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PHOSPHORUS DETERMINATION PREPARED BY Student name TD tereer Student name ID #teeeee Student name TD teteee IN PARTIAL FULFILLMENT OF THE REQUIREMENT FOR CIVL 4136 ENVIRONMENTAL ENGINEERING | SUBMITTED Month day, Year INTRODUCTION ‘Natural waters and wastewaters contain phosphorus in the form of phosphates. These phosphorous forms are classified as orthophosphates, condensed phosphates and organically bound phosphates. Phosphates occur in solution, in particles or detritus, or in the bodies of aquatic organisms. They can also occur in bottom sediments and in biological sludges, both as precipitated inorganic forms and incorporated into organic compounds (Standard Methods, 1998). ‘There are many sources for phosphates contamination. In water treatment, phosphates are widely used for softening and for the treatment of boiler waters to control scale formation, and corrosion. In wastewaters, polyphosphates can be introduced from commercial detergents and to a smaller degree from water treatment processes. Fertilizers are the primary source for orthophosphates that enter natural water systems through runoff and melt water. Biologi activities normally produce organic phosphates but not to a (Lab 2 handout, 2007). nificant water quality concern In this lab, phosphate analysis will be conducted using the vanadomolybdo- phosphoric method. Six samples will be tested for phosphate concentrations. Sample 1 is an untreated mixture of 56.2 mg/L KzHPOs, 22.9 mg/L POs and 88.8 mg/L DPPA (CiHigNsOsP), sample 2 is Acid hydrolyzed mixture of sample 1, sample 3 is digested mixture of sample 1, sample 4 is untreated 1000 mg/L Sparkleen detergent, sample 5 is Acid hydrolyzed 1000 mg/L Sparkleen detergent and sample 6 is 1000 mg/L Sparkleen detergent. The objectives of this lab are to: ‘© determine a standard curve for phosphate concentrations, with absorbance at 470 nm, ‘© determine the reactive phosphate, acid hydrozysable phosphate, organic phosphate and total phosphate of the six samples and ‘+ determine the percentage by weight of total phosphate, polyphosphate, organic phosphate and orthophosphate in the original detergent that was used to prepare the samples METHODOLOGY The material and procedure followed in this laboratory is outlined in lab handout found in Appendix A. RESULTS ‘A standard curve as shown in Figure 1 was developed from the standard taken from the phosphate stock solution concentrations ranging from 0 (blank) to 20 mg/L. P. for each concentration, two replicates were taking and the average of these replicates were used to develop the standard curve by plotting phosphate concentration versus the average absorbance values (see Table BI in Appendix B). The results obtained showed a clear linear relationship between absorbance and phosphate concentration with R? of 0.998. The slope of the standard curve equation can be used to determine the phosphate concentration of the six diluted samples as mg/L P by dividing the absorbance value for the sample by the slope value. Table B2 in Appendix B summarizes the absorbance values (in replicates) for the six samples at different dilution levels. The absorbance value increases as the concentration of the sample increases except for sample 4 (see the discussion part for details). 036 02s. 01s: ‘Average absorbance 005: Phosphorous cone. mg/L P Figure 1: Standard curve for phosphate concentration (mg/L P) Results of the phosphate analysis are shown in Table 1. The results are the actual concentrations averages of the samples after discarding improper concentration values (see discussion part for more details). Sample calculations based on the standard curve are provided in Appendix C (see Table C1 for all concentrations observed). Table 2 shows the expected and observed concentrations in the six samples. The expected concentrations were determined using the information provided in the lab handouts and (see Appendix A). Table Cl in Appendix C). Sample calculations are provided in Appendix C. Table 1. Results for phosphate analysis ‘Concentration of phosphate in mg/L P Sample A B c D Mixture PI 10.26 9.47 28.95 9.21 ‘Mixture P2 