CN115541565A - Detection device and method for heavy metal bioavailability - Google Patents
Detection device and method for heavy metal bioavailability Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention provides a device and a method for detecting the bioavailability of heavy metal. The invention provides a detection device for the bioavailability of heavy metal, which comprises a filtering membrane, a microbial membrane and a shell, wherein the shell comprises an accommodating cavity and an opening for communicating the inside and the outside of the accommodating cavity; from being close to opening one side to keeping away from opening one side, filtration membrane and microbial film stack gradually and set up and hold intracavity portion. On the other hand, the device provided by the invention adopts the in-situ cultured microbial film as the heavy metal stationary phase, monitors the heavy metal in the environment by utilizing the in-situ growth and metabolism process of the microorganism, and realizes the biological effectiveness detection of the heavy metal with low cost, high efficiency and high truth.
Description
Technical Field
The invention relates to a detection device and a use method for heavy metal bioavailability, and relates to the technical field of heavy metal bioavailability detection.
Background
With the development of industrialization and urbanization, sewage, waste gas or solid waste containing heavy metals, such as the use of pesticides and fertilizers containing heavy metals, gold mine exploitation, the discharge of automobile exhaust, the accumulation of waste residues and sludge discharged by metal smelting, and the like, are generated in human production and life; it is generally believed that heavy metals can be harmful to living beings through three processes: the form of heavy metal in external environment, the reaction of heavy metal and biomembrane, heavy metal increase in vivo and then produce the toxic reaction, therefore, relevant workers realize that the total amount of heavy metal can not be accurate the heavy metal pollution situation in the reaction environment, need to combine the biological availability to heavy metal to evaluate the pollution degree, namely heavy metal bioavailability, it is as measuring heavy metal migration and important parameter of ecological effect, play a direct guide role to the risk evaluation of heavy metal in the environment, it is the key index of the technique of repairing heavy metal pollution in situ of assessing the microorganism at the same time.
The detection method of the biological effectiveness of the heavy metal is mainly a chemical extraction method, but the form of the heavy metal is changed in the extraction process, and in addition, the chemical extraction method is based on the equilibrium distribution principle, neglects the migration between a solid phase and a liquid phase, and cannot truly reflect the biological effectiveness of the heavy metal. The Donnan Membrane Technique (DMT) and the gradient in-depth-films Technique (DGT) based on the in-situ chemical extraction process partially solve the problem of in-situ extraction, but the two techniques are mainly based on the chemical extraction and the fixed extraction process, and cannot truly reproduce the biological effectiveness of the heavy metal mediated by microorganisms. Since the biological effectiveness is the capability of the heavy metal to be migrated and converted by organisms, but the currently reported method is mainly based on a chemical extraction mode, the obtained data are indirect data, the migration and conversion way of the microorganisms to the heavy metal is difficult to quantify, and the biological effectiveness of the metal cannot be efficiently and accurately predicted. Therefore, more and more attention is paid to how to develop a heavy metal bioavailability detection technology, and solve the problems that the existing bioavailability analysis method cannot obtain direct data and the migration and transformation approach cannot be quantified.
Disclosure of Invention
The invention provides a detection device and a detection method for heavy metal bioavailability, which are used for solving the problems that the existing bioavailability analysis method cannot obtain direct data and the migration and transformation approach cannot be quantized, and realizing heavy metal bioavailability detection with low cost, high efficiency and high degree of truth.
The invention provides a detection device for the bioavailability of heavy metal, which comprises a filtering membrane, a microbial membrane and a shell, wherein the shell comprises an accommodating cavity and an opening for communicating the inside and the outside of the accommodating cavity;
the microbial film comprises a microbial fixed film and a microbial protective film, the microbial fixed film is positioned close to one side of the opening, the microbial protective film is arranged on one side of the microbial fixed film away from the opening, and the microbial fixed film comprises microbes and a substrate film for fixing the microbes.
