CN101819148A - Three-dimensional fluorescence spectrum method for measuring chlorine disinfection by-product precursor in water - Google Patents
Three-dimensional fluorescence spectrum method for measuring chlorine disinfection by-product precursor in water Download PDFInfo
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Abstract
The invention belongs to the environmental monitoring and analysis technical field, which can be used for measuring a chlorine disinfection by-product precursor in water, and provides technical support for pollution control. Aiming at the problems of the measuring method of the existing chlorine disinfection by-product precursor, such as complicated steps and indefinite results, the feasibility for characterizing the chlorine disinfection by-product precursor by three-dimensional feature fluorescence parameters is researched, the correlation between the feature fluorescence characteristic parameters of the chlorine disinfection by-product precursor and the generation potential thereof is confirmed, and the simple and fast method for measuring the chlorine disinfection by-product precursor in water is developed. The measuring method comprises the following steps: establishing a linearity correction equation between the feature fluorescence intensity of the chlorine disinfection by-product precursor and the generation potential thereof; scanning a water sample to be tested with a three-dimensional fluorescence spectrum; and calculating the generation potential of the chlorine disinfection by-products and performing result correction. By adopting the method, the chlorine disinfection by-product precursor in water can be classified and analyzed without complex sample processing and testing; the average relative error is about 10%; and a sample structure is not damaged, and on-line inspection is easily realized.
Description
Technical field
The invention belongs to environmental monitoring and analysis, be applied to measure DBPs precursor in the resurgent water, the control of can be used for regenerating water quality safety guarantee technical research and chlorine disinfection by-product precursor; Also be applicable to the control of chlorine disinfection by-product in the potable water.
Background technology
(1) assay method of chlorine disinfection by-product precursor in the potable water
DBPs (DBPs, Disinfection by products) is the material to the toxic effect of human body that the dissolved organic matter reaction generates in sanitizer and the water.When adopting chlorhexidine-containing disinfectant, mainly generate haloform (THMs) and halogen acetic acid (HAAs) chlorine disinfection by-product, dissolved organic matter then is called as chlorine disinfection by-product precursor in the water.
According to the domestic and foreign literature report, soil ulmin such as humic acid, fulvic acid class material is the main precursor substance of chlorine disinfection by-product in the natural water body.Soil ulmin is a kind of natural high molecular polymer, is mainly derived from the biological metabolism residue, is present in widely in water body, soil and the surrounding environment thereof.(HumicAcid is to be dissolved in alkali in the soil ulmin and the part that is insoluble to acid HA) to humic acid, and (Fulvic acid is FA) then for promptly dissolving in alkali, acid-soluble part again for fulvic acid.Be subjected to the prior art horizontal constraints, with the natural water body is in the water treatment system water outlet at water source, inevitably can remaining a spot of soil ulmin class dissolved organic matter, generate DBPs with the chlorhexidine-containing disinfectant effect, drinking water safety and health are had a negative impact.For improving the drinking water quality security, must strengthen the control of DBPs precursor in the water.Therefore, need to measure the DBPs precursor, judge its material composition and source thereof, so that take measure targetedly to be controlled by qualitative, quantitative test.
Complicacy in view of the humic acid structure, so far, molecular composition and chemical constitution for humic acid still are in the conceptual phase, because the existence of this ambiguity, for research control based on DBPs precursor in the natural water of soil ulmin, also many variation tendencies of representing this type of material by round-about way.More the domestic and international at present sign for chlorine disinfection by-product precursor in the natural water adopts DBPs to generate potential or claims to generate gesture (DBPFP, DBP Formation Potential), 4 kinds of methods of ratio (SUVA) of analog ligand grid system testing (Simulated Distribution System Test), unified formation condition test (Uniform FormationCondition), ultraviolet absorptivity and organic carbon concentration are carried out quantitative measurement, wherein, widely used is DBPFP and SUVA.
