TTaEX: JOURNAL OF AOAC INTERNATIONAL VOL, 99, No.4, 2016 915. After the SLV demonstrated satisfactory accuracy, provision, ruggedness, and selectivity for both extraction alternatives in inorganic fertilizers, Bartos et al. (1) proposed the method for consideration to the AOAC ERP for fertilizers. The method protocol follows. AOAC Official Method 2015.18 Determination of Phosphorus and Potassium in ‘Commercial Inorganic Fertilizers Inductively Coupled Plasma-Optical Emision Spectrometry First Action 2015, A. Scope This method is applicable for the determination of both citrate-EDTA-soluble Pand K (Alternative A) and acid-soluble P and K (Alternative B) in commercial inorganic fertilizers by ICP-OES, Citrate-EDTA-soluble P and K (Altemative A) is directly synonymous with “available phosphate” and “soluble potash,” respectively. Acid-soluble is sometimes referred to as total P and K; however, Altemative B may underestimate the total P and K content when acid-insoluble compounds are present, Values of r for citate-soluble P and K, expressed as RSD, range from 0.28 to 1.30% for Pand from 0.41 to 1.52% for K. Values oft for acid-soluble P and K, expressed as RSD, range from 0.71 to 1.13% for P and fom 0.39 to 1.18% for K. Note: For liquid fertilizers costaining phosphite and for organic fertilizers, an alternative AOAC Method such as 960.03 or 993.31 should be used because the ICP-OES will cover P that is not considered readily plant available in these materiale Alternative A: Neutral Ammonium Citrate-Disodium EDTA-Soluble P and K using ICP-OES B. Apparatus (a) Analytical halance—Readability to 0.1 mg, AT 200 (Metler Toledo, Columbus, OH), or equivalent. (b) pH Meter —Readabilty to pH 7.00, Model 8005 (VWR_ Scientific, Radnor, PA), or equivalent (©) pH Combination electrode —Orion 9102BNWP (Thermo Fisher Scientific, Waltham, MA), or equivalent, (@ Constant-iemperature waterbath —Capable of ‘maintaining bath temperature of 65 4 2°C, BKS3 (Yamato Scientific, Santa Clara, CA), oF equivalent (@) Heated shaking water bath—Capable of maintaining bath temperature of 65 = 2°C, and set to approximately 200 reciprocations'min, (0) ICP-OES instrument-—Vista-PRO axial view (Agilent Technologies, Santa Clara, CA), or equivalent (8) Gated rifle spliver—SP-177 Jones Standard Aluminum Splitter (Gilson Co,, Inc., Lewis Center, OH), or splitter with ‘equivalent or improved splitting performance (such as a rotary splite). (b) Grinding mill—Model ZM200 rotor mill (Retsch, Haan, Germany) equipped with 20.5 mm sereen, or equivalent. Grinding to 2 fineness of 0.420 mm corresponding to US. standard sieve size No. 40 or Tyler No. 35 mesh is preferred 03/10/2019 ©. Reagents (2) Ammonium citrate, dibasic 4NHi)sHCHs0>, formula ‘weight (FW) 226.19, American Chemical Society (ACS) grade, purity >98% (EMD Chemicals, Darmstadt, Germany), (b) EDTA, disodium salt, dihydrate —C Fy N:N8:0e 2H,0, FW 372.24, purity >99% (J.T. Baker Chemicals, Center Valley, PA), (©) Ammonium hydraxide—NILOH, FW35.05,28.0-30.0% as NH (Mallinckrodt Chemicals, Center Valle, PA). (@ Nitric acid —HNOs, 67-10%, OmniTrace grade (EMD (Chemicals (6) Potassium dikydrogen phosphate —KH,PO,, certified at 22.73% P and 28.73% K, National Institue of Standards and ‘Technology (NIST) 2002 (Gesithersburg, MD), hep:/wwwnist govisrm. @ Potassium chloride KCI, FW 74.55, ACS grade, putty 99% (Mallinckrodt Chemical) (g) Potassium nitrate—KNOs, certified at 38.66% K, NIST 193 (8) Triton X-100.—Oetylphenol ethoxylate (LT. Baker Chemicals), (19000 pg/ml. beryllium (Be) standard.—In 4% HNOs, Cat, No. 1OMS-I (High-Parity Standards, Charleston, $C). () 10000 jg/mL Seundium (Se) standard —In 4% HNO, Cat. No. 1OM48-1 (High-Purity Standards). 