FERTILIZER SAMPLING and ANALYTICAL METHODS Fourth Edition The Fertilizer Institute 501 Second Street, NE. Washington, D.C. 20002 July, 1982FOREWORD ‘Quality products for the consumer depend upon quality control. In the case of fertilizers, ‘quality control depends primarily upon their chemical composition and physical properties because these products are sold and bought on the basis of guaranteed nutrient composition, Nutrient composition, in turn, can be determined only with chemical analytical methods. Only with careful production processes, combined with chemical analyses, can there be a high degree of confidence in the chemical composition or nutrient conterit of the final product. It is this combination of effort ~ careful production processes and chemical analyses ~ ‘that assures the fermer and others buying fertilizers that they get the quantity and quality of plant nutrients they pay for. Fertilizers provide 13 of the 16 essential nutrient elements for plants. Each of these elements has several different methods for chemical analysis — some being more accurate than others, some being more reliable, and of course, some being more elaborate or expensive. Obviously, results of nutrient analyses of two or more laboratories depend upon both laboratory accuracy and uniformity of methods. If methods are not uniform, neither will be the results. Thus, uniformity in using proven, accepted methods becomes critical. Those “officially” recognized by the Association of Official Analytical Chemists (AOAC) have become the reference or basic methods for most accurate comparisons. They are the result of years of work by chemists where each detait was scrutinized carefully for accuracy and repeatability before the final stamp of “official” was given. The AOAC methods, however, are written in condensed form which present difficulty, even to experienced chemists, in interpreting them uniformly. Also, many techniques and details are omitted in the AOAC methods. In recognition of these conditions, quality control chemists in the fertilizer industry issued in 1961 the first edition of an “Analytical Methods” handbook. Its objective was the same as is for this edition - to provide chemists and others with fertilizer quality control responsibilities a convenient reference for detailed description of the best analytical methods for fertilizers, plus information on other critical procedures such as sampling and physical tests. The 1961 edition, known as the NPF1 (National Plant Food Institute now The Fertilizer Institute) Analytica! Methods, was foliowed in 1964 by the second edition with the second printing of the latter in 1968. The Product Quality Committee of The Fertilizer institute (TFI] was instrumental in producing a third edition in 1974. That edition included an ex~ panded section on “Sampling,” as well as a section on “Rapid Methods.” Also, sampling and analytical methods for fluids and solids were organized into separate sections. Development of this fourth edition was an effort of the Product Quality Subcommittee of TFI's Resource Management Committee. This edition includes revisions of procedures for obtaining representative samples of solid material es well as the determination of total nitrogen content of any fertilizer ~ fluid or solid. Furthermore, a manual describing analytical methodology for secondary and micronutrient analysis has been developed by the Product Quality Subcommittee and can be utilized as an Addendum to the fourth edition.FOREWORD (continued) Each of these editions has been a product of chemists who are specialists in the field of fertilizer quality control. With extensive use of the most current AOAC methods and publications of the AAPFCO, and their extensive experience, each edition continues to provide the best available methodology for fertilizer analysis. ‘The fertilizer industry owes a debt of gratitude to the Product Quality Subcommittee for the valuable work and time devoted to the task of producing this edition. Those to whom special acknowledgement is due are: F, J. Johnson, Tennessee Valley Authority C.G, Meier, Farmland Industries, Inc. M. V. Moore, USS Agri-Chemicals J. R. Perrin, Estech, Inc. E. J. Huber, Agrico Chemical Co. Douglas Caine, Estech, Inc. W. W. Harwood, International Minerals and Chemical Corp. Notice We believe that the information and data included in this manual are true and accurate, Any recommendations or suggestions are made without warranty or guaranty of any kind. Con~ sequently, we can assume no respon’ connected with the use of any reagent chemicals, apparatus, or information included herein. The Fertilizer Institute or its members shall not be responsible for any incidental or consequential damages resulting from the use of the contents of this manual whatsoever.ABBREVIATIONS, DEFINITIONS AND EXPLANATORY NOTES ABBREVIATIONS 1. 8, 9, g =sram mg = milligram 38 = microgram L = Liter mL = milliliter mm = millimeter nm = nanometer (formerly-described as millimicrons) N- =normality A =absorbanee DEFINITIONS AND NOTES 1 2. “Water” or “HzO” means distilled or deionized water. In expressions (1 + 2), (5+ 4), etc., used in connection with liquid reagents, the first numeral refers to volume of reagent and the second to volume of water. In solutions defined in percentage, it is understood that it is prepared as weight of reagent in volume of solution, unless otherwise described. “Sulfuric acid, nitric acid”, ete., when not further defined, means concentrated reagent grade according to American Chemical Society specifications. All other reagents, unless otherwise described, conform to requirements of the American Chemical Society. rdinary labware” means labware normally stocked in fertilizer laboratories. Exact types and sizes needed for the determination are designated in the pro~ cedure. All volumetric glassware listed means Class A as defined in NBS specifications. “Temperature is expressed as degrees celsius. Sieve designations refer to the Tyler series, The term “alcohol” means 95% ethanol unless otherwise specified.W 12, 13. The term “paper” means filter paper unless otherwise specified. “Pipet” means volumetric transfer pipet unless otherwise specified. ‘The reference to supply companies or manufacturers by name is used only for convenience and does not constitute an endorsement.TABLE OF CONTENTS Page 1,” SAMPLING A. AMMONIA 1. Anhydrous Ammonia... 1 2. Aqua Ammonia B. FLUIDS 1. Low Pressure N Solutions. . 2. Medium Pressure N Solutions .... 3. _N Solutions at Extreme Temperatures. . 4... Liquids, Suspensions and Non= pressure Solutions . a. Subsampling in the Laboratory... SOLIDS 1, Bagged Goods . 2. Bulk Goods. a. Transfer Belt or Spout. b. Single Compartment Truck c, Multi~compartmented Truck and Hopper Cars. ¥. Material in Frontend Loader. . Reduction and Preparation . a. Reduction of Unground Sample | b, Preparation of Sample. . c, Quartering Technique I, ANALYTICAL METHODS A. NITROGEN 1. Total Nitrogen (Comprehensive Method)... .- ae 2. Total Nitrogen (Modified Comprehensive Method). 3. Total Nitrogen (Raney Catalyst Powder Method) . 4. Ammoniacal and Organic Nitrogen...... 5.. Total Ammoniacal Nitrogen... +++ 6." Combined Ammoniacal Nitrogen (Formaldehyde M 7. Free Ammonia ......sereeeee 8, Nitrate Nitrogen (Robertson Method) . 