CN102854221A - In-situ measurement device and method for sediment breathing and nitrogen endogenous release - Google Patents

In-situ measurement device and method for sediment breathing and nitrogen endogenous release Download PDF

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CN102854221A
CN102854221A CN2012103869363A CN201210386936A CN102854221A CN 102854221 A CN102854221 A CN 102854221A CN 2012103869363 A CN2012103869363 A CN 2012103869363A CN 201210386936 A CN201210386936 A CN 201210386936A CN 102854221 A CN102854221 A CN 102854221A
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electrode
measurement
situ
dissolved oxygen
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张路
杜应旸
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Nanjing Institute of Geography and Limnology of CAS
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Nanjing Institute of Geography and Limnology of CAS
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Abstract

一种底泥呼吸及氮内源释放的原位测定装置,包括测定箱和测量电极,所述的测定箱包括箱体、透明的顶盖和限位裙边;所述的顶盖上开有圆形排水孔并安装单向阀;顶盖上还设有一组内嵌密封环的电极装配孔;所述的测定箱内设有循环水泵;所述的测量电极至少包括溶解氧电极和氨电极,测量电极插入顶盖上的电极装配孔中。测量电极连接测定仪后,将原位测定装置缓慢降到底泥表面,测定箱内形成底泥上覆水的密封空间,测定并记录电极读数,得到溶解氧、氨氮浓度的时间序列,线性回归分析后可计算得到底泥呼吸和氮内源释放速率。本发明的装置和方法能够原位、同步、快速地测定底泥呼吸及氮内源释放速率。

Figure 201210386936

An in-situ measurement device for sediment respiration and nitrogen endogenous release, comprising a measurement box and a measurement electrode, the measurement box includes a box body, a transparent top cover and a limit skirt; the top cover is provided with A circular drainage hole and a one-way valve are installed; a set of electrode assembly holes with a built-in sealing ring is also provided on the top cover; a circulating water pump is provided in the measurement box; the measurement electrodes include at least a dissolved oxygen electrode and an ammonia electrode , the measuring electrode is inserted into the electrode assembly hole on the top cover. After the measuring electrode is connected to the measuring instrument, the in-situ measuring device is slowly lowered to the surface of the sediment, and a sealed space is formed in the measuring box to form a water-covered sediment on the sediment, and the electrode readings are measured and recorded to obtain the time series of dissolved oxygen and ammonia nitrogen concentrations. After linear regression analysis The sediment respiration and endogenous release rate of nitrogen can be calculated. The device and method of the invention can measure the bottom mud respiration and nitrogen endogenous release rate in situ, synchronously and rapidly.

Figure 201210386936

Description

In-site detecting device and the assay method of a kind of bed mud breathing and nitrogen internal loading
Technical field
The present invention relates to a kind of determinator and method for polluted water body deposit endogenous pollutions such as lake, river and wetlands, be particularly related to a kind of endogenous pollution of substrate sludge determinator and method that is determined as feature with bed mud breathing and ammonia nitrogen release in-situ synchronization, belong to the ecosystem environment technical field.
Background technology
In recent years, along with lake, river and wetland etc. are subjected to the effect of human activity, the pollution of these water bodys gets over seriously.Because bed mud is the final containing person of these water pollutants, its pollution situation reflection and recorded the pollution situation in water body and basin.Simultaneously, polluted bed mud also produces close retroactive effect to the environmental aspect of these water bodys, is called endogenous pollution.And the endogenous pollution of the respiration of bed mud and ammonia nitrogen usually is that performance is the most obvious and strong in the endogenous pollution of substrate sludge.Its main cause is that endogenous pollution comes from the sediments organic, comprises aerobic respiration and the mineralising of organic nitrogen, and the anaerobic respiration of more strong lower floor's bed mud and organic nitrogen mineralising.Previous process has at first formed the consumption of bed mud to oxygen, with bottom-dwelling the direct utilization of oxygen is formed the bed mud respiration jointly, and produces accumulating of upper strata bed mud ammonia nitrogen.Although its speed of anaerobic respiration effect in the rear process is slow than aerobic respiration, but because the obstruct of upper strata bed mud, often forming a large amount of ammonia nitrogens in bed mud lower floor accumulates, and under the effects such as molecular diffusion, bottom-dwelling disturbance, current disturbance, to the water body migration, thus the endogenous load of formation nitrogen.The anaerobic condition that bed mud breathe to form, the accumulating and discharge of strong effect bed mud ammonia nitrogen.Therefore, the mensuration of bed mud breathing and nitrogen endogenous pollution has vital role for the source of understanding water pollution and intensity etc.
