CN109596679B - Detection apparatus for on-spot short-term test soil heavy metal content - Google Patents
Detection apparatus for on-spot short-term test soil heavy metal content Download PDFInfo
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Abstract
The invention provides a detection device for rapidly detecting the heavy metal content in soil on site, which is completely different from the prior art principle, and comprises: the device comprises a sensor, a programmable signal generator, a current sampler, a voltage sampler, an instrument amplifier, an A/D converter, an interface circuit, an MCU, input equipment, a temperature control module and a power supply module; the sensor is also internally provided with an electric heater and a thermocouple; during detection, the collected soil sample is filled in the sensor. The heavy metal content of the soil can be inverted according to the shapes of the Cp-f curve and the Tan (Delta) -f curve of the soil sample obtained by measurement.
Description
Technical Field
The invention relates to a detection device for rapidly detecting the heavy metal content in soil on site.
Background
The heavy metal pollution of the soil refers to the phenomenon that the content of heavy metal in the soil is obviously higher than a background value and causes the existing or potential soil quality degradation and ecological and environmental deterioration because the heavy metal is brought into the soil due to natural reasons or human activities. The heavy metal sources of soil are wide, and mainly comprise atmospheric dust fall, sewage irrigation, improper stacking of industrial solid wastes, mining activities, pesticides, chemical fertilizers and the like. In the industry using heavy metals and materials containing heavy metals as raw materials for production, the heavy metals can be discharged in the production process, and if the heavy metals are not properly disposed, environmental pollution can be caused.
Heavy metal pollution in soil seriously harms human health. Lead, cadmium, mercury, arsenic and other heavy metals are enriched in the human surrounding environment due to the development of industrial activities, enter the human body through atmosphere, water, food and the like, and are accumulated in certain organs of the human body to cause chronic poisoning and harm to the health of the human body.
In the process of preventing, monitoring and treating heavy metal pollution of soil, the detection of the content of heavy metal in the soil is a very important link. The quantitative detection and analysis technology of heavy metals generally comprises the following steps: ultraviolet spectrophotometry (UV), Atomic Absorption Spectroscopy (AAS), Atomic Fluorescence (AFS), Inductively Coupled Plasma (ICP), X-ray fluorescence spectroscopy (XRF), and inductively coupled plasma mass spectrometry (ICP-MS). In addition to the above methods, there is also spectroscopic detection. Also, X-ray fluorescence spectroscopy (XRF) was used for analysis.
The atomic absorption spectrometry is a new instrument analysis method established in the 50 th generation of the 20 th century, is complementary with the atomic emission spectrometry mainly used for the qualitative analysis of inorganic elements, and has become a main means for the quantitative analysis of elements of inorganic compounds.
The atomic absorption analysis process is as follows: preparing a sample into a solution (blank at the same time); preparing a series of calibration solutions (standards) of known concentrations of the analytical elements; sequentially measuring corresponding values of the blank and the standard sample; drawing a correction curve according to the corresponding value; measuring the corresponding value of the unknown sample; and obtaining the concentration value of the sample according to the calibration curve and the corresponding value of the unknown sample.
The ultraviolet visible spectrophotometry (UV) detection principle is as follows: the heavy metal and the color developing agent are usually organic compounds, and can generate complex reaction on the heavy metal to generate colored molecular groups, and the color depth of the solution is in direct proportion to the concentration. Colorimetric detection at a specific wavelength. There are two kinds of spectrophotometric analysis, one is to measure the absorption of ultraviolet and visible light by the material itself; the other is to generate a colored compound, i.e., "color development", which is then measured.
Atomic Fluorescence Spectroscopy (AFS) is a method for measuring the content of an element to be measured by measuring the intensity of fluorescence emission generated by atomic vapor of the element to be measured under irradiation with energy at a specific frequency. Atomic fluorescence spectroscopy is an emission spectroscopy, but is closely related to atomic absorption spectroscopy, and has the advantages of both atomic emission and atomic absorption analysis methods.
The electrochemical method is based on the classical polarographic method, and on the basis, oscillographic polarography, anodic stripping voltammetry and other methods are derived. Anodic stripping voltammetry is an electrochemical analysis method combining potentiostatic electrolytic enrichment with voltammetry measurement. Anodic stripping voltammetry measurements were carried out in two steps. The first step is "electrowinning", i.e. electrowinning the ions to be measured at a constant potential, concentrating on the working electrode and mercury on the electrode to form an amalgam. The second step is "stripping", i.e. after the end of enrichment, typically after standing for 30s or 60s, applying a reverse voltage to the working electrode, from a negative positive scan, reoxidizing the metal in the amalgam into an ionic return solution, generating an oxidation current, and recording a voltage-current curve, i.e. a voltammetry curve. The curve is peak-shaped, the peak current is in direct proportion to the measured concentration in the solution and can be used as the basis of quantitative analysis, and the peak potential can be used as the basis of qualitative analysis.
