CN109540981B - Method for detecting ultralow-concentration formaldehyde in water body by using ultrasensitive electroactive biomembrane - Google Patents
Method for detecting ultralow-concentration formaldehyde in water body by using ultrasensitive electroactive biomembrane Download PDFInfo
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Abstract
A method for detecting formaldehyde with ultra-low concentration in a water body by using an ultra-sensitive electroactive biomembrane mainly aims to detect the formaldehyde in the water body by using the ultra-sensitive electroactive biomembrane, firstly, the electroactive biomembrane is cultured by an electrochemical reactor, the electrochemical reactor consists of polytetrafluoroethylene cylinders with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, sodium acetate of 0.1-0.5 g/L is adopted as a carbon source to culture the electroactive biomembranes with different sensitivities, the cultured electroactive biomembranes respectively detect the formaldehyde with the concentration of 0.0001%, and the formaldehyde with the trace concentration can be detected or not according to the response degree. The invention has the advantages that: the method for culturing the ultrasensitive electroactive biomembrane is simple and easy to operate, can realize linear response to the concentration of trace formaldehyde, and provides a research method for the electroactive biomembrane sensor in the field of trace pollutants.
Description
Technical Field
The invention belongs to the technical field of bioelectrochemistry, and particularly relates to a method for detecting ultralow-concentration formaldehyde in a water body by using an electroactive biomembrane.
Background
With the rapid development of economy, the emergence of new pollutants poses serious hazards to the health of human beings and the balance of the ecosystem. Some trace contaminants in water have been increasingly valued for their potential hazard, but these trace contaminants are difficult to remove or detect by conventional water treatment techniques. The formaldehyde is very easy to dissolve in water as a common pollutant in home decoration, the formaldehyde in the water has high cytotoxicity, can react with amino acid and DNA molecules to generate hydroxymethyl amino acid derivatives and generate a cross-linking reaction, once the water containing the formaldehyde contacts with a human body, a very serious poisoning reaction can be generated, the formaldehyde with high concentration in the water can be removed or quickly detected, but the detection of the formaldehyde with trace concentration is a very delicate problem. Although physical and chemical sensors can improve sensitivity and respond to trace pollutants through material modification and the like, the sensors are too expensive to manufacture and maintain and are not favorable for mass production, while biosensors have the problems of low sensitivity and long culture period. Therefore, it is necessary to find an ultra-sensitive sensor in the face of trace contaminants.
Disclosure of Invention
The invention aims to solve the problems of low sensitivity and high detection limit in the prior art that the response to the trace concentration formaldehyde in the water body is difficult to meet, and provides a method for detecting the ultralow concentration (trace concentration) formaldehyde in the water body by using an optimized electroactive biomembrane.
The method for detecting the ultralow-concentration formaldehyde in the water body by the ultrasensitive electroactive biomembrane is realized by the following steps:
1) culture of ultrasensitive electroactive biofilm
The electrochemical reactor consists of a polytetrafluoroethylene cylinder with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, solution of domestic sewage or mixed liquid of effluent of a microbial fuel cell domesticated for a long time and phosphoric acid buffer solution is added into the electrochemical reactor, 0.1-0.5 g/L of sodium acetate is added to serve as a carbon source, an electric active biological membrane culture method with different sensitivities is carried out by adopting a chronoamperometry, and the operation is carried out for 3-5 days to form the electric active biological membranes with different thicknesses and shapes.
2) Response of ultrasensitive electroactive biofilms to formaldehyde
Adding 0.0001-0.005% formaldehyde solution into the electrochemical reactor which forms the stable electroactive biomembrane, and determining the response capability of the ultrasensitive electroactive biomembrane to different formaldehyde concentrations by calculating the slope change of a time-current curve so as to reflect the concentration of formaldehyde in the water body and draw a standard curve;
3) measurement and calculation of formaldehyde concentration in water body to be measured by using ultrasensitive electroactive biomembrane
And (3) respectively detecting the formaldehyde concentration of the water body to be detected by utilizing the ultrasensitive electroactive biomembranes formed by carbon sources with different concentrations, and reversely deducing the formaldehyde concentration in the water body to be detected by utilizing a formula through the change coefficient of current (the change slope of the current along with time) in combination with the standard curve of the second step.