Domestic so in the world many countries all with Sediment Dredging as one of means of improving the more serious endogenous pollution of substrate sludge of lake, river and wetland water body, and the decision-making of the factors such as the position of dredging, area usually depends on the analysis of bed mud breathing and ammonia nitrogen release strength.And the effect of Sediment Dredging, also with the improvement of bed mud respiration and ammonia nitrogen release strength as one of index.Therefore, the assay method that a kind of energy is quick, original position is carried out bed mud breathing and nitrogen internal loading will help the solution of the problems referred to above.
The respiration of bed mud and ammonia nitrogen internal loading are measured, and the step that adopts traditionally bed mud post sample collection-indoor cultivation-lab analysis-result to calculate obtains.Because the physicochemical characteristic of lake, river and wetland bed mud spatially often there are differences (bed mud special heterogeneity), therefore, the bed mud post sample of small diameter often can only represent the less bed mud feature of scope.And because the restriction of bed mud post sample sampling thief often can not obtain the larger bed mud post sample of diameter, must solve by the multicolumn sample is parallel, also therefore increased the workload of sampling and follow-up culture assays.The bed mud post sample that gathers is before entering laboratory cultures, often need long-distance transportation, jolting and rock compacting and the disturbance effect of bringing in the transportation, tend to change bed mud, particularly affect the physicochemical characteristics of the sediments of bed mud breathing and internal loading key, so that sample and the original position sample cultivated have different.Thereby the variation that often brings the sediments physicochemical characteristic in the process of sample collection and cultivation, such as dissolved oxygen DO, upper strata water body nutrient concentrations etc.Solution shortens transportation range and careful transportation often in the prior art.And these solutions often can not thoroughly solve the problem of sample representativeness.In the indoor incubation, no matter be the static culture method, the cultivation that flows all carries out under simulated field condition (such as temperature, dissolved oxygen DO, pH), although simulated conditions can be near field condition, but still can't reproduce on-the-spot environmental baseline fully.The dissolved oxygen DO that indoor cultivation mensuration bed mud breathing and ammonia nitrogen dispose procedure must be measured overlying water changes and the ammonia nitrogen variation, therefore relate to more complicated sample analysis work, although the replacement scheme of other mensuration is arranged, tediously long and the complicated of operation of incubation still can't overcome.
The mensuration of bed mud breathing and ammonia nitrogen internal loading also can calculate by means of bed mud Diffusion of interstitial water model.But, obtaining of bed mud Interstitial Water, the balance (Peeper method) that often needs long-time (20-30 days), after perhaps needing to gather undisturbed sediment, adopt again squeezing, centrifugal, Rizhon extracting, the modes such as DET, DGT, although obtain technology by some complicated Interstitial Waters, can obtain the vertical variation section of Interstitial Water, and utilize on this basis release flux on the Fick First Law theory of computation, but, the complicacy of technology and operation tediously long all is the unvanquishable shortcoming of Diffusion of interstitial water model.Simultaneously, the release flux that diffusion model calculates is theoretic often, have certain hypotheses and condition, be controlled by the factors such as concentration gradient of solubilised state ammonia nitrogen fully as not considering bottom-dwelling disturbance, diffusion process, also so often can not represent the actual release of the original position flux of ammonia nitrogen.
By above analysis as can be known, a kind of energy is used for open-air, the assay method that situ Rapid Determination bed mud respiration and ammonia nitrogen discharge, to help and relate in Ecology, the Study of Water Environment that bed mud is breathed and ammonia nitrogen internal loading solution of problem, and the context parameter of dredging solution formulation and dredging effect analysis obtains.
Summary of the invention
Defective for prior art in above-mentioned bed mud breathing and the nitrogen internal loading assay method, the object of the present invention is to provide a kind ofly be convenient in the lake, river and wetland scene carry out in-situ synchronization and measure that bed mud is breathed and the apparatus and method of nitrogen internal loading, reach effective reduction sample collection and lab simulation analysis and measure workload, improve the effect of sample representativeness and accuracy of analysis.
Content of the present invention comprises the making of in-site detecting device and in-situ determination method.Wherein, the in-site detecting device provides the sealing water body of bed mud breathing and nitrogen internal loading, and adopt dissolved oxygen DO and the ammonia nitrogen electrode (and other complementary mensuration electrodes) with quick response and measurement function, obtain the real time measure, the material concentrations such as time dependent Dissolved Oxygen in Water and ammonia nitrogen; Carry out data acquisition and calculating by data line and analyzer, but concentration and the rate of change of the materials such as Real-time Obtaining dissolved oxygen DO, ammonia nitrogen.
