainty in atmospheric particulate matter source profiles | |
| US20240241044A1 (en) | System and method for detecting mercury and total organic carbon in burnt product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220208 |