CN102680421A - Method for monitoring farmland ammonia volatilization in real time based on laser absorption spectrum technology - Google Patents
Method for monitoring farmland ammonia volatilization in real time based on laser absorption spectrum technology Download PDFInfo
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Abstract
Farmland ammonia volatilization method of real-time based on laser absorption spectroscopy,Determination step are as follows: ammonia concentration in air at volatile source upwind and lower wind direction is measured using open long-optical path diode laser absorption spectrometer simultaneously; Near volatile source with three-D ultrasonic anemobiagraph measurement three-dimensional velocity,The meteorological datas such as temperature,Or with section meteorological system measurement different height wind speed,Temperature,Wind direction data; Based on ammonia density and meteorological data,The motion profile of position is monitored from volatile source to gas concentration by inverse analog gas particle,To estimate the theoretical than (C/Q) sim of gas concentration and rate of volatilization,Gaseous volatilization rate Q (μ gm-2s-1) can be calculated by following formula
According to the simulation value of meteorological data rejecting abnormalities. This method is suitable for the volatile source of any scale and shape, and this method can realize non-contact, highly sensitive, highly selective, high time resolution continuous real time on-line monitoring ammonia volatilization.
Description
Technical field
The present invention relates to a kind of farmland ammonia volatilization monitoring method, particularly a kind of field ammonia volatilization realtime on-line monitoring method based on open long light path diode laser absorption spectrum technology.
Background technology
Main soil balancing method, confined chamber method, the microclimate method of adopting measured in the farmland ammonia volatilization.The soil balancing method is estimated the volatile quantity of ammonia by rate of fertilizer application, plant absorbing amount, soil residual quantity and leaching loss amount, because the mensuration project is many, and does not consider denitrification, general error is bigger, basically need not now.The confined chamber method is a current application method the most widely, and its device is fairly simple, and condition is easy to control, can estimate the mass exchange of certain some soil-ammonia, is suitable for plot experiment and multifactor comparative study.But the ammonia volatilization process under the air-tight state is different from state of nature fully, and different under ammonia concentration gradient, barometric gradient, turbulent flow pulsation and gas flow and the natural conditions, result of study is qualitatively basically; In addition because it is less to measure yardstick, for the field piece and more farmland ammonia volatilization mensurations of large scale need a large amount of monitoring points, labor capacity is big, and the common influence of also not considering the overground part plant.Ammoniameter calculation face of land ammonia volatilization in the turbulent flow conditions of micrometeorology method through measuring surface layer and the air; It is not because disturb the field natural environmental condition; The actual state that has reflected the farmland ammonia volatilization truly; Extensively thought to measure the better method of ammonia volatilization, the large tracts of land farmland ammonia volatilization that is suitable for smooth homogeneous is especially measured.But the micrometeorology method is owing to have relatively high expectations for meteorological, ammonia concentration determination instrument and equipment, this to a great extent limit the practical application of micrometeorology method.
The development key of farmland ammonia volatilization method is the development of monitoring technology.All there is very big uncertainty in defining of emission factor in the emission intensity inventory estimation of our times various countries, and particularly ammonia loss by volatilization amount in farmland is difficult to accurate mensuration.Main cause is owing to ammonia concentration in the air is very low, belongs to trace gas, and the analytical technology of current routine is difficult to directly detect; Must at first collect for a long time to increase the concentration of sample the ammonia sample; The collection of traditional ammonia sample all is to adopt acid or acidic materials to absorb the ammonia that the farmland evaporates, and in the laboratory, extracts then, adopts the conventional chemical methods analyst; Like the spectrophotometric colourimetry etc., finally adopt confined chamber method or micrometeorology method to calculate ammonia volatilization.This is a complicacy and time-consuming procedure; As the sample collection of confined chamber method, want 24 hours, often need several days time when concentration is low, the sampling thief method sample collection that facings the wind is also at least more than 2 hours; Not only be difficult to obtain the Real-time and Dynamic Changing Pattern of farmland ammonia volatilization; And long-time ammonia sample collecting makes ammonia volatilization research have to ignore the influence of miniature scale turbulence characteristics, has inevitably influenced the true and reliable property of determination data.Simultaneously,, form the deposition of ammonia easily on sampling pipe, instrument surface, and dispose procedure subsequently all can cause sampling loss, memory effect, also cause testing result that certain error is arranged because ammonia is very easily water-soluble.Therefore press for research and development and measure new method, long-term to realize, continuous, dynamic basic data monitoring based on the farmland ammonia volatilization of hi-tech.
