CN114839290B - Method for screening colored organic substances in water body - Google Patents

Method for screening colored organic substances in water body Download PDF

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CN114839290B
CN114839290B CN202210462284.0A CN202210462284A CN114839290B CN 114839290 B CN114839290 B CN 114839290B CN 202210462284 A CN202210462284 A CN 202210462284A CN 114839290 B CN114839290 B CN 114839290B
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李昆
张盼伟
赵晓辉
徐静
刘盈斐
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China Institute of Water Resources and Hydropower Research
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Abstract

The invention discloses a method for screening colored organic matters in a water body, which is used for identifying colored soluble organic matters related to water color characteristics in a research area based on analysis related to CDOM (440) detection values and physicochemical property analysis by utilizing a high-throughput screening technology. The method can screen out the soluble organic pollutants in the water body, and after the important attention to the pollutant types affecting the water color characteristics is determined, the relevant experiments of the verification of the relationship between the water color characteristics of the water body and the pollutants are carried out, so that the relationship between the water color characteristics of the water body and the pollutants is researched, and the important attention to the pollutant types affecting the water color characteristics is determined.

Description

Method for screening colored organic substances in water body
Technical Field
The invention relates to the technical field of water screening, in particular to a method for screening colored organic substances in a water body.
Background
Colored soluble organic matters (Chromophoric Dissolved Organic Matter, abbreviated as CDOM), suspended matters and phytoplankton are important factors influencing remote sensing of water color, and are called water color three elements. CDOM exists in all bodies of water and is an important component of soluble organics. Consists of a series of substances such as humic acid, fulvic acid, aromatic hydrocarbon polymer and the like, and is mainly the degradation products of soil and aquatic plants. CDOM represents an important class of light absorbing substances in a body of water whose concentration and composition can significantly alter the underwater light field. Currently, research on CDOM in water is mainly focused on the aspects of CDOM light absorption characteristics, fluorescence characteristics, photochemical degradation and water color remote sensing of CDOM and DOC. And CDOM water color remote sensing studies can be roughly divided into two directions: firstly, how to eliminate CDOM interference when carrying out water color remote sensing of phytoplankton and suspended matters, thereby improving the remote sensing precision; and secondly, researching how to directly detect the spatial-temporal distribution of CDOM and DOC.
Along with water temperature, salinity and transparency, water color belongs to one of the oldest time series water quality data, and is an important content in traditional ground water quality investigation. In recent years, water color has been planned by the world meteorological organization and global climate observation system as one of the basic climate variables of lakes. The water color change is directly related to the concentration change of the optical components in water, is an important optical characteristic of the water, can monitor the space-time change of the water quality of the water, such as the chlorophyll concentration change and turbidity change of ocean water, the turbidity change of lake and reservoir water and the like, and can find natural events and artificial activity interference of the water, such as harmful algae burst, black water mass, urban black and odorous water, colored sewage discharge and the like.
Therefore, in order to study the colored soluble organic matters in the watershed water body and collect the surface layer samples in the typical watershed reservoir water body, the invention adopts a high-throughput screening technology to identify the colored soluble organic matters related to the water color characteristics in the study area based on the analysis related to the CDOM (440) detection value and the physicochemical property analysis.
Disclosure of Invention
The invention aims to provide a method for screening colored organic matters in a water body, which can screen soluble organic pollutants in the water body, and after the important attention to the pollution types affecting the water color characteristics is determined, the relevant experiments are verified through the relationship between the water color characteristics and the pollutants of the water body, and the relationship research between the water color characteristics and the pollutants of the water body is carried out so as to determine the pollution types affecting the water color characteristics.