X-ray fluorescence spectroscopy (XRF) is a method of qualitatively or quantitatively determining components in a sample using the change in the absorption of X-rays by the sample with and how much the components in the sample change. When a sample is irradiated by x-rays, high-energy particle beams, ultraviolet light and the like, high-energy particles or photons collide with atoms of the sample, electrons in inner layers of the atoms are ejected to form holes, the atoms are in an excited state, the ion life of the excited state is short, when the electrons in the outer layers transit to the holes in the inner layers, redundant energy is emitted in the form of the x-rays, new holes are generated in the outer layers, new x-ray emission is generated, and therefore a series of characteristic x-rays are generated. Characteristic x-rays are inherent to various elements and are related to the atomic coefficients of the elements. So as long as the wavelength λ of the characteristic x-ray is measured, the element that produces that wavelength can be determined.
Inductively coupled plasma mass spectrometry (ICP-MS) consists of three parts, an ICP torch as the ion source, an interface device and a mass spectrometer as the detector. The ionization source used by ICP-MS is Inductively Coupled Plasma (ICP), the main body of the ICP-MS is a torch tube consisting of three layers of quartz sleeves, a load coil is wound on the upper end of the torch tube, the three layers of tubes are respectively communicated with carrier gas, auxiliary gas and cooling gas from inside to outside, and the load coil is coupled and powered by a high-frequency power supply to generate a magnetic field vertical to the plane of the coil. If the argon gas is ionized by the high frequency device, the argon ions and electrons collide with other argon atoms under the action of the electromagnetic field to generate more ions and electrons, and eddy current is formed. The strong current generates high temperature, and the argon is instantly formed into a plasma torch with the temperature of 10000 k. The sample to be analyzed is introduced into the argon gas stream, usually in the form of an aerosol of an aqueous solution, and then enters the central region of an argon plasma at atmospheric pressure excited by radio frequency energy, the high temperature of which causes desolvation, vaporization dissociation and ionization of the sample. Part of the plasma enters the vacuum system through different pressure zones, and positive ions are pulled out and separated according to the mass-to-charge ratio in the vacuum system.
In the detection methods, the adopted instruments and equipment are precise, expensive and large in size, and need to be fixed and used after being installed and debugged in a laboratory, and cannot be carried about for use.
When the heavy metal pollution condition of soil needs to be detected and analyzed quickly, a detection instrument and a detection method which can be used for field detection, are convenient to carry and are low in cost are urgently needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a brand-new detection instrument and a measurement method for the heavy metal content in soil, which are completely different from the prior art.
The specific technical scheme for realizing the purpose of the invention is as follows:
the utility model provides a detection apparatus for on-spot short-term test soil heavy metal content, includes:
the device comprises a sensor, a programmable signal generator, a current sampler, a voltage sampler, an instrument amplifier I, an instrument amplifier V, an A/D converter I (ADC-I), an A/D converter V (ADC-V), an interface circuit, an MCU (micro control Unit, Microcontroller Unit; MCU, also called a single-chip microcomputer), an input device, a temperature control module and a power supply module; the sensor is also internally provided with an electric heater and a thermocouple; during detection, the collected soil sample is filled in the sensor;
the input device is electrically connected to the MCU, the controlled input end of the programmable signal generator is electrically connected to the MCU, the signal output end of the programmable signal generator is electrically connected to the sensor, the current sampler is electrically connected with the sensor, the voltage sampler is electrically connected with the signal input end of the instrument amplifier I, the voltage sampler is electrically connected with the signal input end of the instrument amplifier V, the signal output end of the instrument amplifier I is electrically connected to the analog signal input end of the A/D converter I (namely ADC-I), the signal output end of the instrument amplifier V is electrically connected to the analog signal input end of the A/D converter V (namely ADC-V), and the digital signal output end of the A/D converter I and the digital signal output end of the A/D converter V are both electrically connected to the MCU through the interface circuit;
current samplers are usually made up of a small resistor in series with the sensor; the voltage sampler is usually made up of a tapped large resistor in parallel with the sensor; wherein the resistance value of the small resistor is significantly less than the resistance value of the soil sample, and the resistance value of the large resistor is significantly greater than the resistance value of the soil sample; the resistance values of the small and large resistors are determined by the accuracy of the measurement;
the sensor comprises a pair of parallel round sheet-shaped metal plates, and each metal plate is connected with an alternating current signal input end and a signal output end of the programmable signal generator; an electric heater and a thermocouple are also arranged in each metal plate, namely two electric heaters and two thermocouples are arranged in the sensor; the electric heater and the thermocouple extend out of the metal plate through the lead wires, and the electric heater and the lead wires are electrically insulated from the metal plate, namely the electric heater and the lead wires are provided with insulating sleeves; the electric heater and the thermocouple are connected to the temperature control module through leads, so that the temperature of the soil sample is kept at a temperature value preset by the MCU during detection;
