CN116067952A - Seawater COD detection method - Google Patents
Seawater COD detection method Download PDFInfo
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- CN116067952A CN116067952A CN202211657375.6A CN202211657375A CN116067952A CN 116067952 A CN116067952 A CN 116067952A CN 202211657375 A CN202211657375 A CN 202211657375A CN 116067952 A CN116067952 A CN 116067952A
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Abstract
A method for detecting seawater COD belongs to the technical field of seawater detection. In order to solve the defects that the existing seawater oxygen demand titration method is complex in operation, complex in steps, long in measurement time and unsuitable for on-site rapid measurement, the invention adopts the following steps: weighing a quantitative seawater sample, adding a sodium hydroxide solution, uniformly mixing, adding a potassium permanganate solution for oxidation, carrying out constant-temperature timed digestion, and cooling to room temperature; sequentially adding sulfuric acid solution and potassium iodide solution, mixing, standing, and pouring into a colorimetric device; and placing the colorimetric device in a tester for colorimetric measurement to obtain the COD value of the seawater sample. The invention is mainly used for detecting seawater COD.
Description
Technical Field
The invention belongs to the technical field of seawater detection, and particularly relates to a seawater COD detection method.
Background
When seawater contains a large amount of organic matters, a large amount of microorganisms in the seawater can grow and reproduce, so that the content of dissolved oxygen in the seawater is reduced, the marine ecological environment is deteriorated, and the marine culture is greatly influenced, so that the supervision of marine environmental pollution is required to be continuously increased. In order to standardize the quality detection of the ecological environment of the offshore area, protect the ecological environment and ensure the scientificity, accuracy, systematicness, comparability and representativeness of the environmental monitoring of the offshore area of the whole country, the current measurement method of the national standard HJ/T132-2003 adopts a basic potassium permanganate method to measure the chemical oxygen demand of the seawater.
Chemical oxygen demand COD (Chemical Oxygen Demand) is the measure of the amount of reducing species in a water sample that need to be oxidized chemically. Oxygen equivalent of substances (typically organic substances) in the water sample that can be oxidized by the strong oxidizing agent.
The basic potassium permanganate COD in the national standard adopts a titration method, and firstly, potassium iodate is used for calibrating sodium thiosulfate; then oxidizing oxygen demand in seawater with potassium permanganate, then reducing potassium permanganate with potassium iodide, adding a starch indicator, titrating with calibrated sodium thiosulfate solution, and finally calculating oxygen consumption according to the amount of consumed sodium thiosulfate. The titration method is to add a large amount of excessive oxidant to ensure that the organic matters are oxidized, then to titrate with sodium sulfate, consume the rest of the oxidant, and convert the oxidant actually consumed in oxidizing the organic matters.
Therefore, there is a need for a seawater COD detection method that can be used for batch detection, has high efficiency, short measurement time, and is not easily affected by the detection environment.
Disclosure of Invention
The invention aims to overcome the defects that the existing seawater oxygen demand titration method is complex in operation, complex in steps, long in measurement time and unsuitable for on-site rapid measurement, and provides a seawater COD detection method which is high in batch detection, high in efficiency, short in measurement time and not easily affected by detection environment.
The invention relates to a method for measuring seawater COD, which comprises the following steps:
s1, measuring A ml of seawater sample, placing the seawater sample in a digestion tube, adding (A/10) ml of sodium hydroxide solution with the concentration of 3mol/L into the digestion tube, and uniformly mixing to obtain primary mixed solution;
s2, adding (A/10) ml potassium permanganate solution with the concentration of 0.002mol/L into the mixed solution for oxidation, and uniformly mixing again to obtain secondary mixed solution;
s3, placing the secondary mixed solution in a constant-temperature digestion device for closed digestion, so that organic matters in the secondary mixed solution are oxidized, and a digestion solution is obtained;
s4, immediately taking out the test tube after digestion is finished, and cooling the test tube to room temperature;
s5, adding (1+3) sulfuric acid solution (A/10) ml into the cooled digestion solution, uniformly mixing, then adding (A/10) ml potassium iodide solution with the concentration of 2.5g/100ml, and capping and uniformly mixing;
s6, standing for 2-20 minutes, and pouring into a colorimetric device;
s7, placing the colorimetric device in a water quality tester for colorimetric measurement or placing the colorimetric device in a spectrophotometer for reading absorbance for measurement;
s8, obtaining the COD value of the seawater sample based on the corresponding relation between the COD and the standard colorimetric card or the standard curve of the COD and the absorbance.