6) Cesium chloride —CsCl, FW 168.36, purity »99.999% (Sigma-Aldrich, St Louis, MO). () Lithium nitrate —LINOs, FW 68.95, purity >99%, (EM, Science, Gibbstown, ND) (im) Citrate-EDTA extraction solution (0.11 M ammonium citrate and 0,033 M disodium EDTA) —Weigh and completely transfer 25 g disodium EDTA (see b above) and 50 ¢ dibasic ammonium citrate (see a above) to a2 L volumetvie Mask containing approximately 1500 mL. deionized (or equivalent) ‘water. Adjust the pll to near neutral by adding 30 mL of a solution of ammonium hydroxide-water (1+ 1, viv; see above) ina fume hood. Adjust the final pH to 7.00 (+0.02) using ‘pH electrode [see Alternative A: Neutral Ammaniun Citrate Disodium EDIA-Soluble P and K using ICP-OBS, section B(b)] and meter [see Alernative A, section B(e)) while adding the ammonium hydroxide-water (1 + 1, wv) solution drop-by- NA 27S eS «14 15:5 18:25 oNTa2 08 2 250 100 aootsur NA 25500055027 335 aHS 1 a 20100 6 NA 80 15—ntas «ss? wat 78 aaTeoa8 4 ee ee 5 250 0015 NA 150k gasasT «72109 a8 men 6 250100 aa NA 220 5H osOA 252835 osaes «87 7 250 100 -90NA 00 BT nseTs tk «a7 55 SG? 28 10 20 100 NAY 25 NANA NANA 74700080084 2 20100 NA 35 NANA NANA 046260 .12600 8 5 Sook 1 = 2500 yi Psiock standart: 27481 9 pelassum ayérogen phosphate (K:PO,)250 prepared in deorized wate, took 2= 7472 ug K stock standard: 3.5815 9 potasslum creo 4.8209 g ptassum ntats260 mL In dlonized wate. ‘Sera ton tom anoter standard (e.g, 10 of Std Avolume of 2 mLcan be achieved by using @ 18m anda 7 mL dase A pips, or equivalent combination. NA® Not apple sud 10m. fom Standard 7, 03/10/2019TTHIEX: JOURNAL OF AOAC INTERNATIONAL VOL. 99,NO.4,2016 917g Table 2015:188. ICP calibration standards from commercial custom blend stock standard solutions Soandaré Vous, Gwale, Stock, Stock? Pooren, Piz Py —~PiOs_ Keone, KO KO KO 0 me mL mut mlm gm soltion % friar % ugly sokion, feria, Bae oe ° 7 ° ° 7 ° 7 7 ° 2 100% tOokSwET 102k SUSE zy 0st ates 3 100 tOokSew #5] OTtMG «Bake uzea KS ‘ 100 5 6 > 29 mes tT amntes08 ’ 104018 NAY 200 G7. 0.08874 kN NANA 8 ee " 004 NA NANA NANA on 728 ora at 2 to NA NANA NANA 750030000452 8 no NA 0A NANA NA 0010880841842 Stock 1 = 2000 yim Ps PO, custom stock standard [soa Atematve A section G() > stock 2 2000 gm K tom KCl custom stock standard [se Ateratve A, secon Cf NA= Net appesbe only for calibration within the batch of tes solutions with which they were extracted, These standard extract solutions have the same shelf life (Le., approximately 16 h) as the other fertilizer extracts and must be prepared fresh with each run. Caleulations for converting the percentage POs in these. materials to riligrams per liter P are provided in the Calculations section (see Alternative A, section H). Fertilizer materials below 40% 0s (approximately 350 jgiml.P) typically do not experience this suppression issue, so standards below this concentration can be obtained using those listed in Tables 2015.18. and 2015188. Empirical calibration isnot the preferred option and should be used a alas resor. ‘The test solution and intersal standardionie bulfer solution [see Atemative A, section C(o)] are blended usingaY-connector Table 2015.18¢. Sota lon fom another standaré (9.5 of Si 8 = ad 5 mL rom Standard 6). (Part No. 30703-90; Cole-Parmer, Bunker, CT) or Feonnector (Part No, 116-0522-01; Bran+Lucbbe, Mequon, WI) jest before ‘the nebulizer, using the conditions described in Table 2015.18, E, Sample Preparation Collect a primary field sampleusingone ofthe recommended AOAC sampling procedures (i.e., Method 929.01, 969.01, or 992.33) or other recognized protocol, Prepare solid fertilizer ‘materials by rifling [see Aleernative A, section B(g)] the entire laboratory sample to select an approximate 100 g subsample, Grind the entire 100 g subsample [see Alternative A, section ‘B(Q)] to pass through a 0.50 mm mesh sereen. Place the ‘ground analytical sample into a one-quart (0,946 L) glass jar Calibration criteria for directavailable P and soluble K by ICP-OES Foment ‘Wovlongin aa? alivaton ange, vain Slander used? Curves Speavel deconvauton P TTAB o-i00 Blank L234 ine None P 1778942) 100-500 45.6,7.8.9 near None P sre220(0 0-100 Blank. 