The objective of the invention is to be achieved through the following technical solutions:
A kind of bed mud is breathed and the in-site detecting device of nitrogen internal loading, comprises and measures case and potential electrode, and described mensuration case comprises casing, transparent top cover and spacing shirt rim; Have the circular row water hole on the described top cover and retaining valve is installed; Also be provided with the electrode pilot hole of one group of embedded sealing ring on the top cover; Be provided with water circulating pump in the described mensuration case; Described potential electrode comprises dissolved oxygen electrode and ammonia electrode at least, in the electrode pilot hole on the potential electrode insertion top cover.
Preferably, described casing is made of stainless steel or organic glass cylinder.
Described spacing shirt rim is horizontally fixed on the casing outside around casing, is positioned at the bottom half 2-10cm that makes progress.
The effect of described retaining valve is, the water that uniaxially will be measured in the case in launch process is discharged from osculum, descends in water body when arriving the bed mud surface thereby measure case, and what retain in the case is the bed mud overlying water, but not superficial water.A specific implementation of retaining valve described in embodiment, comprises valve body, magnetic steel array and hinge; Wherein, described valve body is circular comprehensive silicon film, the liner round iron plate, and its radius is greater than the osculum radius; Described magnetic steel array, for embedding the permanent-magnet steel of one group of circle-shaped arrangement in the top cover, the circle at place, magnet steel center and osculum form concentric circles, and the magnet steel end face is a little less than the top cover surface; Described valve body is connected through the hinge on the top cover and flat overlaying on the osculum.Retaining valve is pressed in the comprehensive silicon film according to magnetic force between the round iron plate of its valve body liner and permanent-magnet steel array to form around the osculum of top cover and seals.
Described potential electrode can increase according to measuring needs, such as the pH electrode etc.The preferred fluorescence method dissolved oxygen electrode of dissolved oxygen electrode, this electrode response fast, does not consume oxygen; Ammonia electrode is preferably the quick ion-selective electrode of ammonia (ISE).
Also comprise the input base on the described mensuration case, throw in base and be fixed on the top cover, be used for connecting input rope or release control etc.
In the described in-site detecting device, potential electrode is connected with analyzer by electrode cable, reads in real time determination data, is used for analyzing and calculating.
The invention still further relates to the above-mentioned in-site detecting device of a kind of employing, the method for the breathing of in site measurement bed mud and nitrogen internal loading, its technical scheme is as follows:
The in-situ determination method of a kind of bed mud breathing and nitrogen internal loading comprises the steps:
(1) assembling in-site detecting device: assemble described in-site detecting device, the potential electrode of calibration in advance, demarcation is inserted the electrode pilot hole on the top cover and formed sealing, described potential electrode comprises dissolved oxygen electrode and ammonia electrode at least; Potential electrode is connected with analyzer by electrode cable;
(2) throw in the in-site detecting device: measuring the scene, the in-site detecting device is put into water, connect the water circulating pump power supply, open retaining valve; The in-site detecting device is slowly dropped to the bed mud surface, and make mensuration case insertion bed mud reach the bed mud surface to spacing shirt rim, closing one-way valve is measured formation seal cavity in the case;
(3) measure starting point: after the mensuration case was thrown in and put in place, water body evenly mixed under the water circulating pump effect in the case, after the electrode stable reading to be determined, and the beginning timing;
(4) measure: the beginning timing is designated as constantly " 0 ", and records the determination of electrode reading, and dissolved oxygen DO, ammonia nitrogen concentration are designated as respectively D0 and N0; Measure reading in t chronometry and recording electrode, dissolved oxygen DO, ammonia nitrogen concentration are designated as respectively Dt and Nt; Obtain the time series of determination of electrode reading;
(5) measure terminal point: when Dt/D0≤0.7, be designated as the mensuration terminal point; Perhaps, the trend that occur to raise when dissolved oxygen DO is then when Dt/D0 〉=1.3, as the mensuration terminal point;
(6) measurement result is calculated: with dissolved oxygen DO, ammonia nitrogen concentration the time is carried out linear regression, obtain following regression equation:
Dt=A D+ B D* t, wherein B DBe slope
Nt=A N+ B N* t, wherein B NBe slope
Slope B D, B NThe product of the height (H) that pushes up to case with bed mud surface is rate of release, that is:
Bed mud respiratory rate (SOD)=B D* H
Ammonia nitrogen rate of release (F N)=B N* H.
The present invention compared with prior art it is advantageous that:
(1) device of the present invention and assay method can be in the river, lake and the on-the-spot directly mensuration of wetland, need not through processes such as over-sampling, cultivation, mensuration, can original position quick obtaining bed mud respiration and ammonia nitrogen rate of release.
(2) measure the process undisturbed, do not destroy the original-shape of bed mud, better reflect the physics and chemistry characteristic of on-the-spot bed mud.