13.55 5.92 3171 12.24 Mixture P3 12.63 7.89 28.95, 8.42 Sparkleen P1 14.74 Rejected Rejected NIA Sparkleen P2 36.97 26.05 60.79 0.00 Sparkleen P3 34.74 79.21 uz 3.16 ‘Table 2. Comparison between Observed and expected values Phosphate concentration in Sample Ping P % Error Expected | Observed i 10 | _12.15 215 2 20 1991 0.45 3 30.01 29.87 OAT 4 WA 28.82 NA 3 NA 81.45 N/A 6 NA 88.95 NA Percentages by weight of the various types of phosphate found in the detergent were calculated using the data in Table 1. Sample calculations are found in Appendix C. Organic phosphate has the lowest percentage while polyphosphate is the dominant phosphate species in this detergent. ‘Table 3: Percentages by weight of the types of Phosphate in the Detergent Observed 5 Type of concentration |” Weight phosphate my) Total Phosphate 88.95 890% Polyphosphate 52.63 5.26% Organic Phosphate 75 0.75% Orthophosphate 28.82 2.88% DISCUSSION The phosphorus concentration measured in sample I was the reacti phosphate, since it responded to colorimetric tests without preliminary hydrolysis or oxidative digestion of the sample. The observed phosphorus concentration was 12.15 mg/L with expected 10.0 mg/L. with an error of 21.5%. The difference may be due to procedural error or due to the fact that a small fraction of any condensed phosphate present could be hydrolyzed unavoidably in the procedure and that reactive phosphorous can be found in both dissolved and suspended forms (Standard Methods, 1998). The observed phosphorus concentration in sample 2 was 19.91 mg/L while the expected value was 20.0 mg/L with error of -0.45%. This result is quite good and the observed difference could be due to the release of some phosphate from the organic compound, Normally, the release of phosphate from the organic compound can be minimized by selection of optimum acid strength and hydrolysis time and temperature (Standard Methods, 1998). ‘The observed and expected phosphorus concentrations in sample 3 were 29.87 mg/L and 30.01 mg/L, respectively. The error associated with these values is -0.47%, which is a small figure indicating that good results have been achieved, The observed concentrations of the various forms of phosphate found in the detergent sample were, total phosphate as 88.95 mg/L, polyphosphate as 52.63 mg/L, organic phosphate as 7.5 mg/L. and orthophosphate as 28.82 mg/L. The concentration of polyphosphate was the highest. ‘This means that the detergents are the primary source of polyphosphate. The percentages by weight of the observed concentrations are 8.90% for the 5. total phosphate, 5.26% for the polyphosphate, 0.75% for the organic phosphate and 2.88 % for the orthophosphate. It is difficult to comment on these values, since the concentration of the sample was provided in the handouts instead of the molecular weight of the forms of phosphate in it The orthophosphate was determined with little interference from the other forms of phosphate. To determine polyphosphate, the sample was acid hydrolyzed, which converted the polyphosphate into orthophosphate. The orthophosphate concentration was then determined and extrapolated for polyphosphate concentration. The extrapolation may not have given the true concentration since other forms of phosphate could have been converted to orthophosphate and then measured. The same problem may have been encountered in extrapolating for organic phosphate. According to Standard Methods (1998), for analyzing the concentration of orthophosphates in a sample containing roughly 0.02 % P, it is recommended to use the stannous chloride method or the ascorbic method. As mentioned in the theory part, these two methods are more suited for the range of 0.01 to 6 mg/L P. The Vanadomolybdophosphoric acid method is most useful for routine analyses in the range of 1 to 20 mg/L P (Standard Methods, 1998). It is therefore not appropriate for analyzing samples with phosphate concentration of 40 mg/L. P. The nit acid-sulfuric acid method is stated by Standard Methods (1998) to be the method that is recommended for most samples. Therefore, it should be appropriate for samples with phosphate concentration of 40 mg/L P. In acid hydrolysis, 