The measuring principle of DBPFP is: the chlorine that adds capacity, in the fully long time with water in DBPs precursor complete reaction, detect DBPs haloform THMs and the halogen acetic acid HAAs that generates then, characterize whole precursors potential in the water indirectly, comprise that haloform generates potential and halogen acetic acid generates potential.Main mensuration process is as follows:
1. chlorine dosage is definite: because different bigger, the required chlorine dosage differences of water quality situation difference, so preceding at mensuration haloform generation potential (THMFP) and halogen acetic acid generation potential (HAAFP), necessary earlier definite chlorine dosage.Free chlorine residual amount when the principle of determining is reaction end in the water sample is 5mg/L.
2. the collection of water sample: the vial of getting the anti-chewing-gum plug of tool of two 100mL, add 1g ascorbic acid (b bottle) in a vial therein, what do not add ascorbic acid is a bottle, respectively adds the 100mL water sample respectively in two bottles, measures haloform and halogen acetic acid amount in the b bottle in the 24h;
3. sample chloridized: add a certain amount of liquor natrii hypochloritis in a bottle, place the incubator reaction 5 days of (25 ± 2) ℃;
4. measure chlorine residue: from incubator, take out a bottle, measure chlorine residue and add the 1g ascorbic acid;
5. measure haloform and halogen acetic acid growing amount: adopt haloform and halogen acetic acid growing amount in vapor-phase chromatography or the gas chromatography-mass spectrum method mensuration a bottle.
The advantage of DBPFP test is that heavy dose of chlorine and long-time reaction can make the precursor substance complete reaction in the water generate DBPs, a maximal value (just precursor substance generates the potential of DBPs) is provided, but the adding of heavy dose of chlorine and actual conditions are runed counter to, and relative error is bigger; Test duration numerous and diverse property long and process of mensuration has all influenced the practical application of this method simultaneously; This method is by indirect determination DBP in addition
SGrowing amount represent the content of precursor in the water sample, can not clearly reflect the kind and the content thereof of precursor intuitively, thereby for actual production, this method can not instruct the pollution control of DBPs precursor targetedly.
Main organism in the natural water body, as soil ulmin, be living beings and metabolism residual mixture thereof, contain a large amount of phenyl ring and carboxyl, hydroxyl, heteroatoms etc. in the molecular structure, studies show that this type of material major part belongs to the precursor of DBPs, they have absorption significantly at ultraviolet region, use ultraviolet absorptivity UV
254Can represent the comprehensive content of this type of material in water; Organic carbon concentration is then represented whole organic content in the water, and both ratio (SUVA) can be used for representing the shared ratio of chlorine disinfection by-product precursor in the water.Its assay method is: water sample is surveyed its absorbance and total organic carbon analyzer with ultraviolet spectrophotometer respectively and is surveyed total organic carbon TOC behind 0.45 μ m membrane filtration at ultraviolet wavelength 254nm place, measurement result is compared.This method pre-treatment step is simple, and minute is short, but the instrument aspect also needs total organic carbon analyzer except that ultraviolet spectrophotometer, and equipment requirements is comparatively complicated.Moreover the SUVA method is an overall target, what reflect is the shared amount of dissolved organic matter that absorption is arranged at ultraviolet region in the water sample, the DBPs precursor is a part wherein, therefore this index belongs to the non-specificity index of DBPs precursor, and the control of directive function pollute to(for) the DBPs precursor is still clear and definite inadequately.
In sum, at present long, step is numerous and diverse at the DBPFP method minute of natural water body, can not clearly reflect DBPs precursor kind and realize online METHOD FOR CONTINUOUS DETERMINATION; The SUVA method has general property at object and to instrument and equipment requirement weak point such as complexity comparatively, above-mentioned two kinds of methods all are difficult to instruct targetedly the pollution control to the DBPs precursor.
(2) assay method of chlorine disinfection by-product in the resurgent water
Resurgent water is a municipal effluent through the water outlet after biological two stage treatment and the advanced treating, can be used for that municipal administration is used mixedly, urban waterscape, architectural intermediate water, industrial chilled water etc.Because the complicacy of its water source and water treatment procedure, regeneration water quality is comparatively complicated, and the dissolved organic matter kind of biological metabolism remnants is many, the content height.Still continue to use the assay method of potable water at present at the assay method of chlorine disinfection by-product precursor in the resurgent water, but for the water quality resurgent water many than the natural water body complexity, adopt above-mentioned indirect or synthesis measuring method, can't the various DBPs precursors of classification and determination, its measurement result has more ambiguity, can not resolve the source of DBPs, lack directive function targetedly for chlorine disinfection by-product in the control resurgent water.