Tunable diode laser absorption spectroscopy technology (Tunable Diode Laser Absorption Spectroscopy; TDLAS) be a gas concentration monitoring technology of newly-developed in the world, have good, the characteristics of (millisecond magnitude) dynamically fast of highly sensitive (ppb magnitude), selectivity.It utilizes diode laser narrow linewidth (< 10MHz) and fast frequency tuning characteristic; Change the absorption line through detecting isolated shaking that absorbs molecule; Obtain the absorption information of tested gas; Calculate the absorption cross section of gas molecule and then the concentration of inverting gas by linear, live width that measure to obtain and intensitometer.Through combining, can realize the gas detection sensitivity of ppbv even pptv magnitude with long light path technology.When opening the light path gasmetry,, therefore be suitable for the continuous on-line monitoring of trace gas momentary fluctuation especially especially owing to there is not topic between pool wall absorption or loss etc.
Diode laser absorption spectrum technology provides new technology for the mensuration of ammonia concentration, but wants the ammonia volatilization situation in clear and definite farmland, at first must the research method organic combination of new technology and ammonia volatilization be set up the new method based on hi-tech.Main and the eddy current correlation method of diode laser absorption spectrum technology; Micrometeorology methods such as gradient flux method and reverse Lagrangian STOCHASTIC DIFFUSION theory combine to measure ammonia volatilization, and wherein reverse Lagrangian STOCHASTIC DIFFUSION theory is considered to combine to measure the most effectively microclimate method of ammonia volatilization with open long light path diode laser absorption spectrum technology.This method also is in the research exploratory stage in the world, is mainly used in the ammonia monitoring of plant, compost, rarely has the farmland of using it for ammonia volatilization monitoring, and its domestic application research is also at the early-stage.Therefore; This method is planned open long light path diode laser absorption spectrum technology and is effectively combined with reverse Lagrangian STOCHASTIC DIFFUSION is theoretical; Carry out the farmland ammonia volatilization research based on high time resolution data, the ammonia volatilization Application in Monitoring provides foundation in the farmland for open long light path diode laser absorption spectrum technology from now on.
Summary of the invention
Goal of the invention: the present invention is directed to the deficiency that exists in the above-mentioned existing farmland ammonia volatilization assay method, provide a kind of be applicable to the high sensitivity in farmland, in real time, dynamic ammonia volatilization monitoring method fast.
Technical scheme: based on the farmland ammonia volatilization method of real-time of laser absorption spectrum technology, determination step is:
A. adopt open long light path diode laser absorption spectrometer to measure ammonia concentration value in volatile source upwind and the following wind direction place air simultaneously;
B. obtain three-dimensional wind speed, temperature and wind direction weather data in the spectrometer placement with three-D ultrasonic anemoscope or section meteorological system mensuration simultaneously;
C. with step a gained ammonia concentration value and step b gained weather data; Import reverse Lagrangian Stochastic Diffusion Model software WindTrax2.0; Movement locus through the inverse analog gas particle from volatile source to the gas concentration monitoring location, the theory that calculates gas concentration and rate of volatilization is than (C/Q)
Sim, gaseous volatilization speed Q (μ gm
-2S
-1) can obtain by computes:
Wherein, C is a monitoring point gas mean concentration, μ gm
-3C
bBe background gas concentration, μ gm
-3
D. according to the gaseous volatilization velocity simulation numerical value of weather data rejecting abnormalities, obtain farmland ammonia volatilization rule and monitor in real time with accumulation ammonia volatilization amount data completion farmland ammonia volatilization.
