CN113702474A - Method for enhancing early warning stability of toxicity of water environment - Google Patents
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Abstract
The invention relates to a method for enhancing water environment toxicity early warning stability, and belongs to the technical field of water body biotoxicity early warning. The invention discloses a novel early warning method for enhancing water environment toxicity, which is carried out by adopting a differential coulomb method, and the principle of the method is that sodium acetate with the concentration of more than or equal to 384.6mg/L is added into a water sample to be tested, so that the utilization rate of microbial enzyme on an anode is saturated, coulomb quantity after the sodium acetate is added for 2-5 hours is collected as an analytic signal, and the Inhibition Rate (IR) of the coulomb quantity is calculated to carry out toxicity early warning.
Description
Technical Field
The invention belongs to the technical field of water body biotoxicity early warning, and relates to a method for enhancing water environment toxicity early warning stability.
Background
In recent years, MFC (microbial fuel cell) sensors are widely used for detecting various water quality indexes, and have strong practicability particularly in water environment toxicity early warning. The toxic substances can inhibit the electrochemical activity of the anode biomembrane, so that the electric signal of the MFC sensor is weakened, and the water environment toxic pollution condition can be judged according to the Inhibition Rate (IR) of the electric signal. It is known from the existing research that BOM (biochemically degradable organic matter) can provide nutrients to anode microorganisms, participating in the electron production of MFC sensors. When the MFC sensor is used for toxicity early warning, under the composite impact of toxic substances and BOM, the MFC sensor electric signal suppression rate is distorted.
In order to improve the anti-interference capability of the MFC sensor on BOM fluctuation, Spurr et al construct a three-stage MFC sensor group, and can distinguish BOD without adding organic matters5And a decrease in signal due to toxic substances. Jiang et al used two different concentrations of BOD5As the baseline concentration of organic matter of MFC sensor, qualitative differentiation from BOD can be achieved by comparing the response maps prepared in advance5Four typical electrical signal changes caused by toxic substances. The methods provide important ideas for enhancing the organic matter interference resistance of the MFC sensor. However, current research is more directed to simulated wastewater of some specific concentration, and there is a certain distance from the complex actual wastewater toxicity detection. In addition, the toxic effects of toxic substances on the anodic biofilm cause changes in the composition of the microbial community and even inactivation of the microorganisms. How to reduce the side effect on the microorganism while ensuring the toxicity detection requirement is favorable for the recovery and the reuse of the MFC sensor. Pan et al added a Quorum Sensing (QS) inducer to the MFC sensor anode to enhance the recovery of the anode biofilm. The results show that even after addition of the inducer, the MFC sensor was loaded with Cu at 10mg/L2+When a water sample is tested, the voltage can be recovered to the original state, but the method has the problem of high cost, and further research is still needed for improving the recovery capability of the anode microorganisms.
Therefore, new methods for enhancing the toxicity early warning stability of the water environment need to be researched.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for enhancing the toxicity early warning stability of an aqueous environment.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a method for enhancing the early warning stability of the toxicity of the water environment is carried out by adopting a differential coulometry method, whereinThe method comprises the following specific steps: placing the MFC sensor in a water sample to be detected, adding sodium acetate until the concentration of the sodium acetate in the water sample is more than or equal to 384.6mg/L, and collecting coulomb quantity CY within 2-5 h after the sodium acetate is added2The inhibition rate IR is calculated.
Preferably, the anode material in the MFC sensor is any one of carbon cloth, carbon brush, carbon felt, carbon nanotube, graphite rod, or graphite fiber brush; the cathode material is an air cathode carbon cloth material; the membrane material is a cation exchange membrane or a proton exchange membrane.
The air cathode carbon cloth material comprises a substrate layer carbon cloth, a waterproof layer and a catalytic layer, wherein the waterproof layer and the catalytic layer are respectively coated on the substrate layer, the waterproof layer is a mixture of a plastic agent and an adhesive, and the catalytic layer is Pt/C, wherein the mass ratio of Pt to C is 2: 8;
further preferably, the anode material is cultured in a large cell cultured in a sodium acetate matrix for long-term operation for more than one month. Preferably, the calculation formula of the inhibition ratio IR is:
IR(％)＝100*(CY1-CY2)/CY1
wherein, IR is inhibition rate; CY1The coulomb amount in the maintenance phase is C; CY2Is the coulomb quantity in the test phase in C.