9. Ammoniacal and Nitrate Nitrogen (Devarda Method) 10. Ammoniacal and Nitrate Nitrogen (Ferrous Sulfate- Zinc Method) 11, Water Insoluble Nitrogen. : 12. Nitrogen Acitivity Index, Al... 13. Organic Nitrogen....... 14, Urea (Urease Method)... 15, Urea (Spectrometric Method) 16. _Biuret (Spectrometric Method)... . 17, Biuret (Indirect AAS Method) .....M e TABLE OF CONTENTS (continued) Page PHOSPHORUS 1. Preparation of sample solutions. 9 a. Total Phosphorus . 291 b, Water Soluble Phosphorus. 293 ©. Neutral Ammonium Citrate Insoluble Phosphorus . 195 d. Direct Available Phosphorus 297 e. Ortho Phosphorus. 299 2. Total Phosphorus 2101 a. Volumetric Ammonium Mo “101 b. Gravimetric Quimaciac . . 1105 c. Spectrometric Molybdovanadate. -107 d. Automated Molybdovanadate.. 3. Available Phosphorus (Indirect) . 4. _Non- orthophosphate (Indirect) . POTASSIUM 1, STPB Volumetric 2. Flame Photometric . oe Total Water (Thermal Oven) . 2 Free Voter (Vacuum Oven) . 3. Free Water (Vacuum Desiccation) . 4. Total Water (Karl Fischer) .. 135 5. Total Water (Distillation Procedure) 2139 6. Free Water (Dioxane Extraction) 143 SPECIAL 1. Water in Anhydrous Ammonia 145; 2. Residue in Anhydrous Ammoni 14 3. Solids in Phosphoric Acid . “18 4. Solids in Superphosphoric Acid. 5. Free Acid in Superphosphates. BariD METHODS SAMPLE PREPARATION . 157 NITROGEN 1. Distillation/Titrimetric 159 2. Ammonia Electrode 181 PHOSPHORUS POTASSIUM c. D, 1. STPB Volumetric 2. Flame Photometric . 3, Indirect Chloride Titrimetric. 165 169 171 vi‘TABLE OF CONTENTS (continued) IV, PHYSICAL TESTS A. SIEVE ANALYSIS/PARTICLE SIZE DISTRIBUTION . B, PARTICLE HARDNESS. C. BULK DENSITY. 1. Apparent. 2. Tapped « D. SPECIFIC GRAVITY OF LIQUIDS 1, Hydrometer. 2. Weight of Known Volume... 3. Pycnometer, V, PREPARATION OF STANDARD SOLUTIONS A. STANDARD ACID SOLUTIONS B, STANDARD BASE SOLUTIONSMethod I. A. 1. 1 SAMPLING A. SCOPE AMMONIA 1. Anhydrous Ammonia This method is based on the assumption that anhydrous ammonia contains a small ‘amount of water, usually about 0.2% by weight as a stress corrosion inhibitor for certain metals. Take duplicate samples from each tank or vessel sampled, APPARATUS ‘Tubes for Sampling ~ Tubes, heat resistant glass, conical centrifuge type, 200 mL. ‘with lower 100 mL graduated from 0-2 mL in 0.05 mL divi sions, 2-4 mL. in 0.1 mL divisions, 4~ 10 mL in 0.5 mL. divisions, and 10 100 mL in 1.0 mL divisions, Type tube is shown in Figure 1. 2. Stoppers for tubes, rubber, with bent tube vent as in Figure 1. 3. Sample carrier, constructed of plywood or aluminum as in Figure 1. 4 ‘Sampling line and connection assembly, constructed as in Figure 2, with flexible stee! sampling hose 48” long, %" N.P.T. coupling at each end and 1/8” insulated stee] tubing delivery tip at one end. 5. ‘Sample tube adapter, constructed from rubber stopper and 6 mm O.D. glass or steel tubing as in Figure 1. Protective equipment (Note a). REAGENT 1. Charcoal, reagent 14-20 mesh (Note b). PROCEDURE 1 Place two dry, clean sampling tubes in the sample carrier (Note b). Weigh each tube if Method It. E. 2. is to be used and equip each tube with the prescribed stopper. 2. Connect the sampling line connection assembly to the unloading valve of the tank, vessel, or line to be sampled. 3. Open the valves slowly and purge the sampling ling connection assembly thoroughly by venting 3-4 L of ammonia. Clase the sample line globe valve. 4, Remove the vented stoppers from the tubes and insert the adapter end of the sampling ine connection assembly.9. 10. NOTES a Method 1. A. 1. ‘Open the sample line valve and slowly fill the sampling tube to the 100 mL mark. Close the sample line valve. Remove the sampling line adapter and insert the vented stopper in the sampling tube. Repeat steps 4, 5 and 6 and fill the second tube. Close tank discharge valve and remove the sampling line connection assembly. Either know or note the vessel, container, or line pressure of material sampled. Tag the collected samples for identification and submit to the laboratory for processing by following methods in this manual. Rubber or other non— porous gloves, offering complete protection to the hands and lower arms, must be worn when sampling anhydrous ammonia. Full coverage goggles must also be worn to protect the eyes unless an approved gas mask is used. ‘The gas mask need only be used if sampling cannot be done without possible inhalation of the vapors. |i the sample is expected to contain excessive amounts of water (1% or more) , ‘one piece of the charcoal may be added to each tube before introduction of the sample. Liquid anhydrous ammonia causes severe burns on contact. It evaporates readily releasing the gas which may cause varying degrees of irritation of the skin and mucus membranes and may injure severely the respiratory mucosa with possible fatal outcome. Avoid contacting liquid ammonia, In case of contact, immediately flush the affected parts with plenty of water for at least 15 minutes. Get medical attention at once in case of burns, especially to the eyes, nose and throat, or if the victim is unconscious. Ammonia gas in concentrations of 6,000 to 10,000 ppm (by volume) is lethal within a few minutes, Irritation of the eyes, respiratory tract and throat results from concentrations as low as 500 to 1,000 ppm; a concentration of 2,000 ppm produces convulsive coughing and may be fatal after a short exposure, i.., less than half an hour. ‘The maximum concentration tolerated by the skin for more than a few seconds is 2% {i.e., when suitable respiratory protection is worn}. The maximum alloweble concentration for eight- hour working exposure is 50 ppm. This is the least detectable odor level. ‘Obtain medical attention if exposure to the gas produces distress of any type.METHOD L.A.1. Flexible sample tine Somple tube adapter SAMPLE TUBE SPECIAL CENTRIFUGE TYPE FIGURE 1. ANHYDROUS AMMONIA SAMPLE TUBE ANO TUBING -3-METHOD I.A.1 Yq'U.D.) TUBING FIGURE 2 ANHYDROUS AMMONIA SAMPLING LINE AND CONNECTION ASSEMBLY =~4-Method 1. A. 2. 1, SAMPLING A. AMMONIA 2. Aqua Ammonia (NHs determination by hydrometer) SCOPE This method is for sampling aqua ammonia (range of 830% ammonia) and determination of ammonia content by means of a glass hydrometer. This method assures testing of an ammonie—weter solution near ambient temperature with the sampling and determination as one continuous operation, For more accurate determination of ammonia, Method 11, A. 7. should be used for assay. APPARATUS Ae Hydrometer cylinder, of glass or clear plastic, equipped with wide base, liquid inlet, liquid outlet, and a vapor outlet. Cylinder must be of such size to give 12 mm clearance between hydrometer used and eylinder wall as well as thermometer used (Figure 3). Suitable cylinders may also be purchased. 2. Hydrometer, specific gravity (light), precision grade, 325 mm long, specfic gravity range of 0.880 to 0,950, subdivision 0.0005, calibrated at 15.56". 3. Thermometer, general laboratory, 305 mm long, 76 mm immersion, to cover range — 20 ta 100° in 1° subdivisions. PROCEDURE 1, Attach the sample inlet of the hydrometer jar to the sample source by means of rubber or aluminum tubing. 2. With hydrometer and thermometer in jar, allow the sample to pass through the hydrometer cylinder to waste until line has been purged (Note a). 