JP2003247919A - Sampling device and sampling method for underwater pollutant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sampling device and a sampling method for underwater pollutant suitable as a means for catching pollutant over a long period of time to accurately measure a small amount of various pollutants suspended or dissolved in various environment water or waste water, capable of easily and securely catching a small amount of pollutant in a large amount of water, and recovering it with a high concentration magnification ratio. <P>SOLUTION: This sampling device or this sampling method for underwater pollutant comprises a filtering means for catching suspended substance in a water sample by filtering through a stack of particles comprising different average particle diameters, the larger, the higher they position, and an absorption means in which adsorbent is filled to catch dissolved substance in the water sample by absorption. The filtering and absorption means are connected in series, and a pump is connected with these means to allow the water sample to pass through continuously. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a device and a method for collecting water pollutants, and more specifically, for highly sensitively measuring pollutants present in environmental water or waste water,
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aquatic pollutant sampling apparatus and sampling method capable of simply and reliably collecting a trace amount of a pollutant from a large amount of water for a long time and recovering it at a high concentration ratio.

[0002]

2. Description of the Related Art In the field of measuring pollutants in water,
Since ancient times, a method has been widely used in which a small amount of water sample is sampled in a short time with a bucket or a dipper, and then extracted with an organic solvent. Although this method has the feature that it does not require a specific device, collecting trace amounts of pollutants such as dioxins from a large amount of water involves various difficulties such as containers and transportation, and also changes There is a problem in that only instantaneous measured values of environmental water or drainage can be obtained. Furthermore, there is a big problem that the amount of suspended substances mixed in varies depending on the personal technique of water sampling, and reproducible measurement values of pollutants easily adsorbed to suspended substances cannot be obtained.

On the other hand, very rarely, a water sampler by a filtration / adsorption system is used. This collection method can collect a large amount of water from a large amount of water for a long time for a water sample with a low concentration of suspended substances, but uses a filter paper as a filter material and uses an ion exchange performance to collect organic pollutants as an adsorbent. It is basically based on the use of non-ion-exchangeable adsorbent resin, which does not have a non-ion exchange property, and desorbs and collects the adsorbed organic pollutants with an organic solvent. In addition, it is basically used to discharge the water after passing water to an open system by using a large pump driven by an AC power source. However, in such a collection method, environmental water or drainage having a high concentration of suspended matter and a high degree of pollution causes the filter paper to be clogged in a short time, making it difficult to pass water. In addition to the pressure loss of the clogged filter paper, it is necessary to use a large AC drive pump that can withstand the pressure difference that pumps only the height from the water surface to the device. There is a problem that it cannot be used in. Also,
Since a large filter paper and a large amount of adsorbent are used, there is a problem that a large amount of organic solvent is required when extracting contaminants after collection. Furthermore, since an adsorption resin having no ion exchange performance is used, there is a problem that metals, submetals, or ionic contaminants such as fluorine and boron cannot be recovered.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to determine the concentration of various trace pollutants suspended or dissolved in various environmental waters or wastewaters. For accurate measurement, it is suitable as a means to collect pollutants for a long time, and it is possible to collect trace pollutants in a large amount of water easily and surely and to recover them at a high concentration ratio. To provide a device and a method for collecting underwater pollutants.

[0005]

In order to solve the above-mentioned problems, an apparatus for collecting underwater pollutants according to the present invention comprises particles having different average particle diameters, larger particles being stacked on top of each other, and filled. A filter means for collecting suspended matter in a water sample by filtration and an adsorbing means filled with an adsorbent for collecting dissolved substances in a water sample by adsorption are connected in series to these means. It is characterized in that a pump is connected for continuous water flow.

In addition, the method for collecting underwater pollutants according to the present invention comprises a filtration means which is connected in series and in which larger particles are stacked on top of particles having different average particle sizes, and an adsorbent is filled. A water sample is continuously passed through the adsorption means using a pump, suspended substances and dissolved substances in the water sample are collected by each means, and trace contaminants in the water sample are concentrated and recovered. The method is characterized by.

