CN113945663A - Method for measuring dissolved organic carbon isotopes in water by TOC-IRMS (Total organic carbon-iron sulfide) coupling technology - Google Patents
Method for measuring dissolved organic carbon isotopes in water by TOC-IRMS (Total organic carbon-iron sulfide) coupling technology Download PDFInfo
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Abstract
A method for measuring dissolved organic carbon isotopes in water by a TOC-IRMS combined technology comprises the following steps: filtering a sample by a filter membrane; acidifying a water sample, wherein the pH value is less than 2; standing for three days at room temperature after ultrasonic oscillation; oxygen is introduced to remove dissolved CO2And volatile organic carbon; directly injecting water sample into the high-temperature oxidation tube to oxidize the dissolved organic carbon into CO at high temperature2；CO2Under the blowing of carrier gas of 80ml/L, carrying out water removal, purification, enrichment and separation; introducing IRMS to measure the dissolved organic carbon isotope delta in the water sample13CDOC. The carbon conversion rate is 90.00-1 percent for testing the DOC standard solution of caffeine, glucose, phthalic acid, potassium acetate and sodium humate with different concentrationsBetween 14.33%, delta13The standard deviation of the C value is between 0.01 per thousand and 0.57 per thousand, and delta13The measured value of the C value is consistent with the reference value, which shows that the method can accurately test the composition of the dissolved organic carbon isotopes in the water sample.
Description
Technical Field
The invention relates to the field of organic carbon isotope determination, in particular to a method for determining dissolved organic carbon isotopes in water by using a TOC-IRMS (Total organic carbon-iron-manganese-Mass Spectrometry) combined technology.
Background
Dissolved Organic Carbon (DOC) is an important environmental chemical of the geochemical cycle and generally refers to a Dissolved organic substance that can pass through a 0.4 μm filter and is not lost by evaporation during its subsequent use in the assay. Mainly comes from bacterial decomposition products, animal and plant secretion, excrement generated in the biological metabolism process, substances input on land and the like. The method is an important component of carbon cycle of the water body, and can effectively identify DOC sources in the water body by researching carbon isotope values of the DOC sources, reveal the biogeochemical cycle process of carbon in the water body and the like. And through the stable isotope determination technology, the limitation of content test in the DOC research process can be made up, and clues can be provided for the source, migration and conversion of DOC, which are attributed to the balance and kinetic effect of carbon isotopes.
The carbon stable isotope testing technology is successfully applied to reduction of CO through photosynthesis for the first time in 19602The metabolite study, followed by stable isotope technology, is widely used in various scientific fields as an effective method. In recent years, some new technologies for testing DOC carbon isotopes have appeared at home and abroad. The principle of the wet oxidation method is that different oxidants are added into a water sample, and DOC is oxidized into CO by off-line heating or ultraviolet irradiation and the like2CO formed2By testing the carbon isotope composition through IRMS, the method has the problem of low oxidation efficiency on some DOC components (such as humic acid and the like) which are difficult to oxidize. The EA-IRMS combined high-temperature oxidation method needs to convert DOC in a water sample into a solid sample through freeze drying, and has the problems of large required sample amount, increased blank influence and time and labor waste in the conversion process. An off-line high-temp sealed tube combustion method features that the water sample is sealed in oxygen-filled quartz tube and heated to oxidize DOC to generate CO2Gas, CO after removal of moisture, halogens and other impurity gases2The isotope composition is determined by IRMS, and the method has the advantages of small sample amount, high conversion efficiency and complex and relatively complex conversion and purification processExperimental errors are easily introduced.