Further preferably, the maintenance stage is specifically a stage of 0-2 hours after the sodium acetate is added.
Further preferably, the testing stage is specifically a stage 2-5 hours after the sodium acetate is added.
The invention has the beneficial effects that:
the invention discloses a method for enhancing the toxicity early warning stability of a water environment, which is carried out by adopting a coulomb method, and has the following principle: adding sodium acetate with the concentration of more than or equal to 384.6mg/L into a water sample to be detected to enable the utilization rate of microbial enzyme on an anode to reach saturation, collecting coulomb quantity after the sodium acetate is added for 2-5 hours as an analytic signal, and calculating the Inhibition Rate (IR) of the coulomb quantity to perform toxicity early warning. The method can avoid the fluctuation influence of the biochemical degradable organic matter (BOM), and has the following advantages: 1) toxic substances of different types and concentrations have different influences on voltage signals of the MFC sensor, some of the toxic substances are immediately reduced, and some of the toxic substances have obvious lag phase to be reduced, so that the toxic substances are difficult to accurately early warn, and compared with instantaneous indexes such as maximum voltage or current, the accumulated indexes such as coulomb quantity can more accurately express the toxic influences; 2) the differential coulometry method adopts the local coulomb quantity that the utilization rate of the microbial enzyme reaches the saturation stage, shortens the contact time of the microbes and the toxic substances, reduces the influence of the toxic substances on the microbes, and is beneficial to the quick recovery of the MFC sensor.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of toxicity early warning of a water environment by a differential coulometry method;
FIG. 2 is a voltage acquisition curve of the MFC sensor during the start-up phase of the culture;
FIG. 3 is the relative abundance of microbial community species on the surface of the anode after culture stabilization;
FIG. 4 is an SEM image of the surface microorganisms of the anode after the culture stabilization;
FIG. 5 is a CLSM image of anode surface microorganisms after culture stabilization;
FIG. 6 is a graph of voltage acquisition for MFC sensor degradation for different concentrations of sodium acetate;
FIG. 7 is a coulomb collection float range for MFC sensor degradation concentrations of sodium acetate equal to or greater than 384.6 mg/L;
FIG. 8 is a graph of the electrochemical performance of the MFC sensor changing when the concentration of sodium acetate is 384.6mg/L or more, where a is a maximum power density comparison graph, b is an anode impedance spectrum of the MFC sensor, and c is an anode CV graph of the MFC sensor;
FIG. 9 shows the control of the concentration of sodium acetate in the simulated wastewater to 384.6mg/L (BOD)5Value of 200mg/L), MFC sensor is tuned to different concentrations of Cu2+The early warning effect of (1), wherein a is the voltage curve change, b is the coulomb inhibition ratio, and c is the recovery curve of the voltage;
FIG. 10 shows Cu2+When the concentration of the sodium acetate is two orders of magnitude of 0.5mg/L and 5mg/L, the sodium acetate with different concentrations has influence on the inhibition rate;
FIG. 11 is a graph showing the results of toxic membrane contamination with sodium acetate added at different concentrations;
FIG. 12 is a graph of the ratio of live to dead cells, wherein the concentrations of sodium acetate in a, b, c and d are 384.6mg/L, 576.9mg/L, 961.5mg/L and 1538.4mg/L, respectively;
FIG. 13 is a graph of anode microbial community composition and viable cell ratio changes;
FIG. 14 is a graph showing the effect of different organic species on differential coulombic stability;
FIG. 15 shows the results of the early warning analysis of different toxic substances by differential coulometry, wherein a, b, c, d, e and f are Hg (II), Cr (VI) and Zn (respectively)2+、Cd2+Paraformaldehyde solution and experimental wastewater.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
A novel differential coulometry method carries out toxicity early warning on a water environment, the flow is shown in figure 1, and firstly, sodium acetate medicament is added into a water sample to be detected so as to achieve the purpose of sufficient BOM in the sample. Sodium acetate is selected as an additive agent, on one hand, because sodium acetate is easily degraded and metabolized by an anode biomembrane, the enzyme utilization rate of microorganisms on the anode can quickly reach saturation; on the other hand, compared with other BOMs, the sodium acetate is not easy to generate complex precipitation with toxic substances, so that the accuracy of water toxicity early warning can be ensured.