(3) device of the present invention and assay method are economical and practical.Adopt these apparatus and method to carry out the mensuration of bed mud breathing and nitrogen internal loading, do not need the processes such as sample transportation, cultivation, mensuration, except the battery charging, its consumables and consumption costs are zero substantially.
(4) device of the present invention adopts the large aperture retaining valve, after having guaranteed that the in-site detecting case is thrown in successfully, memory box stays water sample to be overlying water, break through traditional box method and can not obtain rapidly the shortcoming of bed mud overlying water, can carry out immediately in-site detecting, do not need to have saved incubation time through stable.
(5) because device of the present invention and assay method have the box method of original position, therefore the not exchange of the outer water body of water body and case, is carried out along with bed mud is respiratory in its case, and descending can appear in dissolved oxygen concentration in the casing.Adopt dissolved oxygen DO to change less than 30% as end-point method, guaranteed to greatest extent the stable of environmental baseline in the mensuration process.
(6) device of the present invention and assay method can also utilize the variation of other other indexs of electrode Simultaneous Monitoring, such as pH, have extensibility.
(7) device of the present invention and assay method can overcome the bed mud special heterogeneity to greatest extent.Utilize the in-site detecting case to measure, the waters bed mud of reflection is breathed and nitrogen discharges more representative.
Describe the present invention below in conjunction with embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Description of drawings
Fig. 1 is the in-site detecting device perspective view of bed mud breathing of the present invention and nitrogen internal loading.
Fig. 2 is the structural representation of retaining valve in the in-site detecting device of the present invention.
Fig. 3 is the structural representation of throwing in base in the in-site detecting device of the present invention.
Fig. 4 is that bed mud of the present invention is breathed and the change curve of the in-situ determination method of nitrogen internal loading ammonia nitrogen and dissolved oxygen concentration in the mensuration process.
Embodiment
The present invention relates to a kind ofly can be used for lake, river and the wetland polluted water body deposit is breathed and the nitrogen internal loading carries out method and the device thereof of in-site detecting.
As shown in Figure 1, the in-site detecting device of a kind of bed mud breathing and nitrogen internal loading comprises and measures case and potential electrode.Wherein, measure cylindrical box 1, top cover 3 and spacing shirt rim 2 that case comprises that organic glass is made, in the electrode pilot hole 6 on dissolved oxygen DO, ammonia, three kinds of potential electrode insertions of the pH top cover 3.Except having 3 electrode pilot holes 6, also have a large aperture osculum 11 and retaining valve 5 is installed on the top cover 3; Top cover 3 upper ends are fixed with throws in base 4; Measure in the case and be fixed with water circulating pump 9, water circulating pump 9 is connected with direct supply 8.
As shown in Figure 2, above-mentioned retaining valve 5 comprises the hinge 14 of valve body 13, magnetic steel array 12 and fixed valve body.Valve body 13 is circular comprehensive silicon film, the liner round iron plate.Magnetic steel array 12 comprises one group of permanent-magnet steel on the top cover 3, is circumferential arrangement at radius greater than the concentric circles of osculum 11, forms circle-shaped magnetic steel array.The radius of a circle of magnetic steel array is less than valve body 13 radiuses.Valve body 13 is hinged on the top cover 3 and flat overlaying on the osculum 11 by hinge 14.
The concrete grammar that above-mentioned in-site detecting device is made is as follows:
(1) measuring case adopts transparent plexiglass to make.For shallow lake, river and the more shallow characteristics of the wetland water body depth of water, in the situation that water transparency is higher, light compensation depth is often greater than the depth of water, and therefore, the bed mud surface often is subjected to illumination effect.Adopt transparent material to make and measure case, be convenient to truly reflect the light conditions of bed mud, and can measure the photosynthesis of bed mud breathing and benthic algae, and measure the nitrogen internal loading that is subjected to illumination effect.This design when the bed mud surface that particularly has benthic algae and hydrophyte to cover is measured, has significant advantage at the shallow water wetland.
(2) casing 1 of mensuration case is cylindrical, is convenient to casing 1 water flow inside and evenly distributes and mixing.The water circulating pump 9 of while casing 1 built-in direct-current drive, the basis of design box volume size of its flow is determined.Can fix a direct current power supply 8(accumulator at top cover 3) be water circulating pump 9 power supplies, generally the amount of trying to please is 20 ampere-hour lithium batteries.Direct supply 8 adopts waterproof to be connected with water circulating pump 9, is penetrated in the casing by power lead 10 to be connected with water circulating pump 9.