3. After purging, close cylinder exit and allow sufficient sample solution to collect in cylinder to float the hydrometer. Close cylinder vent and stop sample flow. 4. When the hydrometer has come to rest, floating freely, and the temperature is constant (0.5°), read the hydrometer to the nearest scale division (0.0005) on hydrometer stem (Note b].Method I. A. 2. 5. Opencylinder exit, discard sample and repeat 2, 3 and 4, for duplicate sample. 6, Record the hydrometer and temperature readings obtained. CALCULATION Using the recorded temperature and specific gravity, enter alignment chart, Figure 4, and read the corresponding weight per cent ammonia in the sample. ‘As an example: If recorded temperature and specific gravity of a sample were 35.0° and 0.882 g/mL, respectively, then a line extended through these two points of the chart to the left would give a 30.0% by weight ammonia content for the sample. NOTES. a, Asa safety measure, goggles and rubber gloves stiould be worn by personnel per— forming this test. b. The correct reading is that point on the scale at which the surface of the liquid cuts the scale.METHOD L.A. 2. ;-HEAT RESISTANT GLASS OR CAST ACRYLIC CYLINDER HYDROMETER —_| SAMPLE IN FIGURE 3 HYDROMETER APPARATUS FOR AQUA AMMONIA -7- .METHOD IA.2. 20 & e 40 48 50. FIGURE 4. ALIGNMENT CHART FOR AQUA AMMONIA, -e- ‘Method |. B. 1. 1. SAMPLING B. FLUIDS 1. Low Pressure N Solutions SCOPE This method applies to F solutions of low vapor pressure, including any fertilizer solution containing urea, nitrate compounds, and free ammonia with the latter generally present in an amount of 10% or less. The temperature of the sampled ‘material and of the sampling system must remain above the salting- out temperature of the sampled material. APPARATUS 1. Bottle, polyethylene, tall form, 250mL capacity. Bottle must be marked at levels to indicate a 200 mL content and a 235 mL content (Note a). 2. Sample apparatus, stainless steel, insulated if required - Figure 5. 3. Balance, metric, 500 g capacity, sensitivity of 0.02 g, with class S~1 weights if required by balance used. 4. Carrying case, plywood or aluminum, if desired for sample bottles. Case may be constructed so that the 200 mL and 235 mL marks on the bottles are visible. 5. Flask, volumetric, 1 L (Note a). REAGENT 1, Distilled or deionized water. PROCEDURE 1, For each sample to be taken, obtain a clean bottle as specified and add 195 to 200 mL of water. Stopper each bottle, weigh (W1}, and record weight of each bottle and contained water to nearest 0,02 g (Note b), Place bottle(s) in carrying case. 2. At the vessel, container, or line to be sampled, attach a %4”" clean, stainless steel sampling tube (Note c) to a %" stainless steel sampling needle valve which has been previously installed at each sampling place required. 3. Purge the sample tube with 500-1,000 mL of material asa flush of the entire sampling system {Note d). Close the valve. 4. Insert the sampling tube into the sampling bottle to where the tip of the tube is, just below the water level.Method 1. B. 1. 5. Open the sample valve cautiously to obtain a slow, even flow of sample into the bottle, No vapor bubbles should break through the surface of the water. Fill the bottle to the 235 mL mark and close the valve. 6. Remove the bottle from the sampling tube, stopper, and return to the laboratory. 7. Remove the sampling tube from the valve and clean, 8. Reweigh (W2) the sample bottle to the nearest 0.02 g (Note e). 9. Transfer the contents of the sample bottle, with thorough washing of the bottle, toa 1 L volumetric flask (Note a). Dilute contents of volumetric fiask exactly to mark with water and thoroughly mix. CALCULATION Weight of sample (W) = W2 - W1 NOTES a. Where there is little danger in breakage of container, and to save in time by avoiding sample transfer, the sample may be taken directly into a marked L volumetric flask in lieu of the polyethylene bottle. For most accurate weighing, a simhilarly prepared sampie bottle should be used as a counterpoise, Semple tube may be of any length convenient, When sampling solutions of high salting~out temperature or in cold weather, the sample tube must be insulated to prevent adverse formation of solid material in sampling tube. Sampling valve must also be insulated and/or steam traced, All fertilizer liquids can be irritating to the skin. Care should be taken to make sure that skin contact is avoided. Goggles should be worn during sampling. If material is spilied on bottle during sampling, the bottle must be carefully cleaned and dried before reweighing. -10-METHOD I, 8.1 Vy STAINLESS STEEL . NEEDLE VALVE > VESSEL OF SAMPLED. Vg PIPE S.S. a Yq! UNION Vg STAINLESS STEEL SAMPLE TUBE yt. POLYETHYLENE BOTTLE OR LITER VOLUMETRIC FLASK FIGURE 5 SAMPLE APPARATUS, LOW PRESSURE N SOLUTIONS m— Ji-12-Method |. B. 2. 1. SAMPLING B, FLUIDS 2, Medium Pressure N Solutions SCOPE ‘This method applies to most fertilizer solutions except anhydrous ammonia and other materials of a high vapor pressure. In general, and under normal conditions, this procedure may be followed for samples containing free ammonia in the range of 40-30% by weight. The temperature of the sampled material and of the sampling system must remain above the salting out temperature of the sampled materiai. APPARATUS 1. Bottle, polyethylene, tall form, 500 mL capacity. 2. Sample line assembly, fabricated as shown in Figure 6. 3. Balance, metric, 500 g capacity, sensitivity of 0.02 g, with S~ 1 weights if required by balance used. 4, Carrying case, plywood or aluminum, if desired for sample bottles. 5. Flask, volumetric, 1 L. REAGENT 1. Distilled or deionized water. PROCEDURE 1. For each sample to be taken, obtain a clean bottle as specified and add 195 to 200 ml. of water. Stopper each bottle, weish {W1}, and record weight of each bottle and contained water to nearest 0.02 g (Note a). 2 Atthe vessel, container, or line to be sampled, attach cleaned sampling apparatus toa sampling block valve (A) which has been previously installed at each sampling place required. 3, With sample valve (B) closed, open valves A and C and flush line with 500- 1,000 mL ‘of material to waste (Note b}. 4, Remove stopper from sample bottle, partially collapse sample bottle, without loss cof water, and insert sample tube and sample tube stopper to give ¢ tight seal with ‘tubing just below the surface of the water. in the sample bottle.Method 1. B. 2. 5. With a small flow of material to waste through valve C, slowly open sample valve and collect about 30-35 mL of sample {Note c). 6. Close sample vaive, remove sample tubing, partially collapse bottle, and cap bottle tightly. 7. Allow sample to coo! to room temperature, if necessary, and reweigh (W2) the sample bottle to the nearest 0.02 g. 8. ‘Transfer the contents of the sample bottle with thorough washing of the bottle, toa 1 L volumetric flask. Dilute contents of volumetric flask exactly to mark with water and thoroughly mix. 9. Remove and clean sampling line assembly. CALCULATION Weight of sample (W) = W2~ W1 NOTES a For most accurate weighing, a similarly prepared sampie bottle should be used as a counterpoise. All fertilizer liquids can be irritating to the sicin. Care should be taken to make sure that skin contact is avoided. Eye protection should be worn during sampling. Care should also be taken to control the flow to avoid spraying and to avoid inhaling vapors of ammonia. The bottle should not expand to full size during this sampling time, A little practice with the sample bottle and the sampling line assembly should allow samples to be taken of a size within + 2 g of the sample size desired. ~14-METHOD 1.8.2. HOSE CONNECTOR S.S TYGON TUBING RUBBER STOPPER TUBING SS. GLASS or STAINLESS STEEL TUBING i) APPROX. 