1.2.3.4 neat None P 178.220(2) 100-500 4,5.8,7.8.9 Linear None P 23818 (9) 0-100 Bank, 1.2.3.4 near caz13.s0e P 213.8182) 100-500 45.6,7,89 Line ca213.s08 P 21418 (0) 0-100 Blank, 1.2.3.4 Unoar cu214.08 P 214.914 (2) 100-500 4,5.6,7.8.9 near cu214.098 k 798.495 (1) 128 Blank 1.2.3.4 cuneate None k 798.485 (2) sore 84,5.8.7 uscrate None k rea4a7 126-505 45.6.78 uocrate Possible LN; K 404724 505-1066 8,9,10,1,12 Quadate None. The standards correspond those sted in Table 2015.18A, 03/10/2019 The designators (7) and (2) are ud to etingulh between te same wavelength elected wie o cover wo separa concaiation ranges918 THIEX: JOURNAL OF AOAC INTERNATIONAL VOL. 99, NO. Table 2015.18D. Final ICP-OES conditions used for cltrate-EDTA-soluble P and K validation Far Seting Power RA 145 Plasma Now, Lin 195 ‘usar tow, Un 228 Nebulzer pressure, Lmin or Nebulizer ye Seassry Spray chamber oyetonie Sample pump ibe ack Buflorntsral standard pump tube Geayiray? CC onl tle onan, M oor Internal standard and conn, va 10 Btls mati 96 nite acs No. ofexposues a Ringe tine. 6 36 Total analysis timo, min 2 ‘An orange sample pump tbe and a rade bieriotamal "anard pump tbe prove apostate sr ton factor, bt Unolecs volume of aon, Enaure ha» etseny ge waste pomp ‘ube le ured prevent foodng of th spray chamber and mix by careful rotation and inversion, For liquid materials, shake the laboratory sample vigorously to thoroughly mix Invert and rotate the container again (for solid materials) ot shake (fr liquids) immediately before selecting atest portion. Other validated sample preparation techniques that result in 4 representative test portion are also acceptable. When the analytical sample i split or the mass is reduced for any reason, the splitting process should be validated to not introduce unintended sampling error. F Extraction Weigh a ~0.5 g test portion to the nearest 0.01 g (see Alternative A, section B) and completely transfer to 8250 rl wide-mouth class A volumetic flask, Dispense 100 mL 65 = 2°C preheated citrate-EDTA extraction solution [see Alternative A, section C(m)] into each flask and insert a rubber stopper. Shake test solutions in a 65 ‘water bath set to approximately 200 reciprocations/min for 660+ 1 min, remove from the water bath, allow to cool to room temperature (20-25°C), dilute to volume with deionized (or equivalent) water, stopper, and mix, Filter any test solution containing suspended debris using P- and K-tiee filters. Due toa very limited shelf life, analyze test solutions within 16 h of extraction, After repeated heating and cooling eyeles of the 250 mL volumettie sks, check the calibration of the flasks by adding 250 g deionized (or equivalent) water and verify that the volume is at the meniscus. When a flask loses ealibration, either use the corrected volume established by water weight, or discard it . ICP-OES Conditions The optimal instrument conditions identified during method validation of itrate-EDTA-soluble P and K are listed in 03/10/2019 4.2016 ‘Table 2015.18D, Monitor the rinse time and buffer concentration losely, because they are sensitive to change (1) ICP-OES instruments differ in thei design and options, so ‘minor adjustment to the conditions listed in Table 201S.18D may be nevessary; however, any adjustments to these conditions ‘must be performance based and validated. Special altention should he paid to the recovery of P in fertilizer concentrates o