0.5 mL (1 drop) phenolphthalein indicator solution is added to a 100 mL sample or a portion diluted to 100 mL. It is then boiled gently for at least 90 minutes, adding water to keep the volume between 25 and 50 mL. Calibration curves are prepared by carrying a series of standards containing orthophosphates, through the above method. The phosphorus concentrations of treated portions are determined using the vanadomolybdophosphoric acid method, the stannous chloride method or the ascorbic acid method (Standard Methods, 1998). In the persulfate digestion method, a 50 mL or suitable portion of sample is thoroughly mixed. Then, 0.05 mL (1 drop) phenolphthalein indicator solution is added H,$0, solution is added in dropwise to discharge red color if it develops. The sample is boiled on a preheated hot plate for 30 to 40 minutes or until @ final volume of 10 mL is reached. It is cooled, diluted to 30 mL with distilled water and 0.05 mL (1 drop) phenolphthalein indicator solution. The color is neutralized to faint pink with NaOH. The phosphorus contents are determined by any of the colorimetric methods, as in acid hydrolysis method (Standard Methods, 1998). Harmful algae are microscopic, single-celled plants that live in the sea, They grow very fast and accumulate into dense, visible patches near the surface of the water. They produce potent neurotoxins that can be transferred through the food, where they affect and even kill the higher forms of life such as shellfish, fish and even humans who get exposed to such contaminated food (The harmful of algae homepage, 2002). CONCLUSION The results obtained from this laboratory experiment were fairly good. The reactive phosphate (orthophosphate) for sample 1 was found to be 12.15 mg/L P with 21.5% deviation from the expected value. This deviation might be due to unavoidable acid hydrozysble phosphate. Sample 2 showed very good results with only ~0.45% error. Good observations have been obtained for sample 3 as well with only ~0.47% error. The concentration of polyphosphate in the detergent samples was found to be the highest. This concludes that the detergents are primary sources of polyphosphate. The percentages by weight of the observed concentrations are 8.90% for the total phosphate, 5.26% for PO,*, 0.75% for the organic phosphate and 2.88 % for the orthophosphate. There was no way to compare detergents results with expected values since the molecular compositions of the detergents were unknown. REFERENCES Greenberg, A.E., L.S. Clesceri and A.D, Eaton, editors.(1998) Standard Methods for Examination of Water and Wastewater, Section 4500, 20" ed. Washington, D.C.: American Public Health Association , American Water Works Association, and Water Environment Federation. Lab Handout (2007). Phosphate Analysis, Department name, University name, Country name, pp 1-?. The harmfal of algae homepage, 2007, hrtp:/hvww.whoi.ediredtide htm! APPENDIX A (LAB HANDOUT) APPENDIX B RAW DATA Samples Phosphate stock solution (50.0 mg/L ~ phosphorus) Sample 1: Untreated mixture: 56.2 mg/L. KHPOs, 22.9 mg/L POs and 88.8 mg/L DPPA (CigHioNsOsP) Sample 2: Acid hydrolyzed mixture: 56.2 mg/L K2HPO,, 22.9 mg/L P20s and 88.8 mg/L. DPPA (Ci2HigNsOsP) Sample 3: Digested mixture: 56.2 mg/L KHPO,, 22.9 mg/L P;Os and 88,8 mg/L DPPA, (Cr2HioNsOsP) Sample 4: untreated 1000 mg/L Sparkleen detergent Sample 5: Acid hydrolyzed 1000 mg/L Sparkleen detergent Sample 6: Digested 1000 mg/L Sparkleen detergent ‘Table B1. Standard solution results ‘Standard | Volume added] Phosphorus | Absorbance | Absorbance? | Average Solutions | °fS0lution | Concentration | (Replicate 1) | (Replicate 2) | Absorbance mt mgf.P | (at470nm) | (at470nm) | (at 470 am) Baink 0 0 0 0 o ‘Standard 1 5 25 [oe 0.062 0.053 ‘Standard 10 5 0.086 0176 0.104 ‘Standard 3 16 75 0.135 0.162 0.149 Standard 4 [20 10. 