In one embodiment, the filter membrane includes a first filter membrane and a second filter membrane, the first filter membrane is located on a side close to the opening, the second filter membrane is located on a side far from the opening, the first filter membrane is a glass fiber membrane, and the second filter membrane is a cation exchange membrane.
In one embodiment, the matrix film comprises sodium alginate, and the microorganism immobilization film comprises chitosan and nutrients required for the growth of the microorganisms.
In one embodiment, the microorganism comprises one or more of urease producing bacteria, carbonic anhydrase producing bacteria, acid producing bacteria, phosphatase producing bacteria, desulfurization microorganisms, denitrification microorganisms, and nitrogen fixing microorganisms.
In one embodiment, the thickness of the microorganism-immobilized membrane is 10 to 100. Mu.m.
In one embodiment, the thickness of the microbial protective film is 10 to 100 μm.
In a specific embodiment, the diameter of the filter membrane and the microbial membrane is the same as the inner diameter of the accommodating cavity.
In one embodiment, the method for preparing the microbial film comprises the following steps:
dispersing sodium alginate in a solvent, sterilizing to obtain a sodium alginate solution, and performing liquid fermentation on microorganisms to obtain a microorganism solution; under the aseptic condition, uniformly mixing the sodium alginate solution and the microbial bacteria solution to obtain a microbial fixing solution, and blade-coating the microbial fixing solution on the surface of the filtering membrane far away from the opening to obtain a microbial fixing membrane;
uniformly mixing chitosan and nutrient substances required by the growth of the microorganisms, and sterilizing to obtain a microorganism protection solution; and under the aseptic condition, the microorganism protection liquid is coated on the surface of the microorganism fixed film far away from the opening by scraping to obtain the microorganism fixed film.
In one embodiment, the OD of the microbial broth 600 Is 0.2-2.
The second aspect of the invention provides a detection method using any one of the devices, wherein an opening of any one of the devices is upward, the opening is immersed in an environment to be detected, heavy metals in the environment to be detected are adsorbed by microorganisms, and after adsorption is finished, the device is taken out to detect the heavy metals adsorbed by the microorganisms;
the environment to be detected is one or more of water, soil and sediment.
The invention provides a detection device and a detection method for heavy metal bioavailability, which adopt an in-situ culture microbial film as a heavy metal stationary phase, monitor heavy metal in the environment by utilizing the in-situ growth and metabolism process of microorganisms, can obtain direct information and data of heavy metal bioavailability, solve the problems that the prior bioavailability analysis method cannot obtain direct data and the migration and transformation path cannot be quantized, and realize the heavy metal bioavailability detection with low cost, high efficiency and high degree of truth.
The device and the method for detecting the biological effectiveness of the heavy metal have better applicability, and can evaluate the capability of the microorganism for repairing the heavy metal pollution in situ by adopting typical microorganisms in a specific environment as a component of a fixed membrane.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
Fig. 1 is an assembly schematic diagram of a detection apparatus according to an embodiment of the invention;
FIG. 2 is a diagram showing the morphology of metallic nickel in the microorganism-immobilized phase in example 1 of the present invention;
FIG. 3 is an EDS energy spectrum of the stationary phase spot1 of the microorganism in example 1 of the present invention;
FIG. 4 is an EDS energy spectrum of the stationary phase spot2 of the microorganism in example 1 of the present invention;
FIG. 5 is a linear fit graph of diffusion coefficients of heavy metal nickel measured using staphylococci as the stationary phase of the microorganism in example 1 of the present invention;
fig. 6 is a schematic view of an adsorption effect of the detection apparatus provided in embodiment 1 of the present invention on heavy metal nickel in different pH environments;
fig. 7 is a schematic view of an adsorption effect of the detection apparatus provided in embodiment 1 of the present invention on heavy metal nickel in environments with different ionic strengths.
