CN103364473A - Device and method for study on release of heavy metals and/or phosphate in sediments - Google Patents
Device and method for study on release of heavy metals and/or phosphate in sediments Download PDFInfo
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- CN103364473A CN103364473A CN2013103302827A CN201310330282A CN103364473A CN 103364473 A CN103364473 A CN 103364473A CN 2013103302827 A CN2013103302827 A CN 2013103302827A CN 201310330282 A CN201310330282 A CN 201310330282A CN 103364473 A CN103364473 A CN 103364473A
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Abstract
Provided is a device for study on release of heavy metals and/or phosphate in sediments. The main body of the device is a sediment-water interface system and a dissolved oxygen control device. The sediment-water interface system is composed of a tank. The bottom of the water tank is parallelly inserted with a plurality of sets of plate-type DGTs along the length direction of the central line. A microelectrode control system is arranged at the top of the water tank. The microelectrode control system is composed of a four-channel host, a motor controller, and pH, DO, ORP probes. Both sides of the tank are engraved with grooves. Staggered baffle plates are arranged in the grooves. A joint is arranged at one end of the water tank and connected with the dissolved oxygen control device through a peristaltic pump. A joint of the other end of the water tank is close to the upper liquid surface and connected with the dissolved oxygen control device directly. The dissolved oxygen control device is a water tank. The water tank contains a filtered water sample inside. Two joints are arranged at the top of the tank. One ends of the joints are respectively connected with a N2 steel cylinder and an O2 steel cylinder. The other ends of the joints are connected with aeration heads. The aeration heads extend into water for aeration. The invention also discloses a method for study on release of heavy metals and phosphate in sediments.
Description
Technical field
The invention belongs to the Ecology research field, relate to particularly a kind of equipment of simulating Heavy Metal In Sediments and/or phosphate release.
The invention still further relates to the method for utilizing the said equipment research Heavy Metal In Sediments and/or phosphate to discharge.
Background technology
In the biogeochemical cycle of lake, sediment is being played the part of the dual role of source and remittance simultaneously, and the pollutants such as the nitrogen in the sediment, phosphorus, heavy metal can carry out physics, chemistry and biological exchange interaction by Interstitial Water and overlying water and be discharged in the water body.This process influence the concentration of nutritive salt component in overlying water and the Interstitial Water, caused producing between the water/sediment interface concentration gradient.Along this concentration gradient, pollutant constantly discharges or deposition at water/sediment interface, so that water/sediment interface always is in the biomass geochemistry dynamic balance state.Wherein, heavy metal and phosphate are pollutants main in the sediment, heavy metal is by man-made pollution sources such as mining, smelting and processing of metals, Chemical Manufacture, agricultural fertilizers, the natural source forms such as geologic erosion, weathering that reach enter water body, and be deposited in the bed mud, its content is several orders of magnitude in the high water outlet often.Different from nitrogen, phosphorus can not disappear after entering water body, is easy to be deposited in the bed mud, and when environmental baseline changed, the phosphorus in the sediment again intermittent palingenesis can occur, thereby promotes body eutrophication.Therefore, be necessary Heavy Metal In Sediments and phosphatic release conditions are studied.
Material exchange process between sediment and overlying water is very complicated, comprises being adsorbed in desorb, precipitation and dissolving etc. of biological cycle, syndiagenesis, solubilised state material.Since the nineties in last century, successively research is also arranged, usually adopt open-air in-situ observation and sediment dystopy test simulation method, the former is simple, convenient, and the result is more consistent with reality, but field condition is complicated, and influence factor is numerous, and conclusion is different.The latter adopts grab bucket or other devices to get sediments, put into experiment container and carry out static state or dynamic simulation experiment, be applicable to study the relation between pollutant release and the influence factor, or by the endogenous integral load to the lake of rate of release estimation, the method is simple to operation, thereby is widely used.
Under most of situations, this class research concentrates on sediment to the releasing research of pollutant under the various conditions, and about in the dispose procedure, the physics of water/sediment interface, the impact of chemical change are studied less.
Summary of the invention
The object of the present invention is to provide a kind of equipment of studying Heavy Metal In Sediments and/or phosphate release.