Wherein the mixing volume ratio of the domestic sewage or the effluent of the long-term trained microbial fuel cell in the step 1) to the phosphoric acid buffer solution is 3-1: 1.
The step 2) of determining the response capability of different electroactive biological films to different formaldehyde concentrations by calculating the slope change of a time-current curve means that the sensitivity of the electroactive biological films to formaldehyde is reflected by the change of the current with time, and the standard is that the larger the slope is, the more sensitive the formed electroactive biological films are to formaldehyde.
The invention has the advantages and beneficial effects that:
compared with the prior art, the method realizes the rapid detection of the formaldehyde with trace concentration in the water body by optimizing the electroactive biomembrane, overcomes the defects of low sensitivity, high detection limit and high cost of the traditional detection technology, and provides a new technology for the detection of the sensor in the field of trace pollutants.
Drawings
FIG. 1 is a graph of the response trace concentration of 0.0001% formaldehyde of an electroactive biofilm with 0.5g/L sodium acetate as a carbon source, wherein A is the detection current of the electroactive biofilm with 0.5g/L sodium acetate to formaldehyde, and B is a linear fit.
FIG. 2 is a graph of the response trace concentration of 0.0001% formaldehyde of an electroactive biofilm with 0.2g/L sodium acetate as a carbon source, wherein A is the detection current of the electroactive biofilm with 0.2g/L sodium acetate to formaldehyde, and B is a linear fit.
FIG. 3 is a graph of the response trace concentration of 0.0001% formaldehyde of an electroactive biofilm with 0.1g/L sodium acetate as a carbon source, wherein A is the detection current of the electroactive biofilm with 0.1g/L sodium acetate to formaldehyde, and B is a linear fit.
FIG. 4 is a graph of the response trace concentration of 0.0001% formaldehyde of an electroactive biofilm with 1.0g/L sodium acetate as a carbon source, wherein A is the detection current of the electroactive biofilm with 1.0g/L sodium acetate to formaldehyde, and B is a linear fit.
FIG. 5 is a graph showing the change of formaldehyde concentration and current attenuation coefficient in response to formaldehyde concentration in an electroactive biofilm using 0.5g/l sodium acetate as a carbon source.
FIG. 6 is an amperometric graph of the response of an electroactive biomembrane with 0.5g/L sodium acetate as a carbon source to the change of the concentration of formaldehyde in the water body to be detected.
Detailed Description
Example 1: method for detecting formaldehyde by using 0.5g/L sodium acetate as carbon source and electroactive biomembrane
1) Culture of electroactive biofilms
The electrochemical reactor consists of a polytetrafluoroethylene cylinder with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, mixed liquid of effluent of the microbial fuel cell which is acclimated for a long time and phosphoric acid buffer solution is added into the electrochemical reactor, the mixing volume ratio is 2:1, 0.5g/L of sodium acetate is added as a carbon source, the electric active biological membrane culture is carried out by adopting a chronoamperometry, and the operation is carried out for 3 days.
2) Response of ultrasensitive electroactive biofilms to formaldehyde
The formaldehyde solutions at concentrations of 0.0001%, 0.0002%, 0.0005% and 0.0010% were added to the electrochemical reactor in which the stable electroactive biofilm had been formed, and the ability of the electroactive biofilm to detect the formaldehyde concentration was determined by calculating the change in the slope of the time-current curve. When 0.0001% formaldehyde solution is added, the current changes as shown in figure 1, and it can be seen that the electroactive biomembrane formed by the sodium acetate with the concentration is started can sensitively detect the trace formaldehyde in the water body. By plotting the change in current with formaldehyde concentration for four formaldehyde concentrations, as shown in fig. 5, the formula is: 6683.6x +0.5649, R2＝0.976。
3) Measurement and calculation of formaldehyde concentration in water body to be measured by using ultrasensitive electroactive biomembrane
The formaldehyde concentration of the water body A to be detected is detected by using the ultrasensitive electroactive biomembrane, and the formaldehyde concentration in the water body A to be detected is reversely deduced by using a formula by combining the standard curve of the second step through the change of current. As shown in fig. 6, the current variation coefficient is 1 × 10-8Corresponding to a formaldehyde concentration of 0.0006%.