Disclosure of Invention
The invention aims to solve the problems of complicated pretreatment, low acidification efficiency, incapability of on-line continuous test and uncertain test conditions of the conventional method for testing the dissolved organic carbon isotope in water in the prior art, and provides a method for testing the dissolved organic carbon isotope in water by using a TOC-IRMS (total organic carbon-iron-manganese) combined technology2The error of the operation process improves the testing efficiency; the measured carbon conversion rate is between 90.00 and 114.33 percent and delta13The standard deviation of the C value is between 0.01 per thousand and 0.57 per thousand, and delta13The measured value of the C value is consistent with the reference value, which shows that the method can accurately test the composition of the dissolved organic carbon isotopes in the water body.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for measuring dissolved organic carbon isotopes in water by a TOC-IRMS combined technology comprises the following steps:
1) filtering the collected water sample by a filter membrane to remove organic carbon particles and insoluble impurities;
2) acidifying the water sample obtained in the step 1), and adjusting the pH of the water sample to be less than 2;
3) ultrasonically oscillating the water sample obtained in the step 2) to remove dissolved inorganic carbon in the water sample;
4) putting the water sample obtained in the step 3) into a TOC automatic sample feeding disc, and introducing O2Continuously bubbling to remove dissolved CO in the sample2And volatile organic carbon;
5) absorbing the water sample in the step 4) through a TOC sample introduction system and directly injecting the water sample into a high-temperature oxidation tube, and combusting the dissolved organic carbon in the water sample with oxygen at high temperature under the action of a Pt catalyst to generate CO2；
6) CO formed in step 5)2Under the purging of carrier gas, removing water in the sample gas through a semiconductor refrigerator and a chemical water removal trap, then introducing into an IRMS stable isotope mass spectrometer after freezing enrichment by liquid nitrogen and separation and purification by a chromatographic column, and dissolving an organic carbon isotope delta in a test water sample13CDOC；
7) Accurately weighing standard samples of glucose, phthalic acid, potassium acetate, sodium humate and caffeine, wrapping the samples with tin cups, and measuring the delta of the solid standard samples by an element analyzer-stable isotope mass spectrometer13C value;
8) preparing DOC standard solution of glucose, phthalic acid, potassium acetate, sodium humate and caffeine, and repeating the steps 1) to 6) to test the dissolved organic carbon isotope delta of the DOC standard solution13CDOC。
In the step 1), the filter membrane is a filter membrane with the pore diameter of 0.45 μm.
In the step 2), the acid added into the water sample is hydrochloric acid.
In the step 3), the oscillation is carried out for 15-20 min at normal temperature, and then the mixture is stood at room temperature and reacts for three days.
In step 4), O is introduced2The flow rate is 5ml/min, and the continuous bubbling time is 15-20 min.
In the step 5), the oxidation temperature of the high-temperature oxidation tube is 850 ℃.
In the step 5), the catalyst is a Pt catalyst.
In the step 5), the flow rate of oxygen introduced into the high-temperature oxidation tube is 10ml/min, and the oxygen introduction time is 20 s.
In the step 6), the carrier gas is high-purity helium, and the flow rate is 80 ml/L.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the method has simple pretreatment process, does not need sample freeze-drying, directly injects the acidified water sample into the oxidation tube, and converts DOC in the water body into CO under the optimal oxidation efficiency by adjusting the temperature, the oxygen introducing time and the carrier gas flow rate of the oxidation tube2. Then, under the blowing of carrier gas of 80mL/min, the sample gas is subjected to dehydration, purification, freezing enrichment and chromatographic column separation and purification, and then an IRMS stable isotope mass spectrometer is introduced, so that the organic carbon isotope delta dissolved in the test water sample13CDOC。
The invention fills the blank of the method for testing the dissolved organic carbon isotope in the water body by using the TOC-IRMS combination, and compares the methodThe acidification efficiency of hydrochloric acid and phosphoric acid on a water sample is determined, and the pretreatment time for acidification is determined to be three days; the optimal reaction conditions such as the temperature, the oxygen introduction amount, the carrier gas flow rate and the like of the oxidation tube are verified, the continuous and automatic batch test of the dissolved organic carbon isotopes in the water body is realized, and the conversion of manual off-line DOC into CO is reduced2The error of the operation process improves the testing efficiency. The method has reliable result and high accuracy, and the test of DOC standard solutions with different concentrations has the carbon conversion rate of between 90.00 and 114.33 percent and delta13The standard deviation of the C value is between 0.01 per thousand and 0.57 per thousand, and delta13The measured value of the C value is consistent with the reference value, which shows that the TOC-IRMS combined method can accurately test the composition of the dissolved organic carbon isotopes in the water body.
Drawings
FIG. 1 shows the relationship between the pretreatment time duration of different acids and the delta ratio between lake water and karst water13Influence of the C value.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
A method for determining dissolved organic carbon isotopes in water by using TOC-IRMS comprises the following steps:
(1) after the sample is collected, the sample is filtered by a filter membrane of 0.45um to remove organic carbon particles and insoluble impurities, and the sample is refrigerated and stored at low temperature.
(2) Measuring 15mL of the sample obtained in the step (1), putting the sample into a 40mL glass sample bottle, adding acid, acidifying the water sample, and adjusting the pH value of the water sample to be less than 2.
(3) And (3) placing the sample obtained in the step (2) into an ultrasonic water bath oscillator, oscillating for 15-20 min at normal temperature, standing at room temperature, and fully removing the dissolved inorganic carbon in the sample.