1. According to the Mie's equation (formula 1.1), when the substrate concentration exceeds a certain concentration, the utilization rate of the enzyme in the microorganism can reach 100%, and the concentration of the organic matters is no longer a factor influencing the degradation rate.
Wherein V0The reaction speed is mg/min; kmIs the Michaelis constant; [ S ]]Substrate concentration, mg/L; vmaxMg/min for maximum degradation rate.
Therefore, when the content of the BOM in the sample is sufficient, the voltage signal does not change along with the fluctuation of the BOM concentration in a certain period of time in the detection process of the MFC sensor. Therefore, toxic substances in the water sample can be detected by means of the coulomb quantity signal of the time period when the BOM content is sufficient, and the interference of the BOM to the signal is avoided.
2. Actuation and microbial characterization of MFC sensors
The MFC sensor is characterized in that a carbon cloth (wherein the carbon cloth is cultured for more than one month in a sodium acetate substrate cultured large cell which runs for a long time) is used as an anode material, an air cathode carbon cloth material (comprising a substrate layer carbon cloth, a waterproof layer and a catalytic layer, wherein the waterproof layer is a mixture of a plastic agent and an adhesive, the catalytic layer is Pt/C, the mass ratio of Pt to C is 2: 8), and the carbon cloth material is used as a cathode material, then the MFC sensor is transferred to a test cell, and BOD is used5Starting the MFC sensor by using the sodium acetate culture solution with the value of 200mg/L, and replacing the nutrient solution every 24h by using the voltage acquisition curve of the MFC sensor in the culture starting stage in the figure 2. After 8 days of culture, errors in coulomb collection were observed to be within 1% for three consecutive test cycles, as shown in the tableThe bright anode microorganisms reach a stable state. The maximum voltage reaches 559.85mV when the culture is stable, and the coulomb quantity collected in the stable maintenance period is 18.22C.
FIG. 3 is a graph showing the relative abundance of microbial community groups on the surface of the anode after culture stabilization, and the electrogenic bacteria in the first 10 genera were determined to include: the ratio of the Geobacter (Geobacter, 39.02%), the golden yellow bacillus (12.03%), the Aquamicrobium (3.31%), the Pseudomonas (2.36%) and the electrogenic bacteria is as high as more than 56.72%. In addition, the anodic biofilm also included other miscellaneous bacteria such as dechlorination bacteria (Dechlorosoma, 5.07%), denitrificans (Ignavibacterium, 4.41%), Azospirillum (Azospirillum, 3.23%), Gordonia (Gordonia, 2.02%), Legionella (Legionella, 2.03%) in a proportion of 16.76%. This indicates that the dominant bacteria of the microorganisms on the anode are electrogenic bacteria, and most other bacteria are anaerobic fermentation bacteria. The zymophyte can degrade larger organic matters into smaller organic matters, and then the smaller organic matters are completely degraded by the electrogenesis bacteria to generate electricity, and the anaerobic zymophyte with a certain proportion is beneficial to the degradation of the organic matters and the electricity generation.
FIG. 4 is an SEM image of the microorganisms on the surface of the anode after the anode is stably cultured, and it is obvious from the SEM image that a layer of microorganisms is attached to the surface of the anode carbon cloth, the strains are compact and most of the microorganisms are rod-shaped. As can be seen from the analysis of FIG. 4, most of the bacillus microorganisms are the dominant species, i.e., Bacillus species, in the anodic biofilm. FIG. 5 is a CLSM graph of anode surface microorganisms after culture stabilization, and it can be seen that the proportion of living cells in a biological membrane is high, a small part of aged and inactivated cells exist, and the inactivated cells still have certain electron transfer capacity.
In conclusion, the MFC sensor with stable electrochemical activity is cultured in an experiment and can be used for early warning of water toxicity.
