Method of measuring concentration of dissolved organic nitrogen in sewage

Abstract

A method of measuring concentration of dissolved organic nitrogen in sewage. The method includes: filtering a sewage sample using a filter membrane; measuring the concentrations of total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), and nitric nitrogen (NO.sub.3.sup.−) in the sewage sample, respectively designated as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I); calculating the ratios of (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I))/C.sub.TDN(I) and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I), and according to the ratios, calculating the concentration of dissolved organic nitrogen (DON) in the sewage sample.

Claims

1. A method of measuring a concentration of dissolved organic nitrogen in sewage, the method comprising: (1) extracting a sewage sample from an anaerobic stage or an aerobic stage of a wastewater treatment plant and filtering the sewage sample using a filter membrane to obtain a filtered sewage sample; (2) measuring concentrations of total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), and nitric nitrogen (NO.sub.3.sup.−) in the filtered sewage sample, respectively designated as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I); and (3) when (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I))/C.sub.TDN(I)≥0.7 and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I)<1, dialyzing the filtered sewage sample in a suspended dialysis bag for between 34 and 38 hours to obtain a dialyzed sewage sample, and measuring concentrations of total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) in the dialyzed sewage sample, respectively designated as C.sub.TDN(III), C.sub.NH4.sup.+.sub.(III), C.sub.NO3.sup.−.sub.(III), and C.sub.NO2.sup.−.sub.(III), and obtaining a concentration of dissolved organic nitrogen (DON) in the sewage sample as follows: DON=C.sub.TDN(III)—C.sub.NH4.sup.+.sub.(III)—C.sub.NO3.sup.−.sub.(III)—C.sub.NO2.sup.−.sub.(III); wherein: the suspended dialysis bag is a cellulose ester membrane; the suspended dialysis bag is hydrophilic; and the suspended dialysis bag has a molecular weight cut-off (MWCO) of 100-500 Da, and a hydraulic retention time of a dialysate in the sewage sample is 4 h.

2. The method of claim 1, wherein the filter membrane has a pore size of 0.45 μm.

3. The method of claim 1, wherein the concentrations of the total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) are measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry, respectively.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flow chart of a method of measuring concentration of dissolved organic nitrogen in sewage as described in the disclosure; and

(2) FIG. 2 is a comparison diagram of concentrations of dissolved organic nitrogen measured by conventional methods and the method as described in the disclosure;

(3) FIG. 3 is a diagram of measured DON concentrations of urea solution, glutamic acid solution, and bovine serum albumin (BSA) solution having a solute concentration of 1 mg/L and varying DIN/TDN ratios;

(4) FIG. 4 is a diagram of 95% confidence intervals of the measured DON concentrations of FIG. 3;

(5) FIG. 5 is a diagram of removal rates of NO.sub.3.sup.− by dialyzing NW/NO.sub.3.sup.− solutions using dialysates having different hydraulic retention times; and

(6) FIG. 6 is a diagram of the high average absolute deviation of the concentration of DON with respect to the actual concentration of DON in urea solution, glutamic acid solution, and BSA solution measured after dialysis of different dialysis time.

DETAILED DESCRIPTION

(7) Measurement conditions affecting the method of measuring the DON concentration in sewage are described below in details with reference to the drawings.

(8) 1. Influence of DIN/TDN Ratio on the Measurement of DON Concentration:

(9) Three nitrogen-containing organic compounds having different molecular weights, including urea, glutamic acid, and bovine serum albumin (BSA), were dissolved in water at a concentration of 1 mg/L, respectively. Concentrations of the nitrogen-containing organic compounds in the sample solutions were measured without dialysis. As shown in FIG. 3, when DIN/TDN≤0.7, the measured DON concentrations of the three nitrogen-containing organic compounds are close to their actual concentration of 1 mg/L, and the 95% confidence intervals (95% C.I.) of the measured DON concentrations are less than 0.4. When DIN/TDN≥0.7, the measured DON concentrations of the nitrogen-containing organic compounds obviously deviate from the actual concentration of 1 mg/L. For example, when DIN/TDN=0.92, the measured concentration of glutamic acid is 1.82±0.88 mg/L, while 95% C.I.=1.72. FIG. 4 shows that 95% C.I. increases with the increase of DIN/TDN ratio.