Dissolved organic matter in the resurgent water mostly is biological metabolism residual substances such as soil ulmin class greatly, and aromatic hydrocarbon or two key, carbon back, carboxyl equiconjugate system are arranged in these material molecular structures mostly, has stronger fluorescent characteristic.Adopt three-dimensional fluorescence spectrum (three-dimensional excitation emission matrixfluorescence spectroscopy, specificity fluorescent information when 3DEEM) technology can obtain excitation wavelength and emission wavelength and changes simultaneously is fit to be used for studying organic chemistry and physical property very much.Studies show that three-dimensional fluorescence spectrum method can be used for disclosing organic classification situation in the water, characterize common organic kind and content in the water.When sample concentration was low, the characteristic fluorescence intensity of various materials was directly proportional with its material concentration, characteristic fluorescence intensity is pairing excite relevant with emission wavelength with substance classes.There is the applying three-dimensional fluorescence method to analyze the research of dissolved organic matter in the natural water body abroad, and with its Ex/Em (ExcitationWavelength, Ex; Emission Wavelength, Em) the fluorescence peak position is summarized as shown in the accompanying drawing 1.Wherein, characteristic fluorescence peak I (Ex/Em 350-440/430-510) is referred to as class humic acid fluorescence (humic-like); Characteristic fluorescence peak II (Ex/Em 310-360/370-450) and characteristic fluorescence peak IV (Ex/Em 240-270/370-440nm) are class fulvic acid fluorescence, are called visible soil ulmin (visible fulvic-like) and UV soil ulmin (UV fulvic-like); The III of characteristic fluorescence group (Ex/Em260-290/300-350) is albuminoid fluorescence (protein-like), also can be subdivided into class tryptophane fluorescence (tryptophan-like again, Ex/Em 270-290/320-350) and class tyrosine fluorescence (tyrosine-like, Ex/Em 270-290/300-320).Can obtain the classification information of organic contaminant in the water in view of the above.
The three-dimensional fluorescence spectrum technology has highly sensitive (10
-9The order of magnitude), consumption few (1～2mL), selectivity is good, do not destroy sample structure and simple operation and other advantages, is easy to realize online and continuous monitoring.But the result that three-dimensional fluorescence spectrum method obtains is organic kind and content information, can not be used for the direct representation chlorine disinfection by-product precursor, does not also see at present to be used for the report that the secondary indication chlorine disinfection by-product generates potential.
The present invention obtains the subsidy of project of national nature science fund project (50778004) and Beijing's natural science fund project (8082006).
The present invention is based on existing existing defective of chlorine disinfection by-product precursor assay method and three-dimensional fluorescence spectrum know-why, form by main chlorine disinfection by-product precursor in the screening resurgent water, the feasibility of analyzing three-dimensional characteristic fluorescence parameter characterization chlorine disinfection by-product precursor, correlationship and correction factor between DBPs precursor fluorescence characterization parameter and its generation gesture have been confirmed, developed the easy of chlorine disinfection by-product precursor in the resurgent water, rapid assay methods, be the control chlorine disinfection by-product precursor, ensure the regeneration water quality safety, provide a kind of easy, chlorine disinfection by-product precursor assay method fast.
Summary of the invention
Technical matters to be solved by this invention
(1) classification of three-dimensional feature fluorescence spectrum characterizes the feasibility of chlorine disinfection by-product precursor;
(2) the three-dimensional feature fluorescence intensity of humic acid, fulvic acid and its chlorine disinfection by-product generate the correlativity of gesture.
Water quality complicacy based on resurgent water, the present invention selects the common organism (humic acid, fulvic acid, proteinoid) of several classes in the resurgent water, find by analyzing the DBPs generative capacity of each type organic when the variable concentrations, humic acid and fulvic acid are chlorine disinfection by-product precursors main in the resurgent water, and their DBPs generates gesture and is directly proportional with its concentration.