The method that the open long light path diode laser absorption spectrometer of said employing is measured ammonia concentration value in volatile source upwind and the following wind direction place air simultaneously is: 5m to 20m establishes at the place spectrometer monitoring volatilization plume hollow gas ammonia concentration to wind direction apart from the volatile source edge under volatile source, establishes spectrometer monitoring background air ammonia concentration in the place that the volatile source upwind is not influenced by volatile source; Survey line is long select 100m to 200m all can, following wind direction place survey line is vertical with volatilization plume center line as far as possible, upwind place survey line is parallel with following wind direction place survey line; The survey line height is made as 1.0m to 1.5m (according to the plant height adjustment, placing on the crop canopies); The spectrometer data acquiring frequency is 2～3 times/second, the ammonia concentration data calculating mean value of every 15min to 120min; It is the survey line height that said survey line height is got spectrometer transmitter height, corner reflector height and survey line mid point height flat average.Preferably with said acquisition time 30min ammonia concentration data calculating mean value.
Said weather data assay method is: adopt the three-D ultrasonic anemoscope to obtain three-dimensional wind speed and temperature record in the spectrometer placement, three-dimensional anemoscope height is at 2m to 3m; Perhaps adopt section meteorological system to measure differing heights wind speed, temperature, wind direction data, survey five differing heights weather datas at least, each height is between 0.5m to 10m; The weather data calculating mean value time interval that obtains is identical with the ammonia concentration data.
Said reverse Lagrangian Stochastic Diffusion Model estimation ammonia volatilization method is: the basis of reverse Lagrangian Stochastic Diffusion Model is a Monin – Obukhov similarity theory, need obtain four indexs when therefore using this model: friction wind speed u*, air stability length L, wind direction β and surfaceness Z
o, it can be imported reverse Lagrangian Stochastic Diffusion Model software WindTrax2.0 by the weather data that the front obtains and calculate; Model based on the theory of four calculation of parameter gas concentrations and rate of volatilization than (C/Q)
Sim, with (C/Q)
SimCan calculate ammonia volatilization speed with the ammonia concentration data.
Said method according to weather data rejecting abnormalities simulation value is: reject friction wind speed u*≤0.15m/s (wind speed is on the low side) or air stability Monin-Obukhov length L: | the analogue value in L|≤2m (atmosphere stabilizer pole or extremely unstable) period.
Beneficial effect: open long light path diode laser absorption spectrum technology can realize noncontact, high sensitivity, the high selectivity of larger area farmland air ammonia concentration, the real time on-line monitoring of high time resolution in the method, is the maximum innovation of relative classic method; This technology combined with reverse Lagrangian Stochastic Diffusion Model measure the farmland ammonia volatilization, no matter big or small, the shape of volatile source all can accurately be estimated the farmland ammonia volatilization; The continuous on-line monitoring of farmland ammonia volatilization is for the diurnal variation rule of farmland ammonia volatilization and improve research such as utilization rate of nitrogen fertilizer important techniques and method support are provided.
Description of drawings
Fig. 1 ammonia volatilization diurnal variation (fertilising back 24～36 hours);
Fig. 2 ammonia volatilization interdiurnal change (applying fertilizer back 232 hours in);
Fig. 3 absorption spectrum-reverse Lagrangian method and mass balance method, venting method are measured the contrast of ammonia volatilization speed; Wherein scheming A is that absorption spectrum-reverse Lagrangian method and mass balance method are measured 1: 1 linear graph of result; Wherein scheming B is that absorption spectrum-reverse Lagrangian method and venting method are measured 1:1 linear graph as a result.
Embodiment
Survey line: the light path between spectrometer and the catoptron; Survey line is long: the distance between spectrometer and the catoptron.
The used open long light path diode laser absorption spectrometer of the present invention is by Anhui Inst. of Optics and Fine Mechanics, Chinese Academy of Sciences's development (Chinese patent ZL200610098155.9); Or the GasFinder open circuit gas detecting instrument (GasFinders that adopts Canadian Boreal Laser company to produce; Boreal Laser Inc.; Edmonton, Canada), the key technical indexes is following:
| Project | Technical indicator |
| Optical maser wavelength | 1.544μm |
| Sweep frequency | 100Hz |
| Modulating frequency | 17kHz |
| Maximum monochromatic light journey | 500m |
| LDL | 0.016ppm |
| Averaging time | Adjustable from 2s to 24 hour |
| Drift | In the maintenance phase less than 4% of measurement range |
Embodiment 1:
1, test apparatus
Test adopts open long light path diode laser absorption spectrometer to measure air ammonia concentration, and table 1 is seen in its sensitivity of measuring ammonia concentration; Adopt CSAT3 three-D ultrasonic anemoscope (production of U.S. Campbell company) to gather weather data, critical piece comprises: CR1000 data acquisition unit, the ultrasonic anemoscope of CSAT3.Reverse Lagrangian Stochastic Diffusion Model simulation ammonia volatilization is accomplished by business software WindTrax2.0 (Thunder Beach Scientific, Nova Scotia, Canada exploitation).