(4) Putting the solution obtained in the step (3) into a TOC automatic sample feeding disc, and introducing O with the flow rate of 5mL/min2Continuously bubbling for 15-20 min to remove dissolved CO in the sample2And volatile organic carbon.
(5) Absorbing 1mL of water sample in the step (4) through a TOC sample introduction system and directly injecting the water sample into a high-temperature oxidation tube, wherein oxygen and dissolved organic carbon in the water sample are introducedUnder the action of Pt catalyst, CO is burnt at high temperature2。
(6) CO produced in step (5)2Under the purging of carrier gas, the water in the sample gas is removed through a semiconductor refrigerator and a chemical water removal trap. After liquid nitrogen freezing enrichment and chromatographic column separation and purification, introducing an IRMS stable isotope mass spectrometer (Isopirime 100), and dissolving the organic carbon isotope delta in the test water sample13CDOC。
(7) In the step (2), lake water and karst water samples are selected and divided into two parts, hydrochloric acid is respectively added into the lake water 1 and the karst water 1, phosphoric acid is added into the lake water 2 and the karst water 2, the PH is adjusted to be less than 2, and the steps (4) to (6) are repeated under 4 hours, 24 hours, 48 hours, 72 hours and 120 hours. As shown in FIG. 1, the lake water and karst water added with hydrochloric acid can obtain stable delta at 48h and 72h respectively13CDOC(ii) a The lake water and the karst water added with phosphoric acid take 120 hours to obtain stable delta13CDOC. Therefore, hydrochloric acid (6mol/L) is selected to carry out acidification treatment on a water sample, and the water sample is kept stand for three days to fully remove dissolved inorganic carbon in the sample.
(8) Accurately weighing solid standard samples of glucose, phthalic acid, potassium acetate, sodium humate and caffeine, and weighing at 4 × 6cm2And (5) packaging the sample in a tin cup. Determination of delta in solid standards by means of an elemental analyzer-stable isotope mass spectrometer (EA-IRMS)13C value (the measurement results of the reference values are-33.90 ‰, -12.43 ‰, -28.52 ‰ -24.75 ‰, -23.40 ‰).
(9) Accurately weighing the same solid standard substance as the solid standard substance in the step (7), and respectively configuring a concentration gradient: 0.5mg/L, 1mg/L, 5mg/L, 10mg/L glucose, phthalic acid, potassium acetate, sodium humate and caffeine DOC standard solution. Repeating the steps (1) to (6), and testing the dissolved organic carbon isotope delta of the DOC standard solution13CDOC。
TABLE 1
TABLE 2
Determination of delta of five standard solutions of different concentrations by TOC-IRMS13CDOCValue, delta, of the same solid standard sample as determined by EA-IRMS in step (7)13And C values are compared, and SD (n is 6) is calculated to verify the feasibility and the accuracy of the method, and specific test results are shown in tables 1-2, wherein the table 1 shows the conversion rate of the dissolved organic carbon of the five standard compounds at different concentrations, and the table 2 shows the measurement results of the isotope values of the dissolved organic carbon of the five standard compounds at different concentrations. The carbon conversion rate of the standard solution is between 90.00 and 114.33 percent, delta13The standard deviation of the C value is between 0.01 per thousand and 0.57 per thousand, and delta13CDOCThe measured value of the value corresponds to the reference value.
(10) In the step (5), the water sample is directly injected into the high-temperature oxidation tube, and the oxidation efficiency of the sample is related to the temperature of the oxidation tube. Under the condition that other test parameters are not changed, the oxidation temperature of the high-temperature oxidation tube is changed, and the temperature of the oxidation tube is respectively set to be 800 ℃, 850 ℃ and 900 ℃. TABLE 3 DOC Standard solution carbon conversion and delta at different Oxidation temperatures13C value (n ═ 6), and it was found by comparison that the carbon conversion of DOC standard solution of glucose, phthalic acid, potassium acetate, caffeine and sodium humate was the closest to the theoretical value at an oxidation degree of 850 ℃, and the δ obtained was measured13CDOCThe standard deviation of the values is minimum, and the range of the standard deviation is between 0.01% and 0.05%. Therefore, the temperature of the oxidation tube is controlled to be 850 ℃ in the invention.