500ml. LA POLYETHYLENE BOTTLE TYGON TUBING TO WASTE FIGURE 6 SAMPLE LINE ASSEMBLY FOR MEDIUM PRESSURE N SOLUTION 15>~16-Method I. 8.3. 1, SAMPLING B. FLUIDS 3. _N Solutions at Extreme Temperatures SCOPE Use this method in obtaining samples of all types of fertilizer liquids except anhydrous ammonia. While Method I. 8. 1. or |. B. 2, may be preferred if applicable, this method must be used for sampling materials having a very high vapor pressure and/or temperature. ‘This sampling procedure may also be of value for sampling at very low ambient temperatures or at temperatures below the salting out temperature of the material sampled. APPARATUS. 1. Bottle, polyethylene, tall form, 250 mL, capacity, equipped with 1/8” stainless steel needle valve, Figure 7. 2. Sampling line assembly, stainless steel, insulated or steam traced (if required), installed at vessel, container, or line to be sampled as shown in Figure 7. 3. Balance, metric, 500 g capacity, sensitivity of 0.02 g with class S- 1 weights if required by balance used. 4, Carrying case, plywood or aluminum, if desi 5. Flask, volumetric, 1 L.” 6. Beaker, 800 mL. 1d for sample bottles. REAGENT 1, Distilled or deionized water. PROCEDURE 1. For each sample to be taken, completely fill a sample bottle assembly with water. Next, carefully press the bottle and expe! 38 to 40 mL of water through the valve. While holding the bottle in the partially collapsed condition, firmly close the valve. Bottle must remain in the partially collapsed condition. Dry outside of valve and bottle, Weigh (W1) sample bottle assembly and contained water to nearest 0.02 g (Note a). 2. At the vessel, container, or line to be sampled, open both valve A and B (Figure 7) and purge the sample line to waste, using 500~ 1,000 mL of material, with plug of sample tee in place as shown (Note b). 7Method 1.8.3. 3. Next close valve A, remove plug, and attach sample bottle assembly firmly in the place of the plug. 4, Open valve A fully, throttle valve B to maintain small flow of solution, then partially and carefully open sample botile assembly valve. Introduce sample into sample bottle until sample bottle has just regained its original shape. Close sample bottle needle valve, close valve A, and replace plug. 5, Return sampie to laboratory, thoroughly clean any residue from outside of valve, and again weigh (W2) the sample bottle assembly and contents to nearest 0.02 g. 6. Place 350 mL of water in an 800 mL beaker. Open valve of bottle assembly, place ‘the end of the bottle assembly valve under the surface of the water, and then discharge the sample into the water. Transfer the contents of the beaker to a 1 L volumetric flask. Next add 250 mL of water to the beaker, consecutively draw in and discharge water several times from the bottle into the beaker, Transfer contents of beaker and add to solution in the volumetric flask, Wash beaker and bottle assembly with a few mL of water and add washings to volumetric flask. Dilute contents of flask exactly to mark with water and thoroughly mix. CALCULATION Weight of sample (W) = W2- W1 NOTES a. For most accurate weighing, a similarly prepared sample bottle should be used asa counterpoise. b. All fertilizer liquids can be irritating to the skin. Care should be taken to make sure that skin contact Is avoided. Goggles should be worn during sampling. ~18-METHOD 1.8.3. VESSEL OR LINE TO BE SAMPLED YVENT PIPE wine PLug ss. TEFLON PLUG POLYETHYLENE CAP t TO WASTE POLYETHYLENE SAMPLE BOTTLE FIGURE 7 SAMPLING LINE ASSEMBLY FOR N SOLUTIONS AT EXTREME TEMPERATURES a 19--20-Method 1. B. 4. 1. SAMPLING B. FLUIDS 4, Liquids, Suspensions and Non- pressure Solutions SCOPE Mixed liquids (fluids), non- pressure nitrogen solutions, and suspensions (slurries) may be sampled by the following procedure, APPARATUS 4. Glass or polyethylene bottles. 2. Nylon rope, 1/8- 1/4”, 20" length. 3. Missouri or Indiana sampling bottles and cage Figure 8. PROCEDURE 1. Acritical requirement in getting a representative sample of a fluid fertilizer is to take the sample directly from the main body of the material without contamination, Avoid, whenever possible, taking samples from lines and valves. Listed below, in order of preference, are general procedures for sampling fluids: a Take samples directly from mixing vat. b. Take sample from the top opening of the storage or transport tank with a weighted— restricted sampling bottle. In the case of suspensions or slurries, ‘take the sample only after agitating at least 15 minutes. c. Take a sample from a delivery line or recirculating line immediately after a large quantity has been pumped out. d. Take sample from a recirculation line after at least 15 minutes of recirculation (with agitation if the fluid is a suspension or slurry). fe. Asa last resort, use a valve or a delivery line after thorough flushing, and after agitation if the fluid is a suspension or slurry. Never take a sample rom a product that was in the delivery or manifold line before your arrival. Before taking a sample from these lines, pass through them a volume at least, twice their holding volumes. -21-Method I. B. 4. 2. Several techniques are important in using the weighted- restricted sampling bottle, especially in the case of suspensions or slurries. Lower the samplin: bottle from port or top opening to bottom of tank. Raise slowly while filling at such a rate that the sampling bottle is not quite full when withdrawn. It is important to leave air space above sample to permit agitation during subsequent handling in the laboratory. If bottle is completely full, the sample may not represent the entire depth of the tank. Empty, and take another sample with~ drawing the bottle at a faster rate. After securing the sample, replace the sampling cap with a permanent cap. If the latter is unavailable, very carefully ‘transfer the sample to a sample bottle. Alll sample bottles should be tightly fastened to prevent leakage or evaporation. REFERENCE 1. Inspectors Manual, AAPFCO, ard Edition (1977) ~22-500mL ae lyethylene frre” holes: Nylon cord METHOD I.B. 4. Air escape hole 3mm Fluid intoke tube: 7mm for solutions, 40mm for suspensions and slurries. Ls Wire hanger Fluid intake tube: BS 7mm for solutions, 'Omm for suspension ond slurries. Air escape. hole 3mm —> acne 500mL polyethylene bottle: INDIANA BOTTLE Air escape Nylon cord hole 3mm. Fluid intake ‘tube: 7mm for soiutions 1mm for suspensions and siurries. MODIFIED INDIANA BOTTLE 700g of lead wt. (may be placed inside or attached out side of bottie) MISSOURI BOTTLE FIGURE 8 WEIGHTED SAMPLING BOTTLES -23--24-Method |. B. 4. 2. 1, SAMPLING B, FLUIDS 4. Liquids, Suspensions and Non— pressure Solutions a. Sub~sampling in the Laboratory SCOPE Mixed liquids (fluids), non- pressure nitrogen solutions, and suspensions (slurries). APPARATUS i 4. Balance - analyti 2. Beakers-50 mL. 3. Glass tubing for pipetting. 4. Blender-high speed. 5.- Weighing boats. 