the input device is used for inputting preset measurement parameters and detection instructions to the MCU;
the programmable signal generator can receive an instruction sent by the MCU and generate an alternating current signal with frequency and amplitude preset by the MCU according to the instruction sent by the MCU; during detection, presetting the generated alternating current signal as an alternating current signal with frequency f changing along with time t and amplitude keeping unchanged;
the programmable signal generator outputs the alternating current signal to the sensor to detect the soil sample;
during detection, the MCU also sends an instruction to the temperature controller to enable an electric heater arranged in the sensor to work and control the temperature value of the sensor to be maintained at a preset value;
the AC current signal passing through the sensor passes through a current sampler and then is output to an instrument amplifier I for amplification, and then an A/D converter I converts the amplified analog signal into a digital signal to obtain the digital value of the AC current signal passing through the sensor; alternating voltage signals at two ends of the sensor pass through a voltage sampler and are output to an instrument amplifier V for amplification, and an A/D converter V converts the amplified analog signals into digital signals to obtain digital values of the alternating voltage signals at two ends of the sensor; the digital value of the alternating current signal passing through the sensor and the digital values of the alternating voltage signals at two ends of the sensor are transmitted to the MCU in real time through the interface circuit and are stored by the MCU in real time, the MCU also calculates the apparent capacitance real part Cp, the apparent capacitance imaginary part Cp' and the loss tangent value Tan (Delta) of the soil sample according to the amplitude and the phase of the alternating current signal passing through the sensor and the alternating voltage signals at two ends of the sensor, and simultaneously stores the calculation result in real time;
when the heavy metal content of the soil sample is detected, the MCU normalizes an apparent capacitance real part-frequency curve, namely a Cp-f curve and a loss tangent value-frequency curve, namely a Tan (Delta) -f curve of the soil sample, identifies the characteristic degree of the normalized curve, automatically matches the normalized curve with a curve in a standard curve library prestored in a memory arranged in the MCU, and obtains the heavy metal content of the collected soil sample by referring to a numerical value in the standard curve library, wherein the standard curve library records the normalized apparent capacitance real part-frequency curve, namely the Cp-f curve and the loss tangent value-frequency curve, namely the Tan (Delta) -f curve of a plurality of standard soil samples which are measured in advance and have different heavy metal contents.
Each curve in the standard curve library, from daily work: when the heavy metal content in the soil is detected by adopting any one of an ultraviolet spectrophotometry (UV), an atomic absorption method (AAS), an atomic fluorescence method (AFS), an inductively coupled plasma method (ICP), an X fluorescence spectrum (XRF) and an inductively coupled plasma mass spectrometry (ICP-MS), the technical scheme of the invention is adopted to measure the real part-frequency curve of the apparent capacitance of the soil sample, namely a Cp-f curve, and the loss tangent value-frequency curve, namely a Tan (Delta) -f curve, and the measured Cp-f curve, the Tan (Delta) -f curve, the corresponding heavy metal species and the content of the heavy metal of the soil sample are recorded into a standard curve library.
Preferably, the sensor comprises a pair of parallel metal plates, each of the pair of parallel metal plates being in the form of a thin circular sheet;
preferably, the thin sheet metal plate has a dimension in the order of centimeters and a thickness in the order of millimeters;
preferably, the input device includes a keyboard, buttons, touch screen, or the like;
the two electric heaters may be electrically connected to the temperature control module in series or in parallel;
a Micro Control Unit (MCU), also called a Single Chip Microcomputer (Single Chip Microcomputer) or a Single Chip Microcomputer (MCU), is to reduce the frequency and specification of a Central Processing Unit (CPU), and integrate peripheral interfaces such as memory, counter (Timer), USB, a/D conversion, UART, PLC, DMA, etc., and even an LCD driving circuit on a Single Chip to form a Chip-level computer, which is controlled by different combinations for different applications.
The measurement principle of the present invention is described as follows:
when the solid medium is subjected to the action of an external electric field, an electric polarization effect can occur, and the electric action and influence are shown in an electric polarization mode with the misaligned positive and negative charge centers; the main role played in this is the bound charge (positive and negative ions in the solid matter, extra-nuclear electrons bound by the nucleus). The electric polarization rule of bound charges in the solid medium under the action of an electric field is closely related to the microstructure of the medium.
The basic process of electrical polarization is three: firstly, the distortion polarization of electron cloud outside the nucleus; (relative) displacement polarization of positive and negative ions in molecules; and the steering polarization of the inherent electric moment of the molecule. Under the action of an external electric field, the dielectric constant epsilon of the medium comprehensively reflects the macroscopic physical quantities of the three microscopic processes; it is a function epsilon (f) of the frequency f.