Example 2
The toxicity early warning of the water environment is carried out by adopting a differential coulometry method, and the specific method comprises the following steps:
(1) preparing an MFC sensor: the method comprises the following steps of taking carbon cloth (wherein the carbon cloth is cultured for more than one month in a sodium acetate substrate cultured large battery which runs for a long time) as an anode material, and taking an air cathode carbon cloth material (comprising a substrate layer carbon cloth, a waterproof layer and a catalytic layer, wherein the waterproof layer and the catalytic layer are respectively coated on the substrate layer, the waterproof layer is a mixture of a plastic agent and an adhesive, and the catalytic layer is Pt/C, wherein the mass ratio of Pt to C is 2: 8) as a cathode material;
(2) adding sodium acetate into the water sample to be detected until the concentration of the sodium acetate in the water sample is 384.6mg/L, wherein the BOD is a corresponding standard product5The values are respectively 200mg/L, then the MFC sensor is placed in a water sample to be detected containing sodium acetate, coulomb quantities before and after the water sample to be detected containing sodium acetate is added are collected and are respectively recorded as CY1(18.22C) and CY2(9.54C)；
(3) The inhibition rate IR was calculated according to the formula of 47.64%, wherein the inhibition rate IR was calculated according to the formula of:
IR(％)＝100*(CY1-CY2)/CY1＝100*(18.22C-9.54C)/18.22C＝47.64％。
example 3
1. Selection of acquisition signals
The method comprises the following steps of taking carbon cloth (wherein the carbon cloth is cultured for more than one month in a sodium acetate substrate cultured large battery which runs for a long time) as an anode material, and taking an air cathode carbon cloth material (comprising a substrate layer carbon cloth, a waterproof layer and a catalytic layer, wherein the waterproof layer and the catalytic layer are respectively coated on the substrate layer, the waterproof layer is a mixture of a plastic agent and an adhesive, and the catalytic layer is Pt/C, wherein the mass ratio of Pt to C is 2: 8) as a cathode material; adding sodium acetate into the water sample to be detected until the concentration of the sodium acetate in the water sample is 192.3mg/L, 384.6mg/L, 576.9mg/L, 961.5mg/L and 1538.4mg/L respectively, and obtaining the corresponding standard BOD5The voltage acquisition curves for MFC sensor degradation at different concentrations of sodium acetate are shown in FIG. 6, for values of 100mg/L, 200mg/L, 300mg/L, 500, and 800mg/L, respectively. When the concentration of sodium acetate is more than or equal to 384.6mg/L, the voltage acquisition curves are basically overlapped within 2-5 h, the coulomb collection floating range is from 9.54-9.60C (as shown in figure 7), and the relative standard deviation is 0.3%, which shows that when the concentration of sodium acetate reaches a certain value (384.6mg/L), the electron transfer rate of the anode biomembrane is not influenced by the change of the concentration of organic matters any more; when the voltage of the MFC sensor is collected at the initial stage of testing (0-2 h after adding sodium acetate), the voltage is slightly collectedThe organism is in an adaptation stage, namely a maintenance stage, the electron transfer rate is unstable, and the difference of the collected voltage rising curves is obvious. When the detection time exceeds 5h, the BOM concentration is reduced and gradually becomes a main factor for limiting the electron transfer rate of the anode microorganisms.
In summary, the adoption of the MFC sensor to pre-alarm the toxic substances in the water sample comprises the following steps: firstly, adding sodium acetate into a water sample for pretreatment to ensure that the concentration of the sodium acetate in the water sample is more than 384.6 mg/L; and then selecting coulomb quantity within 2-5 h as an analytic signal to perform toxicity early warning analysis in the test process. Therefore, on one hand, the interference caused by the BOM with unknown concentration in the water sample can be effectively avoided, on the other hand, the early warning response time can be shortened, the influence degree of toxic substances on the anode microorganisms is reduced, and the MFC sensor can be quickly restored after the detection is completed.