Further: in S1, the seawater sample sampling amount a satisfies: 25ml is more than or equal to A is more than or equal to 5ml.
Further: in S3, the temperature of the digestion device is 100-120 ℃.
Further: in S5, the (1+3) sulfuric acid solution is a solution obtained by mixing 3 parts of distilled water with 1 part of sulfuric acid (ρ=1.84 g/ml) having a mass ratio of 98%.
Further: in S6, the rest time is 5 minutes.
Further: in S7, the colorimetric assay is completed within half an hour from the pouring into the colorimetric device.
Further: in S7, the colorimetric device is a cuvette or a cuvette.
The beneficial effects of the invention are as follows: the full scale detection of the invention can be basically controlled to be completed within half an hour, and compared with the traditional titration method, a great amount of time can be saved, and the rapid, convenient and accurate detection method for seawater COD, which is suitable for laboratory and field, can be realized. The detection wavelength of the invention in the spectrophotometer is 420nm visible light. The reagent and chloride ions in the method exist simultaneously, and the visible light with the wavelength of 420nm adopted is not obviously absorbed, so that the chloride ions have no influence on the method in the colorimetric process. In the scheme, the content of potassium permanganate meets the set optimal range, and the method ensures that the concentration of potassium iodide presents obvious step-type distribution in the range. Adding sulfuric acid, and quantifying potassium iodide, wherein the potassium iodide is controlled in a certain range, otherwise, the color comparison is affected. And (3) reducing potassium permanganate in an acidic environment, releasing iodine to make the solution yellow, and measuring the concentration of oxygen consumption in water by inversely proportional to the absorbance and the concentration of the solution at the wavelength of 420 nm.
Drawings
FIG. 1 is a flow chart;
FIG. 2 is a schematic diagram of the color chart of example 1.
Detailed Description
The following preferred embodiments of the present invention are provided, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. The examples described below are only for the purpose of illustrating the invention and should not be construed as limiting the invention, which is intended to be covered by the claims. The following detailed description of embodiments of the invention is provided for convenience in describing the invention and simplifying the description, and technical terms used in the description of the invention should be construed broadly, including but not limited to conventional alternatives not mentioned in the present application, including both direct implementation and indirect implementation.
Example 1
The embodiment will be described with reference to fig. 1 and 2, and the method for measuring seawater COD disclosed in the embodiment includes the following steps:
s1, accurately measuring 5ml of seawater sample in a digestion tube, adding 0.5ml of sodium hydroxide solution with the concentration of 3mol/L into the digestion tube, and uniformly mixing to obtain alkaline primary mixed solution;
s2, adding 0.5ml of potassium permanganate solution with the concentration of 0.002mol/L into the mixed solution for oxidation, covering and mixing uniformly to obtain secondary mixed solution, wherein the time is about 1 minute;
s3, placing the secondary mixed solution into a digestion device with constant temperature, wherein the constant temperature range of the digestion device is 100-120 ℃, so that organic matters in the secondary mixed solution are oxidized, and oxygen-consuming substances in water are oxidized to obtain digestion solution; this step takes about 15 minutes;
s4, taking out the test tube immediately after digestion is finished, and cooling the test tube to room temperature by water, wherein the time is about 2-3 minutes;
s5, adding 0.5ml of sulfuric acid solution into the cooled digestion solution, wherein the concentration of the sulfuric acid solution is 1+3, namely, 1 part of 98% concentrated sulfuric acid and 3 parts of ultrapure water are mixed to obtain sulfuric acid solution, uniformly mixing, then adding 0.5ml of potassium iodide solution with the concentration of 2.5g/100ml, adding a cover, uniformly mixing, and taking about 1 minute;
s6, pouring the mixture into a cuvette or a colorimetric tube after standing for 5 minutes;
s7, placing the cuvette or the colorimetric tube in a spectrophotometer for colorimetric determination, wherein the detection optical path in the spectrophotometer is 10mm; the colorimetric determination is completed within half an hour after the sample is poured into the colorimetric device, and the COD value of the seawater sample is obtained. The spectrophotometer is internally provided with a seawater COD standard curve or a built-in curve calibrated on site for colorimetric determination, and the time for this step is about 1 minute.
According to the scheme, the adding sequence, concentration and adding amount of each reagent are accurately controlled, so that the concentration of potassium iodide in a finally obtained sample shows obvious step-type distribution within the COD content range of 0-5mg/L, and the direct reading of the numerical value by a spectrophotometer is facilitated.