The open long light path diode laser absorption spectrometer of table 1 is measured air ammonia concentration sensitivity
| Gas | Sensitivity (ppm-m) | 1m | 10m | 100m |
| Ammonia | 5 | 5 | 0.5 | 0.05 |
2, test design
The milpa of test outside Fengqiu farmland ecosystem country of Chinese Academy of Sciences field science observation study station carries out; The lightweight moisture soil that this ground topsoil soils type is grown for the Yellow River sediment; For avoiding the influence of farmland ammonia volatilization on every side, the test site corn topdresses than moves about 20 days behind local peasant's dressing time.The south wind owing to should prevail season in the locality; So a spectrometer respectively is set in north and south experimental field; The spectrometer of wind direction plume hollow gas ammonia concentration is located at apart from 8m place, volatile source edge under the monitoring volatile source; The spectrometer of monitoring background air ammonia concentration is located at the place that the volatile source upwind is not influenced by volatile source, and the survey line height is made as 2.5m, the long 150m of survey line; Gather weather data in the spectrometer placement with CSAT3 three-D ultrasonic anemoscope (high 3m) simultaneously; The spectrometer data acquiring frequency is 3 times/second, and ammonia concentration and weather data are all got 30min mean value.
3, ammonia volatilization is calculated
The weather data that ammonia concentration value and three-D ultrasonic anemoscope are measured (three-dimensional wind speed u, v, w (m/s), temperature T (℃), variance<u ' ^2>,<v ' ^2>,<w ' ^2>(m/s)
2,<t ' ^2>(℃
2), covariance<u ' v ′>,<u ' w ′>,<v ' w ′>(m/s)
2,<u ' T ′>,<v ' T ′>,<w ' T ′>(℃ m/s)) Input Software WindTrax2.0, software can calculate voluntarily friction wind speed u* (m/s), air stability length L (m), wind direction β (°) and surfaceness Z
o(cm), then software based on the theory of four calculation of parameter gas concentrations and rate of volatilization than (C/Q)
Sim, and then with (C/Q)
SimCalculate ammonia volatilization speed Q with the ammonia concentration value:
Wherein, C is a monitoring point gas mean concentration, μ gm
-3C
bBe background gas concentration, μ gm
-3Reject friction wind speed u*≤0.15m/s (wind speed is on the low side) or air stability Monin-Obukhov length L: | the analogue value in L|≤2m (atmosphere stabilizer pole or extremely unstable) period.
4, test findings
4.1 ammonia volatilization diurnal variation
As shown in Figure 1; Ammonia volatilization speed raise from about 7 o'clock 30 minutes to 9 o'clock gradually, reduced gradually to about 10 o'clock afterwards, possibly be because north dew condensation at night in summer; The ammonia of volatilization at night is dissolved in and is difficult in the dew to external diffusion; And in morning next day, along with the disappearance of dew, be dissolved in wherein ammonia also thereupon the diffusion due to; Ammonia volatilization speed raise gradually from 10 o'clock to 14 o'clock; Reach peak value in a few days, this raises with temperature, and to have improved gas diffusivity relevant, reduces rapidly subsequently; Possibly be since high-intensity ammonia volatilization to make in the soil that ammonia nitrogen transforms under-supply, the ammonia volatilization substrate is supplied in to due to the restriction factor.
4.2 ammonia volatilization interdiurnal change
Can be found out that by Fig. 2 fertilising back ammonia volatilization speed raises very fast, be peaking next day after fertilising, but the volatilization peak period time is shorter, mainly concentrates on preceding four days.Ammonia volatilization is influenced by temperature mainly early stage, and diurnal variation is bigger, also receives soil NH simultaneously
4 +-N content influence changes bigger in the daytime; Later stage mainly receives soil NH
4 +-N content influence, diurnal variation and change in the daytime less.The relation that this shows ammonia volatilization and temperature receives the regulation and control of substrate supply.