(3) 5cm place, casing 1 bottom level is welded the annular stop shirt rim 2 that a width is 50mm.Its Main Function is: when lake and the placement of bed mud in river top layer, guarantee the contact area that shirt rim and bed mud surface are larger, reduce casing to the normal pressure of bed mud, prevent that casing from sinking, guarantee that casing and bed mud surface enclose fixing of volume.
(4) measure on the top cover 3 of case and have 3 electrode pilot holes 6, the embedded rubber seal ring in every hole, and fix with the agent of silicon sulfide glue glued adhesion, the sealing ring internal diameter is slightly less than potential electrode measuring junction external diameter, is convenient to electrode and inserts casing 1, and form and seal.
(5) retaining valve 5 is made
This retaining valve 5 guarantees to open in launch process, so that water body can be discharged from from large aperture osculum 11 in casing 1 decline process in the mensuration case, measure case when arriving the bed mud surface thereby make, what retain in the casing 1 is the bed mud overlying water, but not superficial water.After casing 1 inserted bed mud, this valve was closed, thereby formed the overlying water environment of sealing.
Concrete method for making is as follows:
Valve body 13 adopts the circular comprehensive silicon film of gummed, liner round iron plate.Iron plate by seamless binding in the middle of circular silica gel piece.
Open round osculum 11 on the top cover 3 of mensuration case, radius is that the round iron plate radius subtracts 1.0 cm.
Along osculum 11 peripheries, be that osculum 11 radiuses add on the concentric circles of 0.5 cm at radius on the top cover 3, the circumference radius is the circular permanent-magnet steel of 2mm, and the magnet steel center pit forms circle-shaped permanent-magnet steel array 12 apart from being 8mm.The magnet steel top is a little less than measuring case top cover 3 surperficial 1mm, on use silica gel sealing.
Valve body 1 is with hinge 14 flat 11 upper ends, circular row water hole that overlay on, and forms sealing around silica gel piece being pressed in the osculum 11 of top cover 3 according to magnetic force between the round iron plate of its liner and magnetic steel array.
(6) delivery device of mensuration case
As shown in Figure 3, measure the organic glass input base 4 of fixing a circular band internal thread (φ 50mm) on the case top cover 3 with ABS glue, and strengthen being fixed on the top cover 3 with STAINLESS STEEL HEX SOCKET CAP SCREWS 15, fixed screw 15 is by top cover 3 through holes, to throw in from bottom to top base 4 fixing, to strengthen throwing in the bond strength of base 4 and top cover 3.Other joins a release control, and release control adopts the hollow stiff rod of ABS, bottom band external thread (φ 50mm), and length is decided according to the on-the-spot depth of water.Usually, its length should be advisable greater than on-the-spot depth of water 1-2m.Long then not easy to operate, too shortly then can't exert oneself.
(7) electrode is selected and assembling
Select the underwater survey electrode, anti-water depth and electrode cable length are all greater than measuring water depth.Select dissolved oxygen DO, ammonia, three kinds of electrodes of pH.Wherein dissolved oxygen electrode is for responding fast, do not consume the fluorescence method dissolved oxygen electrode of oxygen, and ammonia electrode is that ion is selected ammonia gas-sensing electrode (ISE), and the pH electrode is traditional pH glass electrode.Potential electrode is inserted the electrode pilot hole 6 on the top cover 3 and formed sealing.
After above-mentioned in-site detecting device completes, namely can adopt following methods to carry out the in-site detecting of bed mud breathing and nitrogen internal loading, comprise the steps:
(1) in-site detecting device assembling: measuring the above-mentioned in-site detecting device of assembled in situ, three kinds of all calibration in advance, demarcation in the laboratory of electrode, measuring on-the-spot electrode pilot hole 6 and formation sealing of inserting on the top cover 3, the measuring junction of potential electrode stretches into casing 1 interior approximately 2cm.With electrode cable potential electrode is connected with hand-held analyzer, hand-held analyzer can directly be read the measured value of three kinds of electrodes.
(2) the in-site detecting device is thrown in: measuring the scene, release control is being screwed in throw in base 4, will measure case and put into water, connecting water circulating pump 9 power supplys in the case, opening retaining valve 5.Hand-held release control slowly is reduced to the bed mud surface with the in-site detecting device, makes the mensuration case insert bed mud to spacing shirt rim 2 and reaches the bed mud surface.Closing one-way valve 5 is measured and is formed seal cavity in the case.
(3) measure starting point: the mensuration case is placed about 1min after throwing in and putting in place, so that water body forms mixed uniformly water body in the case under water circulating pump 9 effects, after the electrode stable reading to be determined, begins timing.