Description of reference numerals:
1-a filtration membrane;
11-a first filter membrane;
12-a second filter membrane;
2-a microorganism fixed film;
3-microbial protective film;
4-a shell;
41-opening.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is an assembly schematic diagram of a detection apparatus provided in an embodiment of the present invention, as shown in fig. 1, the detection apparatus includes a housing 4, the housing 4 includes a containing cavity and an opening 41 communicating the inside and the outside of the containing cavity, a substance exchange between the inside and the outside of the containing cavity can be realized through the opening 41, a filtering membrane 1, a microorganism fixing membrane 2, and a microorganism protecting membrane 3 are sequentially stacked and arranged in the containing cavity from a side close to the opening 41 to a side far from the opening 41, and diameters of the filtering membrane 1, the microorganism fixing membrane 2, and the microorganism protecting membrane 3 are the same as an inner diameter of the containing cavity; in the assembling process, the filtering membrane 1, the microorganism fixing membrane 2 and the microorganism protective membrane 3 are placed at the bottom of the shell 4 according to the sequence shown in figure 1, because the upper cover and the lower cover at the left side and the right side of the shell 4 are provided with threads, the filtering membrane 1, the microorganism fixing membrane 2 and the microorganism protective membrane 3 are tightly combined by screwing the upper cover and the lower cover, after air bubbles between the membranes are discharged, the assembly of the heavy metal biological effectiveness detection device is completed, and the following parts are elaborated in detail:
The microorganism fixed film 2 comprises microorganisms and a substrate film for fixing the microorganisms, the microorganisms carry out biological immobilization on heavy metal cations passing through the first filtering film 11 and the second filtering film 12 under the action of metabolites and thalli, so that the heavy metals in the environment to be detected are monitored by utilizing the in-situ growth metabolic process of the immobilized microorganisms in the substrate film, and the direct information and data of the biological effectiveness of the heavy metals are obtained.
In a specific embodiment, the substrate membrane comprises sodium alginate, the sodium alginate is used as a polysaccharide compound with negative charges, and has the characteristics of stability, solubility, viscosity and safety, the carrier material used as a microorganism immobilization carrier has the advantages of no biotoxicity, good mass transfer performance and convenience in immobilization, and meanwhile, the sodium alginate has a strong complexing effect on heavy metals, and can provide driving force for the heavy metal cations to pass through the first filtering membrane 11 and the second filtering membrane 12, so that the immobilization effect of microorganisms on the heavy metal cations is strengthened, in addition, the sodium alginate as the substrate membrane can be adhered to the surface of the second filtering membrane 12, and the preparation of the microorganism immobilization membrane 2 is facilitated.
The microorganisms can be microorganisms in an environment to be detected, for example, the biological effectiveness of heavy metals in a certain water body environment needs to be detected, the microorganisms in the water body environment are firstly obtained by adopting the conventional technical means in the field, then are cultured in a laboratory, and finally are fixed in the microorganism fixed film 2, and the biological effectiveness of the microorganisms to the heavy metals in the water body environment is detected.
In addition, the microorganism fixed film provided by the invention can fix microorganisms with heavy metal restoration capacity, such as one or more of urease-producing bacteria, carbonic anhydrate bacteria, acid-producing bacteria, phosphatase-producing bacteria, desulfurization microorganisms, denitrification microorganisms and nitrogen fixation microorganisms, and can detect the utilization rate of the microorganisms to heavy metal ions by adding the microorganisms with specific functions, thereby evaluating the restoration capacity of the microorganisms to heavy metal pollution.
Considering that the mass transfer between the heavy metal ions and the microorganisms is affected by the excessively high thickness of the microorganism immobilization membrane 2, the heavy metal immobilization process of the microorganisms is also severely interfered by the excessive sodium alginate, and the detection accuracy of the biological effectiveness of the heavy metals is affected by the load of the microorganisms and the excessively low thickness of the microorganism immobilization membrane 2, the thickness of the microorganism immobilization membrane 2 is 10-100 μm, and further 20 μm.