Only at frequencies of zero or very low frequencies (e.g. 200Hz) are the three microscopic processes involved, where the dielectric constant ε (0) is a constant for a given dielectric, known as the dielectric constant, which is the electrostatic dielectric constant ε s or the low frequency dielectric constant. The polarization of the molecular intrinsic electric moment gradually lags the change of the external field as the frequency increases, and the dielectric constant takes the form of a complex number epsilon (omega) -epsilon ' (f) -j epsilon ' (f), wherein the imaginary part epsilon ' (omega) represents the dielectric loss; (although the capacitance of a dielectric varies with frequency, the "dielectric constant" is not a constant, but the term "dielectric constant" is often used in the art); it is caused by the fact that the electric polarization process does not follow the change of the external field. The real part drops significantly with increasing frequency and the imaginary part peaks. The frequency increases again, the real part ε' (f) decreases to a new value, and the imaginary part ε "(f) becomes zero, indicating that the steering polarization of the molecular intrinsic electric moment has failed to respond. When the frequency enters an infrared region and the vibration frequency of positive and negative ion electric moments in molecules and an external field resonate, the real part epsilon '(f) is suddenly increased and then suddenly decreased, and the epsilon' (f) has a peak value; after that, the displacement polarization of the positive and negative ions no longer plays a role.
For a solid medium with a compact structure, the solid medium is always defective, and under the action of an external electric field, charged defects jump from one equilibrium position to another equilibrium position, or ions vibrate back and forth in a certain local area, and the effect is equivalent to the turning of an electric moment. Some solids with strong ionicity (bond) have electrostatic dielectric constant s much larger than n2, and the difference is caused by the jump of charged defects under the action of external electric field except the contribution of ion displacement polarization.
It is obviously important to analyze the structure of molecules and solids, the nature of chemical bonds, the rotation of molecules, the vibration of ions, and the like to study the change of dielectric constant with frequency, i.e., study the dispersion relation of dielectric constant, and study dielectric loss, dielectric absorption, and dielectric relaxation.
In the case of a solid medium with defects (particularly impurity ions), under the action of an external electric field, not only an electric polarization process but also a conductance process exists, and a macroscopic conduction current effect is shown.
For a soil sample polluted by heavy metal, because the mass of heavy metal ions is obviously greater than that of ions/atoms of other elements, the frequency response process of ions with different masses in an alternating electric field is obviously different, and in the process that the frequency of the alternating electric field is gradually increased, the heavy metal ions are more and more difficult to follow the direction change of the additional alternating electric field, and the ions with larger masses are more and more; and because the heavy metal ions exist in the soil sample in the form of impurity ions, when the soil sample is subjected to an external electric field, loss caused by conduction current also exists, the resistance effect is shown, the more impurity ions contained in the soil sample, the larger the leakage current is, and the apparent capacitance imaginary part Cp' and the loss tangent value Tan (Delta) are shown to be increased during the test.
In a soil sample polluted by heavy metals, the types and the contents of the heavy metals obviously influence the shapes of a real part of apparent capacitance-frequency curve, namely a Cp-f curve, a loss tangent value-frequency curve, namely a Tan (Delta) -f curve, the distortion degree of the curve shape and the distortion position, and reflect the weight of substances with different components in the soil.
The shapes of a real apparent capacitance part-frequency curve, namely a Cp-f curve and a loss tangent value-frequency curve, namely a Tan (Delta) -f curve of the soil sample obtained by experimental measurement can be inverted to show the heavy metal content of the soil. During inversion, the accuracy of the heavy metal content of the soil depends on the sample abundance degree of the established standard curve library.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
The invention has the beneficial effects that:
compared with the prior art, the technical scheme of the invention has the following remarkable advantages:
the detection instrument can be made to be small in size and portable, and the testing device does not have precise and delicate components such as ultraviolet spectrophotometry (UV), Atomic Absorption Spectroscopy (AAS), Atomic Fluorescence (AFS), Inductively Coupled Plasma (ICP), X fluorescence spectroscopy (XRF) and inductively coupled plasma mass spectrometry (ICP-MS), so that the detection instrument is very suitable for field rapid detection.
Because the processing of normalizing the test data is adopted, the area and the distance of the parallel metal plates are not required to be substituted to convert the dielectric constant in the previous step, and even if the soil sample is compacted between the parallel metal plates, the soil sample is not really and completely filled in the space between the parallel metal plates, and even if partial holes and defects exist, the measurement deviation of the apparent capacitance real part Cp and the apparent capacitance imaginary part Cp' can be brought, but after the normalization processing, the influences disappear, and in the subsequent data processing, the absolute size of the measured values is not required to be considered, but only the shape of the measured curve is required to be considered. This brings convenience to the measurement.
In the ultraviolet spectrophotometry (UV), Atomic Absorption Spectroscopy (AAS), Atomic Fluorescence (AFS), Inductively Coupled Plasma (ICP), X fluorescence spectroscopy (XRF), and inductively coupled plasma mass spectrometry (ICP-MS), no precise and careful pretreatment of the sample is required, and care must be taken in the measurement.
In addition, the technical scheme of the invention is suitable for field rapid detection, and the operation is very simple and convenient, so that the monitoring efficiency in environmental protection work is greatly improved.