In order to achieve the above object, the present invention is realized by the following technical scheme: a method for screening colored organic substances in a water body comprises the following steps:
1. sample collection: collecting a water sample at a sampling point, washing the sampler and the water sample container for 2-3 times, then collecting the water sample into the container, adding a fixing agent, shaking uniformly, and labeling;
2. qualitative analysis of actual samples: for actual samples, the qualitative analysis of pollutants (sample collection is not less than 2 water periods) is completed by means of high-throughput screening equipment, GC x GC-TOF-MS analysis is recommended, the sample injection mode is automatic sample injection, the sample injection volume is 1 mu L, and the ion scanning range is as follows: 50-500, ion source temperature: 240 ℃, interface temperature: ionization energy at 280 ℃): 70eV, chromatographic column: one-dimensional column: DB-5MS (30 m.times.0.25 mm.times.0.25 μm); two-dimensional column: rxi-175Sil MS (1.2 m.times.0.15 mm.times.0.15 μm), carrier gas flow rate: 1.5mL/min, quantitative method: internal standard method for quantifying internal standard: accumustandrd Z-104J; gas chromatography temperature programming conditions: one-dimensional column temperature programming: the initial temperature is 60 ℃, and the temperature is kept for 0.5min; raising the temperature to 200 ℃ at a rate of 6 ℃/min; then raising the temperature to 235 ℃ at a speed of 3 ℃/min; finally, raising the temperature to 300 ℃ at a speed of 4 ℃/min, and keeping for 2min; two-dimensional furnace temperature compensation temperature 5 ℃, modem compensation temperature: 15 ℃; the modulation period is 7s, and the hot blowing time is 1.4s;
3. quantitative analysis of actual samples: for the actual sample, the quantitative analysis of the contaminants was done by means of a gas chromatography mass spectrometer, recommended to use GC-MS analysis, equipped with 30 mdb-5 MS (5% diphenyl/95% dimethylpolysiloxane, 30 mx0.25 mm x 0.25 μm film); adopts a non-split sampling mode, the carrier gas is high-purity He, and the constant flow is 1.5 mL.min -1 The sample injection amount is 1 mu L; the ion source and the transfer rod are at 230 ℃ and 250 ℃ respectively;
4. sample absorbance analysis: for actual samples and laboratory samples, the spectrometry is completed by means of an ultraviolet-visible spectrophotometer, and the recommended detection method is as follows: a wavelength range of 240 to 750nm; the measurement uses ultrapure water as blank reference; the absorption coefficient of CDOM is then derived from the following equation:
ag′(λ)＝2.303×D(λ)/r
ag(λ)＝ag′(λ)-ag′(700)×λ/700
wherein ag' (λ) and ag (λ) represent an uncorrected CDOM absorption coefficient and a scattering corrected absorption coefficient (m) of wavelength λ, respectively -1 ) The method comprises the steps of carrying out a first treatment on the surface of the D (λ) represents the absorbance measured by the instrument at wavelength λ; and r represents the optical path length (m) of the cuvette;
because of the complex composition of CDOM, its concentration is difficult to measure directly, the concentration of CDOM is represented by using 355nm absorption coefficient (ag (355)), 400nm absorption coefficient (ag (400)) or 440nm absorption coefficient (ag (440)); the specific absorption coefficient of CDOM at 254nm band (SUVA 254) was used to characterize the absorption capacity of CDOM for light per DOC concentration, derived from the following equation:
SUVA254＝ag(254)/DOC
the spectral slope of CDOM is calculated by a nonlinear regression mode using a single exponential function according to the following formula:
ag(λ)＝ag(λ0)×exp[-Sg(λ-λ0)]
wherein λ0 represents the reference wavelength (nm), sg represents the spectral slope (μm) of the exponential function curve -1 )；
5. And (3) data processing: the types of pollutants detected by high-throughput screening are various, so that detection data are selected, and the specific selection principle is that the matching degree of a compound spectrogram is more than 700; the detection rate of the compound is more than 50 percent. The association relation between the concentration of the pollutant and the absorbance is analyzed by an exponential method; the absorbance fitting utilizes SPSS software to perform fitting calculation on the relevant indexes.
The invention has the beneficial effects that: the invention identifies colored soluble organics associated with water color characteristics in a research area based on analysis related to CDOM (440) detection values and physicochemical property analysis by utilizing high throughput screening technology. The screening method is convenient and reliable to operate, good in detection effect and high in practicability.