2. Effect of added substrate on MFC sensor electrochemical Performance
To further illustrate the feasibility of the method of the present invention in resisting organic interference, electrochemical measurements were performed to test the change in electrochemical performance of the MFC sensor when the concentration of sodium acetate in the water sample was 384.6mg/L or more (384.6, 576.9, 961.5, and 1538.4mg/L, respectively), as shown in fig. 8. In FIG. 8, a is a comparison graph of the maximum power density of the MFC sensor under different sodium acetate concentration matrixes, and it can be seen that the maximum power density has a small floating range (1033.54-1074.10 mW/m)2) The Relative Standard Deviation (RSD) is 1.6%, which shows that when sodium acetate with the concentration of more than 384.6mg/L is added, the substrate concentration reaches saturation, and excessive organic matters do not have obvious influence on the electron transfer rate of the MFC sensor. In fig. 8, b is an anode impedance spectrum of the MFC sensor, the impedance spectra are highly overlapped under several sodium acetate concentration matrixes, the ohmic internal resistance (4.53 Ω -4.70 Ω) and the activation internal resistance (2.34 Ω -2.84 Ω) are maintained within similar values, and the corresponding RSDs are 2.10% and 8.20%, respectively. This indirectly also indicates the stability of the electrochemical activity of the anode microorganism after saturation of the substrate concentration. The cyclic voltammetry Curve (CV) can reflect the extracellular electron transfer capability of the anode microorganism, the potential of an oxidation peak value is between-0.28V and-0.29V, and the maximum current density is between 3.57 and 3.64 muA/cm2In the meantime.FIG. 8 c is a graph of anode CV of MFC sensor, showing that the extracellular electron transfer capacity of the anode microorganism remains relatively stable after saturation of the substrate concentration.
3、Cu2+Toxicity early warning test
FIG. 9 shows the control of the concentration of sodium acetate in the simulated wastewater to 384.6mg/L (BOD)5Value of 200mg/L), MFC sensor is tuned to different concentrations of Cu2+The early warning effect. As can be seen from a in FIG. 9, when the collection voltage is 2-5 h, the Cu in the water sample is carried out2+The concentration is increased (0.5-8 mg/L), the voltage curve is gradually reduced, and obvious gradient distinction is carried out, and the results of calculating the corresponding coulomb inhibition rates are respectively 1.38 +/-0.03%, 2.03 +/-0.13%, 3.05 +/-0.03% and 3.86 +/-0.21% (as shown in b in figure 9), which shows that the differential coulomb method has a relatively stable early warning effect on toxic substances. In FIG. 9 c is Cu of different concentrations2+After the test, the recovery curve of the voltage, from which it can be seen that when Cu is present2+When the concentration detection range is 0.5-8 mg/L, after the detection is finished and the MFC sensor is replaced by normal nutrient solution, the acquisition voltage of the MFC sensor can be quickly recovered to the initial state within 1.5 h.
In conclusion, the differential coulometry can be used for treating Cu in a water sample2+And the early warning is carried out stably, and the recovery capability of the anode biomembrane can be enhanced.
4. Different concentrations of organic matter to Cu2+Toxicity early warning stability impact
The experiments prove that the differential coulometry method can be used for treating Cu in the water body when the BOM in the water sample is stable and unchanged2+The content of (A) is subjected to accurate toxicity early warning. In addition, taking sodium acetate as an example, whether the changed BOM concentration in a water sample can influence the stability of the differential coulometry method or not is examined. Compare Cu in water sample2+At concentrations of two orders of magnitude, 0.5mg/L and 5mg/L, the effect of different concentrations of sodium acetate on the inhibition rate is shown in FIG. 10. When the concentration of sodium acetate in the simulated wastewater is 384.6mg/L, 576.9mg/L, 961.5mg/L and 1538.4mg/L, the simulated wastewater contains 5mg/L of Cu2+The early warning result of the toxicity of the water sample is stable, the coulomb inhibition rates are respectively 3.04 +/-0.03%, 3.13 +/-0.16%, 3.07 +/-0.09% and 3.25 +/-0.18%, and the coulomb inhibition rate after all the detection data are gathered is3.12 +/-0.15%. When the concentration range of sodium acetate in the simulated wastewater is 384.6-961.5 mg/L, the simulated wastewater contains 0.5mg/L of Cu2+The toxicity early warning of the water sample is hardly influenced, the coulomb inhibition rates are respectively 1.38 +/-0.03 percent, 1.39 +/-0.17 percent and 1.37 +/-0.07 percent, but when the concentration of sodium acetate reaches 1538.4mg/L, namely BOD5At a value of 800mg/L, 0.5mg/L of Cu is contained2+The coulomb inhibition rate of the water sample is obviously reduced and is only 0.67 +/-0.06 percent. This illustrates when Cu is present in the water sample2 +If the value is low, the detection sensitivity of the differential coulometry method is lowered, and errors are likely to occur.