6. Volumetric flask-1 L. PROCEDURE A. Liquids H equipment capable of rapid weighings to 0.1 mg is available, individual portions for analysis may be taken by this method, omitting the need for an aliquot procedure. 1. Shake well. 2. Weigh out 10-20 g into suitable container. 3. Transfer and wash into 1 L volumetric flask. Make to mark and mix well. 4. Aliquot as necessary for individual determinations. B. Suspensions containing only easily soluble components. : Suspensions are slurries containing crystals and particles held in suspension by some type of gelling agent. When diluted with sufficient water, the small water soluble ingredients dissolve, but the suspending gel is destroyed causing larger, less soluble particles to drop out of suspension. Therefore, if the sample contains insoluble compounds such as metal phosphates, procedure C should be used, cate being taken thet large insoluble particles are reduced in size sufficiently to give ahomogeneous mixture.Method |. B. 4. a, Shake well. Weigh out 10-20 g into suitable container. Transfer and wash into 1 L volumetric flask, Make to mark and mix well. When solution is complete, aliquot as necessary for individual deter— minations. ‘Suspensions of unknown composition or suspected of containing large crystals or metallic phosphates. 1. 2 3. 4. Shake well Transfer to high speed blender and mix until homogeneous. Weigh individual portions in weighing boats or other suitable containers, using glass tubing to extract samples from blender while mixing. ‘Transfer or wash into appropriate glassware.Method I. C. 1. 1, SAMPLING c. SOLIDS 1. Bagged Goods SCOPE A method is described for obtaining a representative sample from a given lot* of fertilizer packaged in bags greater than 10 pounds. {f packaged in bags of 10 pounds or less, select entire bag for sample. *For purposes of obtaining an official sample, a “lot” shall be represented by an identifiable quantity of commercial fertilizer that can be sampled according 0 AOAC procedures, up to and including a freight car load or 60 tons (45.35 metric tons} maximum, or that amount contained in a single vehicle, or that amount delivered under a single invoice. For industry quality control purposes, a “lot” shall be represented by the quantity of a given product made during a specified time period, in storage at, or shipped from a single production point. APPARATUS 1. Aslotted single or double tube trier (Figure 9) with solid core tip constructed of stainless steel or brass. Stainless stee! is required for samples on which micronutrients are to be determined. The minimum dimensions of the trier are: Length, exclusive of handle (approximate length of filled bag) 25 63.5 Slot length 23 584 Slot width 172 13 Inner diameter 5/8 16 it may be obtained from — Seedburo Equipment Company 1022 West Jackson Blvd, Chicago, 1L 60607 2. Container for unground sample ~ Capacity 1 L or as required and constructed of corrosion— resistant material with a moisture- proof barrier, or fabricated from material which will not permit moisture to enter or leave the sample. -27-Method 1. C. 1. PROCEDURE If lot contains 10 bags or more, randomly select 10 bags and withdraw one core from each. If lot contains less than 10 bags, withdraw 10 cores, with at least one core from each bag. 1. Place bag in a horizontal position, then roll or flip over one or more times, 2. If valve~type bag, sample through valve. If sewn bag, make an x—cut with a knife ear seam at the corner. 3. With single tube trier, insert so that it extends diagonally from corner to corner (Figure 10) with siot down. Turn it one-half turn to bring the slot up, jar bag slightly to fill the trier, and remove carefully so as not to drag material out of it with the bag edges. or 3a. With double tube trier, insert as above with trier closed and the slot up. Open trier to fill, jar bag slightly, close trier, and remove from bag. 4, Transfer all 10 cores to the container for unground samples or if desired, each core may be completely transferred to a narrow stainless steel U-shaped trough, slightly longer than the trier length. It is usually fitted with a handle at one end and a pouring spout at the opposite end. The trough is used to transfer sample portions to the larger container which holds the entire composite sample. This is especially helpful when using single tube triers to avoid spillage or loss. 5. Label container of the.composited sample with all pertinent information. 6. Forward to laboratory for preparation and analysis. REFERENCES 1, Methods of Analysis, AOAC, 2.001 (a), 13th Edition (1980) 2. Tnspectors Manual, AAPFCO, 3rd Edition (1977)METHOD 1.C.1 \ Wood hangie \Must be 2 25" long SINGLE TUBE TRIER Wood handles 39" long DOUBLE TUBE TRIER FIGURE 9METHOD I.C.1. TURN ond WITHDRAW, SLOT UP. FIGURE 10 BAG SAMPLING TECHNIQUE = 30~Method 1, C. 2. 1, SAMPLING c. SOLIDS 2. Bulk Goods ‘SCOPE Methods are described for obtaining representative samples from a given lot* of fertilizer in bulk, They are applicable to material during transfer, in single or multi-compartmented ‘trucks, in rail cars, in storage, and in front-end loaders. *For purposes of obtaining an official sample, a “lot” shall be represented by an identifiable quantity of commercial fertilizer that can be sampled by AOAC procedures, up to and including a freight car load or 50 tons (45.35 metric tons) maximum, or that amount contained in a single vehicle, or that amount delivered under a single invoice, For industry quality control purposes, a “lot” shall be represented by the quantity ofa given product made during a specified time period, in storage at, or shipped {rom a single production point. APPARATUS 1. Stream Sampling Cup~ As shown in Figure 11 and may be obtained from— Walsdorf Sheet Metal Works 108 Highway 17-92 North Haines City, FL 33844 ‘A permanent sampling system may be constructed by supporting the cup on @ track of two steel rods so that the mouth of the cup is in the path of, and at right angles to the stream flow. Guides attached to the cup and a handle on the side permit use of this device. 2, Double tube triers as described below: Compartment Trier Length OD. ‘No. _ Size Missouri 591i 1-1/8 in, 7/Bin. 8 Bin, Compartmented (1.5 m.) (290m.) (2.2em.) (7.8 em.) 552 Grain” 63 in. 1-3/Bin, 1-1/8in. 11 3-1/2in. (1.6 m) (3.5 em.) (29em.) 48.9 em.) Missouri “D™ 52in. t-14in, tin, 145m. (3m) (32cm) (25em.) (1.1m) @ Seedburo Equipment Company, 1022 West Jackson Bivd., Chicago, IL_60607 bamerican Tool and Die, 917 Maple Street, West Des Moines, IA 50265 ~31-Method 1, C. 2, 3. Container for Unground Sample- Capacity 1 L or as required and constructed of corrosion- resistant material with a moisture proof barrier, or fabricated from material which will not per PROCEDURE 1. Collect the sample according to the appropriate following techniqui a. it moisture to enter or leave the sample, ‘Transfer belt or spout Take sample by passing the stream sampling cup (Figure 12) completely ‘through the stream of material as the material drops from a transfer belt or spout, -The long slot in the top of the sampling cup should be perpendicular to the falling stream. Pass the cup through the complete stream at a uniform speed, such that the cup will collect approximately equal amounts each pass, but will never overfiow. Empty contents of the cup from each pass into a suitable container. For sampling material with uniform stream flow of 3 minutes