CN113845234B - Sand column device for simulating oxidation-reduction zone of underground water and using method - Google Patents
Sand column device for simulating oxidation-reduction zone of underground water and using method Download PDFInfo
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- CN113845234B CN113845234B CN202111113252.1A CN202111113252A CN113845234B CN 113845234 B CN113845234 B CN 113845234B CN 202111113252 A CN202111113252 A CN 202111113252A CN 113845234 B CN113845234 B CN 113845234B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
A sand column device for simulating an underground water redox zone and a using method thereof, mainly comprising the following structures: 1) A water tank; 2a) A rubber water guide pipe I; 2b) A rubber water guide pipe II; 3a) A peristaltic pump I; 3b) A peristaltic pump II; 4) A water inlet funnel; 5) A cylinder; 6a) A first nylon net; 6b) A second nylon net; 7) A water outlet funnel; 8) Water chemistry parameter probes/probes; 9) And (4) inputting a microbial culture solution into a bottle. The invention simulates N in the groundwater through targeted setting 2 And O 2 The proportion, the regulation and control simulation column body forms different redox zones of the underground medium, the designed complete set of sand column system can be used for researching the underground water organic pollution mechanism and repairing medicaments, the device can flexibly regulate and control the water body redox potential, is simple and convenient to operate, and is a powerful device for underground water research.
Description
Technical Field
The invention belongs to the technical field of water body pollution remediation, and particularly relates to a sand column device for simulating an underground water redox zone and a using method thereof.
Background
At present, the large-scale use of halogenated hydrocarbons has made them one of the most widespread pollutant species in ground water. Because the halogenated hydrocarbon pollution of the underground water is stable in structure, high in toxicity and difficult to degrade in the underground water, the halogenated hydrocarbon pollution of the underground water becomes one of the hot spots for the international prevention, control and protection of the underground water pollution at present. Among the numerous halocarbon treatment technologies, the in situ microbial remediation treatment technology is most economically efficient.
The in-situ microbial repairing technology is to utilize the metabolism of microbes to degrade or convert halohydrocarbon into less toxic or non-toxic product by means of stimulating the growth and propagation of indigenous microbes in natural environment or injecting specific flora. At present, various medicament research and development models aiming at stimulating microorganisms still have the problem that the vertical migration mechanism of halohydrocarbon polluted water bodies in different redox zones and the effect and the influence factors of pollution remediation medicaments cannot be well reflected.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a sand column device for simulating an oxidation-reduction zone of underground water and a method for researching the oxidation-reduction conditions of halogenated hydrocarbon by using the device,
in order to achieve the purpose, the invention adopts the technical scheme that:
a sand column device for simulating an underground water redox zone comprises a column body filled with a filling reagent, wherein the upper end of the column body is connected with a water inlet funnel, the lower end of the column body is connected with a water outlet funnel, the inlet of the water inlet funnel is connected with one end of a rubber water guide pipe I with a peristaltic pump I and one end of a rubber water guide pipe II with a peristaltic pump II, the other end of the rubber water guide pipe I is connected with a water tank for containing simulated halohydrocarbon polluted underground water, the other end of the rubber water guide pipe II is connected with a microorganism culture solution input bottle, and the column body is connected with water chemistry parameter probes/probes at different heights.