(10) The measurement of DON concentration is calculated by subtracting DIN (sum of the concentrations of NH.sub.4.sup.+, NO.sub.3.sup.−, and NO.sub.2.sup.−) from TDN. Because each species of inorganic nitrogen would produce a concentration error during the measurement, the subtraction of DIN that includes concentrations of multiple species from TDN would amplify error in the DON measurement. Therefore, when DIN/TDN≥0.7 in the sewage, the accuracy of DON measurement is low (95% C.I.>0.4) and, therefore, dialysis pretreatment is required to improve measurement accuracy.

(11) 2. Hydraulic Retention Time of Dialysates:

(12) The inorganic nitrogen species in sewage are mainly NH.sub.4.sup.+ and NO.sub.3.sup.−, and additionally NO.sub.2.sup.− at a low concentration. To determine the influence of the dialysates' hydraulic retention time on DON measurement, solutions respectively containing 5 mg/L of NH.sub.4.sup.+ and 15 mg/L of NO.sub.3.sup.− were prepared as sample solutions. Dialysis of the sample solutions was conducted by using dialysates having a hydraulic retention time of 1, 2, 4, 8, 12, and 24 h, respectively, for 12 or 24 h. The concentrations of remaining NH.sup.4+ and NO.sub.3.sup.− in the dialysis bags were measured after dialysis. The results are shown in FIG. 5. When the hydraulic retention time of the dialysate increases from 1 h to 4 h, the concentrations of remaining NH.sub.4.sup.+ and NO.sub.3.sup.− in the dialysis bag do not increase significantly. When the hydraulic retention time of dialysate is greater than 4 h, as the dialysate hydraulic retention time increases, the concentrations of remaining NH.sub.4.sup.+ and NO.sub.3.sup.− in dialysis bags change obviously. For example, when the original concentration of NO.sub.3.sup.− is 15 mg/L and the hydraulic retention time of the dialysate increases from 4 h to 8 h, the ratio of the concentration of the remaining NO.sub.3.sup.− to the original concentration of NO.sup.3− (C/C.sub.0) increases from 0.48 to 0.63 after dialysis for 12 h, and increases from 0.29 to 0.34 after dialysis for 24 h. Thus, shorter hydraulic retention time of the dialysate results in greater removal rate of NH.sub.4.sup.+ and NO.sub.3.sup.−. When the hydraulic retention time of the dialysate is less than 4 h, the removal rate of NH.sub.4.sup.+ and NO.sub.3.sup.− does not increase with the decrease of the dialysate's hydraulic retention time.

(13) 3. Dialysis Time:

(14) Urea, glutamic acid, BSA, and a lyophilized sewage sample comprising organic nitrogen were dissolved in solutions having a variety of NO.sub.3.sup.−/NH.sub.4.sup.+ ratios. The concentrations of urea, glutamic acid, BSA, and lyophilized sewage sample in the sample solutions were 1 mg/L. The hydraulic retention time of the dialysate was 4 h. The DON concentrations of the prepared solutions were measured after dialysis for different time. The results are shown in FIG. 6.

(15) The NO.sub.3.sup.−/NH.sub.4.sup.+ ratio of the sample significantly affects the measured DON concentration. As shown in FIG. 6, when the dialysis time (t) is 24 h and the NO.sub.3.sup.−/NH.sub.4.sup.+ ratio≥1, the average absolute deviation of the measured concentration of DON with respect to the actual concentration (1 mg/L) of the solutions of urea, glutamic acid, BSA, and the lyophilized sewage sample are smaller than those when NO.sub.3.sup.−/NH.sup.4+<1. In particular, when NO.sub.3.sup.−/NH.sub.4.sup.+<1 and DIN/TDN=0.92, the average absolute deviation of the measured concentration of DON with respect to the actual concentration of BSA is as high as 19.0%. The isoelectric point of the dialysis membrane used in the dialysis is pH=2.2. When the pH is greater than 2.2, the membrane is negatively charged and attracts the positively charged NH.sub.4.sup.+ so as to prevent NH.sub.4.sup.+ from passing through the dialysis membrane, which leads to a removal rate of NH.sub.4.sup.+ lower than that of NO.sub.3.sup.− and a high average absolute deviation of the measured concentration of DON with respect to the actual concentration of DON when NO.sub.3.sup.−/NH.sup.4+<1.

(16) As shown in FIG. 6, when NO.sub.3.sup.−/NH.sub.4.sup.+≥1, increase of the dialysis time from 24 h to 36 h or 60 h does not lead to significant change of the average absolute deviation of the measured concentration of DON with respect to the actual concentration of DON.

(17) To further illustrate, examples detailing a method of measuring concentration of dissolved organic nitrogen in sewage are described below. It should be noted that the following examples are intended to describe and not to limit the description.