Drawings
The invention is described in detail below with reference to the drawings and the detailed description;
FIG. 1 is a graph fitted with a CDOM (440) correlation analysis for contaminants of great interest in the present invention;
FIG. 2 is a graph showing a curve fitted to the absorbance of tetradecanoic acid according to the present invention;
FIG. 3 is a graph showing the absorbance fitting curve of the deet of the present invention;
FIG. 4 is a graph showing a fitted curve of the absorbance of di-t-butylbenzoquinone of the present invention;
FIG. 5 is a graph showing a fitted curve of the absorbance of octadecanoic acid according to the invention;
FIG. 6 is a graph showing the parameters associated with the absorbance fitting curve according to the invention;
FIG. 7 is a graph showing absorbance fitting curves according to the invention.
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
Referring to fig. 1-7, the present embodiment adopts the following technical scheme: a method for screening colored organic substances in a water body comprises the following steps:
1. sample collection: collecting a water sample at a sampling point, washing the sampler and the water sample container for 2-3 times, then collecting the water sample into the container, adding a fixing agent, shaking uniformly, and labeling;
2. qualitative analysis of actual samples: for actual samples, the qualitative analysis of pollutants (sample collection is not less than 2 water periods) is completed by means of high-throughput screening equipment, GC x GC-TOF-MS analysis is recommended, the sample injection mode is automatic sample injection, the sample injection volume is 1 mu L, and the ion scanning range is as follows: 50-500, ion source temperature: 240 ℃, interface temperature: ionization energy at 280 ℃): 70eV, chromatographic column: one-dimensional column: DB-5MS (30 m.times.0.25 mm.times.0.25 μm); two-dimensional column: rxi-175Sil MS (1.2 m.times.0.15 mm.times.0.15 μm), carrier gas flow rate: 1.5mL/min, quantitative method: internal standard method for quantifying internal standard: accumustandrd Z-104J; gas chromatography temperature programming conditions: one-dimensional column temperature programming: the initial temperature is 60 ℃, and the temperature is kept for 0.5min; raising the temperature to 200 ℃ at a rate of 6 ℃/min; then raising the temperature to 235 ℃ at a speed of 3 ℃/min; finally, raising the temperature to 300 ℃ at a speed of 4 ℃/min, and keeping for 2min; two-dimensional furnace temperature compensation temperature 5 ℃, modem compensation temperature: 15 ℃; the modulation period is 7s, and the hot blowing time is 1.4s;
3. quantitative analysis of actual samples: for the actual sample, the quantitative analysis of the contaminants was done by means of a gas chromatography mass spectrometer, recommended to use GC-MS analysis, equipped with 30 mdb-5 MS (5% diphenyl/95% dimethylpolysiloxane, 30 mx0.25 mm x 0.25 μm film); adopts a non-split sampling mode, the carrier gas is high-purity He, and the constant flow is 1.5 mL.min -1 The sample injection amount is 1 mu L; the ion source and the transfer rod are at 230 ℃ and 250 ℃ respectively;
4. sample absorbance analysis: for actual samples and laboratory samples, the spectrometry is completed by means of an ultraviolet-visible spectrophotometer, and the recommended detection method is as follows: a wavelength range of 240 to 750nm; the measurement uses ultrapure water as blank reference; the absorption coefficient of CDOM is then derived from the following equation:
ag′(λ)＝2.303×D(λ)/r
ag(λ)＝ag′(λ)-ag′(700)×λ/700
wherein ag' (lambda) andag (λ) represents an uncorrected CDOM absorption coefficient and a scattering-corrected absorption coefficient (m -1 ) The method comprises the steps of carrying out a first treatment on the surface of the D (λ) represents the absorbance measured by the instrument at wavelength λ; and r represents the optical path length (m) of the cuvette;
because of the complex composition of CDOM, its concentration is difficult to measure directly, the concentration of CDOM is represented by using 355nm absorption coefficient (ag (355)), 400nm absorption coefficient (ag (400)) or 440nm absorption coefficient (ag (440)); the specific absorption coefficient of CDOM at 254nm band (SUVA 254) was used to characterize the absorption capacity of CDOM for light per DOC concentration, derived from the following equation:
SUVA254＝ag(254)/DOC
the spectral slope of CDOM is calculated by a nonlinear regression mode using a single exponential function according to the following formula:
ag(λ)＝ag(λ0)×exp[-Sg(λ-λ0)]
wherein λ0 represents the reference wavelength (nm), sg represents the spectral slope (μm) of the exponential function curve -1 )；
5. And (3) data processing: the types of pollutants detected by high-throughput screening are various, so that detection data are selected, and the specific selection principle is that the matching degree of a compound spectrogram is more than 700; the detection rate of the compound is more than 50 percent. The association relation between the concentration of the pollutant and the absorbance is analyzed by an exponential method; the absorbance fitting utilizes SPSS software to perform fitting calculation on the relevant indexes.
