GULF STANDARD U.A.E, STANDARD NO:642/1996 N0:642/1997 FD tS a sea Aad EL ca METHODS OF TEST FOR DRINKING AND MINERAL WATER-- PART 6:DETERMINATION OF NITRATE, FLUORIDE AND BORATE a ee United Arab EmiratesStandardization & Metrology Organization for G.C.C. (GSMG) P.O. Box - 85245 RIYADH - 11691 METHODS OF TEST FOR DRINKING AND MINERAL WATER — PART 6: DETERMINATION OF NITRATE, FLUORIDE AND BORATE ICS 67,160.20 This Standard is issued on the basis of the decision of the Board of Directors in accordance with the decision of the Supreme Council of the G.C.C, States in its Third Session, held in Bahrain on 1403-01-23 (corresponding to 1982-11-09). Date of Board of Directors’ Approval 27-05-1417 Corresponding to Q9.10-1996 Date of Publication in the Official Gazette 22-09-1417 Corresponding to 3101-1997 Date of Enforcement 22-03-1418 Corresponding to 26.97.1997 ISSN : 1319 - 2337 All rights reserved to this organizationGULF STANDARD GS 642/1996 METHODS OF TEST FOR DRINKING AND MINERAL WATER — PART DETERMINATION OF NITRATE, FLUORIDE AND BORATE 1- SCOPE AND FIELD OF APPLICATION This standard is concerned with methods of test for determining nitrate, fluoride and borate in drinking and mineral water. 2. METHODS OF TEST 2.1 Determination of nitrate 2.1.1 Nitrate electrode method 24.1.1 Apparatus - Expanded scale or digital pH meter. ~ Nitrate ion electrode. ~ Magnetic stirrer: with Teflon - coated stirring bar. 2.1.1.2 Reagents Note: All reagents used should be of recognized analytical grade type (Analar), ~ Stock nitrate solution: Prepare by dissolving 721.8 mg anhydrous potassium nitrate (dried at 105°C for 24 hours) in distilled water and dilute to 1000 mi (each 1 ml from this solution contains 100 yg nitrogen). This solution can be maintained for at least 6 months by the addition of 2 ml of chloroform/litre. ~ Standard nitrate solutions: Prepare by diluting 1, 10 and 50 ml of stock nitrate solution to 100 ml with distilled water to obtain standard solutions of 1, 10 and 50 ppm nitrogen respectively. ~ Sodium hydroxide solution 0.1 N. ~ Buffer solution: Prepare by dissolving 6.66 g aluminium sulfate ALSO4-18H,0, 3.12 g silver nitrate, 1.24 g hydrogen borate and 1.94 g sulfomic acid in about 400 ml distilled water. Adjust to pH 3.0 by slowly adding 0.10 N sodium hydroxide solution. Dilute to 1000 ml with distilled water. Keep away from light.GULF STANDARD GS 642/1996 213 21.1.3.1 2113.2 2114 212 21.21 Note: ‘The sensitivity of nitrate electrode for effectiveness not for concentration, so the ionic length for electrode shall be constant in all standard solutions and test samples. Buffer solution containing silver sulfate is used for removing chloride, bromide iodide, sulfide and cyanide ions, and sulfomic acid is used for removing nitrate, and aluminium sulfate is used for removing organic acids, and adjustment of pH at 3 for decreases the effect of bicarbonate. Procedure Preparation of calibration curve: Transfer about 100 ml of standard nitrate solution (1 ppm nitrogen) to a 150 ml beaker and add same amount from buffer solution, Immerse the tips of the electrodes while stirring with the magnetic stirrer and record the Millivolt reading after one minute from immersing the electrodes. Remove the electrodes from the solution, rinse and dry. Repeat for 10 and 50 ppm standard nitrogen solutions. Plot the electrical potential measurements of the standard nitrate solutions against the nitrate concentration on two-cycle semilogarithmic graph paper, plotting nitrate activity on the logarithmic axis, with the lowest activity to the left of the page, and Millivolts on the linear axis. A. straight line with a slope of +59 (+58 to +59 for solutions at 24° to 26°C) Millivolt/decade should result ‘Treat the samples with the same procedure in standard solutions as mentioned in 2113.1. Calculation Calculate nitrate concentration of the sample as follows: Nitrate concentration (PPM) = curve X 4.43. litrogen concentration (PPM) from the calibration Brucine method Apparatus Filter photometer (spectrophotometer) for use at 410 nm. provided with 1 cm cell. - Pipettes. Stainless steel wire racks to hold tubes in which samples are to be prepared. Water bath provided with stirrer. Maintaining a temperature of at least 95°C when putting the cooled samples therein, Test tubes, made of borosilicate