Example 1

(18) 1. 100 mL of municipal sewage (labeled as sample 1) was filtered using a filter membrane having a pore size of 0.45 μm.

(19) 2. The concentrations of the total dissolved nitrogen (TDN), NH.sub.4.sup.+ and NO.sub.3.sup.− of the sewage were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, and ion chromatography, respectively, and were recorded as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I);

(20) 3. The results showed that (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I))/C.sub.TDN(I)=0.92>0.7 and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I)>1. The sewage was dialyzed in a suspended dialysis bag for 24 hours. The suspended dialysis bag was a cellulose ester membrane, hydrophilic, and had a molecular weight cut-off (MWCO) of 100 Da; and the hydraulic retention time of the dialysate in the sewage sample was 4 h. Thereafter, the concentrations of the total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry, respectively, and recorded as C.sub.TDN(II), C.sub.NH4.sup.+.sub.(II), C.sub.NO3.sup.−.sub.(II), and C.sub.NO2.sup.−.sub.(II), respectively.

(21) 4. The concentration of the dissolved organic nitrogen (DON) in the sewage sample was calculated as follows: DON=C.sub.TDN(II)—C.sub.NH4.sup.+.sub.(II)—C.sub.NO3.sup.−.sub.(II)—C.sub.NO2-(II). The DON in the sample 1 was 0.80 mg/L. To ensure the accuracy and reliability of the measurement, the measurement was performed three times and the measured values were averaged. The results are shown in FIG. 2.

Example 2

(22) 1. 100 mL of municipal sewage extracted from the anaerobic stage of a wastewater treatment plant (labeled as sample 2) was filtered using a filter membrane having a pore size of 0.45 μm.

(23) 2. The concentrations of the total dissolved nitrogen (TDN), NH.sub.4.sup.+ and NO.sub.3.sup.− of the sewage were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, and ion chromatography, respectively, and were recorded as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I);

(24) 3. The results showed that (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I)/C.sub.TDN(I)=0.73>0.7 and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I)<1. The sewage was dialyzed in a suspended dialysis bag for 34 hours. The suspended dialysis bag was a cellulose ester membrane, hydrophilic, and had a molecular weight cut-off (MWCO) of 100 Da; and the hydraulic retention time of the dialysate in the sewage sample was 4 h. Thereafter, the concentrations of the total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry, respectively, and recorded as C.sub.TDN(III), C.sub.NH4.sup.+.sub.(III), C.sub.NO3.sup.−.sub.(III), and C.sub.NO2.sup.−.sub.(III), respectively.

(25) 4. The concentration of the dissolved organic nitrogen (DON) in the sewage sample was calculated as follows: DON=C.sub.TDN(III)—C.sub.NH4.sup.+.sub.(III)—C.sub.NO3.sup.−.sub.(III). The DON in the sample 2 was 2.43 mg/L. To ensure the accuracy and reliability of the measurement, the measurement was performed three times and the measured values were averaged. The results are shown in FIG. 2.

Example 3

(26) 1. 100 mL of municipal sewage extracted from the aerobic stage of a wastewater treatment plant (labeled as sample 3) was filtered using a filter membrane having a pore size of 0.45 μm.

(27) 2. The concentrations of the total dissolved nitrogen (TDN), NH.sub.4.sup.+ and NO.sub.3.sup.− of the sewage were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, and ion chromatography, respectively, and were recorded as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I);

(28) 3. The results showed that (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I))/C.sub.TDN(I)=0.75>0.7 and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I)≥1. The sewage was dialyzed in a suspended dialysis bag for 24 hours. The suspended dialysis bag was a cellulose ester membrane, hydrophilic, and had a molecular weight cut-off (MWCO) of 100 Da; and the hydraulic retention time of the dialysate in the sewage sample was 4 h. Thereafter, the concentrations of the total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry, respectively, and recorded as C.sub.TDN(II), C.sub.NH4.sup.+.sub.(II), C.sub.NO3.sup.−.sub.(II), and C.sub.NO2.sup.−.sub.(II), respectively.

(29) 4. The concentration of the dissolved organic nitrogen (DON) in the sewage sample was calculated as follows: DON=C.sub.TDN(II)—C.sub.NH4.sup.+.sub.(II)—C.sub.NO3.sup.−.sub.(II)—C.sub.NO2-(II). The DON in the sample 3 was 1.89 mg/L. To ensure the accuracy and reliability of the measurement, the measurement was performed three times and the measured values were averaged. The results are shown in FIG. 2.