Drawings
FIG. 1: the invention relates to a structure diagram of a detection device for rapidly detecting the heavy metal content in soil on site.
FIG. 2: in the sensor of the detection device of the present invention, two electric heaters are incorporated in the sensor as shown by broken lines. The insulating sleeves provided for both the electric heater and the lead wires are not shown, nor are the temperature sensors shown.
FIG. 3: the invention relates to a structure diagram of a power module in a detection device.
FIG. 4: in one embodiment of the invention, the structure diagram of the AT89C51 single chip microcomputer adopted by the programmable signal generator is provided.
Detailed Description
For the convenience of understanding, the technical scheme of the invention is specifically described by combining the examples.
As shown in FIG. 1, a device for rapidly detecting the heavy metal content in soil on site comprises:
the device comprises a sensor, a programmable signal generator, a current sampler, a voltage sampler, an instrument amplifier I, an instrument amplifier V, an A/D converter I (ADC-I), an A/D converter V (ADC-V), an interface circuit, an MCU (micro control Unit, MicroControhr Unit; MCU, also called a single-chip microcomputer), an input device, a temperature control module and a power supply module; the sensor is also internally provided with an electric heater; during detection, the collected soil sample is filled in the sensor;
the input device is electrically connected to the MCU, the controlled input end of the programmable signal generator is electrically connected to the MCU, the signal output end of the programmable signal generator is electrically connected to the sensor, the current sampler is electrically connected with the sensor, the voltage sampler is electrically connected with the signal input end of the instrument amplifier I, the voltage sampler is electrically connected with the signal input end of the instrument amplifier V, the signal output end of the instrument amplifier I is electrically connected to the analog signal input end of the A/D converter I (namely ADC-I), the signal output end of the instrument amplifier V is electrically connected to the analog signal input end of the A/D converter V (namely ADC-V), and the digital signal output end of the A/D converter I and the digital signal output end of the A/D converter V are both electrically connected to the MCU through the interface circuit;
the input device is used for inputting preset measurement parameters and detection instructions to the MCU;
the programmable signal generator can receive an instruction sent by the MCU and generate an alternating current signal with frequency and amplitude preset by the MCU according to the instruction sent by the MCU; during detection, presetting the generated alternating current signal as an alternating current signal with frequency f changing along with time t and amplitude keeping unchanged;
the programmable signal generator outputs the alternating current signal to the sensor to detect the soil sample;
during detection, the MCU also sends an instruction to the temperature controller to enable an electric heater arranged in the sensor to work and control the temperature value of the sensor to be maintained at a preset value;
the AC current signal passing through the sensor passes through a current sampler and then is output to an instrument amplifier I for amplification, and then an A/D converter I converts the amplified analog signal into a digital signal to obtain the digital value of the AC current signal passing through the sensor; alternating voltage signals at two ends of the sensor pass through a voltage sampler and are output to an instrument amplifier V for amplification, and an A/D converter V converts the amplified analog signals into digital signals to obtain digital values of the alternating voltage signals at two ends of the sensor; the digital value of the alternating current signal passing through the sensor and the digital values of the alternating voltage signals at two ends of the sensor are transmitted to the MCU in real time through the interface circuit and are stored by the MCU in real time, the MCU also calculates the apparent capacitance real part Cp, the apparent capacitance imaginary part Cp' and the loss tangent value Tan (Delta) of the soil sample according to the amplitude and the phase of the alternating current signal passing through the sensor and the alternating voltage signals at two ends of the sensor, and simultaneously stores the calculation result in real time;
when the heavy metal content of the soil sample is detected, the MCU normalizes an apparent capacitance real part-frequency curve, namely a Cp-f curve and a loss tangent value-frequency curve, namely a Tan (Delta) -f curve of the soil sample, identifies the characteristic degree of the normalized curve, automatically matches the normalized curve with a curve in a standard curve library prestored in a memory arranged in the MCU, and obtains the heavy metal content of the collected soil sample by referring to a numerical value in the standard curve library, wherein the standard curve library records the normalized apparent capacitance real part-frequency curve, namely the Cp-f curve and the loss tangent value-frequency curve, namely the Tan (Delta) -f curve of a plurality of standard soil samples which are measured in advance and have different heavy metal contents.
As shown in fig. 2, the sensor comprises a pair of parallel circular sheet-shaped metal plates, each of which is connected with an alternating current signal input end, AC1 and AC2 respectively, for connecting to a signal output end of a programmable signal generator; an electric heater is also arranged in each metal plate, namely two electric heaters are arranged in the sensor; the electric heater extends out of the metal plate through the lead, the electric heater and the lead are electrically insulated from the metal plate, namely, the electric heater and the lead are provided with insulating sleeves; the electric heater is connected to the temperature control module through a lead wire, so that the temperature of the soil sample is kept at a temperature value preset by the MCU during detection; the two electric heaters are respectively provided with lead terminals Heater1 and Heater1-1, Heater2 and Heater2-2, the lead terminals Heater1-1 and Heater2-2 are electrically connected together, the lead between Heater1-1 and Heater2-2 is a soft lead, and Heater1 and Heater2 are used for electrically connecting to a temperature controller.