In one embodiment, the method for preparing the microorganism-immobilized membrane 2 comprises the steps of:
because sodium alginate is easy to decompose in the microbial fermentation process, and the viscosity of sodium alginate is high, the sodium alginate is not suitable to be directly added into the microbial fermentation liquid, the sodium alginate solution is obtained by dissolving the sodium alginate in deionized water and sterilizing; in order to further obtain the microbial immobilized membrane with satisfactory mechanical strength, the concentration of sodium alginate is not too low, but too high concentration is not easy to coat, so that the volume-to-mass ratio of deionized water to sodium alginate is 100mL: (0.5-8) g, further 50mL:4g of the total weight.
The microorganism to be immobilized is subjected to liquid fermentation by means of conventional techniques in the art, and when at least two microorganisms are included, different microorganisms may be subjected to separate liquid fermentation or mixed liquid fermentation to wait for OD of microorganism fermentation liquid 600 And finishing fermentation after reaching 0.2-2 to obtain fermentation liquor containing microbial thalli.
under the aseptic condition, uniformly mixing the microbial fermentation liquid obtained in the step 1 with a sodium alginate solution to obtain a microbial stationary liquid; in order to ensure that microorganisms are uniformly dispersed and have moderate concentration in the sodium alginate and simultaneously to ensure that the sodium alginate solution is convenient for scraping a membrane and forming a microorganism fixed membrane, the volume ratio of the microorganism fermentation liquid to the sodium alginate solution is 1: (2-20), the viscosity of the microorganism stationary liquid obtained after uniform mixing is 0.2-1.0 Pa.s, and the volume ratio of the microorganism fermentation liquid to the sodium alginate solution is 1.
And under an aseptic condition, carrying out blade coating on the microorganism fixing liquid to one surface of the second filtering membrane, and standing to obtain the microorganism fixing membrane 2.
The microorganism protection film 3 comprises chitosan and nutrient substances required by microorganism growth, and is arranged on one side of the microorganism fixed film 2 far away from the opening 41, the chitosan is a polycation compound and can interact with a sodium alginate polyanion compound, wherein chitosan molecules contain a large amount of primary amino groups, and sodium alginate molecules contain a large amount of carboxyl groups, and the chitosan and the sodium alginate can form polyelectrolyte through electrostatic acting force, on one hand, the interaction can weaken the immobilization effect of the sodium alginate on heavy metals and improve the accuracy of the microorganism for fixing the heavy metals, and meanwhile, the polyelectrolyte layer generated by the reaction is positioned on the contact surface of the microorganism protection film 3 and the microorganism fixed film 2, and the polyelectrolyte layer with a cross-linked structure can improve the strength and the mechanical property of the microorganism fixed film 2, ensure the structural integrity of the fixed film, and further improve the immobilization effect of the microorganism and the uniformity of the heavy metals in the migration process of the fixed film; in addition, the nutrient substances in the protective film can provide carbon sources, nitrogen sources and other trace elements required by the growth of the microorganisms for the growth of the microorganisms, and specific components can be added according to the types of the microorganisms.
Since the excessively thick microbial protective film 3 affects the migration and fixation of heavy metals in the microbial stationary phase by the reaction between the polycation and the polyanion, and the excessively thin microbial protective film 3 cannot provide sufficient nutritional components and sufficient mechanical structural support for the microorganisms, the thickness of the microbial protective film 3 is 10 to 100 μm, and more preferably 50 μm.
In one embodiment, the preparation method of the microbial protection film 3 comprises the following steps:
uniformly mixing chitosan and nutrient substances required by the growth of the microorganisms, and sterilizing to obtain a microorganism protection solution; and under the aseptic condition, the microorganism protection solution is coated on the surface of the microorganism fixed film far away from the opening by scraping to obtain the microorganism fixed film.
Specifically, firstly, acetic acid is dispersed in deionized water to obtain an acetic acid solution, and then chitosan is dispersed in the acetic acid solution to obtain an acetic acid solution of chitosan, wherein the volume ratio of acetic acid to deionized water is 1: (5-20), further 1:9, considering that too high chitosan content can result in poor homogeneity of the culture medium (the solution viscosity is too high), and too low chitosan content can not obtain a solution with moderate viscosity and suitable for film hanging, the volume-to-mass ratio of the LB culture medium to the chitosan is 100mL (1-4) g, and is further preferably 100mL:2g of the total weight.