Humic acid, fulvic acid have stronger fluorescent characteristic.Adopt three-dimensional fluorescence spectrum method can obtain corresponding three-dimensional feature fluorescence spectrum, the architectural characteristic of its characteristic fluorescence peak center excitation/emission wavelength reflection material has stronger specificity, can be used to represent the kind of material; Pairing characteristic fluorescence intensity is directly proportional with humic acid, fulvic acid concentration.
The present invention is based on above-mentioned theory,, propose the three-dimensional feature fluorescence parameter sign chlorine disinfection by-product precursor of can classifying by a large amount of experimental analyses; And research has confirmed that humic acid, fulvic acid characteristic fluorescence intensity and chlorine disinfection by-product generate the correlativity between the gesture.Set up chlorine disinfection by-product precursor method in the three-dimensional fluorescence spectrum method for measuring resurgent water on this basis.This method determination step is as follows:
(1) sets up characteristic fluorescence intensity and chlorine disinfection by-product and generate the gesture dependent equation
1. preparing standard solution
The humic acid standard solution: concentration is controlled in 1.0～7.0mg/L scope;
The fulvic acid standard solution: concentration is controlled in 10.0～70.0mg/L scope.
Select source and similar commodity humic acid, the fulvic acid reagent of sample, also humic acid, the fulvic acid of chamber actual extracting and sample similar performance by experiment as far as possible.
Humic acid dissolves in the lean solution of KOH originally as water-fast organic compound.Can be made into the KOH lean solution of 0.01mol/L as solvent with ultrapure water earlier during preparation.
2. three-dimensional fluorescence spectrum scanning
Set the three-dimensional fluorescence spectrum sweep parameter: excitation wavelength sweep limit 200nm-450nm, emission wavelength sweep limit 200nm-800nm excites slit 10nm, emission slit 10nm, sweep velocity 1200nm/min, sweep spacing 10nm.
Humic acid, fulvic acid standard solution to variable concentrations carries out three-dimensional fluorescence scanning respectively, obtain the three-dimensional feature fluorescence spectrum figure of humic acid, fulvic acid, humic acid, fulvic acid characteristic fluorescence peak center excitation/emission wavelength (Ex/Em) and characteristic fluorescence intensity f thereof that record is corresponding
EX/EM
3. measure chlorine disinfection by-product and generate gesture
The DBPs of measuring the series standard solution of humic acid, fulvic acid variable concentrations according to the DBPFP assay method respectively generates the gesture value, and record haloform separately generates gesture and halogen acetic acid generates the gesture value.
4. set up the characteristic fluorescence intensity of standard solution and the correlation-corrected equation between the DBPs generation gesture
With characteristic fluorescence intensity is independent variable, and haloform generates gesture (THMFP) or halogen acetic acid generation gesture (HAAFP) is a dependent variable, sets up the characteristic fluorescence intensity f of humic acid, fulvic acid standard solution respectively
EX/EM1, f
EX/EM2Dependent linearity correction equation with THMFP, HAAFP.
The correlation-corrected equation that humic acid characteristic fluorescence intensity and DBPs generate between the gesture is:
THMFP
HA＝a
1?f
EX/EM1+b
1 (1)
HAAFP
HA＝a
2?f
EX/EM1+b
2 (2)
The correlation-corrected equation that fulvic acid characteristic fluorescence intensity and DBPs generate between the gesture is:
THMFP
FA＝a
3?f
EX/EM2+b
3 (3)
HAAFP
FA＝a
4?f
EX/EM2+b
4 (4)
In the formula, THMFP
HA, THMFP
FA, HAAFP
HA, HAAFP
FAThe haloform and the halogen acetic acid that are respectively humic acid, fulvic acid generate gesture (μ g/L);
f
EX/EM1, f
EX/EM2Be respectively the characteristic fluorescence intensity (A.U) of humic acid, fulvic acid;
a
1, a
2, a
3, a
4, b
1, b
2, b
3, b
4Be correction coefficient, can obtain by linear regression method.