The total time of the above examples is about 25 minutes, which is a significant time saving over titration. The traditional titration method is used excessively, and the color of the titration method cannot show step distribution in the range of COD.
In this example, the detection wavelength in the spectrophotometer is 420nm visible light, and when chloride ions and certain substances exist simultaneously, some absorption occurs in the ultraviolet region of the spectrum, whereas chloride ions alone do not have significant absorption in the ultraviolet visible region of the spectrum. The reagent in this embodiment is present with chloride ions and does not absorb significantly in the visible light at the wavelength of 420nm used, so chloride ions have no effect on the method during the colorimetric process. The absorbance of the test solution is inversely proportional to the oxygen demand concentration. And accords with lambert-beer law in a range of measuring range. The reagent concentrations and the order of addition used must be exactly the same.
When the method is specifically implemented, a group of standard curves can be firstly made by using standard solution, the standard curves are built in a water quality tester or a spectrophotometer, and the actual measured COD value can be obtained by comparing and inquiring the reading reference standard curves in actual test. After the standard curve is obtained, samples can be processed in batches at the time of practice, for example, 30 samples can be processed simultaneously, because the spectroscopic measurement results are acceptable within 30 minutes after the samples are processed in the above manner, multiple samples can be processed at one time, for example, 3 samples can be processed simultaneously, after the completion, the measurement is performed by a spectrophotometer one by one, assuming that each tube takes 1 minute for reading, 30 tubes take 30 minutes, and 30 tubes are processed simultaneously, the total time of the processing process takes 25 minutes, and the total time of the reading of all the samples takes 30 minutes, 55 minutes, and the measurement time of each sample is equivalent to 2 minutes less than that of a single sample on average, and the efficiency is many times higher than that of the traditional titration method.
The optimal measurement range of the seawater oxygen demand in the embodiment is 0-5mg/L, and the over-range can be used for dilution measurement.
Data verification
Firstly, preparing a standard solution measurement standard curve:
1. preparing seawater standard solutions with oxygen demands of 0mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L and 5mg/L, wherein each standard solution contains 20000mg/L chloride ions, and the standard solutions are respectively processed according to the steps of the method, and then the absorbance X is read by a spectroscope, so that the result is as follows:
| concentration Y | 0mg/L | 1mg/L | 2mg/L | 3mg/L | 4mg/L | 5mg/L |
| Negative absorbance X | 0 | 0.104 | 0.211 | 0.320 | 0.427 | 0.533 |
Based on the above results, a regression curve equation is made:
Y＝9.2872X-0.0075
R＝0.9998
2. six groups of seawater standard solutions with oxygen demand of 2.5mg/L respectively contain chlorine ion concentrations of 1000mg/L, 2500mg/L, 5000mg/L, 10000mg/L, 15000mg/L and 20000mg/L, after the treatment according to the steps of the method, the absorbance X is read by a spectroscope, and the oxygen demand is calculated based on a regression curve, so that a test result is obtained, wherein the test result is as follows:
| concentration of chloride ion | 1000mg/L | 2500mg/L | 5000mg/L | 10000mg/L | 15000mg/L | 20000mg/L |
| Measurement results | 2.61mg/L | 2.49mg/L | 2.44mg/L | 2.38mg/L | 2.61mg/L | 2.58mg/L |
| Error of | 4.4％ | -0.4％ | -2.4％ | 4.8％ | 4.4％ | 3.2％ |
The test result is within + -5%.
3. Offshore and estuary multipoint sampling tests and national standard titration tests were compared:
| sampling point | Offshore 1 | Offshore 2 | Breeding area 1 | Cultivation area 2 | Sea entrance 1 | Sea entrance 2 |
| National standard titration method | 3.57 | 5.40 | 9.09 | 11.2 | 3.09 | 3.21 |
| The present invention relates to a spectroscopic method | 3.40 | 5.54 | 8.81 | 11.6 | 3.12 | 3.15 |
| Error of | -4.8％ | 2.6％ | -3.1％ | 3.6％ | 1％ | -1.9％ |
The spectrophotometry measurement of the embodiment is basically consistent with the comparison result of the national standard titration method.
