CN102890075A - Quickly judging method for underground water polluted by organic matter - Google Patents
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Abstract
The invention relates to a quickly judging method for underground water polluted by organic matter, which comprises the following steps: A) collecting underground water samples in, pollution source areas, the upstream, two sides and the downstream of the pollution source areas; B) filtering collected underground samples, and determining soluble organic carbon concentration; C) converging the three-dimensional fluorescence spectrum matrix data of all underground water samples so as to process parallel factor analysis; and D) judging that the underground water is not polluted if component acquired in the parallel factor analysis does not have fluorescence peaks within a range that an excitation wavelength is larger than or equal to 200nm and is less than or equal to 440nm; and an emission wavelength is larger than or equal to 280nm and is less than 380nm; judging that the underground water is polluted if the component acquired in the parallel factor analysis appears the fluorescence peaks within a range that the excitation wavelength is larger than or equal to 200nm and is less than or equal to 440nm; and the emission wavelength is larger than or equal to 280nm and is less than 380nm, wherein the larger the maximum fluorescence strength of the underground fluorescence component is, the severer the pollution degree of the underground is. According to the invention, the quickly judging method is characterized by little sample quantity, quick analysis and high sensitivity.
Description
Technical field
The invention belongs to groundwater contamination and Prevention Technique field, be specifically related to a kind ofly in underground water, whether exist and relative concentration size is judged the whether contaminated method that reaches pollution level of underground water by mankind's activity source organism.
Background technology
The landfill lack of standardization of house refuse, the random discharging of livestock breeding wastewater, and a large amount of uses of farmland pesticide make some regional underground water be subject to Organic Pollution, have brought hidden danger for the local people masses' safe drinking water.Whether wish is eliminated this hidden danger, guarantees the people masses' safe drinking water, needs at first to determine the whether contaminated pollution level that reaches of underground water, then estimate underground water and can drink and need to administer.
The index of sign underground water Organic Pollution commonly used is CODcr, BOD
5And dissolved organic carbon (DOC).Because soil has very strong adsorbability to organism, therefore, when pollutant when aeration zone enters the water-bearing zone and moves in underground water, its concentration descends very fast, causes behind the certain distance upstream and downstream CODcr, BOD in the underground water
5And the DOC value difference is not little, and the index that is difficult to the sign Organic Pollution by these routines judges whether underground water has been subject to pollution.Moreover, because part underground water is subjected to be in anaerobic environment behind the Organic Pollution, may cause CODcr, BOD
5Measured value and actual value larger error appears, give and judge the whether contaminated error of bringing of underground water.
In consumer waste landfill percolate, livestock breeding wastewater and sanitary sewage, contain a large amount of Dissolved Organic Matters, these organism are water-soluble, migration easily occurs and enter underground water.Dissolved Organic Matter in these waste water contains a large amount of mankind's activity source organism, such as heterogeneous organism (aromatic hydrocarbons, halogenated hydrocarbons, phenols and pesticide), and the easily biodegradable organics such as proteinoid, carbohydrate etc.Organism in the unpolluted natural groundwater is mainly the Humus material, and after underground water was contaminated, wherein plastein material and heterogeneous organic concentration increased.
The detection method that organism is commonly used is the GC-MS coupling technique, still, adopts GC-MS combination analysis organism to form, its complex pretreatment, and technical requirement is high.On the other hand, the heterogeneous organism such as plastein material and aromatic hydrocarbons, phenols has very strong fluorescent characteristic, can adopt the three-dimensional fluorescence spectrum instrument to measure, adopt three-dimensional fluorescence spectrum technical Analysis underground water organism to form, not only pre-treatment is simple, analyze fast, and detectability is low, can reach 10
-9, also hang down two orders of magnitude than the ultraviolet-visible spectrum of routine.When the three-dimensional fluorescence spectrum of sample is combined with the parallel factor analysis method, just can parse the composition of Dissolved Organic Matter in the underground water, disclose and whether contain the mankind's activity source organism such as plastein material, heterogeneous organism in the underground water Dissolved Organic Matter, and then can judge whether underground water has been subject to pollution.