Another purpose of the present invention is to provide a kind of method of utilizing the said equipment research Heavy Metal In Sediments and/or phosphate to discharge.
For achieving the above object, the equipment that research Heavy Metal In Sediments provided by the invention and/or phosphate discharge mainly comprises water/sediment interface system and dissolved oxygen control device; Wherein:
The main body of water/sediment interface system is rectangular parallelepiped organic glass tank, and an end of water/sediment interface system tank is provided with water inlet, and the other end is provided with water delivering orifice; Inner surface deposit and the water sample that is used for the splendid attire collection of water/sediment interface system tank;
Water/sediment interface system water trench bottom is inserted with board-like heavy metal and/or phosphate DGT probe (DGT: diffusive gradients in thin-films) side by side along the centerline length direction, be used for absorption different times different depth sediment heavy metal and/or phosphate that intermittence, water discharged, Active Heavy Metals and/or phosphate content in the in-site detecting Interstitial Water;
Water/sediment interface system sink top is equipped with the microelectrode control system, dissolved oxygen DO) and ORP probe (ORP: oxidation-reduction potential) see through superficial water and insert in the sediment, be used for the variation of Real-Time Monitoring water/sediment interface pH, DO, ORP near main frame in the microelectrode control system is by motor controller control pH probe, DO probe (DO:; Main frame connects a contrast electrode;
Be provided with the array baffle plate in the water/sediment interface system tank, each organizes baffle plate for being staggeredly placed, and is used for simulating the wave that system produces under the different current;
The water inlet of water/sediment interface system tank links to each other with dissolved oxygen control device by peristaltic pump;
The adjacent upper liquid level of the other end interface of water/sediment interface system tank directly links to each other with dissolved oxygen control device, so that unnecessary water is got back to dissolved oxygen control device by the overflow effect;
The main body of dissolved oxygen control device is a rectangular parallelepiped organic glass tank, is used for the splendid attire water sample in the tank, is used for water body situation that is virtually reality like reality;
The top of dissolved oxygen control device tank is provided with two interfaces, and interface one end connects respectively N
2And O
2Steel cylinder, the interface other end connects aeration head, and aeration head stretches into and carries out aeration in the water, is used for control water body dissolved oxygen content.
In the described equipment, water/sediment interface system inboard wall of cistern both sides are provided with groove, are used for mounting plate type heavy metal and/or phosphate DGT probe in the groove, and the nut for fixing board-like heavy metal and/or phosphate DGT probe is housed on the groove.
In the described equipment, the distance between board-like heavy metal and/or phosphate DGT probe and the water inlet can be regulated, with the flow velocity of control water inlet.
In the described equipment, peristaltic pump can accurately be controlled the water inlet flow velocity, is used for simulation static state and the impact of different disturbed conditions on Heavy Metal In Sediments and phosphate release.
In the described equipment, the structure of board-like heavy metal and/or phosphate DGT probe is: top layer and bottom respectively are a hard plate, and ground floor filter membrane, diffusion layer, adsorbed layer and second layer filter membrane are installed between top layer hard plate and bottom hard plate successively.
In the described equipment, the tank of dissolved oxygen control device is equipped with top cover, offers porosely on the top cover, is used for plugging pH probe, DO probe and ORP probe, the variation of dissolved oxygen content in the monitoring tank.
The method of utilizing the said equipment research Heavy Metal In Sediments and/or phosphate to discharge provided by the invention, main flow process is:
1) with the water sample that is collected behind membrane filtration, place dissolved oxygen control device, utilize N
2And O
2Aeration in the dissolved oxygen control device, and the variation by DO content in the dissolved oxygen electrode monitoring water body are with the water body of simulation different dissolved oxygen content;
2) sediment that gathers is tiled in the water/sediment interface system tank, water sample behind aeration pumps in the water/sediment interface system tank by peristaltic pump, when water surface elevation reaches predetermined altitude, by the change modeling of regulating flow velocity static with different disturbed conditions under Heavy Metal In Sediments and phosphatic release conditions; The water that overflows of liquid level flows back to dissolved oxygen control device by conduit on the water/sediment interface system tank other end;
3) plug respectively board-like heavy metal and/or phosphate DGT probe in the water/sediment interface system tank, when water sample passes through board-like heavy metal and/or phosphate DGT probe, filter membrane in the matrix plate type heavy metal of indissoluble and/or the phosphate DGT probe intercepts, the heavy metal ion of solubilised state and/or phosphate arrive the rear regular taking-up that is fixed of adsorbed layer in board-like heavy metal and/or the phosphate DGT probe by filter membrane and diffusion layer, measure heavy metal and/or the phosphatic content of adsorbed layer in board-like heavy metal and/or the phosphate DGT probe;
4) variation of the pH of different depth place, DO and current potential in the microelectrode control system periodic measurement tank of water/sediment interface system realizes robotization control, is used for the Real-Time Monitoring to the physical agent that causes Heavy Metal In Sediments and Nutrient release.