0185 (0.206 0.196 ‘Standard 30 18 0.284 0.264 (0283 ‘Standard 6 40 20, 0375 o37t 0.373 ‘Table B2. Absorbance measured for various dilutions at 470 nm. ‘Sample “Absorbance (at 470 nin) Dilution Pr=04 Dilution PS=O1 RIF Ra RI R2 T 0.083 0.073 0.026 0.022 z 0.155 0.145 ‘0.041 0.037 3 ‘0217 0.223 0.053 0.087 4 ‘0.103 | 0.415 (0.063 0.069. a 0.378 0.383 0.213 0.22 6 0.53 0.534 0.221 0.224 * Replicates APPENDIX C SAMPLE CALCULATIONS Determination of concentrations based on the standard curve From the standard curve of absorbance at 470 nm versus phosphorous (mg/L P), the equation relating absorbance (at 470 nm) of the samples and concentration of phosphorous is determined as follows Concentration (mg/L of P) = absorbance / 0.019 4 (20 mL of the sample + 10 mL of the reagent + 20 mL DI water), the concentration of phosphorous as mg/L P can be a. For sample one at dilution factor of P calculated as follows: Concentration = 0.078 / 0.019 = 4.11 mg/L P This was done for all samples in different dilutions. ‘The actual concentration of phosphorous in the sample can be determined by dividing the concentration of the sample in each dilution by the dilution factor. For sample 1 at PI dilution: Actual concentration = 4.11 /0.4 = 10.28 mg/L P Table C1 shows a summer of the concentration of all samples in different dilutions, It also provides the actual concentr n values of the samples according to each dilution. Table Cl. Concentration of phosphorous in the sample for different dilutions Average] Semple Aatal sample Dion | absorbance | concentration in | conceriaton as (atavonm_|someasmgt P|“ mgP Pi oo at 1028 1 P2 0.052 271 13.55 | P3 0.024 4.26 12.63 Pr 0180 9 974 2 P2 007d mean 3.69 19.47 3 0.038 205 2053 Pi 0720 18 7085 a 2 or2i S34 ait P3_ 0.055 2.89 | 28.95 Pi ota 529 1474 4 P2 z|puan0:141 739 [3697 ac) 0.066 a7 34.74 a 0.07 5 Pa, |_0240 303 | P3 [0217 _ 113.95, Fr O82 70.00 6 2 ont 60.79 P3 [0.208 cir ea * Rejected value (greater than 20 mg/L Py 10 ‘The concentration of phosphorous in each sample can be determined by averaging the actual concentration due to each dilution of the sample excluding sample concentration that are greater than 20 mg/L P (in the 50 mg/L samples). For sample 1: Concentration = (10.26 +13.55 +12.63) /3 = 12.15 mg/L P This value is then compared with the expected value for error determination (See Table 2). Determination of Expected Concentrations Sample I (untreated mixture) Dissolved phosphorous is in the form of PO, in this case named reactive phosphate (A). Concentration of KzHPOs = 56.2 mg/L Molecular mass of K3HPOs = 1742 Molecular Mass of phosphorus, P =3lg Concentration of reactive phosphate, A = 31 x 56.2/ 174.2 = 10.00 mg/L P Sample 2 (acid hydrolyzed mixture) Dissolved phosphorous is in the form of PO, (reactive phosphate, A) and P2Os acid hydrolysable phosphate, B). Caloulation for “A” is as before. Calculation for “B” Concentration of P;05= 22.9 mg/L MW of P:0s =142g Concentration of acid hydrolysable phosphate, B= (2x 31) x 22.9/ 142 = 10.00 mg/L P Sample 3 (Digested mixture) Total phosphate = A +B + D ‘A and B as before. C is the organic phosphate: Concentration of DPPA (CisHigNsOsP) = 88.8 mg/L. MW of C)2HioNsOsP =275¢ Concentration of organic phosphate, D = 31 x 88.8 /275 = 10.01 mg/L P For the Sparkleen detergent sample: expected values of phosphorous cannot be determined because the components of the samples are not known. Determination of Concentrations of types of Phosphate in Detergent from the experiment results: Sample 4: gives only the concentration of orthophosphates (reactive phosphate), Sample 5: gives the sum of concentra ns of orthophosphate and polyphosphate. Sample 6: gives the total phosphate concentration (orthophosphate, polyphosphate and organic). ‘The phosphate concentrations (in mg/L. P) determined in the three detergent samples are: Sample 4: A =28.82 mg/L P Sample 5: (A+B) = 81.45 mg/L P Sample 6: C= 88.95 mg/L P The concentrations of the types of phosphates in the detergent, can be calculated as follows: Total phosphate 38.95 mg/L. Orthophosphate = A = 28.82 mg/L. Polyphosphate = B = (A+B) - A = 81.45 28.82 = 52.63 mg/L. Organic phosphate = D = C - (A+B) 8.95 — 81.45 7.5 mg/L Percentage by weight % Weight = concentration (mg/L. P) x 100 / Concentration of detergent (mg/L) For total phosphate: % Weight = 88.95 x 100/ 1000 = 8.90 % For orthophosphate % Weight = 28.82 x 100/ 1000 = 2.88 % For polyphosphate: % Weight = 52.63 x 100/ 1000 = 5.26% For organic phosphate: % Weight = 7.5 x 100/ 1000 1.75 %