Example 1:
a method for screening colored organic substances in a water body comprises the following steps:
1. sample collection
All index detection samples are respectively collected in Pan Gukou and Danikken reservoir areas, and water samples are specifically collected according to water environment monitoring Specification (SL 219-2013). To ensure the representativeness of the sample, the position of the sampling point is ensured to be accurate, and a positioning instrument (GPS) is used for positioning. And meanwhile, special sampling personnel and special sampling facilities (vehicle-mounted refrigerator, incubator and the like) are arranged, so that the water sample is ensured to be in a conveying environment required by specifications. The sampled water sample is swayed and washed with the sampler and the water sample container for 2 to 3 times, then the water sample is sampled into the container, and the corresponding fixative is added immediately according to the requirement for shaking uniformly, and the label is attached. The quantity of the quality control samples such as the field blank sample, the field parallel sample, the field standard sample and the like reaches 10% -20% of the total quantity of the water samples, and each batch of water samples is not less than 1.
2. Qualitative analysis of actual samples
In the embodiment, the high-throughput screening of the compound is mainly performed by GC×GC-TOF-MS analysis, the sample injection mode is automatic sample injection, the sample injection volume is 1 μL, and the ion scanning range is as follows: 50-500, ion source temperature: 240 ℃, interface temperature: ionization energy at 280 ℃): 70eV, chromatographic column: one-dimensional column: DB-5MS (30 m.times.0.25 mm.times.0.25 μm); two-dimensional column: rxi-175Sil MS (1.2 m.times.0.15 mm.times.0.15 μm), carrier gas flow rate: 1.5mL/min, quantitative method: internal standard method for quantifying internal standard: accumustandrd Z-104J; gas chromatography temperature programming conditions: one-dimensional column temperature programming: the initial temperature is 60 ℃, and the temperature is kept for 0.5min; raising the temperature to 200 ℃ at a rate of 6 ℃/min; then raising the temperature to 235 ℃ at a speed of 3 ℃/min; finally, the temperature is raised to 300 ℃ at a rate of 4 ℃/min, and the mixture is kept for 2min. Two-dimensional furnace temperature compensation temperature 5 ℃, modem compensation temperature: 15 ℃. The modulation period is 7s and the hot blowing time is 1.4s.
3. Quantitative analysis of actual samples
Quantitative analysis of colored organics (six classes of compounds here) of major interest in actual samples using GC-MS was performed with 30 mDB-5 MS (5% diphenyl/95% dimethylpolysiloxane, 30 m0.25mm 0.25 μm film); adopts a non-split sampling mode, the carrier gas is high-purity He, and the constant flow is 1.5 mL.min -1 The sample injection amount was 1. Mu.L. The ion source and the transfer rod are at 230 ℃ and 250 ℃ respectively; temperature program of derivatization standard sample: the initial temperature was 90℃and was kept at a rate of 5℃per minute until it reached 230℃and then at a rate of 15℃per minute until it reached 280℃for 1 minute. No derivatization standard sample temperature elevation program is needed: the initial temperature was 90℃and was kept at a rate of 5℃per minute to 160℃and then at a rate of 15℃per minute to 280℃for 1 minute. The derivatization process comprises the following steps: 50. Mu.L of standard solution was taken into 250. Mu.L of plastic liner tube in a sample bottle, 50. Mu.L of silylation reagent (99:1/BSTFA-TMCS) was added, the bottle cap was immediately screwed down, thoroughly mixed, and then measured on a machine. The whole process should avoid contact with water and the sample and derivatizing reagent should not be exposed to air for long periods of time.