This apparatus and method according to the present invention comprises a filtering means comprising a container in which particles of different sizes are stacked and filled with a water sample, and an adsorption means comprising a container filled with an adsorbent. Are connected in series, and water is continuously supplied for a long time using a pump, preferably for 24 hours or more, so that suspended substances and dissolved substances can be collected in each container. After being collected, the pollutant for measurement is extracted and desorbed with an organic solvent or an aqueous solution of an inorganic compound, and then concentrated and recovered.

In order to prevent clogging in a short time, it is preferable to use substantially spherical particles having a diameter of 2 mm or less, and particularly glass or ceramic particles for trapping the suspended matter. preferable. Also, connect pipes or tubes to the inlet and outlet of the device,
The tip is placed in the water of the water sampling source, that is, the sampling port and outlet of the water sample in the system equipped with the above-mentioned filtration means, adsorption means and pump are put in the water of the sample water source, and the inside of the system is set in advance. After completely filling with water to substantially eliminate the pressure loss for pumping, it is preferable to drive the pump to pass water to concentrate and collect trace contaminants in the water sample. By driving the pump after eliminating the pressure loss for pumping water in this way, it is possible to significantly reduce the power consumption of the pump. Therefore, as a pump, at a flow rate of 35 ml or more per minute (corresponding to 50 liters or more in 24 hours, which is a desirable flow rate for concentrating and recovering a trace amount of contaminants from a large amount of sample water).
In addition, it is possible to use a small metering pump that can be driven by a DC power source such as a general-purpose lead storage battery for 24 hours or more.

Further, a non-ion exchange adsorption resin or a carbon-based adsorbent is used as the adsorbent to collect various organic substances such as dioxins, surfactants, plastic additives, pesticides and the like. You can In addition to extraction / desorption / recovery with an organic solvent, use an ion-exchangeable inorganic adsorbent such as non-ion-exchangeable adsorption resin, carbon-based adsorption agent, ion-exchange resin, chelate resin or activated alumina as the adsorption agent. After adsorbing various ionic pollutants such as metals, submetals, fluorine, and boron through a water sample, extract and desorb through an aqueous solution of an inorganic compound such as acid, alkali, or a salt thereof. It is also possible to recover ionic pollutants.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below together with preferred embodiments, but the present invention is not limited to these modes. In the device and method of the present invention, suspended particles in a water sample are collected by filtration by a particle-filled filtration means connected in series,
The dissolved substance in the water sample is collected by adsorption by the adsorption means filled with the adsorbent. In the filtering means, as shown in Test Example 1 to be described later, a container in which a water sample having an average particle diameter of 2 mm or less and particles having different average particle diameters are stacked and filled with particles having a larger particle diameter. By capturing the suspended solids with, it is possible to prevent clogging and allow water to flow for a long time even at a high flow rate. The particles may be any non-porous particles such as sand, anthracite, anthracite, plastic particles, glass particles, ceramic particles, etc. Particles or particles made of ceramics are preferable, and particularly glass beads or ceramic beads, which have a substantially spherical shape and are uniform, keep pressure loss small even when water is passed at a high flow rate and have excellent handleability, are preferable.

Further, as shown in Test Example 2 which will be described later, according to a method in which the system is initially filled with water to substantially eliminate the pressure loss for pumping, 35 ml / min or more (24 It is also possible to use a pump driven by a DC power source such as a storage battery for a flow rate of 50 liters or more per hour) and for 24 hours or more.

In order to confirm the effects of these basic devices in the present invention, first, the following tests were conducted (Test Examples 1 and 2).

Test Example 1 A filter paper having a diameter of 11 cm (area: about 95 square centimeters) or a container having a diameter of 10.5 cm (cross-sectional area: about 87 square centimeters) had an average particle size of 0.1.
Filled with 4 mm of sand to a depth of 6 cm, or anthracite with an average particle size of 0.8 mm on sand with an average particle size of 0.4 mm
3 cm deep each, or 3 types of glass beads with an average particle size of 0.4 mm, 0.8 mm and 2 mm are stacked on top of each other and the depth is 2 cm. The result of measuring the pressure loss when pressurized water was passed at a flow rate of 500 milliliters per minute with a sample water containing about 10 milligrams of aerobic microorganisms that tend to be clogged per liter using a container filled with each meter. Is shown in Table 1.