In the connection mode, the two electric heaters are connected in series to the temperature controller.
As shown in fig. 3, the power module includes an AC-DC conversion unit, a DC-DC conversion unit, an isolation transformer, a rectifier, and a filter. The power supply module effectively realizes the electrical isolation between the detection device and the commercial power circuit, and improves the safety. The AC-DC conversion unit generally employs a full bridge rectifier.
When the detection device is used for detecting the heavy metal content in the soil, the steps are as follows:
collecting a soil sample on site; removing patrinia scabiosaefolia and macroscopic broken stone particles during collection; the sampling amount of the soil sample is several grams to ten grams, so that the measurement error is not large because the sample amount is too small, and the excessive time and the excessive electric energy consumed for heating and drying because the sample amount is too large are avoided. Generally, for soil samples of several to ten grams, heating and drying are carried out in a compacted state to a constant weight, generally 3 to 5 minutes are required;
crushing the collected soil sample, directly placing the crushed soil sample between a pair of parallel metal plates of a sensor to apply pressure and compress, scraping redundant parts leaking out of the parallel metal plates by a scraping blade, and preparing into a sheet-shaped sample with the same shape and size as the parallel metal plates;
the MCU sends a heating instruction to the temperature controller, and the compacted soil sample is heated and dried to constant weight in a compacted state; the soil sample is dried to constant weight, so that the moisture contained in the sample is prevented from bringing large errors to subsequent electrical measurement. The temperature for heating and drying the compacted soil sample in a compacted state is between 110 and 120 ℃.
Frequency sweep test: at constant temperatureApplying an alternating electric signal vt with constantly changing frequency on a pair of parallel metal plates of a sensor by using a programmable signal generator to act on a dried soil sample, wherein the frequency f of the alternating electric signal vt output by an alternating signal source changes along with the time t, and the signal amplitude of the alternating electric signal vt keeps unchanged; the programmable signal generator is controlled by an instruction sent by the MCU; in one example, the output alternating electrical signal v of the programmable signal generatortThe frequency f of (2) is changed once every 200ms, the frequency is increased from 100Hz, the difference between every two frequencies is 1.1 times, until the frequency is increased to about 1MHz, and the specific frequency list is as follows:
100Hz, 110Hz, 121Hz, 133.1Hz … …, 777.88KHz, 855.67KHz, 941.23KHz, 1.035MHz, 98 frequency points in total, and 49s of time is needed for the test to be completed.
Detecting and recording the electric parameters of the alternating electric signal passing through the pair of parallel metal plates and the soil sample in real time, wherein the electric parameters comprise an apparent capacitance real part Cp, an apparent capacitance imaginary part Cp', a loss tangent value Tan (Delta) and a frequency f of the alternating electric signal; wherein the loss tangent Tan (Delta) is equal to the ratio of the imaginary apparent capacitance Cp' to the real apparent capacitance Cp;
the MCU respectively derives the data obtained by detection and recording to obtain an apparent capacitance real part-frequency curve, namely a Cp-f curve, and a loss tangent value-frequency curve, namely a Tan (Delta) -f curve; in all the apparent capacitance real part-frequency curves, namely Cp-f curves and loss tangent value-frequency curves, namely Tan (Delta) -f curves, the frequency is logarithmic, namely, logf or lgf; the output alternating electric signal v of the programmable signal generatortThe frequency f is as low as Hz magnitude and as high as MHz magnitude; output alternating electric signal v of alternating signal sourcetThe frequency f of (d) varies as a function of time t as a logarithmic rule;
the MCU normalizes the obtained apparent capacitance real part-frequency curve; the loss tangent Tan (Delta) -frequency f curve is a dimensionless and normalized curve without normalization;
when the heavy metal content of the soil sample is detected, the MCU normalizes an apparent capacitance real part-frequency curve, namely a Cp-f curve and a loss tangent value-frequency curve, namely a Tan (Delta) -f curve of the soil sample, identifies the characteristic degree of the normalized curve, automatically matches the normalized curve with a curve in a standard curve library prestored in a memory arranged in the MCU, and obtains the heavy metal content of the collected soil sample by referring to a numerical value in the standard curve library, wherein the standard curve library records the normalized apparent capacitance real part-frequency curve, namely the Cp-f curve and the loss tangent value-frequency curve, namely the Tan (Delta) -f curve of a plurality of standard soil samples which are measured in advance and have different heavy metal contents. In all the curves of the real part of the apparent capacitance versus frequency, the tangent loss versus frequency, the frequency is logarithmic, i.e., logf or lgf. In the standard curve library, each curve further has additional information, and the additional information includes: all extreme points of the normalized apparent capacitance real part-frequency curve and loss tangent value-frequency curve, zero point of the first derivative curve and zero point of the second derivative curve;
the actual test temperature value is the same as the measured temperature in the standard curve library.