4. Sample absorbance analysis
The CDOM absorption coefficient of the actual sample and the laboratory sample is measured by an ultraviolet-visible spectrophotometer. The measurement wavelength range was 240 to 750nm (1 nm interval). The measurement was performed using ultrapure water as a blank reference. The absorption coefficient of CDOM is then derived from the following equation:
ag′(λ)＝2.303×D(λ)/r
ag(λ)＝ag′(λ)-ag′(700)×λ/700
wherein ag' (λ) and ag (λ) represent an uncorrected CDOM absorption coefficient and a scattering corrected absorption coefficient (m) of wavelength λ, respectively -1 ) The method comprises the steps of carrying out a first treatment on the surface of the D (λ) represents the absorbance measured by the instrument at wavelength λ; and r represents the cuvette optical path length (m), the present example uses a 10cm optical path length cuvette for measuring CDOM.
Because of the complex composition of CDOM, its concentration is difficult to measure directly, it is common to use 355nm absorption coefficient (ag (355)), 400nm absorption coefficient (ag (400)) or 440nm absorption coefficient (ag (440)) to represent the concentration of CDOM. This example uses ag (355) to characterize CDOM content. The ratio (E2/E3) of the absorption coefficient of CDOM at 250nm (ag (250)) to the absorption coefficient at 365nm (ag (365)) is used to characterize the size of the CDOM molecular weight. The specific absorption coefficient of CDOM at 254nm band (SUVA 254) was used to characterize the absorption capacity of CDOM for light per DOC concentration, derived from the following equation:
SUVA254＝ag(254)/DOC
the spectral slope of CDOM is calculated by a nonlinear regression mode using a single exponential function according to the following formula:
ag(λ)＝ag(λ0)×exp[-Sg(λ-λ0)]
wherein λ0 represents a reference wavelength (nm), 440nm is selected in this embodiment; sg represents the spectral slope (μm) of the exponential function curve -1 ). In the embodiment, corresponding Sg values (S275-295, S350-400 and S400-600) are obtained by respectively carrying out nonlinear fitting calculation on wave band ranges of 275-295 nm, 350-400 nm and 400-600 nm.
5. Data processing
The types of pollutants detected by high-throughput screening are various, so that detection data are selected, and the specific selection principle is that the matching degree of a compound spectrogram is more than 700; the detection rate of the compound is more than 50 percent, namely more than 4 points are detected at a time; the compound was detected multiple times, and the same peak-to-peak time peak area was selected as the reference area. The correlation between the concentration of the contaminant and the absorbance was analyzed by an exponential method. The absorbance fitting utilizes SPSS software to perform fitting calculation on the relevant indexes.
6. Analysis of results
1) High throughput screening result analysis of colored soluble organics
According to the high-throughput screening pollutant detection method, sample pretreatment and detection are carried out on water samples collected in 9 th 2017 and 6 th 2018, and data analysis is carried out on specific detection results according to the high-throughput screening data selection principle, so 288 kinds of compound information and 66 kinds of compound information are selected in total; the results of the two tests were collected, and 44 total compounds were selected. Correlation analysis is carried out on the correlation detection results of all sampling points in different periods and CDOM (440), and a correlation index R is found 2 A total of 15 compounds above 0.6 are 2-fluorobiphenyl, dibutyl atrazine, deet-alamine, caffeine, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, N-dibutyl formamide, dodecanal, tetradecanoic acid, 2, 6-di-tert-butyl benzoquinone, octadecanoic acid, 2,4, 6-tribromophenol, oleamide, phthalate and 1-eicosol, respectively. The specific correlation fit curve is shown in fig. 1.