Embodiment 2:
1, test apparatus
Ammonia concentration determination is with example 1; Adopt vane anemoscope mensuration 0.8,1.6,2.5,3.5 and 5m highly to locate wind speed in the spectrometer placement, measure the wind direction and the temperature at equal height place simultaneously, one group of data of per 30 seconds records.Reverse Lagrangian Stochastic Diffusion Model simulation ammonia volatilization is accomplished by business software WindTrax2.0 (Thunder Beach Scientific, Nova Scotia, Canada exploitation).
2, test design
The bare area of test behind the Chinese Academy of Sciences Fengqiu farmland ecosystem country outer harvest corn in field science observation study station carried out, the district that does experiment, the circular plot of marking radius at about 100 mu center, farmland and be 20m, and urea is spread fertilizer over the fields on the face of land of pouring water afterwards.The northwester owing to should prevail season in the locality; So experimental field with the east spectrometer (apart from 5m place, volatile source edge) is set respectively in the south in circle, measure volatilization ammonia concentration, the while establishes a spectrometer and surveys background ammonia concentration on north; The survey line height is made as 1.0m, the long 80m of survey line; The spectrometer data acquiring frequency is 3 times/second, and ammonia concentration and weather data are all got 30min mean value.Do contrast with mass balance method and venting method simultaneously and measure ammonia volatilization.
3, ammonia volatilization is calculated
Ammonia concentration value and section meteorological system are measured five highly the wind speed (m/s), wind direction at place (°), temperature (℃) Input Software WindTrax2.0, software can calculate voluntarily the wind speed u* (m/s) that rubs, air stability length L (m), wind direction β (°) and surfaceness Z
o(cm), then software based on the theory of four parameter estimation gas concentrations and rate of volatilization than (C/Q)
Sim, and then with (C/Q)
SimCalculate ammonia volatilization speed Q with the ammonia concentration value:
Wherein, C is a monitoring point gas mean concentration, μ gm
-3C
bBe background gas concentration, μ gm
-3Reject friction wind speed u*≤0.15m/s (wind speed is on the low side) or air stability Monin-Obukhov length L: | the analogue value in L|≤2m (atmosphere stabilizer pole or extremely unstable) period.
4, test findings
In farmland ammonia volatilization monitoring, the mass balance method is generally believed it is ammonia volatilization assay method more accurately, commonly usedly makes the reference method that ammonia volatilization is measured.Can find out that by Fig. 3 absorption spectrum-reverse Lagrangian method monitoring ammonia volatilization speed and mass balance method 1:1 linearly dependent coefficient are 0.95, with venting method be 0.71.Absorption spectrum-reverse Lagrangian method monitoring accumulative total ammonia volatilization amount specific mass balancing method is low by 6%, and is higher by 22% than venting method.Absorption spectrum-reverse Lagrangian method is more consistent with mass balance method monitoring result, and is bigger with venting method monitoring result gap.This possibly be because preceding two kinds of methods all belong to the micrometeorology method; Directly measure ammonia concentration or collected specimens in its air above the test site and measure, can measure the situation of ammonia volatilization under environment, the field of the large tracts of land measurement integrally full-scale condition in not disturbance; And venting method belongs to static chamber method; Incomplete same under indoor ammonia volatilization process and the state of nature; Ignored the ammonia volatilization convective motion; Temperature, wind speed, humidity, illumination etc. differ bigger with true environment in the device in addition, and this test is the surface fertilising, and it is bigger that ammonia volatilization is influenced by temperature, wind speed etc.Test card Benq is in the ammonia volatilization monitoring technology monitor large-area farmland ammonia volatilization effectively of open long light path diode laser absorption spectrum technology and reverse Lagrangian Stochastic Diffusion Model.