The reasons for the above results are mainly two: 1) excess organic matter will react with Cu in the solution2+The complex reaction is generated to generate precipitation, which affects Cu2+Diffusing to the anode to contact the biofilm; 2) the excessive organic matter can also increase the content of the anode biomembrane extracellular polymeric substances, thereby improving the toxicity resistance of the anode microorganisms and causing the reduction of the inhibition rate of the detected coulomb quantity. Thus, BOD of the water sample as pretreated5When the value reaches 800mg/L, the alloy contains 0.5mg/L of Cu2+The toxicity early warning sensitivity of the water sample is reduced, but the water sample contains higher concentration Cu2+The water sample still has stable early warning effect.
5、Cu2+Mechanism of action on anodic biofilm
In the above-mentioned Cu content of 5mg/L2+And after the water sample is tested, the MFC sensor is immediately disassembled, the anode biomembrane is taken out for community analysis and CLSM characterization, and the influence of the sodium acetate with different concentrations on the toxicity pollution of the biomembrane is researched. As shown in FIG. 11, the composition of the anode biofilm community after toxicity detection is not obviously changed, and the percentage of the electrogenic bacteria is within 50-60%.
FIG. 12 is a graph showing the ratio of live cells to dead cells, wherein the concentrations of sodium acetate in a, b, c and d were 384.6mg/L, 576.9mg/L, 961.5mg/L and 1538.4mg/L, respectively. As can be seen from 12, the ratio of live cells to dead cells did not change significantly with increasing sodium acetate concentration, similar to the non-poisoned anodic biofilm CLSM, indicating that the differential coulometric assay used contained 5mg/L Cu2+In the case of toxic waste water, anodic organismsNo significant deactivation of the membrane occurred. Table 1 is an anode impedance information comparison table, and the anode ohmic internal resistance and the activation internal resistance after the contact of the toxic substance are both significantly increased compared to the MFC anode during the maintenance period.
In conclusion, the detection method adopted by the invention promotes the toxic substances to inhibit the electrochemical activity of the anode biomembrane, so that the extracellular electron transfer capability is reduced, and the electric signal is reduced; but the anode microbial community composition and viable cell ratios did not change significantly (as shown in figure 13). Therefore, the differential coulometry method can not only realize toxicity early warning, but also can not cause irreversible damage to the anode biomembrane.
TABLE 1 Anode impedance information comparison Table
6. Effect of different kinds of organic matter on stability of differential coulometry
Separately preparing simulated wastewater containing 50mg/L of Glutamic acid (Glutamic), Sucrose (Sucrose), Glucose (Glucose) and sodium Acetate (Acetate), wherein each simulated wastewater contains 5mg/L of Cu2+. When different kinds of organic matters exist in a research water sample, the influence of the differential coulometry on the toxicity early warning stability is researched. The research result is shown in figure 14, sodium acetate medicament is added into the simulated water sample to ensure that the increased sodium acetate concentration in the simulated water sample is 384.6mg/L, and then the differential coulometry method is adopted for testing.
The results show that Cu is carried out on a water sample containing glutamic acid, sucrose and sodium acetate2+5mg/L of Cu at the time of warning2+The coulomb inhibition rates of the water samples are basically consistent and are respectively 3.07 +/-0.09%, 3.11 +/-0.22% and 3.13 +/-0.26%. But when toxicity early warning is carried out on simulated wastewater containing glucose, 5mg/L of Cu2+The coulomb inhibition rate of the water sample is only 2.07 +/-0.05 percent. This is because glucose is used as a source of glucoseIs easy to be mixed with Cu in solution2+Form a complex, weakening Cu2+Without this affecting the true ionic state of Cu2+Detection of (3).
In addition, municipal Wastewater (Watersater) was used to verify the feasibility of the differential coulometry. The results showed 5mg/L of Cu2+The coulomb amount inhibition rate is 2.65 +/-0.03 percent, and the early warning effect is still stable.