2) Important attention is paid to the analysis of the results of soluble colored organic matters
Physicochemical data collection was performed for the 15 compounds described above, as shown in Table 1. The white or colorless compound is found to be 9 kinds of 2-fluorobiphenyl, dibutyl atrazine, caffeine, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, N-dibutyl formamide, oleamide, phthalate and 1-eicosanol; the colored compounds include deet amine, dodecanal, tetradecanoic acid, 2, 6-di-tert-butylbenzoquinone, octadecanoic acid and 2,4, 6-tribromophenol.
Table 1 focuses on the relevant properties of the soluble colored organic compounds
Figure BDA0003620786140000091
3) Analysis of water color characteristic relation result of soluble colored organic matters and water body
Developing a CDOM absorbance verification experiment in a laboratory aiming at six classes of compounds determined in earlier work, wherein the specific operation steps are as follows: 100ppm standard solution is added into a graduated cuvette filled with 10mL of ultrapure water, six kinds of compound solutions of 500ppb, 1ppm, 2ppm, 5ppm and 10ppm are respectively prepared, after 5min of oscillation, the solution is subjected to ultrasonic treatment for 10min, and the absorbance of the solution is measured at 355nm, 400nm and 440nm wavelengths by using an ultraviolet-visible spectrophotometer, so as to draw a solution absorbance curve. Experimental results show that (figures 2-5), the concentrations of four compounds of tetradecanoic acid, deet, di-tert-butylbenzoquinone and octadecanoic acid in the six compounds have good fitting degree with relevant CDOM values (R under exponential function fitting) 2 0.976). It is inferred that the four compounds in the water body have basic conditions affecting the remote sensing detection of the water body.
4) Analysis of fitting verification result of characteristic relation of actual sample and water color of water body
And acquiring Pan Gukou-large black-statin reservoir water body in 9 months in 2020, and acquiring the characteristic relationship between the six types of compounds and the water color of the water body by detecting the concentration of the six types of compounds of an actual sample and detecting CDOM of the water body.
The CDOM detection aspect of the actual sample: and (5) taking the collected 200mL water sample for processing into a CDOM sample to be tested. Firstly, a water sample is filtered in a filter at low pressure (not higher than 30 kPa) by using a Whatman GF/F glass fiber filter membrane (which is packaged in a muffle furnace in advance and burned for 4 hours at 450 ℃ by using an aluminum foil) with the diameter of 47mm and the pore diameter of 0.7 mu m, the filtered water sample of the part is filtered by using a Millipore filter membrane with the pore diameter of 0.22 mu m, 60mL of the water sample after the re-filtration is taken and stored in a brown glass bottle (the filtered water sample is rinsed three times before) and is taken as a CDOM sample to be refrigerated at the temperature of 4 ℃ in a refrigerator to be tested. The absorbance of the water sample was measured at 355nm, 400nm and 440nm wavelengths using an ultraviolet-visible spectrophotometer.
Table 2 absorbance of Pan Da reservoir Water samples at different wavelengths
Figure BDA0003620786140000101
Figure BDA0003620786140000111
The relevant indexes are subjected to fitting calculation by using SPSS software (the result is shown in figure 6), and the result shows that besides the green leaves, suspended matters and transparency, the fitting significance of the deet is as high as 0.829, and the significance of the selected tetradecanoic acid, octadecanoic acid and tert-butylbenzoquinone is between 0.074 and 0.576. The correlation fit results are schematically shown in FIG. 7.
7. Conclusion(s)
Through the research of the relationship between the water color characteristics of the water body and pollutants, the important focus on the types of the pollutants influencing the water color characteristics is primarily determined.
(1) After 2 high throughput screening of different water periods, a list of organic compounds of great interest containing 44 organic compounds is established; performing correlation analysis with the CDOM (440) detection value of the corresponding sample, and screening out 15 remote sensing related organic compounds; and (3) carrying out physicochemical property analysis on 15 remote sensing related organic compounds to preliminarily determine 6 kinds of remote sensing related colored soluble organic matters.
(2) The laboratory verifies that only four compounds of the deet, the tetradecanoic acid, the octadecanoic acid and the tert-butyl benzoquinone in 6 remote sensing related colored soluble organic matters are fit to obtain the curve relationship between the absorbance and the concentration.