Secondly, nutrient substances required for the growth of the microorganisms are prepared into a liquid culture medium, in a specific embodiment, LB culture medium components, such as tryptone, naCl and yeast extract, can be uniformly dispersed in acetic acid solution of chitosan, the prepared mixed solution can be sterilized to obtain a microorganism protection solution, and then, the microorganism protection solution is scraped on the surface of the microorganism fixed film 2 far away from the opening 41 under the aseptic condition, and is kept still to obtain the microorganism protection film 3.
Through the preparation method, the microorganism fixing film 2 and the microorganism protection film 3 are fixed on the surface of the second filtering film 1-2, the first filtering film 1-1 and the second filtering film 1-2 are cut to the same inner diameter as the shell 4, the first filtering film 1-1 and the second filtering film 1-2 are placed at the bottom of the shell 4 according to the sequence shown in figure 1, in order to not influence the migration of heavy metals and nutrient components, bubbles among the films are removed in a vacuumizing mode, the first filtering film 11, the second filtering film 12, the microorganism fixing film 2 and the microorganism protection film 3 are tightly combined, the upper cover and the lower cover of the shell 4 are screwed, and the assembly of the detection device is completed.
In the detection process, the opening 41 of the detection device shown in fig. 1 is upward, the opening 41 is completely immersed in the environment to be detected, heavy metals in the environment to be detected can pass through the first filtering membrane 11 and the second filtering membrane 12, the heavy metals are utilized by microorganisms through the growth metabolism of the microorganisms, after the detection is finished, the extraction device is used for carrying out heavy metal elution detection on the microorganisms to obtain the biological effectiveness of the heavy metals, under the common condition, the detection time is 48h, and the specific test time can be adjusted according to the detection environment.
In a specific embodiment, the environment to be detected can be one or more of water, soil and sediment, and when the environment to be detected is water, the device is directly thrown into the water to be detected, or the water to be detected is sampled and taken back to a laboratory, and the device is thrown into the sampled water; when the environment to be detected is soil, putting the device into the soil to be detected to ensure that the soil is fully contacted with the first filtering membrane 11, or sampling the soil to be detected and putting the device into the soil to be detected in a laboratory environment; when the environment to be detected is sediment, the device is placed into a water body containing the sediment.
In the detection process, heavy metal cations in the environment to be detected pass through the first filtering membrane 11 and the second filtering membrane 12 and are utilized by microorganisms in the microorganism fixed membrane 2, after the detection is finished, the device is taken out of the environment to be detected, silt on the surface is cleaned, the microorganism fixed membrane is taken out, heavy metal elution is carried out, the content, the type and the morphological characteristics of the heavy metal are determined, and specifically, the type and the morphological characteristics of the heavy metal can be analyzed through an inductively coupled plasma emission spectrometer (ICP-OES);
the biological effectiveness of the heavy metal can be measured by measuring a diffusion coefficient through a standard solution, and the concentration of the heavy metal in the environment to be detected is reversely deduced by utilizing the diffusion coefficient, specifically, the calculation method of the accumulation amount of the heavy metal in the microorganism stationary phase is shown as a formula 1, and the calculation method of the diffusion coefficient is shown as a formula 2:
in formula 1, M is the accumulation of heavy metals, C e Is the concentration of heavy metals in the eluate, V e Volume of eluent, V g Volume of binding phase, f e For elution efficiency.
In the formula 2, D is a diffusion coefficient of a target object in the diffusion layer, C is a concentration of a heavy metal in an environment to be detected, M is an accumulation amount of the heavy metal in the formula 1, t is diffusion time (M/t fitting slope is usually adopted in analysis), a is an opening area of the device, and Δ g is a thickness of the diffusion layer.