Example 2: method for detecting formaldehyde by using 0.2g/L sodium acetate as carbon source and electroactive biomembrane
1) Culture of electroactive biofilms
The electrochemical reactor consists of a polytetrafluoroethylene cylinder with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, mixed liquid of effluent of the microbial fuel cell which is acclimated for a long time and phosphoric acid buffer solution is added into the electrochemical reactor, the mixing volume ratio is 3:1, 0.2g/L of sodium acetate is added as a carbon source, the electroactive biomembrane culture is carried out by adopting a chronoamperometry, and the operation is carried out for 4 days.
2) Response of ultrasensitive electroactive biofilms to formaldehyde
The formaldehyde concentration detection ability of the electroactive biofilm was determined by calculating the slope change of the time-current curve by adding 0.0001%, 0.0005%, 0.0020%, and 0.0050% formaldehyde solution to the electrochemical reactor in which the stable electroactive biofilm had been formed. As shown in FIG. 2, it can be seen that the electroactive biomembrane formed by the initiation of the sodium acetate with the concentration can sensitively detect the trace formaldehyde in the water body. A standard curve is drawn by the change in current caused by four formaldehyde concentrations versus formaldehyde concentration. The formula is as follows: 13603.7x +1.9824, R2＝0.962。
3) Measurement and calculation of formaldehyde concentration in water body to be measured by using ultrasensitive electroactive biomembrane
The formaldehyde concentration of the water body B to be detected is detected by using the ultrasensitive electroactive biomembrane, and the formaldehyde concentration in the water body to be detected is reversely deduced by using a formula by combining the standard curve of the second step through the change of current. Current change was 2.5 x 10-8Corresponding to a formaldehyde concentration of 0.0030%.
Example 3: method for responding electroactive biomembrane to formaldehyde by using 0.1g/L sodium acetate as carbon source
1) Culture of electroactive biofilms
The electrochemical reactor consists of a polytetrafluoroethylene cylinder with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, mixed liquid of effluent of the microbial fuel cell which is acclimated for a long time and phosphoric acid buffer solution is added into the electrochemical reactor, the mixing volume ratio is 1:1, 0.1g/L of sodium acetate is added as a carbon source, the electric active biological membrane culture is carried out by adopting a chronoamperometry, and the operation is carried out for 5 days.
2) Response of ultrasensitive electroactive biofilms to formaldehyde
The electrochemical reactor in which the stable electroactive biofilm had been formed was charged at concentrations of 0.0001%, 0.0002%, 0.0010% and 0.002And (3) determining the detection capability of the electroactive biomembrane on the formaldehyde concentration by calculating the slope change of a time-current curve in 0% formaldehyde solution. As shown in FIG. 3, it can be seen that the start-up of sodium acetate with the concentration is more remarkable than that of 0.2g/L, the increase is 3% at the concentration of 0.0001%, and a remarkable response can also occur at the concentration of 0.0001% formaldehyde, which indicates that 0.1g/L of sodium acetate as a carbon source can realize the detection of formaldehyde with trace concentration. A standard curve is drawn by the change in current caused by four formaldehyde concentrations versus formaldehyde concentration. The formula is as follows: 23930x +2.146, R2＝0.985。
3) Measurement and calculation of formaldehyde concentration in water body to be measured by using ultrasensitive electroactive biomembrane
The formaldehyde concentration of the water body C to be detected is detected by using the ultrasensitive electroactive biomembrane, and the formaldehyde concentration in the water body C to be detected is reversely deduced by using a formula by combining the standard curve of the second step through the change of current. Current change was 2.5 x 10-8Corresponding to a formaldehyde concentration of 0.0010%.
Comparative example: traditionally, the formaldehyde is detected by culturing an electroactive biomembrane by taking 1.0g/L of sodium acetate as a carbon source
1) Culture of electroactive biofilms
The electrochemical reactor consists of a polytetrafluoroethylene cylinder with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, mixed liquid of effluent of the microbial fuel cell which is acclimated for a long time and phosphoric acid buffer solution is added into the electrochemical reactor, the mixing volume ratio is 1:1, 1.0g/L of sodium acetate is added as a carbon source, the electric active biological membrane culture is carried out by adopting a chronoamperometry, and the operation is carried out for 5 days.