fertilizers containing 40% POs, because these materials pose the greatest need for optimal instrument performance. H, Calculations Several variables exist in the instrament software for data reporting, including units, test portion weight, tes solution volume, and dilution factor, The calibration standards re prepared as micrograms per milliliter P and K, and the final fertilizer resulls are reported as percentage PO, and K;0, which requires the following two caleuations, respectively POs, P< (250/W) x 142/31.0 x 29/1000 ‘where P isthe ICP-OES P reading in micrograms per mililiter, 250 is the final volume in milliliters, W is the test portion ‘weight in grams, 142 is the FW of PQs, 31.0 is the FW of P 2 isthe mole ratio of PO to P, and 10000 is the conversion of percentage to mierograms per milliliter; and K,0, % = [K » (250/W) * 94,2/839.1 2)}'10000 ‘where K is the ICP-OPS K reading in mierograms per milliliter, 250i the inal volume in milters, W isthe test portion weight, in grams, 94.2 is the FW of K:0, 39.1 is the FW of K, 2 is the mole ratio of KO to K, and 10000 is the conversion of pereentage to micrograms per milter. Alternatively, the standards can be entered as equivalent theoretical percentages of P20, and KO in solution values, listed in Tables 2015,18A and 2015.18B. ‘When empirical calibration [see Alternative A, section D(d)]} is used, conversion of the percentage P:Os in the certified or ‘consensus material to milligrams per liter P in the calibration solution is obtained by using the following equation: sgl = PO, x 10,000 (W/250}x ((3.0%2)/142) where P, g/mL is the P concentration in the extracted standard Solution; % POs is the certified or consensus value, 10000 is the conversion of percentage to micrograms per milliliter, W is the test portion weight in grams, 250 isthe final volume in milliliters, 31 is the FW of P,2is the mole ratio of PsOP, and 42 is the FW of 0s, 1. Comments Relative to other AOAC Methods (960.03, 978.01, and 993.01), the ICP-OES method can produce lower P recoveries and/or greater data variability (hnspliwww smagruderchecksample.orp). Critical factors and common ‘error sources are included here. For P, three issues are eritieal: addressing matrix challenges, implementing robust plasma ‘conditions, and utilizing proper standards. Carbon in the citrate and EDTA will reduce the plasma efficiency, so it must be addressed, Diluting the matrix by using a smaller sample pumpTTaEX: JOURNAL. OF AOAC INTERNATIONAL VOL, 99, No.4, 2016 919) tube and a larger intomal standardonization buffer pump tube 1 listed in Table 2015.18D isthe approach used in this method. Other options include (1) the use of oxygen addition to the argon tohelp combust the carbon, (2) a separate manual dilution ofthe test solutions and standards in a 4% nitric acid solution, and (3) ‘a complete destruction ofthe carbon with e secondary digestion of the extract solution in ntsc acid. Other factors Usa ean help improve P recoveries include configurations that decrease the volume of aerosol injected into the plasma, such as a slower ‘pump speed, slightly lower nebulizer pressure, and/or a double- pass or baffled spray chamber. Lastly, the final matrix of the calibration standards and the test solutions must match closely Standards prepared fiom salts, as provided in Table 2015.18, hhave the closest match and offer the best P recoveries. When commercial stock standards are used, a source of Pas PO,’ ina ‘matrix that will not adversely change the plI-neural ammonium citrate-EDTA matrix are desirable. Stock standards preserved in acid solusion are not recommended Although ruggedness testing suggested no difference in P data when Se or Re was used as an intemal standard for most fetlizer materials (1), inthe ease of