or more, such 8 a transfer or shipment from a bin or large holding hopper, or for stream sampling from a continuous production unit, a minimum of 10 equal time and spaced stream cuts must be taken during the transfer operation. Divide the total estimated discharge time by not less than 10 to obtain the time interval between stream cuts. An automatic sampler may be applicable, if it is possible to clean it thoroughly before and after sampling the particular lot or shipment. Avoid sampling a trickle of fines or dust. For sampling material from a blender or other batch unit which has only short periods of material flow, take a minimum of 10 stream cuts from a spout or at ‘the end of the transfer belt. Take one or more stream cuts for each batch, but vary the moment of the stream cut on consecutive batches. For example, the first batch might be smpled early in the batch discharge, the second near the middle of the discharge, the third batch near the last third of the discharge. Then repeat the collection using the same intervals, or alter to provide longer or shorter intervals. Single compartment truck Sample the load by the AAC approved vertical probing procedure. Use one of the double tubed triers listed under Apparatus. Draw 10 vertical cores according to the diagram shown in Figure 134. Insert the 52 grain probe or Missouri campartmented trier vertically while closed, normally to a depth of not less than 4 feet (1.2m). (The depth for ‘some of the cores will be less if the side of the truck is sloped.) Open the probe until it is filled, close and withdraw. The Missouri D tube (Figure 14) is inserted to the same distence just given but in the open position, closed and withdrawn, Note: A light teflon spray on the clean, opposed surfaces of the two tubes will help prevent binding of the instrument.4. Method |. C. 2. Multicompartmented truck and hopper cars, When it is necessary to sample a Killebrew~type truck, or a multicompartment hopper car after it is loaded for shipment, or upon receipt before unloading, follow the official AOAC sampling pattern for each compartment, keeping in mind that it is rather easy to take vertical cores before shipment but extremely difficult after the ear or truck is received. ‘The object is to withdraw a minimum of 10 vertical cores, inserting the probe in the positions indicated in either Patterns A or B given in Figure 13B. Do not insert probe in the center of a cone. Carloads Preferably, stream sample (as described previously) the material while loading of unloading the car, If it becomes necessary to sample the material in @ box car, use the vertical probing technique as described for single compartment truck. If the pile of material in a box car is coned or ridged, take cores from the positions indicated in Figure 1A. When there are two sloped piles in a box car, one at each end, ‘then duplicate the sampling pattern described in Figure 13B. Use one of the double tubed triers and insert it to a depth not less than 4 feet. (7.2m) in each of the indicated sampling locations. The closed double— compartmented ‘trier is inserted, opened, filled, closed and withdrawn. ‘The Missouri “D” tube is inserted the same distance as just given but in the open position, then closed and withdrawn. The Missouri "D” tube is the best trier for sampling a car of fertilizer at its destination because it can be driven into the settled mass of fertilizer. Material in storage ‘The procedure described is that of AOAC which has given good results when sempling either coned, ridged, flat or one~sided piles containing up to 100 tons (90,7 metric tons) of material. It is not possible to accurately sample larger piles with the official sampling devices. Sampling points for vertical cores from bulk storage piles are given in Figure 15A and B, Level or flat piles, containing up to 100 tons, are sampled ina fashion similar to that described for the ridged piles. Withdraw 10 cores (to the maximum possible depth of the trier) from positions indicated in the diagram Figure 15A using the 652 grain probe, Missouri compartmented trier or Missouri “D" tube. ‘The sampling devices are handled in the same fashion as described for the single compartment truck.Method I. C. 2. A one-sided or sloped pile is sampled at the points illustrated in the diagram in Figure 1B. Withdraw one vertical core of material from locations 1 and 6, and two cores at locations 2, 3, 4, and 5, ‘These sampling patterns are designed so that cores taken from each location represent approximately equal fractions of the lot. f. Material in front-end foader This method is not an officially approved AOAC procedure. It is rather an industry control method. When material is conveyed by front-end loader, it may be sampled with a double— tube trier of adequate length, by probing from alternate outer corners to the bottom of the loader scoop or bucket (Figure 16). If the trier is long enough, take 10 or more individual cores diagonally from forward corner to opposite lower corner of the scoop. If trier is not long enough for this, take 10 or more cores by probing from an outer corner until the trier touches the bottom of the scoop near its center. Use alternate corners and distribute the sampling evenly throughout the lot to be sampled. If the lot consists of less than 10 loads, probe both corners of enough loads to get 10 cores or a maximum of two cores per load, but take at least one core from each scoop load. Insert the closed double tube trier with the openings for the outer tube facing up. Hold the outer tube steady and turn the inner tube so that its openings are also up. Agitate the open trier slightly so that material will fill it, then close and withdraw. A light tefion spray on the clean, opposed surfaces of the two tubes will help prevent binding. 2. Transfer all 10 cores taken to the container for unground samples. formation, 1d sample with all pertinent i 3. Label container of the comps 4, Forward to laboratory for preparation and analysis. REFERENCES 1, Methods of Analysis, AOAC, 2.001(b), 13th Edition (1980) 2, Inspectors Manual, AAPFCO, 3rd Edition (1977)METHOD 1.¢. 2. Fobricate from: 16GA.GALVANIZED IRON OR 18-20 GA. STAINLESS STEEL, TYPE 304 FIGURE I! STREAM SAMPLING CUPMETHOD I. C. 2. SAMPLE CUP DIRECTION OF SAMPLE CUP MOVEMENT FIGURE 12 USE OF STREAM SAMPLING CUP FOR BELT SAMPLES. ageMETHOD I.¢.2, OPEN RAILCAR, TRUCK OR WAGON PATTERN B (3-4 HATCHES) (MORE THAN 4 HATCHES) 4probes/hatch 2probes/naten ; FIGURE 13B SAMPLE POINTS FOR COVERED HOPPER CARS OR OTHER CARRIERS azeee Length 52” 0.0. 1.25" One Slot 45"Ig- ie FIGURE 14 CLOSED MISSOURI'D'TUBE ~ 38 -METHOD 1.¢.2. FIGURE I5A SAMPLE PATTERN FOR RIDGED PILE Withdraw one vertical core of material from location land 6, and two cores from locations 2,3,4 ond 5. FIGURE ISB SAMPLE PATTERN FOR ONE-SIDED PILE coeMETHOD 1.C. 2. Ce SAMPLING T.RIER FRONT EDGE FIGURE 16 FRONT-END LOADER SAMPLING = 40 =Method I. C. 3. 