In the following, staphylococcus (Staphylococcus Amber) was used as the microorganism component, the first filtration membrane (glass fiber membrane) was purchased from Whatman (260 μm thick), the second filtration membrane (cation exchange membrane) was purchased from hangzhou hua membrane technologies ltd, sodium chloride, tryptone, and yeast extract were purchased from tokyo bostar biotechnology ltd, urea was purchased from mitsunk photorem technologies ltd, nickel chloride was purchased from beijing chemical plant, and aseptic filtration membrane was purchased from sartorius trade ltd, the diameter of the plate culture dish used was 90mm, the size of the triangular flask was 250mL, and DGT apparatus used for comparison was purchased from tokyo smart environmental technologies ltd.
Example 1
The detection device provided by this embodiment is shown in fig. 1, and the preparation method includes the following steps:
weighing 1g of Tryptone (Tryptone), 0.5g of Yeast extract (Yeast extract) and 1g of sodium chloride (NaCl) in 100mL of chitosan acetic acid dilute solution, sterilizing in a high-pressure steam sterilization pot at the temperature of 121 ℃ under the pressure of 0.1MPa for 25min, taking out and cooling to room temperature to obtain a microorganism protection solution;
and 5, coating the microbial protection solution on the surface of the microbial fixed film, which is far away from the cation exchange membrane, in an aseptic environment by scraping, wherein the coating thickness is 50 microns, standing for 60min to obtain a microbial protection membrane, and placing the product in PBS buffer solution for later use.
And 6, cutting the glass fiber membrane and the product prepared in the step into a size which is the same as the inner diameter of the plastic shell under the aseptic condition, wherein the inner diameter of the shell is 1.6cm, assembling according to the sequence shown in the figure 1, removing air bubbles between the membranes, screwing an upper cover and a lower cover to obtain a detection device, and putting the detection device into deionized water for later use.
The effectiveness of the device prepared in example 1 was analyzed as follows:
action characteristics of microorganism for fixing relative heavy metal
Using the heavy metal nickel as the subject, 0.1000g of NiCl was weighed 2 .6H 2 Dissolving O in 1L of water (the concentration of nickel ions is 22.98ppm by ICP-OES), adding water to dilute 100 times to obtain a simulated heavy metal nickel solution with the concentration of 1mg/L, placing the detection device prepared in example 1 in the simulated solution for 12h, taking out the device, observing microorganisms and carrying out EDS (electron discharge spectroscopy) energy spectrum analysis, wherein FIG. 2 is the form of metal nickel in a microorganism stationary phase in example 1 of the invention, FIG. 3 is the EDS energy spectrum of the microorganism stationary phase spot1 in example 1 of the invention, FIG. 4 is the EDS energy spectrum of the microorganism stationary phase spot2 in example 1 of the invention, as shown in FIGS. 2-4, the metal nickel is solidified on the surface of the microorganisms, and the existence of nickel element is clarified by the EDS analysis.
After the microorganism stationary phase is eluted, the content of heavy metal Ni in the eluent is determined by using an inductively coupled plasma emission spectrometer (ICP-OES), and the content of heavy metal Ni in the eluent is 446.2ng through testing.