polyphosphates, Be may result in better P recoveries because bound polyphosphates present additional challenges to the plasma that may not be detected by Se because itis more easily ionized. Because K is easily ionized, it generally poses fewer problems than P. The greatest challenge with K is capturing the broad concentration range found in fertilizers, ecause it produces an intense signal, resulting in a limited linear dynamic range. If possible, K shouldbe readin the radial mode, and it may benefit from slightly lower nebulizer pressures and pump speeds. As described in Table 2015.18, the use of multiple wavelengths (766, 769, sad 404 nm) sndior multiple calibration segments te cover the dynamic concentration range is recommended. (Quadratic curve fit can help expand the useful range of some of these wavelengths, but great caution should be exercised to censure that the curve falls within the sensitive response range without excessive curvature, Also, secondary dilution of high concentration test solutions ean help. Deviation from this method is not recommended, but if small revisions are necessary to accommodate differences in ICP- ‘OES types and design, then these revisions should be validated Within each analytical batch of samples, inclusion of one fo more certified ot consensus fertilizer materials for quality control purposes is recommended, especially for the fertilizer concentrates (.e, PO, >-40% and K,0 >50%). Some sources of these materials include LOSI (htp:www.sgs.com/en/mining! Analytical-Services/Profieiency-Testing- Programs-LQSi aspx) and the Magruder (hup:/vww.magraderchecksample org) and AFPC (htp:liwiwalpesnet) check sample programs. Te presumed “host practice” methods for available phosphate and soluble potash are AOAC Methods 960.03E. and 958.02, respectively, so these consensus values should serve as the preferred reference value Alternative B: Acid-Soluble P and K using ICP-OES B. Apparatus (Alternative B) (8) Balance Readability t9 0.1. mg, Sartorius BP210S (Gottingen, Germany}, or equivalent (b) Hotplate —Model $3015, Lindburg/Blue M (Watertown, Wh, or equivalent. 03/10/2019 (©) ICP-OES instrument Thermo 6500 Duo View (Thermo Scientific, Cambridge, UK), or equivalent, (@) Gated rifle spliver—SP-17 Jones Standard Aluminum Splitter (Gilson Co., Inc), or spliter with equivalent or improved splitting performance (such asa rotary split) (©) Grinding, mill—Model 2200 rotor mill. (Retsct), with 0.5 mm sereen, or equivalent. Grinding to a fineness of 0.420 mm corresponding to US. standard sieve size No. 40 or Tyler No, 35 mesh is preferred, . Reagents (Alternative B) (8) Hydrochloric acid—HCl, 35-38%, trace metal grade, (Cat, No. AS08-500 (Fisher Scientific, Pittsburgh, PA). () Ammonium dilydvogen phosphate—NH.HPOx FW 115.03, trace metal basis, purity >99,999%, Cat, No, 204005- 1006 (Sigma-Aldrich), (6) Potassium chloride —KCI, FW 7455, trace metal basis, purity >99,99%, Cat, No, 204099-250G (Sigma-Aldrich) (@) Scandium oxide —SC;0,, FW 137.1, Item No. OX21- SSN (Stanford Materials Corp, Irvine, CA), (6) Nitric acid —HNO,, 69.2%, eertied ACS plus grade, Cat, No. A200 C212 (Fisher Scientific), (Triton X-100—Polyethylene glycol p-tert-octylphenyl ether, 4-(CHy3)CH«(OCHsCH),OH (v- approximately 10), FW 624, Cat, No, BP151-S00 (Fisher Scientific) (g) Cesium chloride CsCl, FW 168.36, trace metal basis, purity >99,999%, Cat, No, 203025-50G (Sigma-Aldrich). () Lithium nitrate LINO, ReagentPlus grade, FW 68.95, Cat, No. 227986-IKG (Sigma-Aldrich, @) 19000 pgink. Be stock standard —In 5% HNOs, Cat. No, PLBE-10-500 (Exaxol Corp, Clearwater, FL) @ 10000 pgimt Se stock standard —Weigh 153374 g SCO; (see @ above) into a 600 mL beaker. Add 300 ml deionized water and slowly add 100 ml nitric acid (see e above). ‘Heat