1 SAMPLING Cc. SOLIDS 3. Reduction and Preparation SCOPE ‘Samples received in the laboratory must be reduced in mass to 0.5- 1 pound (225-500 g), pulverized, if necessary reduced in mass again, and stored in airtight container. Procedures have been developed to standardize those manipulations necessary to reduce and prepare solid fertilizer samples, It is recommended that these procedures be carried out ina laboratory environment, APPARATUS Sample Reducer or Rifle A riffle (Figure 17 and 18) is.required of corrosion resistant material and so designed that uniform feeding of sample material, at the top of the rectangular openings, divides the sample into representative halves. ‘The size of the riffle shall be appropriate to the quantity of sample being reduced. Receiving pans must fit riffle from end to end of partitioned section. For most unground fertilizer samples, the slot openings should be 3/8” to 1/2” (1.0 em. to 1.3 cm.) wide. Suitable sample reducers are supplied by: Fisher Company Humboldt Company 711 Forbes Avenue 7300 Agatite Avenue Pittsburgh, PA 15219 Norridge, IL 60656 Gilson Company Carpeo Inc. Box 677 4120 Heines Street Worthington, OH 43085 Jacksonville, FL 32206 2. Grinder or Sample Pulverizer- A grinder shall perform as required under procedure without changing the composition of the sample, Suitable models are made by Pulverizing Machinery, 10 Chatham Road, Summit, New Jersey 07901. 3. Sieves~ Eight inch Tyler Nos, 20 and 35 (U.S, Standard Nos. 20 and 40} constructed of brass or stainless steel. The latter is recommended for samples to be analyzed Yor micronutrients. 4. Scoop and Backplate for Quartering Technique - See Figure 19. 5. Containers for Ground Samples ~ Plastic or glass, 250 mL capacity, wide mouth with airtight cap. -41-Method 1. C. 3. PROCEDURES A. Reduction of Unground Sample Make sure that all equipment is clean. 2. Set riffle level, not tilted in any direction. 3. Place two empty pans in position beneath the riffle. Note: When a riffle with cut-off gate (Figure 18) is used for splitting sample, tainer, irrespective of its design. The need for a third and fourth pan is elim~ inated. Step 4 is omitted. Specific handling requirement of Steps 5 and 6 are not necessary as sample splitting does not occur until gate is opened, 4, Transfer the collected sample to one or two of the remaining pans, as required. Each pan should be not more than two-thirds full. Level the surface of the sample in the pan before continuing. 5. Using both hands, position the pan containing the sample lengthwise over the riffle as near the center as possible, at right angles to the partitions. 6. Rapidly tilt the pan to the hopper so the material will flow evenly from the pan onto the riffle. Collect the entire sample in the pans beneath the riffle. 7. When two pans are required in step 4 for the original collected sample, take the second pan through steps 5 and 6 while leaving the pans in step 6 beneath +the riffle. Collect the entire samples in these two pans. Place two empty pans beneath the riffle and repeat steps 5 and 6 at least twice. 8 When required, repeat steps 5 through 7, until sample is reduced to approx- imately 1 Ib. (-5 kg). (If desired, retain the second half as reserve, unti the preparation is completed on the portion to be analyzed.) 9, Transfer final sample to moisture proof container, and mark for identification, Note: The container must be large enough to hold the entire final sample. None should be discarded. If the only available container is too small, sample may be reduced by rifiling twice and saving one-half at each step, resulting in one-fourth of the original sample, but must not be less than 0.5 Ib (.25 ka). 10. When an unground portion of sample is to be supplied to another lab for check analysis, the unground portion sent should be 0.5 Ib. (0.25 kg) or more in accordance with AOAC Method No. 2.007, 13th Edition, 1980. 11. Clean equipment before storing or re-use. -42-B, Method I. C.3. Preparation of Sample 1 10. ". 12. Grind the entire sample after reduction under A. If further reduction to less ‘than 0.5 tb. (.25 kg) is desired, this must be done only on the ground sample, Use the procedure described under paragraph 9 below, a quartering technique as described under Section C, or a suitable small riffle to furnish two or more representative portions. Grind dry fertilizer mixtures to pass No. 35 Tyler Sieve. Feitilizer materials and moist fertilizer mixtures may be ground to pass sieve with one mm circular openings or No. 20 Tyler Sieve. Grind as rapidly as possible to avoid loss or gain of moisture during the grinding operation, but avoid overheating the sample. Periodically check the efficiency of the grinding mill screen by sieving the entire ground sample, including brushings from grinding mill, through a 35-mesh sieve. Regrind oversize with a mortar and pestle and install new screens if necessary. Place entire sample on flexible rolling sheet of glazed butcher’s paper, smooth il cloth, or polyethylene sheet for mixing. Roll sample slowly from four directions until sample has been thoroughly mixed ~ 20 times is usually considered adequate. Rolling too rapidly will cause sliding and no mixing. After completion of mixing, roll sample into a pile in center of rolling sheet and spread sample into a flat circle bout 3/4” (2.0 em) deep (Figure 20) with an instrument such as a plasterer’s hawk. ‘Transfer about 200 g of sample to a 250 mL airtight, widemouth container with @ scoop such as shown in Figure 19. Scoop carefully from the circumference ‘toward the center, keeping the scoop edge next to the sheet. Take portions at about 2 to 4 inches {5 to 10. cm} equal intervals around the circumference Of the flattened pile. Use a becking piste as shown in Figure 19. Container must have air space above the sample. Mark sample number on container and copy this on other records as required. Clean grinding mill after each use. Quartering Technique 1 To divide ground sample into two equal portions when a suitable small riffle is not available, follow procedure under Section B, steps 6, 7, and 8. ~43-Method |. C. 3. 2. Press the thin edge of a spatula all the way through the flat circle of ‘ground sample so that it makes a separation of two equal halves. 3. Holding the spatula edge firmly to the flexible sheet, widen the diameter line about 1/4 in, (6 mm), by carefully pushing the material in each half away from the center. 4, Mark another diameter at right angles to the first with the edge of the spatula, and treat this as in step 3. 5, Introduce the spatula next to the sheet and pick up alf the sample from two opposite corners, or scrape alternate corners to another sheet. Use a small, clean soft bristled brush to help move desired portions from the sheet. Transfer this portion to a sample container. 6. Transfer the remaining alternate quarters to another sample container. 7. \fgrinding, mixing and quartering procedures have been properly done, the two haives are each representative of the original ground sample. REFERENCES. 1, Methods of Analysis, AOAC, 2.007, 13th Edition (1980) 2. Inspectors Manual, AAPFCO, 3rd Edition (1977)METHOD I.C. 3, a, FIGURE I7 STRUCTURE OF SAMPLE RIFFLEMETHOD I.C.3. FIGURE 18 RIFFLE WITH CUTOFF GATE AND TWO PANS ~ 4b(102mm) 4.0" +} 3.5" METHOD 1.¢.3. WOTE: ALL 246A, STAINLESS STEEL CONSTRUCTION Lote 9.75° PATTERN LAYOUT (HALF size) BACKING PLATE (FULL SIZE) 7 0.15" (19mm) eNO ALL'SOLDERED JOINTS ORTHOGRAPHIC VIEWS (FULL SIZE) FIGURE I9 STRUCTURE OF SCOOP FOR SUBSAMPLING -/-a7a-METHOD I.C.3. FIGURE 20 TECHNIQUE FOR SUBSAMPLING OF GROUND. SAMPLE - ¥B-Method II. A. 1. I, ANALYTICAL METHODS A. NITROGEN 1. Total Nitrogen (Comprehensive Method) SCOPE This method determines total nitrogen content of any fertilizer—fiuid or solid. APPARATUS llation units. 