In the described method, the water sample in the step 1 and Yuan Shui refer to the poisons in freshwater of river, lake, reservoir, and make water mixing even through stirring.
In the described method, different disturbances in the step 2 are the waves that produce in the long-pending thing of the different downellings of simulation-water termination system, and wave size and scope can be controlled by the flow velocity of water inlet and the distance between board-like heavy metal and/or phosphate DGT probe and the water inlet.
In the described method, step 3 converses heavy metal and phosphate content in the Interstitial Water according to the Fick law after determining the heavy metal and/or phosphatic content of adsorbed layer in board-like heavy metal and/or the phosphate DGT probe again.
Equipment provided by the invention and method can be studied Heavy Metal In Sediments and phosphatic release, simultaneously the physical agent variation of water/sediment interface characterized, have the characteristics simple and convenient, that applicability is strong, help the deep impact that water/sediment interface place physics, chemical change discharge Heavy Metal In Sediments and phosphate of understanding.
Description of drawings
Fig. 1 is the device synoptic diagram of board-like DGT;
Fig. 2 is the device synoptic diagram of microelectrode control system;
Fig. 3 is device synoptic diagram of the present invention.
Primary clustering symbol description in the accompanying drawing:
1 top layer hard plastic board; 2 ground floor filter membranes; 3 diffusion layers; 4 adsorbed layers; 5 second layer filter membranes; 6 bottom hard plastic boards;
21 water/sediment interface system top boards; 22 motor controllers; The 23X spindle nut; The 24Z spindle nut; The 25Y spindle nut; The 26pH probe; The 27ORP probe; The 28DO probe; 29 contrast electrodes
31 tanks; 32 dissolved oxygen control devices; 33 microelectrode control system; 34 board-like heavy metal (phosphate) DGT; 35 baffle plates; 36 tank top covers; 37 peristaltic pumps; 38 nitrogen cylinders; 39 welding bottle; 40 aeration heads; 41 dissolved oxygen electrodes
Embodiment
The present invention is by combining DGT technology and microelectrode control system and sediment analogue means, is used for physics, chemical change impact near research heavy metal and the phosphate dispose procedure water/sediment interface, provides support for inquiring into releasing mechanism.
The device that research Heavy Metal In Sediments provided by the invention and phosphate discharge mainly comprises water/sediment interface system and dissolved oxygen control device; Wherein:
The main body of water/sediment interface system is rectangular parallelepiped organic glass tank, tank inside the surface deposit that is collected is housed and filter after water sample, bottom of gullet is inserted with board-like heavy metal and phosphate DGT side by side along the centerline length direction, is respectively applied to adsorb heavy metal and phosphate that different times different depth sediment intermittently discharges in the water; Sink top is equipped with the microelectrode control system, the microelectrode control system is made of four-way main frame, motor controller, pH, DO, ORP probe, wherein pH, DO, ORP probe see through in the superficial water insertion sediment, are used for the variation of periodic monitor water/sediment interface pH, DO, ORP near; Groove is carved with in the tank both sides, is provided with three groups of baffle plates in the groove, is staggeredly placed, and is used for simulating the wave that system produces under the different current, and wave size and scope can be controlled by the distance between water flow velocity and baffle plate and the water inlet; Tank one end is provided with interface, links to each other with dissolved oxygen control device by peristaltic pump, and peristaltic pump can accurately be controlled the water inlet flow velocity, is used for simulation static state and the impact of different disturbed conditions on Heavy Metal In Sediments and phosphate release; The adjacent upper liquid level of tank other end interface directly links to each other with dissolved oxygen control device, so that unnecessary water is got back to dissolved oxygen control device by the overflow effect.