(2) chlorine disinfection by-product of measuring in the actual water sample generates gesture
1. carry out three-dimensional fluorescence spectrum scanning
Elder generation through 0.45 μ m membrane filtration, to remove the insoluble organism of graininess in the water sample, carries out three-dimensional fluorescence spectrum scanning to water sample with water sample then, and sweep parameter is the same.According to humic acid, the determined three-dimensional feature fluorescence peak center Ex/Em of fulvic acid standard solution, write down the characteristic fluorescence intensity f of humic acid in the water sample, fulvic acid respectively
EX/EM
2. utilize correlation-corrected equation classified calculating DBPs to generate gesture
Utilize the three-dimensional feature fluorescence intensity of humic acid, fulvic acid in correlation-corrected equation and the water sample, haloform and the halogen acetic acid that can try to achieve humic acid in the water sample, fulvic acid respectively generate the gesture value; Can also obtain the total haloform of water sample, halogen acetic acid generation gesture respectively by adding, that is: with method
∑THMFP＝THMFP
HA+THMFP
FA (5)
∑HAAFP＝HAAFP
HA+HAAFP
FA (6)
(3) result's correction
The all non-one-component of humic acid, fulvic acid, they all are not determine molecular weight, the potpourri of the complexity of on composition, structure, all comparatively bluring, thereby the humic acid of separate sources or fulvic acid, there are differences at aspects such as molecular structure, functional group, molecular weight, its three-dimensional fluorescence characteristic also has difference.Therefore when the three-dimensional fluorescence feature excitation/emission wavelength in order to the humic acid in humic acid, fulvic acid and the water sample of configuration standard solution, fulvic acid when there were significant differences, should introduce correction factor result of calculation is revised.The humic acid of proposed arrangement standard solution, fulvic acid source should be close with determined water sample as far as possible, to reduce error at measurment.
In addition, because regeneration water quality is comparatively complicated, some coexisting substances also might influence the fluorescent characteristic of DBPs precursor such as metallic ion, so also need measurement result is revised.
Find that according to interpretation total haloform, the halogen acetic acid of the water sample that utilizes the correlation-corrected Equation for Calculating to go out generates gesture and have consistent variation tendency with measured value, exists metastable multiple relation.
When needing to revise, can generate gesture according to haloform, the halogen acetic acid of 5～7 water samples of DBPFP assay method practical measurement, and carry out linear regression analysis with the corresponding calculated value, regression coefficient is correction factor.
(4) accuracy and the scope of application
Adopt said method to measure over one hundred resurgent water sample, average relative error is about 10%.
This method is applicable to the mensuration of chlorine disinfection by-product generation gesture in the resurgent water, also is applicable to that chlorine disinfection by-product generates gesture mensuration in natural water body or the tap water simultaneously.
Gordian technique of the present invention is to propose to classify with the three-dimensional feature fluorescence parameter to characterize the DBPs precursor, and has confirmed the correlativity between three-dimensional feature fluorescence intensity and the DBPs generation gesture.
The present invention compared with prior art principal feature is as follows:
(1) the classification quantitative test of realization chlorine disinfection by-product precursor: existing DBPFP assay method can not be distinguished the source that DBPs generates gesture, and what existing SUVA method measurement result was represented is all kinds of organic comprehensive content.This method is by carrying out three-dimensional fluorescence scanning to obtain the characteristic fluorescence parameter of water sample to water sample, utilize the characteristic fluorescence intensity of all kinds of materials and the dependent equation that its DBPs generates gesture, can directly obtain all kinds of organic DBPs and generate gesture, can realize the classification of DBPs precursor is resolved, carry out targetedly and pollute control.
(2) simple to operate, measure rapidly, need not complicated sample and handle and testing process.And existing DBPFP assay method needs complicated sample to handle and 5 days homoisothermal cultivation processes, needs to consume more chemical reagent and medicine.
(3) relative error is little, and average relative error is about 10%.Have foreign study to show, the relative error of existing DBPFP method measurement result reaches 25%.