1. Kieldahl digestion and 2. Kjeldahl flask, B00 mL. 3. Ordinary labware. REAGENTS 1, Sulfuric acid, 0.5 N H2SO« (see Section V). 2. Sodium hydroxide, 0.25 N NaOH (see Section V). 3. Methyl red indicator solution Dissolve 1.0 9 in 200 mL alcohol. 4. Mercury or mereuric oxide, Hg or HgO, nitrogen free. 5. Sulfuric acid, 93-98% HzSO4, nitrogen free. 6. Dilute sulfuric acid-Slowly add 625 mL Hz $04 t0 300 mL Hz 0, cool, "and dilute to 1 L. 7. Potassium sulfate, Kz SOs, nitrogen free. 8. Potassium sulfide or thiosulfate solution~ Dissolve 40 g K2S or 80.9 NazS2Os - 5H20 in 1 L H20. 8. Sodium hydroxide solution, 50% NaOH Dissolve 450 g of solid NaOH in HzO, coo!, and dilute to 1 L. 10. Alundum, 8x14 mesh boiling stones (A, H. Thomas Co.) 11, Zinc, 20 mesh. 12. Chromium metal, 100 mesh, low nitrogen (Fisher Scientific Co. No. C-318, Sargent- Welch Scientific Co. No, SC 11432, or equivalent). 13. Hydrochtoric acid, cone HC PROCEDURE 4. Weigh 0.35 — 2.2 + 0.5 mg of sample an transfer to a Kjeldahl flask. Sample must not contain more than 60 mg of nitrate nitrogen. 2. Add 1.2g chromium powder and 35 mL H2O. For liquids adjust total volume to 35 mL. Let stand for 10 minutes with occasional gentle swirling to dissolve all nitrate salts. 3, Add 7 mL HC! and let stand for at least 30 seconds, but not more than 10 minutes. 4, Place flask on preheated burner adjusted to a 7-7.5 minute boil test. After heating 3.5 minutes, remove from heat and let cool. ~49-10. n. 12, 13, 14, Method II. A. 1. Add 22 9 K2SQx, 1.0 g HgO (or 0.9 g metallic Hg} and several granules (0.8 g) of alundum. Add 40 mL dilute HeSOs. Place flask on preheated burner and heat until dense white fumes of H2SO« clear the bulb of the flask. Heat another 5— 10 minutes. Digestion is now complete for samples containing ammoniacal, nitrate, and urea nitrogen; for all other samples, swirl flask gently and continue digestion for one hour. Remove flask from burner. Allow to cool for 8-10 minutes, then swirl flask a few times to prevent solidification of the digest. After further cooling, add 300 - 350 mL HzO and 25 mL of sulfide or thiosulfate solution and mix well to precipitate the mercury. Cool to 25° or below. To 2.800 mL Erlenmeyer flask add 1 ml 0.5N H2SOs for each 7 mg nitrogen in the sample plus 2 mL in excess. Add 5 drops of methyl red jicator solution and sufficient HO to immerse lower 1/2” of the distillate delivery tube and place the receiving flask under the delivery tube of the Kjeldahl distillation unit. Add 2 ~ 3 g zine to the Kjeldahl flask. With the flask tilted in position on the distillation unit, add sufficient 50% NeQH solution (at least 60 mL) to make contents of Kjeldahl flask strongly alkaline. With the flask tilted the NaOH will layer under the agié and not react violently. Connect the flask immediately to the connecting bulb of the distillation unit, swirl the flask sa.that the contents are mixed well and heat until 150 - 200 mL. of distillate are collected in the receiver. If indicator changes color during distillation repeat the determination, using either a smaller gample size or a larger volume of 0.5 N H2 SO.- Lower the receiver flask, wash the delivery tube with a few mL of HzO into the collected distillate and turn off the burner. Titrate with 0.25 N NaOH to the methyl red endpoint. Run a blank determination using the same reagents, but use only 2 mL of HzSOx in the receiver flask. CALCULATION net meq = Nx mL H2SO« ~ Nx mL NaOH BN 4007 x (net meq for sample ~ net meq for blank) sample wt (g) REFERENCE 1: Methods of Analysis, AOAC, 2.059 ~ 2,060, 13th Edition, (1980) —50-Method U1. A. 2. ll, ANALYTICAL METHODS A. NITROGEN 2. Total Nitrogen - (Modified Comprehensive Method) SCOPE This method determines total nitrogen content of any fertilizer ~ fluid or solid. This is intended to remove the potential environmental hazard posed by the use of mercury in the original comprehensive method. APPARATUS 1, Kjeldaht digestion and distillation unit. 2. Kjeldahl flask, 800 mL. 3. Ordinary labware. REAGENTS. Sulfuric acid, 0.5 N HaSOz (see Section V). Sodium hydroxide 0.25 N NaQH (see Section V). Methyl red indicator solution Dissolve 1.0 g in 200 mL alcohol. Copper sulfate, CuSO+ or CuSO. - 5 HO, nitrogen free, Sulfuric acid, 93-98% H2SOx, nitrogen free. Sulfuric acid, 1+1 H2SO«. Potassium sulfate, K>SOs, nitrogen free. Sodium hydroxide solution, 50% NaOH- Dissolve 450 g of solid NaOH in HzO, cool, and dilute to 1 L. i 8. Alundum, 8x14 mesh boiling stones (A. H. Thomas Co.). 10. Chromium metal, 100 mesh, low nitrogen (Fisher Scientific Co. No. C-318, Sargent-Weleh Scientific Co. No. SC 11432, or equivalent). 11. Hydrochiorie acid, cone HCI, Pr Og aens PROCEDURE 1. Weigh 0.2 - 1.6 g £ 0.5 mg of sample and transfer to a Kjeldahl flask. Sample must not contain more than 60 mg of rlitrate nitrogen. If organics other then uree or ureeform are present, weigh more than 0.5 g. 2. Add 1.2. g chromium powder and 35 mL HzO. For liquids make total volume 35 mL. Let stend for 10 minutes with occasional gentle swirling ‘to dissolve all nitrate salts. 3. Add 7 mL HCI and jet stand for at least 30 seconds, but not more than 10 minutes. -51-10. u 12. 13. 14. Method I. A. 2. Place flask on preheated burner adjusted to a 7~7.5 minute boil test. After heating 3.5 minutes, remove from heat and let cool. Add 15 g K2SO«, 0.4 g of CuSOs or 0.6 g CuSO, - 5 HzO and several granules (0.8 g) of alundum. Add 37 mL (1+ 1) H2SOx. Piace flask on preheated burner and heat until dense white fumes of He S03 clear the bulb of the flask, Heat another 5~ 10 minutes. Digestion is now complete for samples containing ammoniacal, nitrate, and urea nitrogen. For all other sampies, switl flask gently and continue digestion for 75 minutes. Remove flask from burner. Allow to cool for 8~ 10 minutes, then swirl flask a few times to provent solidification of the digest. After further cooling, add about 300 mL H2O and cool to 25° or below. To 2 500 mL Erlenmeyer flask add 1 mL 0.5 N Hz SOs for each 7 mg nitrogen in the sample pius 2 mL in excess. Add 5 drops of methyl red indicator solution and sufficent HzO to cover the lower 1/2" of the distillate delivery tube. Place the receiving flask under the delivery tube of the Kjeldahi distillation unit. Add 0.8 g Alundum granules and with the flask tilted in position on the distillation unit add sufficient 50% NaOH solution (at least 45 mL) to make contents of Kjeldah! flask strongly alkaline. With the flask tilted the NaOH will layer under the acid and not react violently. Connect the flask immediately to the connecting bulb of the distillation unit, swirl the flask so that the conterits are mixed well and heat until 180-200 mL of cistillate are collected in the receiver. If indicator changes color during distillation repeat the determination, using either a smaller sample size or a larger volume of 0.5 N H2SOx Lower the receiver flask, wash the delivery tube with a few mL of HzO into the collected distillate and turn off the burner. ‘Titrate with 0.25 N NaOH to the methyl red endpoint, Run a blank determination using the seme reagents, but use only 2 mL. of Hz SOx in the receiver flask. CALCULATION net meq = (N x mL H2SOs -. N xmL NaOH) %N = 1.4007 x (net meq for sample — net meq for blank) sample wt (g) —52-