(4) measure: the beginning timing is designated as constantly " 0 ", and records three determination of electrode readings, and dissolved oxygen DO, ammonia nitrogen concentration and pH are designated as respectively D0, N0 and P0;
Behind record " 0 " moment reading, measure first group of determination of electrode reading of record behind Δ t=2~30min, dissolved oxygen DO, pH, ammonia nitrogen are designated as respectively D1, P1 and N1.After this, measure and record a group number-reading every Δ t, insert following table 1 (take Δ t=5min as example), obtain the time series of one group of determination of electrode reading.
Table 1 in-site detecting device minute sequence
Figure 865185DEST_PATH_IMAGE002
(5) measure terminal point: measuring time of finishing is determined by the rate of change of dissolved oxygen concentration, and its principle is that dissolved oxygen content changes and is no more than 70%, namely when Dt/D0≤0.7, is designated as the mensuration terminal point.Perhaps, when bed mud exists pasture and water or benthic algae, when under photosynthesis, causing the bottom to put the oxygen process, the trend that dissolved oxygen DO can occur raising, at this moment, with Dt/D0 〉=1.3 as the mensuration terminal point.
(6) measurement result is calculated:
Carry out linear regression with dissolved oxygen DO, ammonia nitrogen concentration and time, obtain following regression equation:
The regression formula of dissolved oxygen DO D is Dt=A D+ B D* t, wherein A DBe the linear regression intercept of D and t, B DBe slope
The regression formula of ammonia nitrogen N is Nt=A N+ B N* t, wherein A NBe the linear regression intercept of N and t, B NBe slope
Slope B D, B NThe product of the height (H) that pushes up to case with bed mud surface is rate of release, that is:
Bed mud respiratory rate (SOD)=B D* H
Ammonia nitrogen rate of release (F N)=B N* H.
Embodiment 1
In the lake of tool Muddy Bottoms bed mud, adopt above-mentioned in-site detecting device to carry out the Simultaneous Determination of bed mud breathing and nitrogen internal loading.Measuring the place is spacious pool, lake, and the lake depth of water is 1.8m.
In the rubber seal with dissolved oxygen DO, pH and ammonia electrode electrode insertion pilot hole 6, measure electrode by the hand-held analyzer of electrode cable access.
Measuring sampling spot with the externally threaded release control screw-in of tool input base 4, utilize release control that the in-site detecting device is slowly put into water, and connect water circulating pump 9 power supplys in the case.Before input, lie in rope one end on the valve body 13 of the retaining valve 5 on the large aperture osculum 11, the other end lies in release control top hand position, retaining valve 5 is stayed open, hand-held release control will be measured case and slowly be reduced to the bed mud surface, firmly make a little casing 1 insert bed mud.In the insertion process, the water in the casing 1 is discharged from casing 1, measures case and arrives front and back, bed mud surface, and speed must be slow, to prevent the bed mud disturbance.Wait to feel that the spacing shirt rim 2 of measuring on the case reaches the bed mud surface, after lower slotting resistance enlarges markedly, stop firmly.Unclamp the rope that lies in the release control top, valve body 13 drops on the top cover 3 under the effect of deadweight, and attracts with magnetic steel array 12 on the top cover 3, and the silica gel piece of valve body 13 is pressed on the top cover 3 of in-site detecting case, forms airtight.
Measure case throw in put in place after, about the summary 1min of etc.ing so that water body forms mixed uniformly water body in the case under water circulating pump 9 acts on, wait electrode stable reading to be determined after, begin timing.Every 5min records one group of dissolved oxygen DO and ammonia nitrogen concentration data.
After the mensuration process finishes, will obtain dissolved oxygen DO and ammonia nitrogen concentration by time sequence mapping (Fig. 4), form the change curve of ammonia nitrogen and dissolved oxygen concentration.According to the endpoint method, choose the mensuration terminal point, time series is carried out linear regression, obtain regression curve and regression equation, difference calculated curve slope (mg/ (L min)), wherein the dissolved oxygen DO rate of change is-0.0256 mg/ (L min), and the ammonia nitrogen rate of change is 0.0011 mg/ (L min).Consider water colunm height 0.2 m that mensuration case and bed mud enclose, calculate bed mud respiratory rate (SOD) and ammonia nitrogen rate of release (F by following formula N):
SOD(mg/(m 2?h)=?-0.0256?mg/(L?min)?×?0.2?(m)?×?1000?(L/m 3)?×?60?(min/h)?=?-307.2?mg/(m 2?h)
F N(mg/(m 2?h)=?0.0011?mg/(L?min)?×?0.2?(m)?×?1000?(L/m 3)?×?60?(min/h)?=?13.2?mg/(m 2?h)
Adopt apparatus and method of the present invention to carry out the mensuration of sediment respiratory rate and ammonia nitrogen rate of release, after the morning, 10:59 divided input in-site detecting device, divide the threshold value that just reaches dissolved oxygen DO variation 70% to 12:24, can finish to measure, whole mensuration process only needs 1 hour 25 minutes, can satisfy original position, synchronously, the requirement of Fast Measurement.