(4) fluorometry has highly sensitively, and amount of samples is few, the characteristics that selectivity is good.
(5) this method is not destroyed sample structure, is easy to realize online detection.
Description of drawings
The common location that the Ex/Em peak occurs among Fig. 1 dissolved organic matter three-dimensional fluorescence spectrum figure
Fig. 2 a haloform generates gesture calculated value, modified value and measured value.
Fig. 2 b halogen acetic acid generates gesture calculated value, modified value and measured value
The revised haloform of Fig. 3 a generates gesture calculated value and measured value error analysis
The revised halogen acetic acid of Fig. 3 b generates gesture calculated value and measured value error analysis
Embodiment
Adopt chlorine disinfection by-product generation gesture in the laboratory reused water processing device water outlet of said method METHOD FOR CONTINUOUS DETERMINATION, it is as follows mainly to measure process:
(1) sets up characteristic fluorescence intensity and chlorine disinfection by-product and generate the gesture dependent equation
1. preparing standard solution
Humic acid: biochemical reagents, the huge maple chemistry in Shanghai Science and Technology Ltd.
Fulvic acid: biochemical reagents.
The preparation of mentioned reagent derives from natural humus acid, in peat, brown coal or some soil.
Take by weighing the 0.1000g humic acid, with the KOH of 0.01mol/L as dissolution with solvents, be mixed with the stock solution that concentration is 100mg/L, again it diluted successively standard solution for 1.0mg/L, 2.0mg/L, 3.0mg/L, 4.0mg/L, 5.0mg/L, 6.0mg/L, 7.0mg/L;
Take by weighing the 1.0g fulvic acid, be mixed with the stock solution that concentration is 1000mg/L, stepwise dilution becomes the standard solution of 10.0mg/L, 20.0mg/L, 30.0mg/L, 40.0mg/L, 50.0mg/L, 60.0mg/L, a series of concentration of 70.0mg/L again.
2. three-dimensional fluorescence spectrum scanning
Set the three-dimensional fluorescence spectrum sweep parameter: excitation wavelength sweep limit 200nm-450nm, emission wavelength sweep limit 200nm-800nm excites slit 10nm, emission slit 10nm, sweep velocity 1200nm/min, sweep spacing 10nm.
Humic acid, fulvic acid standard solution to variable concentrations carries out three-dimensional fluorescence scanning respectively, obtain the three-dimensional feature fluorescence spectrum figure of humic acid, fulvic acid, humic acid, fulvic acid characteristic fluorescence peak center excitation/emission wavelength (Ex/Em) and characteristic fluorescence intensity f thereof that record is corresponding
EX/EM, wherein humic acid has a characteristic fluorescence peak, and fulvic acid has two characteristic fluorescence peaks.Table 1 is the correlativity of humic acid, fulvic acid characteristic fluorescence peak center wavelength and characteristic fluorescence intensity and concentration, from the table on as can be seen, humic acid, fulvic acid concentration and its three-dimensional feature fluorescence intensity have good linear dependence.
The correlativity of table 1 humic acid, fulvic acid concentration and its three-dimensional feature fluorescence intensity
3. measure chlorine disinfection by-product and generate gesture
Adopt the determination step of DBPFP, the DBPs of series standard solution of measuring the variable concentrations of humic acid, fulvic acid respectively generates the gesture value, and record haloform separately generates gesture and halogen acetic acid generates the gesture value.Table 2 is the correlativity that humic acid, fulvic acid concentration and its DBPs generate gesture, has reflected that humic acid, fulvic acid concentration and its DBPs generate gesture and also have linear dependence.
Table 2 humic acid, fulvic acid concentration and its DBPs generate the correlativity of gesture
4. set up the characteristic fluorescence intensity of standard solution and the correlation-corrected equation between the DBPs generation gesture
Table 3 is the characteristic fluorescence intensity of standard solution and the correlation-corrected equation between the DBPs generation gesture.As seen from Table 3, the three-dimensional feature fluorescence intensity of humic acid, fulvic acid and haloform, halogen acetic acid generate gesture and have significant linear dependence, the facies relationship number average reaches more than 0.9, shows that the three-dimensional feature fluorescence intensity of humic acid, fulvic acid can represent that its corresponding chlorine disinfection by-product generates gesture.