According to the embodiment, the experiment result judges that the method meets the accuracy and precision requirements of seawater oxygen demand detection, the complex titration process is not needed, the spectrophotometry is utilized to directly measure the water sample result for only a few seconds, the detection time is greatly shortened, the detection requirements of different environments can be met, and the method is more suitable for field and emergency detection and mariculture detection. The method reduces the dosage of the reagent, reduces the detection cost and reduces the discharge of the detection waste liquid. The method is simple to operate and is easier to master by test staff. The method is suitable for professional water quality detectors and common spectrophotometers. The color comparison of the method can be applied to various modes such as a cuvette, a color comparison tube and the like.
Example 2
The present embodiment is described in conjunction with embodiment 1, and the method for measuring seawater COD disclosed in the present embodiment comprises the steps of:
s1, accurately measuring 10ml of seawater sample in a digestion tube, adding 1ml of sodium hydroxide (concentration is 3 mol/L) solution into the digestion tube, and uniformly mixing to obtain a mixed solution;
s2, adding 1ml of potassium permanganate solution (with the concentration of 0.002 mol/L) into the mixed solution for oxidation, covering and mixing uniformly, and mixing uniformly again to obtain secondary mixed solution, wherein the time for the step is about 1 minute;
s3, placing the secondary mixed solution in a digestion device subjected to constant temperature treatment for carrying out timing digestion for about 15 minutes (+ -5 seconds), wherein the constant temperature condition of the digestion device is that the sealing heating is carried out at 95-100 ℃ (95 ℃ is selected in the operation), so that organic matters in the secondary mixed solution are oxidized, and oxygen-consuming matters in water are oxidized to obtain a digestion solution;
s4, immediately taking out the test tube after digestion is finished, and cooling the test tube to room temperature for about 2-3 minutes;
s5, adding 1ml of sulfuric acid solution with the concentration of 1+3 into the cooled digestion solution, namely, mixing 1 part of 98% concentrated sulfuric acid with 3 parts of ultrapure water to obtain a sulfuric acid solution, uniformly mixing, then adding 1ml of potassium iodide solution (with the concentration of 2.5g/100 ml), covering and uniformly mixing, and taking 1 minute;
s6, after standing for 5 minutes, pouring the sample into a cuvette or a cuvette, wherein the detection optical path in a spectrophotometer is 10mm, and the cuvette or the cuvette can be used;
s7, placing the cuvette or the colorimetric tube into a water quality tester for colorimetric determination, measuring absorbance by placing the cuvette or the colorimetric tube into the water quality tester, and reading the COD concentration value of the sample.
Claims (7)
1. The method for measuring the COD of the seawater is characterized by comprising the following steps of:
s1, measuring A ml of seawater sample, placing the seawater sample in a digestion tube, adding (A/10) ml of sodium hydroxide solution with the concentration of 3mol/L into the digestion tube, and uniformly mixing to obtain primary mixed solution;
s2, adding (A/10) ml potassium permanganate solution with the concentration of 0.002mol/L into the mixed solution for oxidation, and uniformly mixing again to obtain secondary mixed solution;
s3, placing the secondary mixed solution in a constant-temperature digestion device for closed digestion, so that organic matters in the secondary mixed solution are oxidized, and a digestion solution is obtained;
s4, immediately taking out the test tube after digestion is finished, and cooling the test tube to room temperature;
s5, adding (1+3) sulfuric acid solution (A/10) ml into the cooled digestion solution, uniformly mixing, then adding (A/10) ml potassium iodide solution with the concentration of 2.5g/100ml, and capping and uniformly mixing;
s6, standing for 2-20 minutes, and pouring into a colorimetric device;
s7, placing the colorimetric device in a water quality tester for colorimetric measurement or placing the colorimetric device in a spectrophotometer for reading absorbance for measurement;
s8, obtaining the COD value of the seawater sample based on the corresponding relation between the COD and the standard colorimetric card or the standard curve of the COD and the absorbance.
2. The method for measuring seawater COD according to claim 1, wherein in S1, the seawater sample sampling amount a satisfies: 25ml is more than or equal to A is more than or equal to 5ml.
3. The method according to claim 1, wherein in S3, the temperature of the digestion vessel is 95 to 120 ℃.
4. The method for measuring seawater COD according to claim 1, wherein in S5, the (1+3) sulfuric acid solution is a solution obtained by mixing 1 part by mass of 98% sulfuric acid (ρ=1.84 g/ml) with 3 parts by mass of distilled water.
5. The method according to claim 1, wherein the resting time is 5 minutes in S6.
6. The method according to claim 1, wherein the colorimetric determination is performed within a second half hour from the pouring into the colorimetric device in S7.
7. The method according to claim 1, wherein in S7 the cuvette or cuvette is used as the colorimetric device.
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