[0014]

[Table 1]

As shown in Table 1, the filter paper was immediately clogged and the pressure loss reached 33 kPa in 4 hours, and the specified amount of water could not be passed beyond that, and the sand could not be passed for 12 hours or more. While it was not possible, it was shown that water can be passed for 24 hours or more in a container in which large particles having different particle diameters are stacked and filled. In particular, it was revealed that in the device filled with glass beads having three kinds of particle diameters, the pressure loss was extremely small even when water was passed for 24 hours, and clogging was difficult. This is because the glass beads are spherical and uniform, so pressure loss is less likely to occur than conventional amorphous natural filter media such as sand and anthracite, and a large suspension of glass beads with a large particle size is used. Due to the fact that turbidity traps a little smaller suspended matter in a layer of medium-sized glass beads and a smaller suspended matter in a layer of smaller-sized glass beads, the whole container works effectively. .

As the pump, any type of pump such as a bellows pump, a diaphragm pump, a gear pump, a plunger pump or a tube pump may be used.
As shown in Test Example 2, by connecting a pipe or tube to the outlet of the device and putting the tip into the water of a water source such as a river or manhole, the system is completely filled with water in advance to form a communication system. It has been found that the method of driving the pump after eliminating the pressure loss for pumping is effective for significantly reducing the power consumption. In addition, this method and the use of a filter medium container with a significantly small pressure loss in which glass beads having a plurality of particle diameters are laminated enables the pump to operate at a flow rate of 35 ml or more per minute (equivalent to 50 liters or more in 24 hours). Even if there is, it becomes easy to drive the pump with a DC power source such as a general-purpose lead storage battery for 24 hours or more, and it is possible to collect at an arbitrary point outside the AC power source.

Test Example 2 A tube made of "Teflon" (registered trademark) was put into river water and connected to a filter medium container and an adsorbent container placed on a bridge of 5 m in height, power consumption 10 W, maximum flow rate. Is 1 per minute
When I attached a liter bellows pump and sucked river water, I could not suck it at all. However, I connected a vinyl hose to the outlet of the pump and put the end into the river,
First, when a simple plastic foot pump sucked water to fill the system with water and then turned on the pump to start up, 500 ml / min or more of water could be passed.

FIG. 1 shows a basic configuration example of the present invention. Particles having different particle sizes are stacked and packed in layers in the filtering means 1 composed of a filter material container for collecting suspended solids, and the packing particles include glass and ceramic particles, particularly Spherical particles having an average particle diameter of 2 mm or less are preferably used. In the adsorption means 2 composed of an adsorbent container for collecting dissolved substances, a non-ion-exchangeable adsorbent resin, a carbon-based adsorbent,
An adsorbent selected from an ion exchange resin, a chelate resin, an ion exchangeable inorganic adsorbent, etc. is filled. These filtering means 1 and adsorption means 2 are connected in series in this order, and the pump 3
The water sample is passed through, and mainly the suspended substance is continuously collected by the filtration unit 1 and the dissolved substance is continuously collected by the adsorption unit 2. As the pump 3, a small metering pump is preferable, and as described above, it is preferable to form a communication system filled with water and then continuously supply water. In order to efficiently collect and collect the collected trace pollutants, it is preferable to set the flow rate to 35 ml or more per minute, and it can be driven by direct current by a storage battery for 24 hours or more so that it can be continuously operated outdoors. Is preferred. The water pollutants collected for a predetermined time, for example, 24 hours or more, are extracted and desorbed. Extraction and desorption can be performed with an organic solvent or an aqueous solution of an inorganic salt. Even trace amounts of pollutants can be extracted and desorbed in a highly concentrated state because they are continuously collected efficiently for a long time. Further, it can be concentrated if necessary and used for analysis of the sample.

FIG. 2 shows a more specific example of an embodiment, and shows a schematic configuration when the apparatus according to the present invention is applied to a river. An underwater pollutant sampling device 11 according to the present invention is provided for a river 12 as a sampling source. In the sampling device 11, for example, glass beads 13 having different average particle diameters have a large particle size in order from the upstream side. No. 13a, medium particle size 13b, and small particle size 13c are laminated and packed in a filtering means 14, and an adsorbent 15 filled with an adsorbent 15 made of non-ion-exchangeable adsorbent resin or the like. The means 16 are connected in series in this order in the flow direction. A pump 17 is arranged on the downstream side of the adsorbing means 16, a water sample collection port 19 and a discharge port 20 in a system 18 constituted by these are put into the water of the river 12 and the system 18 is filled with water in advance. After the pressure loss for pumping up is eliminated, water can be passed by the pump 17.