The main body of dissolved oxygen control device is a rectangular parallelepiped organic glass tank, and the water sample after the filtration is equipped with in tank inside, is used for water body situation that is virtually reality like reality; Sink top is provided with two interfaces, and interface one end connects respectively N
2And O
2Steel cylinder, the interface other end connects aeration head, and aeration head stretches into and carries out aeration in the water, is used for control water body dissolved oxygen content.
Described device, wherein, board-like heavy metal (phosphate) DGT probe body is made of filter membrane, diffusion layer and adsorbed layer, filter membrane has two-layer, respectively before the diffusion layer and after the adsorbed layer, the main body both sides avoid particle and suspension to enter adsorbed layer (as shown in Figure 1) by the rigid plastic board clamping.After board-like DGT probe inserted in the sediment, when Interstitial Water passed through filter membrane, the matrix of indissoluble was blocked, and the heavy metal ion of solubilised state (phosphate) arrives adsorbed layer by filter membrane and diffusion layer and is fixed.The adsorbed layer material of heavy metal DGT probe is chelating resin, and the adsorbed layer material of phosphate DGT probe is iron oxide.
Described device, wherein, the microelectrode control system is comprised of four-way main frame, motor controller, pH probe, DO probe, ORP probe, the DO probe diameter is 25 μ m, and pH and ORP probe diameter are 1mm, promotes probe by motor controller and does profile analysis along the sediment vertical direction, the longest movable 12cm, minimum step is 1 μ m, and near the variation of pH, DO, the ORP periodic monitor water/sediment interface realizes robotization control (as shown in Figure 2).
Described device, wherein, groove is carved with in the tank both sides, and baffle plate is housed in the groove, is staggeredly placed and can slides along groove, and nut is housed on the groove, is used for fixed dam.
Described device, wherein, the tank of dissolved oxygen control device is equipped with top cover, and the top cover perforate is used for the DO electrode is inserted water, the variation of dissolved oxygen content in the Real-Time Monitoring tank.
The method of utilizing said apparatus research Heavy Metal In Sediments and phosphate to discharge provided by the invention, main flow process is:
1) with the water sample that is collected behind 0.45 μ m membrane filtration, place dissolved oxygen control device, utilize N
2And O
2Steel cylinder is to aeration wherein, and the variation by DO content in the dissolved oxygen electrode monitoring water body, simulates the water body of different dissolved oxygen content.
2) sediment that is collected is tiled in the water/sediment interface system, the water sample behind aeration slowly pumps into along tube wall by peristaltic pump, avoids sedimental and suspends.When water surface elevation reaches certain position, by the change modeling of regulating flow velocity static with different disturbed conditions under Heavy Metal In Sediments and phosphatic release conditions.Because there is baffle plate the tank side, when the water impact baffle plate, can near baffle plate, form opposition and produce wave, the disturbance sediment, water velocity is larger, and disturbance is larger.The water that overflows of liquid level flows back to dissolved oxygen control device by conduit on the tank other end.
3) be plugged respectively in advance the board-like DGT probe of heavy metal and phosphate (hereinafter to be referred as " board-like DGT ") in the water/sediment interface system, regularly take out, with the Teflon cutter adsorbed layer is pressed the 5mm cut-space, precision is not less than 0.1mm, avoids producing error.By measuring heavy metal and phosphatic content in the adsorbed layer, converse heavy metal and phosphate content in the Interstitial Water according to the Fick law again.
4) in the water/sediment interface system microelectrode control system can the periodic measurement tank in the variation of the pH of different depth place, DO and current potential, realization robotization control, be used for the Real-Time Monitoring to the physical agent that causes the release of Heavy Metal In Sediments and phosphate, thus corresponding with the measurement result of DGT.
Described method, wherein, the water sample in the step 1 refers to the poisons in freshwater of river, lake, reservoir.
Elaborate below in conjunction with accompanying drawing.
The present invention combines the DGT technology with the microelectrode control system, cover research Heavy Metal In Sediments and a phosphatic device is provided, and is made of water/sediment interface system and dissolved oxygen control device.