Summary of the invention
Content of the present invention is to provide a kind of method for quick that is subjected to the organism polluted underground water, utilizing three-dimensional fluorescence spectrum that the underground water organism is formed analyzes, whether reach relative concentration size by the organic existence in mankind's activity source in the underground water and judge the whether contaminated pollution level that reaches of underground water, utilize the method can sensitivity to detect efficiently underground water and whether be subject to pollution.
For achieving the above object, underground water provided by the invention is subjected to the method for quick of Organic Pollution, and its key step is as follows:
A) in pollution source area, pollution source area upstream and both sides, pollution source area downstream scope, gather the underground water sample;
B) institute is gathered the underground water sample and filter, survey dissolved organic carbon concentration, carry out three-dimensional fluorescence spectrum and measure;
C) the three-dimensional fluorescence spectrum matrix data of all underground water samples is gathered carry out parallel factor analysis, obtain the three-dimensional fluorescence spectrum figure of number of components, component and the maximum fluorescence intensity of the corresponding component of each underground water sample;
D) if the parallel factor analysis obtained component at 200nm≤excitation wavelength≤440nm, fluorescence peak do not occur in 280nm≤emission wavelength＜380nm scope, then underground water has not been subject to pollution; If the parallel factor analysis obtained component is at 200nm≤excitation wavelength≤440nm, fluorescence peak appears in 280nm≤emission wavelength＜380nm scope, then underground water has been subject to pollution, and the maximum fluorescence intensity of corresponding underground water fluorescent components is larger, shows that underground water is contaminated more serious.
In the described method, the pollution source area in the steps A refers to household refuse landfill sites, livestock and poultry farm and rural activity district.
In the described method, gather the underground water sample in the steps A and be in pollution source area upstream and both sides 10-50m scope, in pollution source area downstream 10-50,50-100 and the 100-500m scope.
In the described method, the underground water sample number that gathers in the steps A is no less than 16.
In the described method, be placed on 4-7 ℃ of low temperature preservation in the insulation can after the underground water sample collection in the steps A.
In the described method, the underground water sample is through 0.45 or 0.22 μ m membrane filtration among the step B.
In the described method, adjust first dissolved organic carbon concentration among the step B and carry out again spectroscopic assay less than 10mg/L.
In the described method, excitation wavelength was 200-440nm when the three-dimensional fluorescence spectrum among the step B was measured, and emission wavelength is 280-520nm, excites with the emission wavelength slit width and is 5nm, and sweep velocity is set in 500-2400nm min
-1In the scope.
In the described method, measure complete rear gained fluorescent matrix data among the step B and export to the excel form, obtain the three-dimensional fluorescence spectrum matrix data of 49 row * 51 row.
The present invention has following advantage:
1, the sample demand is few, and detection sensitivity is high.Adopt this method to detect underground water and whether be subject to pollution, the sample demand few (＜10ml), detection sensitivity is high by (＜10
-9).
2, analyze fast.Sample collection is complete transport the laboratory back after, sample analysis and data processing amount are few, can obtain the whether contaminated information of underground water in 24 hours.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 a, b, c be adopt method of the present invention to the three-dimensional fluorescence spectrum of Dissolved Organic Matter in the household refuse landfill sites underground water through parallel factor analysis obtained component figure.
Fig. 3 a, b, c be adopt method of the present invention to the three-dimensional fluorescence spectrum of Dissolved Organic Matter in the farmland underground water through parallel factor analysis obtained component figure.
Embodiment
Technical scheme of the present invention is:
(A) in pollution source area, pollution source area upstream and both sides 10-50m scope, gather the underground water sample in pollution source area downstream 10-50,50-100 and the 100-500m scope.
(B) institute's collected specimens is crossed 0.22 μ m or 0.45 μ m filter membrane after, transfer organic carbon content to 0＜DOC＜10mg/L, carry out three-dimensional fluorescence spectrum and measure.
Excitation wavelength was 200-440nm when three-dimensional fluorescence spectrum was measured, and emission wavelength is 280-520nm, excites with the emission wavelength slit width and is 5nm, and sweep velocity is set in 500-2400nm min
-1In the scope.
Measure complete rear gained fluorescent matrix data and export to the excel form, obtain the three-dimensional fluorescence spectrum matrix data of 49 row * 51 row.