The present invention will be described below based on examples. Example 1 A filter medium container filled with three types of glass beads having particle sizes of 0.3 mm, 0.6 mm and 2 mm, each having a cross-sectional area of about 87 cm 2 and a depth of 2 cm, and a porous non-ion exchange resin. An adsorbent container filled with 100 ml of polystyrene adsorbent resin, which is an adsorbent, was connected in series, and PCB was added to river water with a concentration of suspended substances of about 7 mg per liter to 5 nanograms per liter. Sample water 4 min.
After adsorbing for 24 hours at a speed of 00 ml, each of the glass bead-filled container and the adsorbent-filled container was
As a result of soxhlet extraction with dichloromethane to obtain a PCB recovery rate, it was found that 97% of PCB was recovered, and that a trace amount of nonionic organic pollutants can be easily and almost completely recovered by the sampling method of the present invention. Was shown.

Example 2 Using the same device as in Example 1 in which a filter medium filling container, an adsorbent filling container device and a small metering pump driven by an automobile battery were connected, a vinyl pipe was connected to the pump outlet,
Put it in river water, fill the inside of the device with a foot pump in advance, and then drive the pump. About 8 milligrams of suspended water concentration per liter of river water is 400 milliliters per minute for 24 hours, about 580 liters. After collecting through the glass beads, air was passed through a glass bead-filled container to remove water, and the suspension was washed off with about 300 ml of ethyl alcohol and collected, and 200 ml of toluene heated to 80 ° C was passed through the suspension to suspend it. The contaminant contained in the product was extracted. Further, after passing about 200 ml of ethyl alcohol through the adsorbent container, 300 ml of toluene heated to 50 ° C. was passed through to extract the adsorbed contaminants. Table 2 shows an example of the results of measuring dioxins according to the JIS method after concentrating these solvents together using a rotary evaporator. It has been shown that the device and method of the present invention reliably collect a very small amount of dioxins, highly concentrate them, and easily analyze them.

[0022]

[Table 2]

Example 3 Using the same apparatus as in Example 2, river water was similarly supplied at a rate of 10 minutes per minute.
Table 3 shows an example of the results of pesticide analysis after collecting and extracting pollutants by passing water through 0 ml for 8 hours, concentrating and purifying according to official methods. That is, it was shown that the method of the present invention enables easy collection and analysis of trace amounts of pesticides in river water.

[0024]

[Table 3]

Example 4 The same equipment as in Example 2 was charged with discharged water from a sewage treatment plant at 10 min / min.
Soxhlet extract the suspended solids, and collect ethyl alcohol as the adsorbent resin.
After desorbing through 00 ml and concentrating, di-phthalate
Table 4 shows the measurement results of 2-ethylhexyl. That is, it has been shown that the method of the present invention can easily analyze the concentration of a small amount of phthalate esters in sewage and easily monitor the change in concentration.

[0026]

[Table 4]

Example 5 The same apparatus as in Example 1 was used, except that a chelate resin was used as an adsorbent.
Using 0 ml, 100 ml / min of drained water leached from the landfill for 1 hour was passed, and 60 ml of 1N hydrochloric acid solution was passed through to be desorbed, and the analysis results are shown in Table 5. That is, in the device and method of the present invention,
It was shown that trace amounts of ionic pollutants such as copper, zinc, lead, and mercury could be highly concentrated and recovered, and could be easily analyzed.

[0028]

[Table 5]

In order to surely collect the pollutant by the adsorbent, as in the embodiment, water is passed at a rate equal to or more than the volume of the adsorbent per minute and 10 times or less to adsorb the pollutant. Then, an organic solvent or a solution of an inorganic compound such as an acid, an alkali, or a salt thereof is passed through an amount not less than 2 times and not more than 10 times the adsorbent volume to desorb adsorbed contaminants, and then 10 ml It is preferable to highly concentrate and recover the pollutant by evaporating the organic solvent or water to an appropriate amount below and without causing precipitation or the like.