Claims (10)

1.一种底泥呼吸和氮内源释放的原位测定装置,其特征在于,所述的装置包括测定箱和测量电极,所述的测定箱包括箱体(1)、透明的顶盖(3)和限位裙边(2);所述的顶盖(3)上开有圆形排水孔(11)并安装单向阀(5);顶盖(3)上还设有一组内嵌密封环的电极装配孔(6);所述的测定箱内设有循环水泵(9);所述的测量电极至少包括溶解氧电极和氨电极,测量电极插入顶盖(3)上的电极装配孔(6)中。 1. An in-situ measurement device for sediment respiration and nitrogen endogenous release, characterized in that the device includes a measurement box and a measurement electrode, and the measurement box includes a casing (1), a transparent top cover ( 3) and the limiting skirt (2); the top cover (3) is provided with a circular drainage hole (11) and a one-way valve (5); The electrode assembly hole (6) of the sealing ring; the circulating water pump (9) is provided in the measuring box; the measuring electrode includes at least a dissolved oxygen electrode and an ammonia electrode, and the measuring electrode is inserted into the electrode assembly on the top cover (3) in hole (6). 2.根据权利要求1所述的原位测定装置,其特征在于,所述的箱体(1)由不锈钢或有机玻璃圆筒构成。 2. The in-situ measuring device according to claim 1, characterized in that, the box (1) is made of stainless steel or plexiglass cylinder. 3.根据权利要求1所述的原位测定装置,其特征在于,所述的限位裙边(2)围绕箱体(1)水平地固定在箱体(1)外侧,位于箱体(1)底部向上2-10cm。 3. The in-situ measurement device according to claim 1, characterized in that, the limit skirt (2) is horizontally fixed on the outside of the box (1) around the box (1), and is located on the box (1) ) bottom up 2-10cm. 4.根据权利要求1所述的原位测定装置,其特征在于,所述的单向阀(5)包括阀体(13)、磁钢阵列(12)及铰链(14);其中,所述的阀体(13)为圆形复合硅胶片,内衬圆形铁片,其半径大于排水孔(11)半径;所述的磁钢阵列(12),为嵌入顶盖(3)内的一组圆周状排列的永磁钢,磁钢中心所在的圆与排水孔(11)形成同心圆,磁钢顶面略低于顶盖(3)表面;所述的阀体(13)通过铰链(14)连接在顶盖(3)上并平覆在排水孔(11)上。 4. The in-situ measurement device according to claim 1, characterized in that, the one-way valve (5) includes a valve body (13), a magnetic steel array (12) and a hinge (14); wherein, the The valve body (13) is a circular composite silica gel sheet, lined with a circular iron sheet, and its radius is greater than the radius of the drainage hole (11); the magnetic steel array (12) is a set embedded in the top cover (3). A group of permanent magnet steels arranged in a circumferential shape, the circle where the center of the magnet steel is located forms a concentric circle with the drainage hole (11), and the top surface of the magnet steel is slightly lower than the surface of the top cover (3); the valve body (13) passes through the hinge ( 14) Connect to the top cover (3) and lay flat on the drain hole (11). 5.根据权利要求1所述的原位测定装置,其特征在于,所述的溶解氧电极为荧光法溶解氧电极,氨电极为氨气敏离子选择电极。 5 . The in-situ measurement device according to claim 1 , wherein the dissolved oxygen electrode is a fluorescence method dissolved oxygen electrode, and the ammonia electrode is an ammonia gas-sensitive ion selective electrode. 6.根据权利要求1所述的原位测定装置,其特征在于,所述的测定箱上还包括投放底座(4),投放底座(4)固定在顶盖(3)上。 6 . The in-situ measurement device according to claim 1 , characterized in that, the measurement box further includes a delivery base ( 4 ), and the delivery base ( 4 ) is fixed on the top cover ( 3 ). 7.根据权利要求1所述的原位测定装置,其特征在于,所述的原位测定装置中,测量电极通过电极电缆与测定仪连接。 7. The in-situ measuring device according to claim 1, characterized in that, in the in-situ measuring device, the measuring electrodes are connected to the measuring instrument through electrode cables. 8.一种底泥呼吸及氮内源释放的原位测定方法,其特征在于,包括如下步骤: 8. An in-situ assay method for sediment respiration and endogenous nitrogen release, characterized in that it comprises the steps: (1)装配原位测定装置:采用权利要求1所述的原位测定装置,将预先校准、标定的测量电极插入顶盖上的电极装配孔并形成密封,所述的测量电极至少包括溶解氧电极和氨电极;测量电极通过电极电缆与测定仪连接; (1) Assembling the in-situ measuring device: using the in-situ measuring device described in claim 1, insert the pre-calibrated and calibrated measuring electrode into the electrode assembly hole on the top cover and form a seal, and the measuring electrode includes at least dissolved oxygen Electrode and