The sand column device for simulating the oxidation-reduction zone of the underground water is characterized in that the water tank and the microorganism culture solution input bottle are both brown thin-opening devices with scales, and the water tank and the microorganism culture solution input bottle can avoid gas leakage and have a light-shielding effect after being sealed; the column body is a main body part of an experiment, is made of polytetrafluoroethylene, is 15cm high, 3-5cm in inner diameter and 4-6cm in outer diameter, is provided with 4 equidistant round holes which are not smaller than 0.1cm along the height direction on one side and are used for sample collection and a water chemical parameter probe/probe, is filled with a filling test medium meeting the experiment requirement before the experiment, and is provided with a layer of nylon net at two ends respectively to prevent the filling test medium from dissipating; the filling test medium is a simulated underground water medium comprising medium sand, fine sand, clay and the like, and is determined according to the local condition of a simulated pollution site, so that the permeability coefficient is ensured to be 6 multiplied by 10 -3 ～3×10 -6 cm/s。
The method for researching the halogenated hydrocarbon redox condition of the sand column device simulating the groundwater redox zone comprises the following steps:
(1) Filling a filling test medium meeting the experimental requirements in the column body;
(2) Adding halogenated hydrocarbons with different concentrations into simulated underground water to simulate the pollution of the halogenated hydrocarbon underground water, putting a simulated halogenated hydrocarbon polluted underground water sample to be tested into a water tank, and putting a halogenated hydrocarbon underground water remediation agent (which may or may not contain a functional microbial inoculum) into a microbial culture solution input bottle;
(3)O 2 and N 2 The nitrogen gas cylinder and the oxygen gas cylinder are connected into the simulated underground water tank through the guide pipe and inserted into the water tank from the lower part of the liquid level to the bottom of the water tank, and the N of the simulated halohydrocarbon polluted underground water sample is adjusted 2 And O 2 Different oxidation-reduction zones are formed in different columns in sequence according to the aeration proportion and time;
(4) The experiment should be formed by three stages, namely, the gradual transition from the strong redox stage to the weak redox stage so as to enhance the stability of the redox zone, and the gradual forming process also relatively accords with the forming characteristics of different redox zones under natural conditions;
(5) Regulating the flow rate of the simulated halogenated hydrocarbon polluted underground water through the peristaltic pump I, and controlling the flow rate of the halogenated hydrocarbon polluted underground water remediation agent through the peristaltic pump II to accurately reduce the underground water polluted site;
(6) Continuously introducing simulated halogenated hydrocarbon polluted underground water into the column, keeping a water saturation state, sampling and monitoring water chemical parameter indexes such as water oxidation-reduction potential and the like in the simulated column every week, collecting reacted water through a water outlet funnel at the bottom end of the column after the sample water reacts, and obtaining the reaction efficiency of the halogenated hydrocarbon polluted underground water in an oxygen reduction zone, a nitrate reduction zone, an iron reduction zone and a sulfate reduction zone respectively;
(7) The concentration parts of the halohydrocarbon in different redox zones are respectively analyzed by utilizing the simulation column system, the degradation effect of the medicament on the halohydrocarbon is sampled and measured, the medicament action principle is researched, and the influence of the underground water on the medicament action in an oxygen reduction zone, a nitrate reduction zone, an iron reduction zone and a sulfate reduction zone is analyzed.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method is suitable for different halohydrocarbon polluted sites, and can be used for pertinently setting and simulating N in the underground water according to experimental requirements 2 And O 2 The proportion and the regulation and control simulation column form different redox zones of an underground medium, and the designed complete sand column system can be used for batch research of the vertical migration mechanism of the halohydrocarbon polluted water body in different redox zones and the problems of the effect and the influence factors of the pollution remediation agent.
(2) The cylinder body one side is equipped with 4 equidistance round holes that are not less than 0.1cm along the direction of height in the device, can realize that a hole is multi-functional, makes things convenient for the sampling survey medicament to halohydrocarbon degradation effect, research medicament effect principle, and the different redox zones of assay groundwater are to the medicament effect influence.
(3) The column body in the device is made of polytetrafluoroethylene, the height is 15cm, the inner diameter is 3-5cm, and the outer diameter is 4-6cm, so that abnormal deposition of a filling test medium can be prevented, the volume is small, and the experimental operation is convenient.
Drawings
FIG. 1 is a schematic view of the sand column device of the present invention.
FIGS. 2 to 5 are views of a set of apparatus for investigating groundwater redox carrying sand column according to the present invention, wherein FIG. 2 shows O 2 Reduction zone, NO is shown in FIG. 3 3 - Reduction zone, fe is shown in FIG. 4 3+ Reduction zone, SO is shown in FIG. 5 4 2- Reducing the zone, and filling the medium with quartz sand.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
As shown in figure 1, the sand column device for simulating the redox zone of the underground water comprises a column body 5 filled with a filling reagent, wherein the upper end of the column body 5 is connected with a water inlet funnel 4, the lower end of the column body is connected with a water outlet funnel 7, the inlet of the water inlet funnel 4 is connected with one end of a rubber water guide pipe I2 a with a peristaltic pump I3 a and one end of a rubber water guide pipe II 2b with a peristaltic pump II 3b, the other end of the rubber water guide pipe I2 a is connected with a water tank 1 for containing underground water polluted by simulated halogenated hydrocarbons, the other end of the rubber water guide pipe II 2b is connected with a microorganism culture solution input bottle 9, and the column body 5 is connected with water chemical parameter probes/probes 8 at different heights; a nylon net I6 a is arranged between the upper end of the column body 5 and the water inlet funnel 4, and a nylon net II 6b is arranged between the lower end of the column body and the water outlet funnel 7; the water tank 1 and the microorganism culture solution input bottle 9 are both brown thin-mouth devices with scales, and can avoid gas leakage and have a light-shielding effect after being sealed; the column 5 is made of polytetrafluoroethylene, the height of the column is 15cm, the inner diameter of the column is 3-5cm, the outer diameter of the column is 4-6cm, and 4 equidistant round holes which are not less than 0.1cm are formed in one side of the column along the height direction and are used for sample collection and a water chemical parameter probe/probe 8.