glass of approximate dimensions 2.5 cm x 15 em. ~ Cold water bath.GULF STANDARD GS 642/1996 2.1.2.2 21.2.3 212.3.1 2.1.2.3.2 Reagents = Stock nitrate solution: Prepare as specified in (2.1.1.2). - Standard nitrate solution: Prepare by diluting 10 ml stock nitrate solution to 1000 ml with distilled water (1 ml from this solution is equivalent to 1 ug nitrogen). Prepare immediately before use. ~ Sodium arsenite solution*: Prepare by dissolving 5 g sodium arsenite in distilled water and dilute to one litre. ~ Burcine-sulphanilic acid solution*: Prepare by dissolving 1 g burcine sulphate and 0.1 g sulphanilic acid in approximately 70 ml hot distilled water. Add 3 ml concentrated hydrochloric acid, cool and make up to 100 ml with distilled water. (This solution is stable for several months). ~ Sulphuric acid solution: Prepare by carefully adding 500 ml concentrated sulphuric acid to 125 ml distilled water. Cool to room temperature before using and keep tightly stoppered to prevent absorption of atmospheric moisture. ~ Sodium chloride solution: Prepare by dissolving 300 g sodium chloride in distilled water and dilute to 1000 ml. Procedure Preparation of nitrate standard solutions: Prepare nitrate standard solutions in the range 0.1 to 1 mg nitrogen/litre by diluting 1, 2, 4, 7, and 10 ml standard nitrate solution to 10 ml with distilled water (1 ml from this solution is equivalent to 1 Wg nitrogen). Pretreatment of sample: If the sample contains residual chlorine, remove by adding one drop (0.5 ml) sodium arsenite solution for each 0.1 mg chlorine and mix, Add 1 drop in excess to each 50 ml sample. Colour development: Set up the test tubes and blank test tube in the wire rack, so that each tube is surrounded by empty spaces. To each tube add 10 ml sample or 10 ml diluted portion containing between 0.1 and 0.8 jig nitrate and place the rack in a cold water bath and add 2 ml sodium chloride solution to each tube, then add 10 ml sulphuric acid solution, mix and allow to cool. Retum the tubes to the cold water bath, add to each 0.5 ml of burcine solution and sulphanilic acid and mix. Replace the rack with tubes in a boiling water bath that maintains a temperature of not less than 95°C. After exactly 20 minutes, remove the tubes from the water bath and immerse in a cold water bath until reaching to room temperature. Dry the tubes with tissue and read the absorbance of standard solutions and samples against the blank solution at 410 nm in filter photometer (spectrophotometer). * Avoid touch with mouth sodium arsenite solution and burcine solution for their toxicity.GULF STANDARD GS 642/1996 241.24 22 224 22.1.1 2.2.1.2 Correct the absorbance reading of the samples by subtracting their sample blank values from their final absorbance sample values. Prepare a standard curve from the absorbance values of the standard solutions minus the blank solution value versus nitrate concentration. Read the concentration of nitrate directly from the standard curve. Calculate the concentration of nitrate for diluted samples with adjusted concentration values which obtained from standard curve according to diluting value for each sample. Calculation Nitrogen content from calibration curve x 1000 ‘Nitrogen content (p.p.m) = sample volume (ml) Nitrate content (p.p.m) = Nitrogen content (p.p.m) x 4.43 Determination of fluoride. Fluoride electrode method Apparatus Expanded scale or digital pH meter or apparatus to measure ion concentrate. Sleeve type reference electrode. Fluoride electrode. Magnetic stirrer, with Teflon-coated stirrer bar. Stop watch. Reagents - Stock fluoride solution: Prepare by dissolving 221 mg anhydrous sodium fluoride in distilled water and dilute to 1000 ml. (1 ml from this solution is equivalent to 100 jig fluoride). - Standard fluoride solutions: Prepare by diluting 5 ml, 10 ml, 20 ml stock fluoride solution to 1000 ml with distilied water (1 ml from this solution is equivalent to 0.5, 1, 2 ppm fluoride). = Buffer solution its pH ranges from 5 to 5.5: Place approximately 500 ml distilled water in one litre beaker and add 57 ml glacial acetic acid, 58 g sodium chloride, and 12 g of sodium citrate dihydrate, stir to dissolve. Place the beaker in a cool water bath and add slowly 6 N sodium hydroxide solution (about 150 ml), with stirring until pH is between 5 and 