According to practical experience, in a low frequency band, the curves of the apparent real capacitance part Cp-frequency f and the loss tangent Tan (Delta) -frequency f of a sample usually change slowly, if the frequency f changes linearly along with time t, the time consumption is too long and reaches several hours from the hundred Hz magnitude to the megaHz magnitude, and the obtained data volume is too much, so that no obvious change can be seen in the low frequency band; the selection frequency f changes according to the logarithmic rule with the time t, so that only about 1 minute is needed, and the change rule can be shown in each frequency band.
In one example, the programmable signal generator is formed by taking an AT89C51 single chip microcomputer as a core. The internal structure of the AT89C51 single chip microcomputer includes a CPU, a memory, a parallel interface, a serial interface, and a timing counter, and the system structure diagram is shown in fig. 4. Each component of the single chip microcomputer is integrated on one chip, and the functions of the single chip microcomputer are as follows: (1) an eight-bit central processing unit CPU comprises an AIU unit which can carry out 8-bit arithmetic operation and logical operation, an 8-bit accumulator ACC, a register B, a program status register PSW and the like. (2) And the on-chip data storage RAM (128B) is used for storing data which can be read/written, such as intermediate results of operation, final results or data which are displayed in advance. (3) And the on-chip program counter ROM/EPROM is used for storing original data, programs and tables. (4) Four 8-bit parallel I/O interfaces P0-P3 port, each port being available for input or output.
When the detection result reports that the heavy metal content in the soil is remarkably over-standard, the soil marking the sampling area is polluted by the heavy metal, and any one of an ultraviolet spectrophotometry (UV), an Atomic Absorption Spectroscopy (AAS), an atomic fluorescence method (AFS), an inductively coupled plasma method (ICP), an X fluorescence spectrum (XRF) and an inductively coupled plasma mass spectrometry (ICP-MS) is adopted for further identifying the heavy metal type and accurately measuring the content.
It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
Sounding: the patent project of the invention is funded by the fund of the 2017Australian Ohwia research project (2017Australian students in China Program), and here shows thank you.
Claims (9)
1. The utility model provides a detection apparatus for on-spot short-term test soil heavy metal content which characterized in that, detection apparatus includes:
the device comprises a sensor, a programmable signal generator, a current sampler, a voltage sampler, an instrument amplifier I, an instrument amplifier V, an A/D converter I (ADC-I), an A/D converter V (ADC-V), an interface circuit, an MCU (micro control Unit, Microcontroller Unit; MCU, also called a single-chip microcomputer), an input device, a temperature control module and a power supply module; the sensor is also internally provided with an electric heater and a thermocouple; during detection, the collected soil sample is filled in the sensor;
the input device is electrically connected to the MCU, the controlled input end of the programmable signal generator is electrically connected to the MCU, the signal output end of the programmable signal generator is electrically connected to the sensor, the current sampler is electrically connected with the sensor, the voltage sampler is electrically connected with the signal input end of the instrument amplifier I, the voltage sampler is electrically connected with the signal input end of the instrument amplifier V, the signal output end of the instrument amplifier I is electrically connected to the analog signal input end of the A/D converter I (namely ADC-I), the signal output end of the instrument amplifier V is electrically connected to the analog signal input end of the A/D converter V (namely ADC-V), and the digital signal output end of the A/D converter I and the digital signal output end of the A/D converter V are both electrically connected to the MCU through the interface circuit;
the sensor comprises a pair of parallel round sheet-shaped metal plates, and each metal plate is connected with an alternating current signal input end and a signal output end of the programmable signal generator; an electric heater and a thermocouple are also arranged in each metal plate, namely two electric heaters and two thermocouples are arranged in the sensor; the electric heater and the thermocouple extend out of the metal plate through the lead wires, and the electric heater and the lead wires are electrically insulated from the metal plate, namely the electric heater and the lead wires are provided with insulating sleeves; the electric heater and the thermocouple are connected to the temperature control module through leads, so that the temperature of the soil sample is kept at a temperature value preset by the MCU during detection;
the input device is used for inputting preset measurement parameters and detection instructions to the MCU;
the programmable signal generator can receive an instruction sent by the MCU and generate an alternating current signal with frequency and amplitude preset by the MCU according to the instruction sent by the MCU; during detection, presetting the generated alternating current signal as an alternating current signal with frequency f changing along with time t and amplitude keeping unchanged;
the programmable signal generator outputs the alternating current signal to the sensor to detect the soil sample;
during detection, the MCU also sends an instruction to the temperature controller to enable an electric heater arranged in the sensor to work and control the temperature value of the sensor to be maintained at a preset value;
the AC current signal passing through the sensor passes through a current sampler and then is output to an instrument amplifier I for amplification, and then an A/D converter I converts the amplified analog signal into a digital signal to obtain the digital value of the AC current signal passing through the sensor; alternating voltage signals at two ends of the sensor pass through a voltage sampler and are output to an instrument amplifier V for amplification, and an A/D converter V converts the amplified analog signals into digital signals to obtain digital values of the alternating voltage signals at two ends of the sensor; the digital value of the alternating current signal passing through the sensor and the digital values of the alternating voltage signals at two ends of the sensor are transmitted to the MCU in real time through the interface circuit and are stored by the MCU in real time, the MCU also calculates the apparent capacitance real part Cp, the apparent capacitance imaginary part Cp' and the loss tangent value Tan (Delta) of the soil sample according to the amplitude and the phase of the alternating current signal passing through the sensor and the alternating voltage signals at two ends of the sensor, and simultaneously stores the calculation result in real time;
when the heavy metal content of the soil sample is detected, the MCU normalizes an apparent capacitance real part-frequency curve, namely a Cp-f curve and a loss tangent value-frequency curve, namely a Tan (Delta) -f curve of the soil sample, identifies the characteristic degree of the normalized curve, automatically matches the normalized curve with a curve in a standard curve library prestored in a memory arranged in the MCU, and obtains the heavy metal content of the collected soil sample by referring to a numerical value in the standard curve library, wherein the standard curve library records the normalized apparent capacitance real part-frequency curve, namely the Cp-f curve and the loss tangent value-frequency curve, namely the Tan (Delta) -f curve of a plurality of standard soil samples which are measured in advance and have different heavy metal contents.