1) Fig. 1 is the device synoptic diagram of board-like DGT: board-like DGT inserts in the water/sediment interface system, its main body is clamped by top layer hard plastic board 1 and 6 protections of bottom hard plastic board, Interstitial Water is by after seeing through ground floor filter membrane 2, particle and microorganism that the aperture is less are blocked, in order to avoid pollute gel; The metallic ion of solubilised state (phosphate) arrives adsorbed layers 4 by diffusion layer 3 and is fixed, and occuring to slide when preventing board-like DGT cutting has increased second layer filter membrane 5 in adsorbed layer 4 back.Adsorbed layer 4 among the board-like DGT can be changed according to research object, such as the impact in the needs research heavy metal dispose procedure, then adsorbed layer 4 is replaced by can Adsorption of Heavy Metals sorbing material as adsorbed layer (such as chelating resin (Chlex-100), polyacrylamide-polyacrylic acid (PAM-PAA), sulfydryl propyl group resin (mercaptoproyl), dithiocar-bamate (dithiocarbamate) etc.), if need the impact in the research phosphate dispose procedure, then adsorbed layer 4 is replaced by can adsorb phosphatic sorbing material as adsorbed layer (such as ferriferous oxide, Zirconium oxide etc.).
2) Fig. 2 is the device synoptic diagram of microelectrode control system: microelectrode control system one end is fixed on the water/sediment interface system top board 21, the other end links to each other with computer by main frame, the pH probe 26, ORP probe 27 and the DO probe 28 that drive by computer control motor controller 22 move downward, also can rotate manually X-axis nut 23, Z axis nut 24, Y-axis nut 25 respectively along level, vertical, seesaw to arrive assigned address.Before the mensuration, need contrast electrode 29 is inserted in the sediment to measure pH and ORP variation.
3) Fig. 3 is equipment synoptic diagram of the present invention, fill superficial water after filtering in the dissolved oxygen control device 32, are connected the aeration head 40 that connects with welding bottle to aeration wherein by nitrogen cylinder 38, the size of aeration rate is controlled by reduction valve separately, and passes through the variation of the fixing dissolved oxygen electrode 41 Real-Time Monitoring dissolved oxygen contents of dissolved oxygen control device top board.When the dissolved oxygen content in the dissolved oxygen control device remains on finite concentration, by peristaltic pump 37 water sample is pumped in the water/sediment interface system tank 31, wherein be covered with the surface deposit that is collected water/sediment interface system tank 31 bottom evens, consist of the water/sediment interface system.The water/sediment interface system is carved with groove in tank 31 sides, slidably five groups of baffle plates 34 are housed in the groove, five groups of gear formulas 35 are for being staggeredly placed, and the height of five groups of baffle plate distance from bottom water/sediment interfaces is different, downward and the tank 31 opposite sides generation shock wave of meeting when the water impact baffle plate, and then the formation wave, in order to simulate heavy metal and phosphatic release conditions in the different hydrodynamic condition deposit thing.The water that overflows of liquid level flows back to dissolved oxygen control device by conduit on tank 31 other ends.Tank 31 bottoms are carved with groove and are used for the fixing board-like DGT35 that inserts, and are used for measuring different times Heavy Metal In Sediments and phosphatic release conditions.Be fixed with microelectrode control system 33 on the water/sediment interface system tank top cover 36, be used for pH, the ORP of monitoring water/sediment interface and the situation of change of DO.
The method that the present invention utilizes said apparatus research Heavy Metal In Sediments and phosphate to discharge, main flow process is:
1) with the water sample that is collected behind 0.45 μ m membrane filtration, place dissolved oxygen control device, utilize N
2And O
2Steel cylinder is to aeration wherein, and the variation by DO content in the dissolved oxygen electrode monitoring water body, simulates the water body of different dissolved oxygen content.