Claims (7)
1. based on the farmland ammonia volatilization method of real-time of laser absorption spectrum technology, it is characterized in that determination step is:
A. adopt open long light path diode laser absorption spectrometer to measure ammonia concentration value in volatile source upwind and the following wind direction place air simultaneously;
B. obtain three-dimensional wind speed, temperature and wind direction weather data in the spectrometer placement with three-D ultrasonic anemoscope or section meteorological system mensuration simultaneously;
C. with step a gained ammonia concentration value and step b gained weather data; Import reverse Lagrangian Stochastic Diffusion Model software WindTrax2.0; Movement locus through the inverse analog gas particle from volatile source to the gas concentration monitoring location, the theory that calculates gas concentration and rate of volatilization is than (C/Q)
Sim, gaseous volatilization speed Q can be obtained by computes:
The μ gm of unit
-2S
-1, wherein, C is a monitoring point gas mean concentration, the μ gm of unit
-3C
bBe background gas concentration, the μ gm of unit
-3
D. according to the gaseous volatilization velocity simulation numerical value of weather data rejecting abnormalities, obtain farmland ammonia volatilization rule and monitor in real time with accumulation ammonia volatilization amount data completion farmland ammonia volatilization.
2. according to the said farmland ammonia volatilization method of real-time of claim 1 based on the laser absorption spectrum technology; It is characterized in that the open long light path diode laser absorption spectrometer of said employing measures the method for ammonia concentration value in volatile source upwind and the following wind direction place air simultaneously and be: 5m to 20m establishes at the place spectrometer monitoring volatilization plume hollow gas ammonia concentration to wind direction apart from the volatile source edge under volatile source, establishes a spectrometer in the place that the volatile source upwind is not influenced by volatile source and monitors background air ammonia concentration; Survey line is long select 100m to 200m all can, following wind direction place survey line is vertical with the plume center line that volatilizees, upwind place survey line is parallel with following wind direction place survey line; The survey line height is made as 1.0m to 1.5m; The spectrometer data acquiring frequency is 2～3 times/second, the ammonia concentration data calculating mean value of every 15min to 120min.
3. according to the said farmland ammonia volatilization method of real-time of claim 1 based on the laser absorption spectrum technology; It is characterized in that said weather data assay method is: adopt the three-D ultrasonic anemoscope to obtain three-dimensional wind speed and temperature record in the spectrometer placement, three-dimensional anemoscope height is at 2m to 3m; Perhaps adopt section meteorological system to measure differing heights wind speed, temperature, wind direction data, survey five differing heights weather datas at least, each height is between 0.5m to 10m; The weather data calculating mean value time interval that obtains is identical with the ammonia concentration data.
4. according to the said farmland ammonia volatilization method of real-time of claim 1 based on the laser absorption spectrum technology; It is characterized in that said reverse Lagrangian Stochastic Diffusion Model estimation ammonia volatilization method is: the basis of reverse Lagrangian Stochastic Diffusion Model is a Monin – Obukhov similarity theory, need obtain four indexs when therefore using this model: friction wind speed u*, air stability length L, wind direction β and surfaceness Z
o, it can be imported reverse Lagrangian Stochastic Diffusion Model software WindTrax2.0 by the weather data that the front obtains and calculate; Model based on the theory of four calculation of parameter gas concentrations and rate of volatilization than (C/Q)
Sim, with (C/Q)
SimCan calculate ammonia volatilization speed with the ammonia concentration data.
5. according to the said farmland ammonia volatilization method of real-time of claim 1, it is characterized in that said method according to weather data rejecting abnormalities simulation value is: reject friction wind speed u*≤0.15m/s or air stability Monin-Obukhov length L based on laser absorption spectrum technology: | the analogue value in L|≤2m period.
6. according to the said farmland ammonia volatilization method of real-time of claim 2, it is characterized in that it is the survey line height that said survey line height is got spectrometer transmitter height, corner reflector height and survey line mid point height flat average based on the laser absorption spectrum technology.
7. according to the said farmland ammonia volatilization method of real-time of claim 2, it is characterized in that with said acquisition time 30min ammonia concentration data calculating mean value based on the laser absorption spectrum technology.
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| CN105628631A (en) * | 2015-12-28 | 2016-06-01 | 天津科技大学 | Rapid detection method of biological catalytic conversion rate of hydrocortisone |
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| CN110987972A (en) * | 2019-11-22 | 2020-04-10 | 南京理工大学 | Near-earth atmosphere SO based on millimeter wave radiometer2Monitoring method |
| CN110987972B (en) * | 2019-11-22 | 2022-07-08 | 南京理工大学 | Near-earth atmosphere SO based on millimeter wave radiometer2Monitoring method |
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