2. The device for rapidly detecting the content of the heavy metals in the soil on site according to claim 1, wherein:
in a soil sample polluted by heavy metals, the types and the contents of the heavy metals influence the shapes of a Cp-f curve which is a real part of the apparent capacitance and a frequency curve, a Tan (Delta) -f curve which is a loss tangent value and a frequency curve, the distortion degree of the curve shape and the distortion position, and reflect the weight of substances with different components in the soil.
3. The device for rapidly detecting the content of the heavy metals in the soil on site according to claim 1, wherein: the frequency f of the output alternating electric signal vt of the alternating signal source is as low as Hz magnitude and as high as MHz magnitude; the frequency f of the output alternating electrical signal vt of the alternating signal source changes logarithmically with time t.
4. The device for rapidly detecting the content of the heavy metals in the soil on site according to claim 1, wherein: the size of the disk-shaped metal plate of the sensor is centimeter level, and the thickness is millimeter level.
5. The detection device for rapidly detecting the heavy metal content in the soil on site according to any one of claims 1 to 4, wherein: the power supply module comprises an AC-DC conversion unit, a DC-DC conversion unit, an isolation transformer, a rectifier and a filter; the power supply module realizes the electrical isolation between the detection device and the mains supply circuit, and improves the safety; the AC-DC conversion unit adopts a full-bridge rectifier.
6. The detection device for rapidly detecting the heavy metal content in the soil on site according to any one of claims 1 to 4, wherein: two electric heaters built in the sensor are electrically connected in series to the temperature control module.
7. The detection device for rapidly detecting the heavy metal content in the soil on site according to any one of claims 1 to 4, wherein: the programmable signal generator is formed by adopting an AT89C51 singlechip as a core, and the internal structure of the AT89C51 singlechip comprises a CPU, a memory, a parallel interface, a serial interface and a timing counter.
8. The detection device for rapidly detecting the heavy metal content in the soil on site according to any one of claims 1 to 4, wherein: in the standard curve library, each curve further has additional information, and the additional information includes: and all extreme points of the normalized apparent capacitance real part-frequency curve, loss tangent value-frequency curve, zero point of the first derivative curve and zero point of the second derivative curve.
9. The application of the detection device for rapidly detecting the heavy metal content in the soil on site according to any one of claims 1 to 8 is characterized in that: when the detection result reports that the content of heavy metals in the soil is remarkably over-standard, the soil of the marked sampling area is polluted by the heavy metals, and any one of an ultraviolet spectrophotometry (UV), an Atomic Absorption Spectroscopy (AAS), an atomic fluorescence method (AFS), an inductively coupled plasma method (ICP), an X fluorescence spectrum (XRF) and an inductively coupled plasma mass spectrometry (ICP-MS) is adopted for further identifying the types of the heavy metals and accurately determining the content of the heavy metals.
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Effective date of registration: 20230821 Address after: 226000 Jiangsu city of Nantong province sik Road No. 9 Patentee after: Nantong University Technology Transfer Center Co.,Ltd. Address before: 226019 Jiangsu Province, Nantong City Chongchuan District sik Road No. 9 Patentee before: NANTONG University |
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Application publication date: 20190409 Assignee: Nantong Hongjingtian Mechanical Equipment Technology Co.,Ltd. Assignor: Nantong University Technology Transfer Center Co.,Ltd. Contract record no.: X2023980049389 Denomination of invention: A rapid on-site detection device for heavy metal content in soil Granted publication date: 20210209 License type: Common License Record date: 20231203 |