5.5. Transfer the solution to a one litre volumetric flask and add distilled water to the mark.GULF STANDARD GS 642/196 2.2.13 2.2.1.3.1 2.21.32 2.2.1.3.3 2.2.1.3.4 2.22 2.2.2.1 2.22.2 Procedure ‘Add to each of the three 100 ml volumetric flasks the standard fluoride solutions. To each flask add by pipet 50 ml of buffer solution (of pH 5 to 5.5), dilute to 100 mi with distilled water and mix well. These standard solutions are equivalent to 0.25, 0.5 and 1 ppm fluoride. Preparation of calibration curve Add 25 ml from standard solution and 25 ml from buffer solution to 100 ml beaker. Immerse electrodes in the fluoride standard solutions, starting with the lowest concentration solution, and measure the potential for each solution while stirring, let electrodes remain in the solution 3 minutes at ieast or unti! reading is constant. Prepare the samples and treat with the samie procedure for standard solutions, adjust sample solution and standard solutions at a unified temperature, preferably room temperature. Immerse the electrodes and measure the developed potential while stirring the test solution, Let the electrodes remain in the solution for at least 3 minutes before taking a final positive millivolt reading. Rinse the electrodes with distilled water and dry from outside between readings. ‘When using the expanded scale pH meter, recalibrate the electrode by checking the potential reading of 1 ppm fluoride standard solution and adjust the calibration, if necessary, until the meter reads as before. Plot the potential measurement of the fluoride standard solutions against the concentration of fluoride on two-cycle semilogarithmic graph paper, plotting the concentration of fluoride (ppm) on the logarithmic axis. Read the fluoride concentration of sample from the standard curve. Alizarin visual method Apparatus ~ Nessler tubes matching 50 ml and 100 ml capacity for colour comparison. Reagents, - Standard fluoride solution: Prepare as in item 2.2.1.2 (1 ml from this solution is equivalent to 10 pig fluoride). ~ Zirconyl-alizarin reagent: Prepare by dissolving 300 mg zirconyl chloride octahydrate in 50 ml distilled water in a one litre volumetric flask. Dissolve 70 mg of alizarin sulphuric acid sodium salt (alizarin red S) in 50 ml distilled water and pour slowly into the zirconyl solution while stirring, The resulting solution becomes clear on standing for few minutes.GULF STANDARD GS 642/1996 ~ Mixed acid solution: Prepare by diluting 101 ml concentrated hydrochloric acid to approximately 400 ml with distilled water. Add carefully 33.3 ml concentrated sulphuric acid to approximately 400 ml distilled water. After cooling, mix the two acids. - Acid-zirconyl-alizarin reagent: To the zirconyl-alizarin reagent in the 1 litre volumetric flask, add the mixed acid solution, complete with distilled water to the mark, and mix well. The reagent changes in colour from red to yellow within an hour and is then ready for use, Store the reagent away from direct sunlight to extend reagent stability to 6 months. - Sodium arsenite solution*: Prepare as in item 2.1.2.2. 2.2.2.3 Procedure If the sample contains residual chlorine, remove by adding 1 drop of sodium arsenite solution/0.1 mg chlorine and mix. Prepare a series of standard fluoride solutions with 0.05 ppm difference by diluting various volumes of standard fluoride solution (1 ml from this solution is equivalent to 10 pig fluoride) to 100 ml in Nessler tubes. Check the standard fluoride solutions so that there is at least one with lower and one with higher fluoride concentration than that of the sample. 2.2.2.3.3 Adjust the temperature of samples and standard solutions so that the deviation between them is not more than 2°C, To 100 ml of the sample or to any of the standard solutions in Nessler tubes, add $ ml of the acid-zirconyl-alizarin reagent using a pipette, mix well and compare the colour of the sample and standard solutions after one hour from the mixing. 2.2.2.4 Calculation Fluoride concentration (ppm) = ‘Sampie volume (ni) * ‘Where: ‘A = Concentration of fluoride determined visually (ug). _B = Is applicable only when a sample is diluted to a volume B, and C Cia portion taken from it for colour development. 