[0030]

INDUSTRIAL APPLICABILITY As described above, the apparatus and method for collecting underwater pollutants according to the present invention are suitable as means for collecting various pollutants that are present in trace amounts in various kinds of environmental water and wastewater. By passing a large amount of environmental water or wastewater over a long period of time, it is possible to provide a sampling device and method for easily concentrating and collecting pollutants, and easily and accurately measuring environmental pollution with high sensitivity. It is possible,
The environmental management value of the present invention is remarkable.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a basic configuration of an apparatus and method for collecting underwater pollutants of the present invention.

FIG. 2 is a schematic configuration diagram of an underwater pollutant sampling device according to an embodiment of the present invention.

[Explanation of symbols]

1 Filtering means 2 Adsorption means 3 pumps 11 Water pollutant sampling device 12 Rivers as sampling sources 13 glass beads 13a Large-sized glass beads 13b Medium-sized glass beads 13c Small size glass beads 14 Filtering means 15 Adsorbent 16 Adsorption means 17 pumps 18 series 19 Collection port 20 Outlet

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroki Koyama             Olga 1-2-8 Shinsuna, Koto-ku, Tokyo             Within the corporation F term (reference) 2G052 AA06 AB22 AB27 BA22 CA12                       EA05 ED01 ED03 ED06 JA10                       JA13 JA16

Claims (12)

[Claims] 1. Particles having different average particle sizes are packed by laminating larger particles on top of each other, and are filled with a filtration means for collecting suspended matter in a water sample by filtration, and an adsorbent,
An aquatic pollutant sampling device characterized in that an adsorbing means for collecting dissolved substances in a water sample by adsorption is connected in series, and a pump is connected to these means so that the water sample can continuously pass through. . 2. The device for collecting underwater pollutants according to claim 1, wherein the particles with which the filtering means is filled are particles of glass or ceramics. 3. The underwater pollutant sampling device according to claim 1, wherein the particles filled in the filtering means are substantially spherical particles having an average particle diameter of 2 mm or less. 4. The underwater pollutant sampling device according to claim 1, wherein the pump comprises a constant flow rate pump that can be driven by a DC power source at a flow rate of 35 ml / min or more for 24 hours or more. 5. The adsorbent according to claim 1, wherein the adsorbent comprises a non-ion-exchangeable adsorbent resin, a carbon-based adsorbent, an ion-exchange resin, a chelate resin, or an ion-exchangeable inorganic adsorbent. Water pollutant sampling device. 6. A water flow system from collection of water sample to discharge
The underwater pollutant sampling device according to any one of claims 1 to 5, which is configured as a closed system capable of being filled with water. 7. A water sample is pumped to a filtration means, which is connected in series, in which larger particles are stacked on top of particles having different average particle diameters, and an adsorption means which is filled with an adsorbent. A method for collecting a pollutant in water, which comprises continuously flowing water, collecting suspended substances and dissolved substances in a water sample by each means, and concentrating and collecting trace pollutants in a water sample. 8. The method for collecting an underwater pollutant according to claim 7, wherein glass or ceramic particles are used as particles to be filled in the filtering means. 9. The method for collecting an underwater pollutant according to claim 7, wherein substantially spherical particles having an average particle size of 2 millimeters or less are used as particles to be packed in the filtering means. 10. The method for collecting submerged pollutants according to claim 7, wherein a constant flow rate pump that can be driven by a DC power supply at a flow rate of 35 ml / min or more for 24 hours or more is used as the pump. 11. A non-ion-exchangeable adsorbent resin, a carbon-based adsorbent, an ion-exchange resin, a chelate resin, or an ion-exchangeable inorganic adsorbent is used as the adsorbent.
The method for collecting water pollutants according to any one of 0. 12. A water sample collecting port and a water discharging port in a system equipped with the filtering means, the adsorbing means and the pump are put into water as a sample water collecting source, and the system is previously filled with water to reduce a pressure loss for pumping. The method for collecting underwater pollutants according to any one of claims 7 to 11, wherein water is passed through with a pump after being substantially eliminated to concentrate and collect trace pollutants in the water sample.