2) sediment that is collected is tiled in the water/sediment interface system, the water sample behind aeration slowly pumps into along tube wall by peristaltic pump, avoids sedimental and suspends.When water surface elevation reaches certain position, by the change modeling of regulating flow velocity static with different disturbed conditions under Heavy Metal In Sediments and phosphatic release conditions.Because there is baffle plate the tank side, be staggeredly placed and baffle plate bottom different apart from the height of water/sediment interface, when the water impact baffle plate, downward and the tank opposite side generation shock wave of meeting, and then the formation wave, in order to simulate heavy metal and phosphatic release conditions in the different hydrodynamic condition deposit thing.The water that overflows of liquid level flows back to dissolved oxygen control device by conduit on the tank other end.
3) be plugged respectively in advance the board-like DGT probe of heavy metal and phosphate in the water/sediment interface system, regularly take out, with the Teflon cutter adsorbed layer is pressed the 5mm cut-space, precision is not less than 0.1mm, avoids producing error.By measuring heavy metal and phosphatic content in the adsorbed layer, converse heavy metal and phosphate content in the Interstitial Water according to the Fick law again.
4) in the water/sediment interface system microelectrode control system can the periodic measurement tank in the variation of the pH of different depth place, DO and current potential, realization robotization control, be used for the Real-Time Monitoring to the physical agent that causes the release of Heavy Metal In Sediments and phosphate, thus corresponding with the measurement result of DGT.
Described method, wherein, water sample refers to the poisons in freshwaters such as river, lake, reservoir.
Be described in further detail below in conjunction with embodiment:
The lake sediment of a selected slight pollution is research object, the surface deposit of collection and former water sample are after filtering placed the water/sediment interface system, this system body is a tank 31, specification is 80cm * 60cm * 45cm, sediment and the water sample of 8cm behind 0.45 μ m membrane filtration of 16cm wherein are housed, the water sample flowing velocity is 0～2L/min, first baffle plate 35 is apart from water inlet 10cm, 35 on every baffle plate is at a distance of 10cm, the microelectrode control system is apart from 20cm place, tank 31 right side, the microelectrode control system is produced by Denmark Unisense company, by the four-way main frame, motor controller 22, pH probe 26, DO probe 28, ORP probe 27, contrast electrode 29 forms, DO probe 28 diameters are 25 μ m, pH probe 26 and ORP probe 27 diameters are 1mm, contrast electrode 29 diameters are 8mm, promote probe by motor controller 22 and do profile analysis along the sediment vertical direction, the longest movable 12cm, minimum step is 1 μ m, near the pH periodic monitor water/sediment interface, DO, the variation of ORP realizes robotization control.1cm and the lower 5cm pH of place, DO, ORP change on each 1 hour automatic mensuration primary depositing thing-water termination, and motor controller motion step-length is 50 μ m.
Be inserted with respectively 5 groups of board-like heavy metals and phosphate DGT34 in the tank, extracted mensuration heavy metal and phosphate content respectively at the 2nd, 5,15,30,50 day.Adsorbed layer 4 materials of board-like heavy metal and phosphate DGT34 are respectively chelating resin and iron oxide, and diffusion layer 3 materials are polypropylene amine, and the first filter membrane 2, the second filter membrane 5, diffusion layer 3, adsorbed layer 4 length are 15cm, and about 13cm inserts in the sediment.
Dissolved oxygen DO control system main body is a tank, and specification is 60cm * 40cm * 40cm, and the water sample of 30cm behind 0.45 μ m membrane filtration wherein is housed, and adopts nitrogen cylinder and the welding bottle of 40L to carry out aeration, and the minimum air pressure in aeration of controlling of reduction valve is 0.02MPa.Steel cylinder connects 3 groups of aeration heads in tank, and measure the variation of in water body dissolved oxygen content with dissolved oxygen instrument every day, Heavy Metal In Sediments and phosphatic release conditions when studying respectively dissolved oxygen content and being 90% and 30%.
The indexs such as heavy metal, phosphate, organic carbon in sediment and the superficial water sample in two tanks of detection in the 0th, 2,5,15,30,50 day.The sediment sampling columnar sampler gathers, each 2cm layering, freeze-drying post analysis.