TABLE 3
TABLE 4
(11) In the step (5), the sample is subjected to high temperature in a high temperature oxidation tubeAnd (3) oxidation reaction, wherein the oxidation efficiency is related to the amount of introduced oxygen. And changing the time length of introducing oxygen under the condition that other test parameters are not changed, setting the flow rate of the oxygen to be 10ml/min, and respectively introducing the oxygen for 10s, 20s and 30 s. TABLE 4 DOC Standard solution carbon conversion and delta at different oxygen addition times13The carbon conversion of the DOC standard solution of glucose, phthalic acid, potassium acetate, caffeine and sodium humate was found to be closest to the theoretical value by comparison with the C value (n ═ 6), and the standard deviation range measured was smallest, between 0.01% and 0.05%, at an oxygen flow time of 20 s. Therefore, the present invention sets the oxygen introduction time period to 20 s.
TABLE 5
(12) In the step (6), the flow rate of the carrier gas is related to the separation and purification of the sample and the ionization efficiency of the mass spectrum. Under the conditions that the temperature of a high-temperature oxidation tube is 850 ℃ and the oxygen introduction time is 20s, the flow rates of carrier gas are respectively set to be 80ml/min and 100ml/min, and caffeine and glucose DOC standard solution delta with the concentration of 5mg/L are respectively tested13And C value. TABLE 5 carbon conversion and delta for standard solutions of caffeine and glucose at different carrier gas flow rates of 5mg/L13And C value (n is 6), and the comparison shows that the carbon conversion rate of the DOC standard solution is closer to the theoretical value when the carrier gas flow rate is 80mL/min compared with 100mL/min, so that the carrier gas flow rate is set to be 80 mL/min.
Claims (8)
1. A method for measuring dissolved organic carbon isotopes in water by a TOC-IRMS coupling technology is characterized by comprising the following steps:
1) filtering the collected water sample by a filter membrane to remove organic carbon particles and insoluble impurities;
2) acidifying the water sample obtained in the step 1), and adjusting the pH of the water sample to be less than 2;
3) ultrasonically oscillating the water sample obtained in the step 2) to remove dissolved inorganic carbon in the water sample;
4) putting the water sample obtained in the step 3) into a TOC automatic sample feeding disc, and introducing O2Continuously bubbling and removingDissolved CO in the sample2And volatile organic carbon;
5) absorbing the water sample in the step 4) through a TOC sample introduction system and directly injecting the water sample into a high-temperature oxidation tube, and combusting the dissolved organic carbon in the water sample with oxygen at high temperature under the action of a Pt catalyst to generate CO2；
6) CO formed in step 5)2Under the purging of carrier gas, removing water in the sample gas through a semiconductor refrigerator and a chemical water removal trap, then introducing into an IRMS stable isotope mass spectrometer after freezing enrichment by liquid nitrogen and separation and purification by a chromatographic column, and dissolving an organic carbon isotope delta in a test water sample13CDOC；
7) Accurately weighing standard samples of glucose, phthalic acid, potassium acetate, sodium humate and caffeine, wrapping the samples with tin cups, and measuring the delta of the solid standard samples by an element analyzer-stable isotope mass spectrometer13C value;
8) preparing DOC standard solution of glucose, phthalic acid, potassium acetate, sodium humate and caffeine, and repeating the steps 1) to 6) to test the dissolved organic carbon isotope delta of the DOC standard solution13CDOC。
2. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the acid added into the water sample is hydrochloric acid.
3. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the oscillation is carried out for 15-20 min at normal temperature, and then the mixture is stood at room temperature and reacts for three days.
4. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in step 4), O is introduced2The flow rate is 5ml/min, and the continuous bubbling time is 15-20 min.
5. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in the step 5), the oxidation temperature of the high-temperature oxidation tube is 850 ℃.
6. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in the step 5), the catalyst is a Pt catalyst.
7. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in the step 5), the flow rate of oxygen introduced into the high-temperature oxidation tube is 10ml/min, and the oxygen introduction time is 20 s.
8. The method for measuring the dissolved organic carbon isotope in water by using the TOC-IRMS combined technology as claimed in claim 1, wherein the method comprises the following steps: in the step 6), the carrier gas is high-purity helium, and the flow rate is 80 ml/L.
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| CN115684325A (en) * | 2022-10-17 | 2023-02-03 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Ultrahigh-resolution mass spectrometry method for dissolving organic carbon and application thereof |
| CN116539773A (en) * | 2023-07-06 | 2023-08-04 | 中国科学院地质与地球物理研究所 | Method for detecting fractionation coefficient of calcium isotope in adsorption process |
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| CN116539773A (en) * | 2023-07-06 | 2023-08-04 | 中国科学院地质与地球物理研究所 | Method for detecting fractionation coefficient of calcium isotope in adsorption process |
| CN116539773B (en) * | 2023-07-06 | 2023-09-15 | 中国科学院地质与地球物理研究所 | Method for detecting fractionation coefficient of calcium isotope in adsorption process |
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