As shown in fig. 2, fig. 3, fig. 4 and fig. 5, according to the purpose of different experiments, the experiment uses a set of devices to form a sand column system, and studies the problems of the vertical migration mechanism of the oxygen reduction zone, the nitrate reduction zone, the iron reduction zone and the sulfate reduction zone of the halogenated hydrocarbon polluted water body, the effect of the pollution remediation agent and the influencing factors in batches.
The method for researching the halogenated hydrocarbon redox condition of the sand column device simulating the groundwater redox zone comprises the following steps:
(1) Filling test media meeting experimental requirements are filled in the column body, including medium sand, fine sand, clay and the like, and the permeability coefficient is ensured to be 6 multiplied by 10 according to the local condition of a simulated polluted site -3 ～3×10 -6 cm/s；
(2) Adding halohydrocarbon with different concentrations into simulated groundwater to simulate the pollution of the halohydrocarbon groundwater, putting a sample of the simulated halohydrocarbon polluted groundwater to be tested into a water tank 1, and putting a halohydrocarbon polluted groundwater remediation agent (which may or may not contain a functional microbial inoculum) into a microbial culture solution input bottle 9;
(3)O 2 and N 2 The nitrogen gas cylinder and the oxygen gas cylinder are connected into the simulated underground water tank through the guide pipe and inserted into the water tank from the lower part of the liquid level to the bottom of the water tank, and the N of the simulated halohydrocarbon polluted underground water sample is adjusted 2 And O 2 The aeration proportion and the aeration time sequentially form different oxygen reduction zones, nitrate reduction zones, iron reduction zones and sulfate reduction zones in different columns 5, and the oxygen reduction zones are required to control the simulated oxidation-reduction potential (Eh) of the underground water to be + 1.1-1.3V (pH = 7), controlling the Eh of simulated underground water in a nitrate reduction zone to be + 0.9-1V 3+ The Eh of the simulated underground water in the reduction zone is controlled to be + 0.7-0.8V 4 2- The Eh of the simulated underground water in the reduction zone is controlled to be 0.1-0.2V. (ii) a
(4) The forming methods and parameters of the oxygen reduction zone, the nitrate reduction zone, the iron reduction zone and the sulfate reduction zone are shown in tables 1, 2 and 3, and the three stages are divided into three stages, wherein the three stages are gradually transited from a strong oxidation reduction stage to a weak oxidation reduction stage so as to enhance the stability of the oxidation reduction zone;
TABLE 1 first-stage parameter Table
TABLE 2 second stage parameter Table
TABLE 3 third-stage parameter Table
(5) Regulating the flow rate of the underground water polluted by the simulated halogenated hydrocarbon to be 4-8 mL/day by using the first peristaltic pump 3a, and controlling the flow rate of the underground water polluted by the halogenated hydrocarbon to be 2-3 mL/day by using the second peristaltic pump 3b to accurately reduce the polluted site of the underground water;
(6) The column body is continuously communicated with simulated halogenated hydrocarbon polluted underground water, the saturated water state is kept, and water chemical parameter indexes such as the oxidation-reduction potential of the water in the simulated column are sampled and monitored every week. Collecting the water body after the reaction by a water outlet funnel at the bottom end of the column after the reaction of the sample water body, and obtaining the reaction efficiency of the halogenated hydrocarbon polluted underground water in an oxygen reduction zone, a nitrate reduction zone, an iron reduction zone and a sulfate reduction zone respectively;
(7) The concentration parts of the halohydrocarbon in 4 kinds of oxidation-reduction zones are respectively analyzed by utilizing the 4 sets of simulation column systems, the degradation effect of the medicament on the halohydrocarbon is sampled and measured, the medicament action principle is researched, and the influence of the underground water on the medicament action in the oxygen reduction zone, the nitrate reduction zone, the iron reduction zone and the sulfate reduction zone is analyzed.