The result shows: along with the carrying out of experiment, sediment begins to descend along profile direction DO content, from about 180 μ M, drop to 0 μ M, minimum point appears at about the following 3-5cm of surface deposit, when dissolved oxygen content is 40% and 90%, pH and ORP content increase first rear slow decreasing and tend towards stability at last, are down to 6.92～6.93 after increasing to 7.46～7.53 from 7.13～7.18 respectively, from be down to after-35～43mV increases to 30～180mV-110～80mV about.When dissolved oxygen content in the overlying water very high (90%), the amplitude of variation of pH and ORP is larger.Along with the carrying out of experiment, the release of Phosphorus in Sediments hydrochlorate and the heavy metals such as Fe, Mn increases gradually and tends towards stability at last, and the releasing effect of Cu is relatively poor.
The lake sediment of a selected intermediate pollution is as research object, the former water sample of the surface deposit that gathers and filtration is placed the water/sediment interface system of embodiment 1, sediment and the water sample of 8cm behind 0.45 μ m membrane filtration of 16cm are housed altogether, the water sample flowing velocity is 0～2L/min, microelectrode system, board-like heavy metal and phosphate DGT are housed equally, the research dissolved oxygen content 40% and 90% the time, Heavy Metal In Sediments and phosphatic release conditions.The result shows: along with the carrying out of experiment, sediment begins to descend along profile direction DO content, drops to 0 μ M from about 130 μ M, and minimum point appears at about 2～3cm, this shows that with serious pollution lake sediment is in anaerobic state mostly, and wherein dissolved oxygen content is lower.When dissolved oxygen content is 40% and 90%, pH and ORP content present equally in the sediment increases first the trend that rear slow decreasing tends towards stability at last, be down to 7.25～7.36 after increasing to 7.78～7.83 from 7.45～7.48 respectively, from-58～30mV increase to-be down to behind 15～110mV-160～-15mV about.Compare with the lake sediment of slight pollution, the rate of release of Phosphorus in Sediments hydrochlorate is very fast, and especially dissolved oxygen content is in 90% situation.
The lake sediment of a selected serious pollution is as research object, with the surface deposit that gathers and the water/sediment interface system that places embodiment 1 through the former water sample of 0.45 μ m membrane filtration, sediment and the water sample of 8cm behind 0.45 μ m membrane filtration of 16cm are housed altogether, the water sample flowing velocity is 0～2L/min, microelectrode system, board-like heavy metal and phosphate DGT are housed in the system equally, the research dissolved oxygen content 40% and 90% the time, Heavy Metal In Sediments and phosphatic release conditions.The result shows: because damage ratio is more serious, sediment drops to 0 μ M along the section dissolved oxygen content is very fast from 95 μ M, and minimum point appears at about 1～2cm.When dissolved oxygen content was 40% and 90%, sediment changed along profile direction pH and ORP and presents generally downtrending, dropped to 7.04～7.07 from 7.53～7.61 respectively, from-100～20mV drop to-280～-150mV.When dissolved oxygen content was 90%, initial, the release of Phosphorus in Sediments hydrochlorate and Zn, Cu was very fast, tends to be steady gradually at last.
Claims (10)
1. an equipment of studying Heavy Metal In Sediments and/or phosphate release mainly comprises water/sediment interface system and dissolved oxygen control device; Wherein:
The main body of water/sediment interface system is rectangular parallelepiped organic glass tank, and an end of water/sediment interface system tank is provided with water inlet, and the other end is provided with water delivering orifice; Inner surface deposit and the water sample that is used for the splendid attire collection of water/sediment interface system tank;
Water/sediment interface system water trench bottom is inserted with board-like heavy metal and/or phosphate DGT probe side by side along the centerline length direction, be used for absorption different times different depth sediment heavy metal and/or phosphate that intermittence, water discharged, Active Heavy Metals and/or phosphate content in the in-site detecting Interstitial Water;
Water/sediment interface system sink top is equipped with the microelectrode control system, main frame in the microelectrode control system sees through superficial water by motor controller control pH probe, DO probe and ORP probe and inserts in the sediment, is used for the variation of Real-Time Monitoring water/sediment interface pH, DO, ORP near; Main frame connects a contrast electrode;
Be provided with the array baffle plate in the water/sediment interface system tank, each organizes baffle plate for being staggeredly placed, and is used for simulating the wave that system produces under the different current;
The water inlet of water/sediment interface system tank links to each other with dissolved oxygen control device by peristaltic pump;
The adjacent upper liquid level of the other end interface of water/sediment interface system tank directly links to each other with dissolved oxygen control device, so that unnecessary water is got back to dissolved oxygen control device by the overflow effect;
The main body of dissolved oxygen control device is a rectangular parallelepiped organic glass tank, is used for the splendid attire water sample in the tank, is used for water body situation that is virtually reality like reality;
The top of dissolved oxygen control device tank is provided with two interfaces, and interface one end connects respectively N
2And O
2Steel cylinder, the interface other end connects aeration head, and aeration head stretches into and carries out aeration in the water, is used for control water body dissolved oxygen content.