Table 3 f
Ex/EmDependent equation with DBPFP
(2) resurgent water sample determination
1. three-dimensional fluorescence scanning
Water sample to remove insoluble organism in the water sample, carries out three-dimensional fluorescence scanning through 0.45 μ m membrane filtration respectively then.The parameter setting of fluorescence spectrum analyzer: excitation wavelength sweep limit 200nm-450nm, emission wavelength sweep limit 200nm-800nm excites slit 10nm, emission slit 10nm, sweep velocity 1200nm/min, sweep spacing 10nm.Obtain
According to the characteristic fluorescence peak center position Ex/Em that has determined, write down the characteristic fluorescence intensity of corresponding humic acid, fulvic acid.Table 4 is the three-dimensional feature fluorescence intensity level of 10 water samples.
The three-dimensional feature fluorescence intensity level of table 4 water sample
2. the haloform that utilizes correction equation to calculate in the water sample generates gesture and halogen acetic acid generation gesture value
Bring humic acid, fulvic acid three-dimensional feature fluorescence intensity into corresponding correction equation respectively, the haloform of trying to achieve humic acid generates gesture value and halogen acetic acid generation gesture value, and the haloform of fulvic acid generates the gesture value and halogen acetic acid generates the gesture value; Also can by add and, try to achieve the total haloform of water sample, halogen acetic acid and generate the gesture value.
(3) correction as a result
Because humic acid, the fulvic acid reagent of configuration standard solution are biochemical reagents in the present embodiment, derive from natural humus, as peat, brown coal or some soil, at aspects such as molecular structure, characteristics of functional groups, molecular weight certain difference is arranged with soil ulmin in the resurgent water sample.In addition, the resurgent water sample background is than standard solution complexity, and coexisting substances also has certain influence.Therefore need revise result of calculation.
According to repeatedly experimental check discovery, the DBPs generation gesture that goes out by the correlation-corrected Equation for Calculating has consistent variation tendency with measured value, exists metastable multiple relation.In the present embodiment, the correction factor that haloform generates gesture is 0.36, and the correction factor that halogen acetic acid generates gesture is 0.47.Accompanying drawing 2 is that haloform, halogen acetic acid generate gesture calculated value, modified value and measured value contrast.
(4) result verification and error analysis
1. correlation analysis
Adopt relevant function method that revised DBPs generation gesture calculated value and measured value are carried out correlation analysis, analysis result sees Table 5.
Table 5 DBPs generates gesture calculated value and measured value correlation analysis result
As can be seen from the table, the related coefficient that haloform, halogen acetic acid DBPs generate gesture calculated value and measured value reaches 0.992,0.984 respectively, all has stronger correlativity; Therefore the significance probability of two-sided test negates null hypothesis all less than 0.01, thinks related coefficient by significance test, thinks that promptly all there are the positive correlation between calculated value and the actual measured value in halogen acetic acid and haloform DBPs.
2. error-tested
Revised calculated value and measured value are carried out error analysis, the results are shown in accompanying drawing 3.
Marked the data point of 10 water sample correspondences in the accompanying drawing 3.Its cathetus y=x has represented the crash consistency of calculated value and measured value, and the straight line that is distributed in the y=x left and right sides represents that the error of calculated value and measured value is 10%, and the left side straight line represents that calculated value exceeds measured value, and the right side straight line represents that calculated value is less than measured value.By accompanying drawing 3 as can be seen, the error of calculated value and measured value is about 10%.
Therefore, the DBPs that adopts said method to measure generates the gesture reliable results.