(3) Proved by a practical sample outside a laboratory, the anti-mosquito amine has higher significance, or is an important soluble organic pollutant affecting the water color characteristics in the research area.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (1)

1. The method for screening the colored organic substances in the water body is characterized by comprising the following steps of:
(1) Sample collection: collecting a water sample at a sampling point, washing the sampler and the water sample container for 2-3 times, then collecting the water sample into the container, adding a fixing agent, shaking uniformly, and labeling;
(2) Qualitative analysis of actual samples: for an actual sample, the qualitative analysis of the pollutants is completed by means of high-throughput screening equipment, GC x GC-TOF-MS analysis is used, the sample injection mode is automatic sample injection, the sample injection volume is 1 mu L, and the ion scanning range is that: 50-500, ion source temperature: 240 ℃, interface temperature: ionization energy at 280 ℃): 70eV, chromatographic column: one-dimensional column: DB-5MS 30m x 0.25mm x 0.25 μm; two-dimensional column: rxi-175Sil MS 1.2mX 0.15mm X0.15 μm, carrier gas flow rate: 1.5mL/min, quantitative method: internal standard method for quantifying internal standard: accumtrand Z-014J; gas chromatography temperature programming conditions: one-dimensional column temperature programming: the initial temperature is 60 ℃, and the temperature is kept for 0.5min; raising the temperature to 200 ℃ at a rate of 6 ℃/min; then raising the temperature to 235 ℃ at a speed of 3 ℃/min; finally, raising the temperature to 300 ℃ at a speed of 4 ℃/min, and keeping for 2min; two-dimensional furnace temperature compensation temperature 5 ℃, modem compensation temperature: 15 ℃; the modulation period is 7s, and the hot blowing time is 1.4s;
(3) Quantitative analysis of actual samples: for the actual samples, quantitative analysis of the contaminants was done by means of a gas chromatography mass spectrometer, using GC-MS analysis, equipped with 30 mdb-5 MS 5% diphenyl/95% dimethylpolysiloxane, 30 mx0.25 mm x 0.25 μm film; adopts a non-split sampling mode, the carrier gas is high-purity He, and the constant flow is 1.5 mL.min -1 The sample injection amount is 1 mu L; the ion source and the transfer rod are at 230 ℃ and 250 ℃ respectively;
(4) Sample absorbance analysis: the method is characterized in that the spectrometry is completed by means of an ultraviolet-visible spectrophotometer for actual samples and laboratory samples, and the detection method comprises the following steps: a wavelength range of 240 to 750nm; the measurement uses ultrapure water as blank reference; the absorption coefficient of CDOM is then derived from the following equation:
ag'(λ)＝2.303×D(λ)/r
ag(λ)＝ag'(λ)–ag'(700)×λ/700
wherein ag' (λ) and ag (λ) represent uncorrected CDOM absorption coefficient and scattering corrected absorption coefficient m of wavelength λ, respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the Dλ represents the absorbance measured by the instrument at wavelength λ; r represents the optical path length m of the cuvette;
because of the complex composition of CDOM, its concentration is difficult to measure directly, so use 355nm absorption coefficient ag (355), 400nm absorption coefficient ag (400) or 440nm absorption coefficient ag (440) to represent CDOM's concentration; the specific absorption coefficient SUVA254 of CDOM in the 254nm band is used for representing the light absorption capacity of CDOM in unit DOC concentration, and is obtained by the following formula:
SUVA254＝ag(254)/DOC
the spectral slope of CDOM is calculated by a nonlinear regression mode using a single exponential function according to the following formula:
ag(λ)＝ag(λ0)×exp[-Sg(λ-λ0)]
wherein λ0 represents the reference wavelength nm, sg represents the spectral slope μm of the exponential function curve -1 ；
(5) And (3) data processing: the types of pollutants detected by high-throughput screening are various, so that detection data are selected, and the specific selection principle is that the matching degree of a compound spectrogram is more than 700; the detection rate of the compound is more than 50%, and the association relation between the concentration of the pollutant and the absorbance is analyzed by an exponential method; the absorbance fitting utilizes SPSS software to perform fitting calculation on the relevant indexes.
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