ammonia electrode; the measuring electrode is connected to the measuring instrument through the electrode cable; (2)投放原位测定装置:在测定现场,将原位测定装置放入水中,接通循环水泵电源,打开单向阀;将原位测定装置缓慢降到底泥表面,并使测定箱插入底泥至限位裙边达到底泥表面,关闭单向阀,测定箱内形成密封空间; (2) Putting in-situ measurement device: at the measurement site, put the in-situ measurement device into the water, turn on the power of the circulating water pump, and open the one-way valve; slowly lower the in-situ measurement device to the surface of the sediment, and insert the measurement box into the bottom When the mud reaches the limit skirt and reaches the surface of the bottom mud, close the one-way valve and form a sealed space in the measurement box; (3)测定起点:测定箱投放到位后,箱内水体在循环水泵作用下均匀混合,待测定电极读数稳定后,开始计时; (3) Measurement starting point: After the measurement box is placed in place, the water in the box is uniformly mixed under the action of the circulating water pump, and the timing starts after the reading of the measurement electrode is stable; (4)测定:开始计时记为时刻“0”,并记录下电极测定读数,溶解氧、氨氮浓度分别记为D0和N0;在t时刻测定并记录电极测定读数,溶解氧、氨氮浓度分别记为Dt和Nt;得到电极测定读数的时间序列; (4) Measurement: start timing and record it as time "0", and record the readings of the electrode measurement, and record the concentrations of dissolved oxygen and ammonia nitrogen as D0 and N0 respectively; measure and record the readings of the electrodes at time t, record the concentrations of dissolved oxygen and ammonia nitrogen respectively are Dt and Nt; obtain the time series of electrode measurement readings; (5)测定终点:当Dt / D0 ≤ 0.7时,记为测定终点;或者,当溶解氧出现升高的趋势,则当Dt / D0 ≥ 1.3时,作为测定终点; (5) Measurement end point: when Dt / D0 ≤ 0.7, it is recorded as the measurement end point; or, when the dissolved oxygen tends to increase, when Dt / D0 ≥ 1.3, it is used as the measurement end point; (6)测定结果计算:以溶解氧、氨氮浓度对时间进行线性回归,得到下述回归方程: (6) Calculation of measurement results: Perform a linear regression with the concentration of dissolved oxygen and ammonia nitrogen on time to obtain the following regression equation: Dt= AD + BD× t,其中BD为斜率 Dt= A D + B D × t, where B D is the slope Nt=AN + BN × t,其中BN 为斜率 Nt=A N + B N × t, where B N is the slope 斜率BD、BN与底泥表面到箱顶的高度H的乘积即释放速率,即: The product of the slope B D , B N and the height H from the bottom mud surface to the top of the tank is the release rate, namely: 底泥呼吸速率(SOD)= BD × H Sediment respiration rate (SOD) = B D × H 氨氮释放速率(FN)= BN × H。 Ammonia nitrogen release rate (F N ) = B N × H. 9.根据权利要求8所述的底泥呼吸及氮内源释放的原位测定方法,其特征在于,所述的步骤(4)中,开始计时后,每隔Δt=2~30min测定并记录溶解氧、氨氮浓度的电极测定读数。 9. The in-situ determination method for sediment respiration and nitrogen endogenous release according to claim 8, characterized in that, in the step (4), after starting the timing, measure and record every Δt=2-30min Electrode measurement readings of dissolved oxygen and ammonia nitrogen concentrations. 10.根据权利要求8或9所述的底泥呼吸及氮内源释放的原位测定方法,其特征在于,所述的溶解氧电极为荧光法溶解氧电极,氨电极为氨气敏离子选择电极。 10. according to claim 8 or 9 described bottom mud respiration and the in-situ assay method of nitrogen endogenous release, it is characterized in that, described dissolved oxygen electrode is the fluorescence method dissolved oxygen electrode, and ammonia electrode is ammonia gas sensitive ion selection electrode.
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CN104459081A (en) * 2013-09-17 2015-03-25 清华大学 Determination method for activated sludge respiration rate and in-situ respiration rate instrument thereof
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CN110031640A (en) * 2019-03-29 2019-07-19 华电电力科学研究院有限公司 A kind of sludge pH detection device and detection method
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CN112198293A (en) * 2020-10-09 2021-01-08 中国环境科学研究院 Ammonia nitrogen release research device in black and odorous water
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