2. equipment according to claim 1, wherein, water/sediment interface system inboard wall of cistern both sides are provided with groove, are used for mounting plate type heavy metal and/or phosphate DGT probe in the groove, and the nut for fixing board-like heavy metal and/or phosphate DGT probe is housed on the groove.
3. equipment according to claim 1, wherein, the distance between board-like heavy metal and/or phosphate DGT probe and the water inlet can be regulated, with the flow velocity of control water inlet.
4. equipment according to claim 1, wherein, peristaltic pump can accurately be controlled the water inlet flow velocity, is used for the static and different disturbed conditions of simulation to the impact of Heavy Metal In Sediments and phosphate release.
5. equipment according to claim 1, wherein, the structure of board-like heavy metal and/or phosphate DGT probe is: top layer and bottom respectively are a hard plate, and ground floor filter membrane, diffusion layer, adsorbed layer and second layer filter membrane are installed between top layer hard plate and bottom hard plate successively.
6. equipment according to claim 1, wherein, the tank of dissolved oxygen control device is equipped with top cover, offers porosely on the top cover, is used for plugging pH probe, DO probe and ORP probe, the variation of dissolved oxygen content in the monitoring tank.
7. method of utilizing the described equipment research Heavy Metal In Sediments of claim 1 and/or phosphate to discharge, main flow process is:
1) with the water sample that is collected behind membrane filtration, place dissolved oxygen control device, utilize N
2And O
2Aeration in the dissolved oxygen control device, and the variation by DO content in the dissolved oxygen electrode monitoring water body are with the water body of simulation different dissolved oxygen content;
2) sediment that gathers is tiled in the water/sediment interface system tank, water sample behind aeration pumps in the water/sediment interface system tank by peristaltic pump, when water surface elevation reaches predetermined altitude, by the change modeling of regulating flow velocity static with different disturbed conditions under Heavy Metal In Sediments and phosphatic release conditions; The water that overflows of liquid level flows back to dissolved oxygen control device by conduit on the water/sediment interface system tank other end;
3) plug respectively board-like heavy metal and/or phosphate DGT probe in the water/sediment interface system tank, when water sample passes through board-like heavy metal and/or phosphate DGT probe, filter membrane in the matrix plate type heavy metal of indissoluble and/or the phosphate DGT probe intercepts, the heavy metal ion of solubilised state and/or phosphate arrive the rear regular taking-up that is fixed of adsorbed layer in board-like heavy metal and/or the phosphate DGT probe by filter membrane and diffusion layer, measure heavy metal and/or the phosphatic content of adsorbed layer in board-like heavy metal and/or the phosphate DGT probe;
4) variation of the pH of different depth place, DO and current potential in the microelectrode control system periodic measurement tank of water/sediment interface system realizes robotization control, is used for the Real-Time Monitoring to the physical agent that causes Heavy Metal In Sediments and Nutrient release.
8. method according to claim 7, wherein, the water sample in the step 1 and Yuan Shui refer to the poisons in freshwater of river, lake, reservoir, and make water mixing even through stirring.
9. method according to claim 7, wherein, different disturbances in the step 2 are the waves that produce in the long-pending thing of the different downellings of simulation-water termination system, and wave size and scope can be controlled by the flow velocity of water inlet and the distance between board-like heavy metal and/or phosphate DGT probe and the water inlet.
10. method according to claim 7, wherein, step 3 converses heavy metal and phosphate content in the Interstitial Water according to the Fick law after determining the heavy metal and/or phosphatic content of adsorbed layer in board-like heavy metal and/or the phosphate DGT probe again.
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