Claims (1)
1. chlorine disinfection by-product precursor in the three-dimensional fluorescence spectrum method for measuring water is characterized in that, this method determination step is as follows:
(1) sets up characteristic fluorescence intensity and chlorine disinfection by-product and generate the gesture dependent equation
1.1 preparing standard solution
Preparation variable concentrations humic acid standard solution: concentration is controlled in 1.0～7.0mg/L scope;
Preparation variable concentrations fulvic acid standard solution: concentration is controlled in 10.0～70.0mg/L scope;
1.2 three-dimensional fluorescence spectrum scanning
Set the three-dimensional fluorescence spectrum sweep parameter: excitation wavelength sweep limit 200nm-450nm, emission wavelength sweep limit 200nm-800nm excites slit 10nm, emission slit 10nm, sweep velocity 1200nm/min, sweep spacing 10nm;
Humic acid, fulvic acid standard solution to variable concentrations carries out three-dimensional fluorescence scanning respectively, obtain the three-dimensional feature fluorescence spectrum figure of humic acid, fulvic acid, humic acid, fulvic acid characteristic fluorescence peak center excitation/emission wavelength Ex/Em and characteristic fluorescence intensity f thereof that record is corresponding
EX/EM
Generate gesture 1.3 measure chlorine disinfection by-product
The DBPs of measuring the series standard solution of humic acid, fulvic acid variable concentrations respectively generates the gesture value, and record haloform separately generates gesture and halogen acetic acid generates the gesture value;
1.4 set up the characteristic fluorescence intensity of standard solution and the correlation-corrected equation between the DBPs generation gesture
With characteristic fluorescence intensity f
EX/EMBe independent variable, haloform generates gesture THMFP or halogen acetic acid generation gesture HAAFP is a dependent variable, sets up the characteristic fluorescence intensity f of humic acid, fulvic acid standard solution respectively
EX/EM1, f
EX/EM2Dependent linearity correction equation with THMFP, HAAFP;
The correlation-corrected equation that humic acid characteristic fluorescence intensity and DBPs generate between the gesture is:
THMFP
HA＝a
1?f
EX/EM1+b
1 (1)
HAAFP
HA＝a
2?f
EX/EM1+b
2 (2)
The correlation-corrected equation that fulvic acid characteristic fluorescence intensity and DBPs generate between the gesture is:
THMFP
FA＝a
3?f
EX/EM2+b
3 (3)
HAAFP
FA＝a
4?f
EX/EM2+b
4 (4)
In the formula, THMFP
HA, THMFP
FA, HAAFP
HA, HAAFP
FAThe haloform and the halogen acetic acid that are respectively humic acid, fulvic acid generate gesture;
f
EX/EM1, f
EX/EM2Be respectively the characteristic fluorescence intensity of humic acid, fulvic acid;
a
1, a
2, a
3, a
4, b
1, b
2, b
3, b
4Be correction coefficient, obtain by linear regression method;
(2) chlorine disinfection by-product of measuring in the actual water sample generates gesture
2.1 carry out three-dimensional fluorescence spectrum scanning
Elder generation through 0.45 μ m membrane filtration, to remove the insoluble organism of graininess in the water sample, carries out three-dimensional fluorescence spectrum scanning, sweep parameter step 1.1 to water sample with water sample then; According to humic acid, the determined three-dimensional feature fluorescence peak center Ex/Em of fulvic acid standard solution, write down the characteristic fluorescence intensity f of humic acid in the water sample, fulvic acid respectively
EX/EM
2.2 utilize correlation-corrected equation classified calculating DBPs to generate gesture
Utilize the three-dimensional feature fluorescence intensity of humic acid, fulvic acid in correlation-corrected equation and the water sample, the haloform and the halogen acetic acid of trying to achieve humic acid in the water sample, fulvic acid respectively generate the gesture value; Also obtain the total haloform of water sample, halogen acetic acid generation gesture respectively, that is: by adding with method
∑THMFP＝THMFP
HA+THMFP
FA (5)
∑HAAFP＝HAAFP
HA+HAAFP
FA (6)
2.3 result's correction
Total haloform, the halogen acetic acid of the water sample that utilizes the correlation-corrected Equation for Calculating to go out generates gesture and has consistent variation tendency with measured value, exists stable multiple relation; When needing to revise, haloform, the halogen acetic acid of measuring 5～7 water samples generate gesture, and carry out linear regression analysis with the corresponding calculated value, and regression coefficient is correction factor.
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