Example 4

(30) 1. 100 mL of treated water extracted from the output of a wastewater treatment plant (labeled as sample 4) was filtered using a filter membrane having a pore size of 0.45 μm.

(31) 2. The concentrations of the total dissolved nitrogen (TDN), NH.sub.4.sup.+ and NO.sub.3.sup.− of the sewage were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, and ion chromatography, respectively, and were recorded as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I);

(32) 3. The results showed that (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I))/C.sub.TDN(I)=0.95>0.7 and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I)≥1. The sewage was dialyzed in a suspended dialysis bag for 25 hours. The suspended dialysis bag was a cellulose ester membrane, hydrophilic, and had a molecular weight cut-off (MWCO) of 100 Da; and the hydraulic retention time of the dialysate in the sewage sample was 4 h. Thereafter, the concentrations of the total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry, respectively, and recorded as C.sub.TDN(II), C.sub.NH4.sup.+.sub.(II), C.sub.NO3.sup.−.sub.(II), and C.sub.NO2.sup.−.sub.(II), respectively.

(33) 4. The concentration of the dissolved organic nitrogen (DON) in the sewage sample was calculated as follows: DON=C.sub.TDN(II)—C.sub.NH4.sup.+.sub.(II)—C.sub.NO3.sup.−.sub.(II)—C.sub.NO2-(II). The DON in the sample 4 was 0.51 mg/L. To ensure the accuracy and reliability of the measurement, the measurement was performed three times and the measured values were averaged. The results are shown in FIG. 2.

Example 5

(34) 1. 100 mL of 0.99 mg/L standard glutamate solution was mixed with 10 mL of 40.09 mg/L potassium nitrate solution. The mixture (labeled as sample 5) was filtered using a filter membrane having a pore size of 0.45 μm.

(35) 2. The concentrations of the total dissolved nitrogen (TDN), NH.sub.4.sup.+ and NO.sub.3.sup.− of the mixture were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, and ion chromatography, respectively, and were recorded as C.sub.TDN(I), C.sub.NH4.sup.+.sub.(I) and C.sub.NO3.sup.−.sub.(I);

(36) 3. The results showed that (C.sub.NH4.sup.+.sub.(I)+C.sub.NO3.sup.−.sub.(I))/C.sub.TDN(I)=0.81>0.7 and C.sub.NO3.sup.−.sub.(I)/C.sub.NH4.sup.+.sub.(I)>1. The sewage was dialyzed in a suspended dialysis bag for 24 hours. The suspended dialysis bag was a cellulose ester membrane, hydrophilic, and had a molecular weight cut-off (MWCO) of 100 Da; and the hydraulic retention time of the dialysate in the sewage sample was 4 h. Thereafter, the concentrations of the total dissolved nitrogen (TDN), ammonia nitrogen (NH.sub.4.sup.+), nitric nitrogen (NO.sub.3.sup.−) and nitrite nitrogen (NO.sub.2.sup.−) were measured using potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite spectrophotometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry, respectively, and recorded as C.sub.TDN(II), C.sub.NH4.sup.+.sub.(II), C.sub.NO3.sup.−.sub.(II), and C.sub.NO2.sup.−.sub.(II), respectively.

(37) 4. The concentration of the dissolved organic nitrogen (DON) in the sewage sample was calculated as follows: DON=C.sub.TDN(II)—C.sub.NH4.sup.+.sub.(II)—C.sub.NO3.sup.−.sub.(II)—C.sub.NO2-(II). The DON in the sample 5 was 1.05 mg/L. To ensure the accuracy and reliability of the measurement, the measurement was performed three times and the measured values were averaged. The results are shown in FIG. 2.

(38) As shown in FIG. 2, when the sewage samples 1-4 were not pretreated using the method described in the disclosure, the standard deviation of the measured values was large, and thus the concentration of the DON in the sewage cannot be concluded, or even a negative value was obtained. According to the measurement method as described in the disclosure, the measured value of the DON concentration of the sample 5 was 1.03±0.03 mg/L, and the standard error between the measured value and the truth value (0.99 mg/L) is 4.04%. The standard error between the DON concentration measured using conventional methods and the truth value in the sample 5 is 33.33%. Therefore, the method of measurement of the concentration of DON is accurate. The standard deviation of the repeated tests is within 10%.

(39) It will be obvious to those skilled in the art that changes and modifications may be made, and therefore, the aim in the appended claims is to cover all such changes and modifications.