solution on a hotplate to a gentle boil, and continue boiling ‘stil the solution becomes cleat. (ky 1% Triton X—Pipet 10 ral Triton X-100 solution (see above) into a 1 L Mask. Dilute to volume with deionized (or equivalent) water and mix. () Internal standardiionization buffer (60 ug’ml Se in 0.035 M CsCI and 22% HNO,)—Ada 6 ml. 10000 ug Sei stock standard (see j above), 6 g CSCI (see g above), 20 ml HNO; (see e above), and 2 mL. 1% Triton X (see k above) to 41 L Mask containing approximately 500 mL. deionized (or equivalent) water, Dilute t0 volume with deionized water and ‘mix, IF LiNO, is used as the ionic buffer, replace the CsCl with 8 g LINO; (see W above). If Be is used as an intemal standard, add I ml. 10000 g/mL. Be stack standard solution (ee i above} to obtain a 10 ug/ml Be internal standard concentration, (im) 4M Hydrochloric acid digestion solution —Add approximately 500 ml. deionized (or equivalent) water to to-a I L volumetric fask, Slowly add 333 ml. concentrated hydrochloric acid (see a above) and dilute to volume with deionized water and mix, D. Calibration (Alternative B) (8) Standard solution—Prepare calibration standards from ammonium dihydrogen phosphate [see Alternative B: Acid-Soluble P and K using ICP-OES (Alternative B), section {C(b)] and potassium chloride [see Alternative B, section Cle]920 as recommended in Table 2018.188. As with Altemative A, ‘many calibration standards are required because (1) multiple ICP-OES wavelengths are used, (2) some wavelengths are split {nto multiple calibration segments, and (3) a minimum of five points/eurve is recommended, Table 2015.18E. provides the P and K concentrations expressed as micrograms per milliliter and their percentage of oxide forms. Note: Better P recoveries were obtained using weighed salts [see Alternative B, section C(b)}, s0 commercially available stock standard solutions are not recommended, (b) ICP-OES calibration—Emission intensity for each of the calibration standards is plotted against concentration. A minimum of five calibration standards is used for each wavelength section C()] to adjust the concentration of the calibration standards and the test solutions, The wavelengths, standards used, concentration ranges, curve fit, and wavelengths that may requite spectral desonvolution ae listed in Table 2015.18F, The ata in Table 2015,18F are based on a radial view for K. When Tinear regression to 1000 upimL K is not poss of the following will be novessary: selecting quadratic curve fit (provided the curvature isnot excessive), ulilzing a wavelength ‘0f 404,721 nm forthe five highest K calibration standards listed in Table 2015.18E, dropping one or more ofthe top K standards listed in Table 2015.18E, andor conducting dilutions ofthe test solutions using 0.16 M HC! The test solution and internal standard/ionie buffer solutions are blended using a T-connector (Part No, 116-0522-01 BrantLuchbe) or Y-consector (Part No. 30703-90; Cole. Parmer) just before the nebulizer, using the conditions described in Table 2015.186, Use an intemal standard [see Alternative B, ‘Table 2015.18, TTHIEX: JOURNAL. OF AOAC INTERNATIONAL VOL. 99, NO. 4, 2016 E. Sample Preparation (Alternative B) Collect primary field sample using one ofthe recommended AOAC sampling procedures (Le., Method 929.01, 969.01, or 992.33) or other recognized protocol. Prepare solid materials by rifling [see Alternative B, section B(@)] the entire laboratory sample to select an approximate 100 g subsample. Grind the entire 100 g subsample [see Alternative B, section B(e)] to pass through a Tyler No. 35 mesh sieve (U'S. standard sieve size No, 40, 0,420 mm or 0.165 in. opening, Fisherbrand stainless steel; Fisher Scientific. Place the ground analytical sample into 4 one-quart (0.946 L) glass jar and mix by careful rotation and inversion, For liguid materials, shake the laboratory sample ‘vigorously to thoroughly mix, Invert and rotate the container again (for solid materials) or shake (for liquids) immediately before selecting a test portion ‘preparation techniques that result in a representative test portion are also acceptable, When the analytical sample is split or the ‘mass is reduced for any reason, the splitting process should be Validated to not introduce unintended sampling error ‘Other validated sample F. Extraction (Alternative B) Weigh -0.5 g test portion tothe nearest 0.01 g and completely ‘wansfe to 8250 mL class A volumetie ask, Slowly add 30 mL deionized (or equivalent) water to each ask. Dispense 10 mL 4 M HCI digestion solution [see Alternative B, section C(em)} into each flask. Place flasks on a preheated hotplate and gently boil for 15 « 1 min, Remove individual flasks that have boiled for 15 + | min and allow them to cool to room temperature ICP-OES calibration standards from stock reagent salts for total P and K Standard Volume, Aad, Wont Poonen, PO, POs _Pi0s, Keonen, KO, KO KO b mk mi? NWHPOw9 WelghtKl.g yam” pgm soliton, sample, aime gi sclusion, % sample, % Blank 10004 ° 0 ° ° 7 o.oo 0 ° 1 1000 40 Moetsae? §=— eos. «hak poze «1 00 mt0 a 2 1000 36 to0orsusto? © ora 47108 ta7S «sak gH 3 500 12 100eFSta10" 100ofsWs4? St 215 NTS 631958 OHS 4 1000 92, oas9 apts tz? 122-28 .2802 #10 5 000-86 «=e tooetsW iat 184 © 420 ateos 21 ttt 5 s000 400.9079 Soars ts 451.0505 28 akg zm 7 s00 404449 safse te 308701 TOOT 35a monet « 1000 404.3610 Nas 27 et} .0eoB 2 NANA NAA, 0 10004087510 Na 4m wa) ovat St NANA NANA. 1" 1000 40 NA 0791 NANA NANA 415,500 ,0500 a8 2 100040 Na 1307 NA NR ONA NR 581700, 070038 18 100040 NA wat NANA NANA 801120011206 1% 100040 NA 1900 NA NANA NA 10481260 12503 Re = Volume of BCLwator (1 +2, i) eaued to make the sander Serial dato tom another slandard (6, 40 of Sts 6» add AD of Standard 8 © N= Not appcabe, 03/10/2019TTHIEX: JOURNAL OF AOAC INTERNATIONAL VOL. 99, NO.4,2016 921 49 Table 2015:18F, Calibration criteria for acid-soluble, ortotal,P and K lonentiO Wavelength an® __Galbyalonrange, paint ___Standardsused?” uve, ‘Special deconvoution ? 2iss1e os Ban h25456 near canis P 213.618 2) raeara 5,6,7,8,9,10 nese ou213.586 P 214ste(n 0-245 Blank 1,2,9,4,5,8 Linear ou714.898 P 214.9142 tear 5.6,7.8,9,10 Uneer ou214.98 k 756485 (1) oss flak 1,2,9,4,5,6,7 Linear Nene k 708.485 (2) 32-1088" 1,12,99,16.15.16.17 nese Nene k 709.897 (1) 0-302 hans, 1,2,9,4,5,6,7 Linear Posse LINO, k 199.897 (2) 32-1086" 11,12,19,16.15.18,17 Une Posse IND * The dosinatore 7) ang (2) are ured ostnguln behveen te same wavelength elected twice to cover wo separate conceriraton anges The standards coegpon to thos ted in Table 205.186. * Potassim viewed in the racial orientation. (20-25°C), Dilute flasks to volume with deionized (or equivalent) water, Filler any tet solution consaining suspended debris using P- and Kee filters. The final acid strength ofthe {est solution is approximately 0.16 M HCI, so any test solutions requiting dilution should be prepared in 0.16 M HCl and stored Jn a glass convainer. Due to a limited shelf life, all analyses should occur within 2 weeks of digestion. ARer repeated heating and cooling cycles of the 250 mL. volumetric flasks, check the calibration ofthe Masks by adding 250 g deionized (or equivalent) water and verify thatthe volume is at the meniscus, When & flask loses calibration, cither use the corrected volume established by water weight, oF discard it G. ICP-OES Conditions (Alternative B) Limitthe deviation of test portion weight of.5 gt0-+0.025 Because K is sensitive to nebulizer pressurelow, closely monitor the nebulizer condition, which can