23 Determination of borate 2.3.1 Apparatus = Colorimetric equipment: One of the following is required: * Avoid to touch sodium arsenite solution with mouth for its toxicity.GULF STANDARD GS 642/196 23.2 23.3 2.33.1 23.3.1. a) Spectrophotometer: For use at 540 nm, with a minimum light path of 1 cm. b) Filter photometer: Equipped with a green filter having a maximum transmittance at 540 nm with a minimum light path of 1 cm. - Evaporating dishes: 100 to 150 ml capacity, of silica-glass, platinum or other suitable material, ~ Glass-stoppered volumetric flasks, 25 ml and 50 ml capacity. ~ Water bath, set at (55 + 2)°C. ~ Ion-exchange column, 50 cm long by 1.3 cm in diameter. Reagents ~ Stock boron solution (1 ml from this solution contains 100 jag boron): Prepare by dissolving 571.6 mg anhydrous boric acid in 900 ml deionized distilled water and dilute to 1 litre. Keep the solution in a plastic bottle tightly stoppered or any other container free from boron. ~ Standard boron solutions: Place 0.0, 0.2, 0.4, 0.6, 0.8 and 1 ml from stock solution in 100 ml bottles, dilute to the mark with deionized distilled water to obtain 0.0, 2, 4, 8 and 10 microgram boron/ml standard solutions. + Curcumin reagent: Prepare by dissolving 40 mg ground curcumin and 5 g oxalic acid in 80 ml 95% ethyl in 100 ml volumetric flask, add 4.2 ml concentrated hydrochloric acid, make up to 100 mi with ethyl alcohol. Filter the reagent if it is turbid. Keep in a refrigerator for several days. This resin is constant for several days if stored in refrigerators. - Ethy! or isopropyl alcohol 95%. ~ Reagents for removal of high hardness and cation interference: a) Strongly acidic cation - exchange resin. b) hydrochloric acid (1 + 5). Procedure Preparation of calibration curve Pipet 0 (for blank test), 0.25, 0.50, 0.75 and 1 j1g from boron standard solution into evaporating dishes of the same type, shape and size, and add distilled water to each dish to bring total volume to 1 ml.GULF STANDARD GS 642/1996 2.3.3.1.2 Add 4 ml curcumin reagent to each dish and swirl to mix contents thoroughly, float dishes on a water bath set at (55 + 2)°C and let them for 80 minutes for complete drying and removal of hydrochloric acid. 2.3.3.1.3 Cool the dishes to room temperature, add 10 ml 95% ethanol to each dish and stir genily with a polyethylene rod to insure complete dissolution of the red colour. Wash contents of each dish into a 25 ml volumetric flask using 95% ethanol Complete the flask to the mark with 95% ethanol and mix thoroughly 2.3.3.1.4 Read absorbance for the standard solutions at a wavelength of 600 nm after setting blank at zero absorbance (absorbance reading shal! be carried out within one hour from drying of dishes). Prepare the calibration curve by plotting concentration against absorbance readings. 2.3.3.2 Sample treatment 2.3.3.2.1 For water containing 0.1 to 1 ppm boron, use 1 ml sample, for water containing more than 1 ppm boron, make an appropriate dilution with boron free distilled ‘water go that 1 ml portion contains approximately 0.5 1g boron 2.3.3.2.2 Pipette 1 ml sample into an evaporating dish, proceed starting from 2.3.3.1.2. 2.3.3.2.3 If the final solution is turbid, filter through Whatman filter paper No. 30 or equivalent, before reading absorbance. 2.3.3.2.4 Calculate boron content from calibration curve. 2.3.3.3. Incase of high hardness content or cation interference: 2,3.3.3.1 Prepare an ion-exchange column of approximately 50 cm x 1.3 cm, charge it with a strongly acidic cation exchange resin, backwash with distilled water to remove entrained air bubbles. 2.3,3.3.2, Pass 50 mi (1 + 5) hydrochloric acid through the column at a rate of 0.2 ml acid/ ml resin in column/minute and wash column with distilled water. 2.3.3.3.3 Pipette 25 ml sample onto the column, adjust rate of flow to about 2 drops/second and collect effluent in a 50 ml volumetric flask, wash the column with small portions of distilled water until flask is filled to the mark. 2.3.3.3.4 Mix the contents of the flask, and transfer 2 ml into evaporating dish, proceed starting from 2.3.3.1.2. 2.3.4 Calculation Ay xC a, Boron content (ppm) = AL XVGULF STANDARD GS 642/1996 Where: A, = Absorbance of the standard solution, Ag = Absorbance of the sample. C = Concentration of standard solution taken (1g). V = Sample volume (ml). 61.8 b. Borate content (ppm) = Boron content (ppm) x 10.8 Where: = conversion factor of boron to boric acid.