(II) diffusion coefficient of device in example 1
Heavy metals are bound to the microbial immobilization via cation exchange membranes, the process of which is controlled by the diffusion coefficient. The device of example 1 was placed at a free metal ion activity of 22.9In 8mg/L simulated heavy metal nickel solution, analyzing the content of nickel adsorbed by the device under the condition of equal time intervals, specifically: according to the first diffusion law of FICK, 1M HNO is used for the microorganism fixed film in the device under different use times 3 The membrane was diluted and the concentration of nickel ions was determined using inductively coupled plasma optical emission spectroscopy (ICP-OES) after leaching for 24 h. Plotting by taking time as an abscissa and heavy metal accumulation mass as an ordinate, as shown in fig. 5;
from the fitted curve provided in FIG. 5, the slope R (i.e., M/t) was calculated and the diffusion coefficient D was calculated according to equation 2, where Δ g is the thickness of the diffusion layer of 0.013cm (i.e., the thickness of the cation exchange membrane), C is the free metal ion concentration (22.98 mg/L), and A is the open area of the device, 2.0096cm 2 Calculated diffusion coefficient D =4.57 × 10 -6 cm 2 /s。
(III) influence of pH on device test Performance
Placing the detection device in a solution with Ni metal ion concentration of 1mg/L, adjusting pH to 3, 4, 5, 6, 7, 8, 9 (0.1 mol/L HCL and 0.1mol/L NaOH solution), adsorbing for 12h, taking out the device, flushing the device shell with ultrapure water, leaching the microorganism fixed membrane in 1mol/L nitric acid for 24h, fixing volume, passing through a 0.45 micron filter membrane, and measuring Ni concentration C in the eluent by ICP-OES Sol ；
Placing conventional DGT device (purchased from Nanjing Zhigan environmental science and technology Co., ltd.) in Ni metal ion concentration 1mg/L solution, adsorbing by the same method, and testing Ni concentration C in eluate after adsorption DGT ；
Calculating C DGT /C Sol And as ordinate, pH is abscissa, the results shown in fig. 6 were obtained.
As can be seen from FIG. 6, C is observed when the pH is 3 to 7 DGT /C Sol All within the desired target value (1. + -. 0.1), indicating that the process is suitable for acidic and neutral conditions, and that the C at pH 8 and 9 DGT /C Sol Values of (a) are relatively low, but still can reach 0.87 and 0.85, it is apparent that the detection apparatus and method provided by the present invention are applicable to both acidic and neutral conditions.
(IV) influence of ion Strength on adsorption Performance of the device
Placing the detection device in a solution with Ni metal ion concentration of 1mg/L, pH of 7, and sequentially adjusting the ion intensity to 1, 10, 50, 75, 100, 150 and 300mmol/L (NaNO) 3 Adjusting), adsorbing for 12h, taking out the device, washing the device shell with distilled water, putting the microorganism stationary phase into 1mol/L nitric acid for desorption for 24h, fixing the volume and passing through a membrane, and measuring the concentration C of Ni in the eluent by an inductively coupled plasma emission spectrometer (ICP-OES) Sol ；
Placing conventional DGT device (purchased from Nanjing Zhigan environmental science and technology Co., ltd.) in Ni metal ion concentration 1mg/L, pH solution of 7, adsorbing by the same method, and testing Ni concentration C in eluate after adsorption DGT ；
Calculating C DGT /C Sol As the ordinate and pH as the abscissa, the results shown in fig. 7 were obtained.
As can be seen from FIG. 7, the ionic strengths of C at 1, 10, 50 and 75mM were respectively DGT /C Sol In a ratio in the ideal range, 100, 150, 300mM of C DGT /C Sol The values of (A) are relatively slightly lower, but the ratios still reach 0.72, 0.77, 0.76. The application range of the prior art is 1-50mM, and the invention can be applied to 1-75mM and has wider application range.
(V) biological effectiveness analysis experiment:
1. heavy metals in water were detected using the detection apparatus provided in example 1:
And 2, washing the shell of the device by distilled water, and placing the device in a sterile operating platform to take out the microorganism fixed membrane.
And 3, putting the microorganism fixed membrane into 1mol/L nitric acid for desorption for 24 hours, measuring the concentration of heavy metal Ni in the eluent by an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the bioavailable concentrations of the nickel ions under different concentrations of 0.182mg/L, 0.267mg/L, 0.465mg/L, 0.786mg/L and 0.943mg/L by combining the tests and utilizing the back calculation of diffusion coefficients.
2. Heavy metals in soil were detected using the detection device provided in example 1:
And 2, cleaning the surface of the device, and taking out the microorganism fixed membrane from the device in a sterile operation table.
And 3, putting the microorganism stationary phase into 1mol/L nitric acid for desorption 24h, measuring the concentration of Ni in the eluent by ICP-OES, and combining the tests to obtain the bioavailable concentrations of nickel ions under different concentrations of 0.171mg/kg, 0.243mg/kg, 0.424mg/kg, 0.746mg/kg and 0.915mg/kg respectively.