7. Early warning analysis of different toxic substances by differential coulometry
The differential coulometry method is adopted to respectively treat Hg (II), Cr (VI) and Zn with the content of 1mg/L2+、Cd2+And paraformaldehyde solution, corresponding coulombic mass inhibition of 9.92%, 3.38%, 27.99%, 4.45%, and 20.58%, respectively (results are shown in a, b, c, d, and e, respectively, in fig. 15). The coulomb inhibition ratio is respectively as follows from large to small: zn2+Paraformaldehyde > Hg (II) > Cd2+＞Cr(Ⅵ)＞Cu2+。
In addition, the experimental wastewater is also used as a toxicity detection water sample, diluted by 100 times and added to the anode of the MFC sensor for detection, and the coulomb inhibition rate is 4.45% (as shown in f in fig. 15). Therefore, the MFC sensor has a stable toxicity early warning effect on common toxic substances in a water environment, and has comprehensive toxicity early warning capability on a complex water body.
In conclusion, the invention provides a novel water environment toxicity early warning method (differential coulometry), aiming at enhancing the anti-interference capability of an MFC sensor on BOM fluctuation. The principle is that sodium acetate medicament is added into a water sample, so that the utilization rate of microbial enzyme on an anode can be quickly saturated, and the interference of organic matters in the water sample can be avoided by adopting coulomb quantity signals in an enzyme saturation stage for toxicity early warning.
The invention mainly has the following advantages:
(1) when the concentration of sodium acetate is more than or equal to 384.6mg/L, the voltage acquisition curves are basically overlapped within 2-5 h, and the electron transfer rate of the anode biomembrane is not influenced by the concentration fluctuation of organic matters, so that the coulomb quantity within 2-5 h is selected as an analytic signal for analysis, so that the interference caused by BOM with unknown concentration in the water sample can be effectively avoided, and the early warning response time can be shortened;
(2) with Cu in the water sample2+When the concentration is increased (0.5-8 mg/L), the voltage curve is gradually reduced and is distinguished by obvious gradients, and when the detection is finished and the nutrient solution is replaced for recovery and maintenance, the output voltage can be recovered to the initial state within 1.5 h. When the concentration range of sodium acetate in the simulated wastewater is 384.6-1538.4 mg/L, the simulated wastewater contains 5mg/L of Cu2+The toxicity early warning of the water sample is not influenced, and the coulomb inhibition rate is maintained to be 3.12 +/-0.15%;
(3) when the differential coulometry method is adopted for detection, the ohmic internal resistance and the activation internal resistance of the anode after the contact of toxic substances are obviously increased, so that the change of an electric signal of an MFC sensor is caused; but the proportion of the electrogenic bacteria and the proportion of living cells of the anode biomembrane are not obviously changed.
Therefore, the differential coulometry method of the invention can not only realize toxicity early warning, but also can not cause irreversible damage to the anode biomembrane, and is convenient for the rapid recovery of the MFC sensor after the detection is finished.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (6)
1. A method for enhancing the toxicity early warning stability of a water environment is characterized by being carried out by adopting a differential coulometry method, and the method specifically comprises the following steps: placing the MFC sensor in a water sample to be detected, adding sodium acetate until the concentration of the sodium acetate in the water sample is more than or equal to 384.6mg/L, and collecting coulomb quantity CY within 2-5 h after the sodium acetate is added2The inhibition rate IR is calculated.
2. The method of claim 1, wherein the anode material in the MFC sensor is any one of a carbon cloth, a carbon brush, a carbon felt, a carbon nanotube, a graphite rod, or a graphite fiber brush; the cathode material is an air cathode carbon cloth material; the membrane material is a cation exchange membrane or a proton exchange membrane;
the air cathode carbon cloth material comprises a substrate layer carbon cloth, and a waterproof layer and a catalytic layer which are respectively coated on the substrate layer, wherein the waterproof layer is a mixture of a plastic agent and an adhesive, and the catalytic layer is Pt/C, wherein the mass ratio of Pt to C is 2: 8.
3. The method of claim 2, wherein the anode material is cultured in a large cell cultured in a long-running sodium acetate matrix for more than one month.
4. The method according to claim 1, wherein the suppression rate IR is calculated by the formula:
IR(％)＝100*(CY1-CY2)/CY1
wherein, IR is inhibition rate; CY1The coulomb amount in the maintenance phase is C; CY2Is the coulomb quantity in the test phase in C.
5. The method according to claim 4, wherein the maintenance phase is specifically a phase of 0 to 2 hours after the addition of sodium acetate.
6. The method according to claim 4, wherein the test phase is in particular 2 to 5 hours after the addition of sodium acetate.
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