Claims (9)
1. The method comprises the steps of carrying out halogenated hydrocarbon redox condition research on a sand column device simulating an underground water redox zone, wherein the sand column device comprises a column body (5) filled with a filling reagent, the upper end of the column body (5) is connected with a water inlet funnel (4), the lower end of the column body is connected with a water outlet funnel (7), the inlet of the water inlet funnel (4) is connected with one end of a rubber water guide pipe I (2 a) with a peristaltic pump I (3 a) and one end of a rubber water guide pipe II (2 b) with a peristaltic pump II (3 b), the other end of the rubber water guide pipe I (2 a) is connected with a water tank (1) for containing underground water polluted by the simulated halogenated hydrocarbon, the other end of the rubber water guide pipe II (2 b) is connected with a microbial culture solution input bottle (9), the column body (5) is connected with hydration chemical parameter probes/probes (8) at different heights, a sand column system is formed by using one set of devices according to the purposes of different experiments, and the problems of vertical migration mechanism of oxygen reduction zone, nitrate reduction zone, iron reduction zone and sulfate reduction zone of the halogenated hydrocarbon polluted water and pollution reduction zone and the problem of the action effect and influence factors of pollution remediation reagents are researched;
characterized in that the method comprises:
step (1), filling test media meeting experimental requirements are contained in a column body (5);
adding halohydrocarbon with different concentrations into simulated underground water to obtain simulated halohydrocarbon polluted underground water, putting a simulated halohydrocarbon polluted underground water sample to be tested into a water tank (1), and putting a halohydrocarbon underground water repairing reagent into a microorganism culture solution input bottle (9);
step (3), O 2 And N 2 The N simulating the halohydrocarbon pollution of the underground water is adjusted by connecting an oxygen cylinder and a nitrogen cylinder into a water tank (1) through a conduit 2 And O 2 The aeration proportion and the aeration time form an oxygen reduction zone, a nitrate reduction zone, an iron reduction zone and a sulfate reduction zone in different columns (5), wherein the oxygen reduction zone simulates the pollution of halogenated hydrocarbon undergroundThe oxidation-reduction potential of water is controlled to be +1.1 to 1.3V, the pH =7, the oxidation-reduction potential of the groundwater polluted by the simulated halogenated hydrocarbon in the nitrate reduction zone is controlled to be +0.9 to 1V, fe 3+ The redox potential of the underground water polluted by the simulated halogenated hydrocarbon in the reducing zone is controlled to be +0.7 to 0.8V 4 2- The redox potential of the underground water polluted by the simulated halogenated hydrocarbon in the reducing zone is controlled within 0.1 to 0.2V;
step (4), regulating the flow rate of the underground water polluted by the simulated halogenated hydrocarbon in the water tank (1) to be 4-8 mL/day through a peristaltic pump I (3 a), and controlling the flow rate of the underground water polluted by the halogenated hydrocarbon to be 2-3 mL/day through a peristaltic pump II (3 b) to accurately reduce the underground water polluted site;
step (5), continuously introducing simulated halogenated hydrocarbon polluted underground water into the column (5), keeping a water saturation state, sampling and monitoring the water chemistry parameter indexes including the water body oxidation reduction potential in the column (5) every week, obtaining the reaction efficiency of the halogenated hydrocarbon polluted underground water in an oxygen reduction zone, a nitrate reduction zone, an iron reduction zone and a sulfate reduction zone respectively, and collecting the water body after the reaction through a water outlet funnel (7);
and (6) respectively analyzing the concentrations of the halogenated hydrocarbon in an oxygen reduction zone, a nitrate reduction zone, an iron reduction zone and a sulfate reduction zone, sampling and measuring the degradation effect of the halogenated hydrocarbon underground water remediation agent on the halogenated hydrocarbon, researching the action principle of the agent, and analyzing the influence of the underground water on the action of the agent in the oxygen reduction zone, the nitrate reduction zone, the iron reduction zone and the sulfate reduction zone.
2. Method according to claim 1, characterized in that a first nylon mesh (6 a) is arranged between the upper end of the column (5) and the inlet funnel (4) and a second nylon mesh (6 b) is arranged between the lower end and the outlet funnel (7).
3. The method according to claim 1, characterized in that the water tank (1) and the microorganism culture solution input bottle (9) are both provided with a scaled brown thin-mouth device, which can prevent gas leakage after being sealed and has a light-shielding effect.
4. The method according to claim 1, characterized in that the column (5) is made of polytetrafluoroethylene, the height is 15cm, the inner diameter is 3-5cm, the outer diameter is 4-6cm, and one side is provided with 4 equidistant round holes not less than 0.1cm along the height direction for sample collection and a water chemistry parameter probe/probe (8).