2) Response of electroactive biofilms to formaldehyde
The formaldehyde solutions with concentrations of 0.0001%, 0.0002%, 0.0005% and 0.0020% were added to the electrochemical reactor in which the stable electroactive biofilm had been formed, and the ability of the electroactive biofilm to detect the formaldehyde concentration was determined by calculating the slope change of the time-current curve. As shown in fig. 4, it can be seen that this concentration of sodium acetate start-up did not achieve a significant response to formaldehyde at a concentration of 0.0001%. By drawing a standard curve of the change of current caused by four formaldehyde concentrations and the formaldehyde concentration. The formula is as follows: 1079.8x +0.5953, R2＝0.8168。
3) Measurement and calculation of formaldehyde concentration in water body to be measured by electroactive biomembrane
As can be seen, the electroactive biomembrane started by 1.0g/L sodium acetate as a carbon source cannot respond well to the formaldehyde content change (R) with known concentration2<0.9), therefore, the detection of formaldehyde in the water body to be detected can not be completed.
Claims (3)
1. A method for detecting ultralow-concentration formaldehyde in a water body by using an ultrasensitive electroactive biomembrane is characterized by comprising the following steps:
1) culture of ultrasensitive electroactive biofilm
The electrochemical reactor consists of a polytetrafluoroethylene cylinder with the upper diameter of 8cm, the lower diameter of 7cm and the height of 12cm, solution of domestic sewage or mixed liquid of effluent of a microbial fuel cell domesticated for a long time and phosphoric acid buffer solution is added into the electrochemical reactor, 0.1-0.5 g/L of sodium acetate is added as a carbon source, an electric active biological membrane culture method with different sensitivities is adopted, and the operation is carried out for 3-5 days to form electric active biological membranes with different thicknesses and shapes;
2) response of ultrasensitive electroactive biofilms to formaldehyde
Adding 0.0001-0.005% formaldehyde solution into the electrochemical reactor for forming the stable electroactive biomembrane, and determining the response capability of the ultrasensitive electroactive biomembrane to different formaldehyde concentrations by calculating the slope change of a time-current curve so as to reflect the formaldehyde concentration in the water body and draw a standard curve;
3) detection and calculation of formaldehyde concentration in water body to be detected by using ultrasensitive electroactive biomembrane
And (3) respectively detecting the formaldehyde concentration of the water body to be detected by utilizing the ultrasensitive electroactive biomembranes formed by carbon sources with different concentrations, and reversely deducing the formaldehyde concentration in the water body to be detected by utilizing a formula through the change coefficient of current, namely the change slope of the current along with time in combination with the standard curve of the second step.
2. The method for realizing the response to the ultralow-concentration formaldehyde by using the ultrasensitive electroactive biomembrane as claimed in claim 1, wherein the mixing volume ratio of the effluent of the domestic sewage or the long-term trained microbial fuel cell in the step 1) to the phosphoric acid buffer solution is 3-1: 1.
3. The method for realizing the response of the ultrasensitive electroactive biofilm to the ultralow-concentration formaldehyde according to claim 1 or 2, wherein the step 2) of determining the response capability of different electroactive biofilms to different formaldehyde concentrations by calculating the slope change of a time-current curve is to reflect the sensitivity of the electroactive biofilm to the formaldehyde by the slope of the change of the current along with the time, and the standard is that the larger the slope is, the more sensitive the formed electroactive biofilm is to the formaldehyde, and the more capable the formed electroactive biofilm can detect the ultralow-concentration formaldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102608181A (en) * | 2012-04-10 | 2012-07-25 | 中国科学院长春应用化学研究所 | Method for detecting biochemical oxygen demand |
| CN106645348A (en) * | 2016-12-23 | 2017-05-10 | 南开大学 | Method for preparing high-stability microbial electrochemical sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102608181A (en) * | 2012-04-10 | 2012-07-25 | 中国科学院长春应用化学研究所 | Method for detecting biochemical oxygen demand |
| CN106645348A (en) * | 2016-12-23 | 2017-05-10 | 南开大学 | Method for preparing high-stability microbial electrochemical sensor |
Non-Patent Citations (2)
| Title |
|---|
| Development of highly selective and stable potentiometric sensors for formaldehyde determination;Yaroslav I. Korpan et.al;《Biosensors & Bioelectronics》;20000331;第15卷;第77-83页 * |
| 应用微生物传感器测定甲醛;崔建升 等;《理化检验-化学分册》;20111231;第47卷(第2期);第144-146、149页 * |
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