deteriorate over time, Tnstrumeat conditions used for method validation of Table 2015:186. Final ICP-OES conditions used for acid- Soluble of total P and K validation Faoe ‘setng owes Ka we Plasma ow, Lin 6 Asli ow, Linn 15 Nebulizer pressure, Lin 040 Spray enamber ‘Scotts eat) ‘Samgte pump tube ‘Orangsnite (0.84 mms) Bufrintrralstandard pump tubo Orangaiwhite (0.64 mm) (CsCl concentration, M 0035 xosureenath, = 0 No.of exposures 3 Ringo ine,s x “Apower of 1.20 KW is required for @ There 8800 (Therme Scie) fatal ve. 03/10/2019 acid-solubleltotal P and K are listed in Table 2015.18G. ICP-OES instruments differ in their design and options, so ‘minor adjustment 10 the conditions listed in Table 2018.18G -may be necessary; however, any adjustments to these conditions should be performance based and validated, Special attention should be paid to the recovery of Pin fertilizer concentrates or ferilizers containing 240% POs, because these materials pose the greatest need for optimal instrument performance, H. Calculations For Alternative B calculations, se Alternative 4, section H |. Comments (Alternative B) The 0.16 M HCL matrix used in Altemative B poses fewer analytical challenges for the ICP-OES than docs the citrate-EDTA solvent used in Altemative A. If minor method ‘modifications ate necessary to accommodate different ICP-OFS types or designs andior to corteet for variable or low recoveries the following ae likely watch area: (1) inereasin the plasma power often benefils P, and (2) decreasing the volume of the aliquot injected into the plasma can also help improve recoveries of materials containing high concentrations fof PB. The latter can be accomplished by using a smaller sample pump tube and/or larger intemal standard/ionization bur pump tube, andior by slightly decreasing the pump speed and/or nebulizer pressure. The final matrix ofthe test solutions and standards should closely match. Standards prepared from salts as provided in Table 2015.18E provide the greatest match and offer the best P recoveries, Stock standards preserved in acid solution are not recommended, The comments provided for K in Alternative 4, section H also apply to K in Alternative B. Deviation from this method is not recommended, but if small revisions are necessary to accommodate differences in ICP-OES types and desig, then these revisions should be validated Discussion The ERP recommended that before First Action method publication, the method protocol should be revised to state that system optimization is based on the instrument manufacturer's recommendationo allow forall manufacturer's equipment, They also suggested the author consider incorporating an alternative922 THIEX: JOURNAL OF AOAC INTERNATIONAL VOL. 99, No. 4, 2016 u for empirical calibration procedures. ERP recommendations hhave been fully incorporated into the method as presented (3). The ERP requested that R data be genetated on a variety of insirument manufucturers’ equipment. The R data will establish whether the method is suitable as screening method of as a confirmatory method (3). ‘Acknowledgments Recognition for this AOAC First Action method goes to James Bartos, Office of the Indiana State Chemist, who coauthored the single-laboratory validation (1) and submited the method to the ERP for fertilizers (3). He has championed 03/10/2019 this method throughout the long and tedious process. His ‘expertise, diligence, input, and effort were essential t properly document the method inte AOAC First Action format. References (0) Boros 1, Boggs BL, Falls, 13h 8 Sige, $.A. (2018) J.AOAC nt 9, 687-688. dont dor 10ST (2) Thos, N,Q014)7 AOAC. 97, 641-542, doit do crg)10.5HOfpoocne SETH (9) Thx, N. 2015) Ide Laboratory Management, AOAC INTERNATIONAL, Rockils MD, NovDec 215 au p. 41-12