5. The method of claim 1, wherein the fill test medium is a simulated groundwater medium comprising medium sand, fine sand, silt fine sand and clay, wherein the fill test medium has a permeability coefficient of 6 x 10, depending on the local conditions of the simulated halocarbon contaminated site -3 ~3×10 -6 cm/s。
6. The method as claimed in claim 1, wherein the halogenated hydrocarbon groundwater remediation agent comprises a water soluble functional microbial inoculum, and the specific components are determined according to the situation of a simulated halogenated hydrocarbon polluted site.
7. Method according to claim 1, characterized in that the conduits of the oxygen and nitrogen cylinders are inserted below the liquid level to the bottom of the water tank (1).
8. The method of claim 1, wherein in step (3), N is inflated 2 The higher the proportion, the lower the redox potential of the simulated halogenated hydrocarbon contaminated groundwater, O 2 The higher the ratio, the higher the redox potential of the simulated halogenated hydrocarbon contaminated groundwater.
9. The method according to claim 1, wherein in the step (3), the oxygen reduction zone, the nitrate reduction zone, the iron reduction zone and the sulfate reduction zone forming method are respectively divided into three stages of gradual transition from strong redox to weak redox, wherein:
in the first stage, O 2 /N 2 The values of the volume ratio, the aeration speed, the aeration time, the total amount of simulated halogenated hydrocarbon polluted underground water and the water saturation time when an oxygen reduction zone is formed are as follows:8:1, 3L/min, 50 min, 0.5L, 3 days; the values at which nitrate reduction zones are formed are: 1:2, 2L/min, 40 min, 0.5L, 3 days; the values when forming the iron reduction zone are: 1:4, 3L/min, 60 min, 0.5L, 3 days; the values for forming the sulfate reduction zone are: 1:9, 3L/min, 60 min, 0.5L, 3 days;
in the second stage, O 2 /N 2 The values of the volume ratio, the aeration speed, the aeration time, the total amount of simulated halogenated hydrocarbon polluted underground water and the water saturation time when an oxygen reduction zone is formed are as follows: 6:1, 3L/min, 50 min, 0.5L, 7; the values at which nitrate reduction zones are formed are: 1:4, 3L/min, 40 min, 0.5L, 7 days; the values at the time of formation of the iron reduction zone are: 1, 10, 3L/min, 60 min, 0.5L and 7 days; the values for forming the sulfate reduction zone are: 1, 15, 3L/min, 60 min, 0.5L and 7 days;
in the third stage, O 2 /N 2 The values of the volume ratio, the aeration speed, the aeration time, the total amount of simulated halogenated hydrocarbon polluted underground water and the water saturation time when an oxygen reduction zone is formed are as follows: 1:1, 3L/min, 50 min, 0.5L, 14 days; the values at which nitrate reduction zones are formed are: 1, 10, 2L/min, 40 min, 0.5L and 14 days; the values at the time of formation of the iron reduction zone are: 1, 20, 3L/min, 60 min, 0.5L and 14 days; the values for forming the sulfate reduction zone are: 1.
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| US3705597A (en) * | 1971-02-26 | 1972-12-12 | Nutrico Inc | Continuous control for introducing material into a flowing liquid |
| BRPI0501652B1 (en) * | 2005-04-20 | 2015-05-26 | Unicamp | Reagent for in situ and ex situ destruction of environmental contaminants |
| CN207440053U (en) * | 2017-11-17 | 2018-06-01 | 中国地质科学院水文地质环境地质研究所 | A kind of experimental system for the injection of nano material in-situ water-bearing layer |
| CN110426477B (en) * | 2019-08-16 | 2024-08-06 | 中国地质科学院水文地质环境地质研究所 | Application method of simulation device of zero-valent iron permeation reaction grid |
| CN113281235B (en) * | 2021-05-24 | 2022-11-29 | 山东科技大学 | Underground water artificial recharge seepage simulation monitoring system and method |
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| US5824134A (en) * | 1997-01-29 | 1998-10-20 | Powers; Jim | Direct reduction of iron ore utilizing organic hazardous materials |
| CN101575634A (en) * | 2008-05-05 | 2009-11-11 | 中国石油天然气股份有限公司 | Method for determining oxygen consumption and oxygen consumption rate of oil reservoir microorganisms |
| CN213506438U (en) * | 2020-08-14 | 2021-06-22 | 中国地质科学院水文地质环境地质研究所 | Simulation restoration device for underground water containing 1,2-dichloroethane and sulfate |
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