(C) the three-dimensional fluorescence spectrum matrix data with all samples is aggregated in the excel form, then adopt the DOMFluor kit to carry out parallel factor analysis at Matlab 7.0 softwares, obtain the three-dimensional fluorescence spectrum figure of number of components, component and the maximum fluorescence intensity Fmax of the corresponding component of each sample.
(D) if the parallel factor analysis obtained component at 200nm≤excitation wavelength≤440nm, fluorescence peak do not occur in 280nm≤emission wavelength＜380nm scope, then underground water has not been subject to pollution; If the parallel factor analysis obtained component at 200nm≤excitation wavelength≤440nm, fluorescence peak occurs in 280nm≤emission wavelength＜380nm scope, then underground water has been subject to pollution, and the Fmax of corresponding underground water fluorescence peak is larger, shows that underground water is contaminated more serious.
, specify embodiments of the present invention below in conjunction with accompanying drawing.
Embodiment 1
Sampling: sample is taken from Beijing refuse landfill and near underground water thereof.This landfill yard is informal landfill yard, does not do any antiseepage and processes, and landfill yard underground water is already by leachate contamination.In this refuse landfill, landfill yard upstream and both sides and landfill yard downstream adopt 16 in common collection underground water sample.Low temperature is preserved in insulation can, transported the laboratory back the same day after, 4 ℃ of freezing preservations.
Filter and measure DOC: after adopting the filter membrane of 0.45 μ m that the underground water sample is filtered, analyze working sample DOC on the analyzer in TOC.When sample DOC concentration is higher than 10mg/L, adopts distilled water to dilute and make 0＜DOC＜10mg/L.
Three-dimensional fluorescence spectrum is measured: all samples is carried out three-dimensional fluorescence spectrum measure, excitation wavelength is made as 200-440nm during mensuration, and emission wavelength is made as 280-520nm, excites with the emission wavelength slit width and all is made as 5nm, sweep velocity 1200nm min
-1Measure complete after, the fluorescent matrix data of 16 samples are exported in the excel form, obtain the three-dimensional fluorescence spectrum matrix data of 16 49 row * 51 row, all matrix datas are positioned in the excel form.
Parallel factor analysis: the fluorescent matrix data in the excel table are carried out non-negative processing, all negative value assignment are 0, then adopt DOMFluor kit (www.models.kvl.dk/source) after Matlab7.0 removes Rayleigh scattering and Raman scattering, carry out parallel factor analysis, get three components and corresponding fluorescent components figure (shown in Fig. 2 a, b, c).
Groundwater contamination is judged: the three-dimensional fluorescence spectrum figure of landfill yard underground water dissolved organic matter is through parallel factor analysis, and in three fluorescent components that obtain, component 1 is that Similar humic substances, component 2 are plastein material for heterogeneous organism, component 3.The existence of underground water plastein material and heterogeneous organism (component 2 and component 3) shows that it contains mankind's activity source organism, and underground water has been subject to pollution.
Embodiment 2
The sampling: the farmland, changzhou and near the collection sampling of ground water.The wide 4.2km of this sheet farmland thing, 6.5km long from south to north plants wheat winter, summer autumn planting planting paddy rice.In the farmland, upstream, both sides and the downstream in farmland gather 16 in underground water sample altogether.Low temperature is preserved in insulation can, transport the laboratory back in 12 hours after, 4 ℃ of freezing preservations.
Filter and measure DOC: the fibrous filter membrane that adopts 0.45 μ m with sample filtering after, analyze working sample DOC on the analyzer in TOC, when sample DOC is higher than 10mg/L, adopt distilled water to transfer sample 0＜DOC＜10mg/L.
Three-dimensional fluorescence spectrum is measured: all samples is carried out three-dimensional fluorescence spectrum measure, excitation wavelength is made as 200-440nm during mensuration, and emission wavelength is made as 280-520nm, excites with the emission wavelength slit width and all is made as 5nm, sweep velocity 1200nm min
-1Measure complete after, the fluorescent matrix data of 16 samples are exported to the excel form, obtain the three-dimensional fluorescence spectrum matrix data of 16 49 row * 51 row, all matrix datas are positioned in the excel form.