3. Heavy metals in sediment-water were detected using the detection apparatus provided in example 1:
And 2, washing the shell of the device by distilled water, and placing the device in a sterile operating platform to take out the microorganism fixed membrane.
And 3, putting the microorganism fixed membrane into 1mol/L nitric acid for desorption 24h, measuring the concentration of Ni in the eluent by ICP-OES, and combining the tests to obtain the bioavailable concentrations of nickel ions of 0.193mg/L, 0.289mg/L, 0.478mg/L, 0.792mg/L and 0.986mg/L under different concentrations.
According to the experimental results, the microbial stationary phase is used for predicting the bioavailability of the heavy metal, the in-situ analysis and detection of the heavy metal can be realized, and the results have good reproducibility in water, soil and sediment environments. In addition, the microbial stationary phase adopted by the invention can be replaced by specific microbial species or populations in the environment, and the influence of heavy metals on the biological effectiveness of the specific microbial species or populations can be effectively analyzed.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The device for detecting the biological effectiveness of the heavy metal is characterized by comprising a filtering membrane, a microbial membrane and a shell, wherein the shell comprises a containing cavity and an opening communicating the inside and the outside of the containing cavity, and the filtering membrane and the microbial membrane are sequentially stacked and arranged in the containing cavity from one side close to the opening to one side far away from the opening;
the microbial film comprises a microbial fixed film and a microbial protective film, the microbial fixed film is positioned close to one side of the opening, the microbial protective film is positioned on one side of the microbial fixed film, which is far away from the opening, and the microbial fixed film comprises microbes and a substrate film for fixing the microbes.
2. The apparatus according to claim 1, wherein the filter membrane comprises a first filter membrane and a second filter membrane, the first filter membrane is located on a side close to the opening, the second filter membrane is located on a side away from the opening, the first filter membrane is a glass fiber membrane, and the second filter membrane is a cation exchange membrane.
3. The device of claim 1, wherein said matrix membrane comprises sodium alginate and said microorganism immobilization membrane comprises chitosan and nutrients required for growth of said microorganisms.
4. The device of claim 1, wherein the microorganisms comprise one or more of urease-producing bacteria, carbonic anhydride bacteria, acid-producing bacteria, phosphatase-producing bacteria, desulfurization microorganisms, denitrification microorganisms, and nitrogen-fixing microorganisms.
5. The device according to claim 1, wherein the thickness of the microorganism-immobilized membrane is 10-100 μm.
6. The device of claim 1, wherein the microbial protective film has a thickness of 10-100 μm.
7. The device according to claim 1, characterized in that the diameter of the filtering membrane, the microbial membrane is the same as the inner diameter of the containing cavity.
8. The apparatus according to claim 3, wherein the preparation method of the microbial film comprises the following steps:
dispersing sodium alginate in a solvent, sterilizing to obtain a sodium alginate solution, and performing liquid fermentation on microorganisms to obtain a microorganism solution; under the aseptic condition, uniformly mixing the sodium alginate solution and the microbial bacteria solution to obtain a microbial fixing solution, and blade-coating the microbial fixing solution on the surface of the filtering membrane far away from the opening to obtain a microbial fixing membrane;
uniformly mixing chitosan and nutrient substances required by the growth of the microorganisms, and sterilizing to obtain a microorganism protection solution; and under the aseptic condition, the microorganism protection liquid is coated on the surface of the microorganism fixed film far away from the opening by scraping to obtain the microorganism fixed film.
9. The device of claim 8, wherein the OD of the microbial fluid is 600 Is 0.2-2.
10. A detection method using the device of any one of claims 1 to 9, characterized in that the opening of the device of any one of claims 1 to 9 is upward, the opening is immersed in an environment to be detected, heavy metals in the environment to be detected are adsorbed by microorganisms, and after the adsorption is finished, the device is taken out to detect the heavy metals adsorbed by the microorganisms;
the environment to be detected is one or more of water, soil and sediment.
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