Parallel factor analysis: the fluorescent matrix data in the excel table are carried out non-negative processing, all negative value assignment are 0, then adopt DOMFluor kit (www.models.kvl.dk/source) after Matlab7.0 removes Rayleigh scattering and Raman scattering, carry out parallel factor analysis, obtain three fluorescent components (shown in Fig. 3 a, b, c).
Groundwater contamination is judged: the three-dimensional fluorescence spectrum of farmland underground water-soluble organic matter is after parallel factor analysis, in three components that obtain, component 1 is that Similar humic substances, component 2 and 3 are plastein material, and wherein component 2 is class tryptophane material, and component 3 is the tyrosine material.The existence of underground water plastein material (component 2 and component 3) shows that this underground water has been subject to Organic Pollution.
Checking: the agricultural chemicals in the collection underground water is detected, and the result is as shown in table 1.Chlopyrifos and 4 in underground water, have been detected, 4 '-DDD, 4,4 '-DDE, 4,4 '-three kinds of organo-chlorine pesticides of DDT, show the pollution that has been subject to agricultural chemicals in the underground water, verified that exogenous organic matter detects the correctness that underground water has been subject to Organic Pollution in the employing three-dimensional fluorescence spectrum.
Table 1 farmland underground water agricultural chemicals distribution (unit: μ g/L)
Claims (9)
1. a underground water is subjected to the quick determination methods of Organic Pollution, and its key step is:
A) in pollution source area, pollution source area upstream and both sides, pollution source area downstream scope, gather the underground water sample;
B) institute is gathered the underground water sample and filter, survey dissolved organic carbon concentration, carry out three-dimensional fluorescence spectrum and measure;
C) the three-dimensional fluorescence spectrum matrix data of all underground water samples is gathered carry out parallel factor analysis, obtain the three-dimensional fluorescence spectrum figure of number of components, component and the maximum fluorescence intensity of the corresponding component of each underground water sample;
D) if the parallel factor analysis obtained component at 200nm≤excitation wavelength≤440nm, fluorescence peak do not occur in 280nm≤emission wavelength＜380nm scope, then underground water has not been subject to pollution; If the parallel factor analysis obtained component is at 200nm≤excitation wavelength≤440nm, fluorescence peak appears in 280nm≤emission wavelength＜380nm scope, then underground water has been subject to pollution, and the maximum fluorescence intensity of corresponding underground water fluorescent components is larger, shows that underground water is contaminated more serious.
2. method according to claim 1, wherein, the pollution source area in the steps A refers to household refuse landfill sites, livestock and poultry farm and rural activity district.
3. method according to claim 1 wherein, gathers the underground water sample and is in pollution source area upstream and both sides 10-50m scope, in pollution source area downstream 10-50,50-100 and the 100-500m scope in the steps A.
4. according to claim 1 or 3 described methods, wherein, the underground water sample number that gathers in the steps A is no less than 16.
5. method according to claim 4 wherein, is placed on 4-7 ℃ of low temperature preservation in the insulation can after the underground water sample collection in the steps A.
6. method according to claim 4, wherein, the underground water sample is through 0.22 μ m or 0.45 μ m membrane filtration among the step B.
7. method according to claim 1 wherein, is adjusted first dissolved organic carbon concentration and is carried out three-dimensional fluorescence spectrum mensuration less than 10mg/L again among the step B.
8. method according to claim 1, wherein, excitation wavelength was 200-440nm when the three-dimensional fluorescence spectrum among the step B was measured, and emission wavelength is 280-520nm, excite with the emission wavelength slit width and be 5nm, sweep velocity is set in the 500-2400nm min-1 scope.
9. according to claim 1 or 7 described methods, wherein, measure complete rear gained fluorescent matrix data among the step B and export to the excel form, obtains the three-dimensional fluorescence spectrum matrix data that 49 row * 51 are listed as.
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| CN115575368A (en) * | 2022-10-11 | 2023-01-06 | 北京工业大学 | Method for judging adsorption affinity of granular activated carbon to organic pollution components |
| CN115575368B (en) * | 2022-10-11 | 2024-03-26 | 北京工业大学 | Method for judging adsorption affinity of granular activated carbon to organic pollution components |
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