TOC/ECITIC Analysis in solids 6 edad, European Field Product Manager, LECO Appicaton & Technology Center, Barth Carbon determination in soli samples by combustion is a well known analytical technobgy ‘The sample is combustee with Oxygen to form CO, whichis later on detected by IR absorption, While total carbon analysis isan estabisned method, the analysis of Caroon phases is causing ‘questions. TO (Organie Cerbon), TIC (Inorganic Catbon) and especially Elemental Carbon (EC) are more dificul to determine and it is especially dificult to diferente between them, ‘TOC components are normally organic chemicals or biologieal materia, inorgante carbon (TIC) are e.g. carbonates. and elemental carbon species (EC) ae e.g. grapnie or coal ‘The taalonal acid treatment methods (erect method, Indirect method) are working quite simply by removing carbonates and measuring the remaining carbon or measuring the CO. released by the acd. Both methods are leading to erroneous results regarding the elemental Catbon. EC in those cases is always detected a8 TOC, which is analyiealy incorrect. ‘Adtonally most analytical equipment using the acid treatment method ls easily corroded and the lifetime is reduced by relabity issues. i owe 1 LECO RC 612 Carnal Phase anayzer Fire 2LECO RC 612 pus Autioaser ‘Therefore, since many years LECO is offering the RC 612 CarborvWater Phase analyze: that i working by temperature separation ofthe 3 Carbon components, TOC, EC and TIC are reacting with Oxygen at diferent temperatures and can be separated by using temperature ramping ola Sample. Aitionally the water Hydrogen poak analysis is avaiable fr further informatio. (uring the analytical combustion only TOC normaly is producing higher amounts of water beside CO.) ‘The new DIN 18539 (2018-08) Investigation of solids - temperature dependent diferertiation of ola carbon (TOC,oROC, TIC" used the same analytical approach. This paper wil cve an ‘example forthe analysis of Samplas and standards according tothe upcoming DIN 19539, Application Example RC 612owe 3LECO RC 012 as Flow Schomatice ‘The LECO RC 612s working with oxygon cartier gas (Nivogen is also avalabe ‘special applications). The oxygen is precleaned ina gas purer and used for combustion ‘ofthe sample in te combustion tube. Samoles are normally iniraduoed within a Sombustion boat using a manual push rod or @ 50 poston autosampler. Tho Carbon and ‘Waterhycragen ofthe sample Is forming CO. and H.0. Afr passing an aftorburer and a ‘at furnaoe the gases are measured with non dispersive IR cells. 21R cells for CO. are _vallable to cover a wide analycal range, from the ppb range up to samples with 80% of Carton and more. The system is driven by a pump and gas ows are contolled wit & mass flow controle. For a thermal separation of he diferent Carbon phases the furnace can be ramped from ‘2g. 100°C to 1100°C with 120 “Cimin maximum heating rate. The special logic of the heating system allows precise temperalureating rate contol to avoid overheating, Data ‘analysis fs done convenientyby the user friendly LECO Genesis software, I & io} 1S) [4 co] % = oI x iit] = Q BS © Bo] r-% 3 4 oo ec ie t Tenperstie ‘ | Ramp Curve =f Pour 4: Anais ofa sansa same as desebed in DIN 18529For a typical TOC, ROC, TIC analysis a 3 step program is applied with 3 temperature steps. (CO, and Water signals are recorded togetner with the tomperatute and ploltel vs, time, In Figure 4a typical analysis is shown determining the diferent Carbon phases. A special standard is analyzed according o DIN 19539. The vee phacos are clearly detected and oparated. Tao 1s showing a epeatabilly test ofa 3 phase standard. as seen clearly he instruments working with highest precision. also for phaso analysis. Reproduceblsy is dven 2a shown in Figure 5. All3 Phases are showing similar pattem, TC precision is bette than 0.5 Yerel Sid Dev. ‘Sample Name | Weight |TOC4o0 | ROC Tie Total ] Carbon Table: Mate Anas of Standart otal ANG: 5: STD: 0.028 RSD: 0.486 m5 EC Figur 6: Ororay 05 options In Figure 6 the expected behaviour ofa typical wastlsoiVenvronmental sample Is shown together wih the expected water peak when heated up witha linear temperature program \Wiateris not lly needed for quantification but available as an adalonal parameter To check for Organic Carbon content it might be valuable. Only organie carbon is producing CO, plis, Water during combustion, EC will only produee CO, as TIC (Carbonates) does. As seen ir ‘igure 7 only the frst peak has an comncident Water signal where the second (EC) peak only has, CO, signal the TIC signal has also no coincident water sighal, The very frat Water signa, ‘come’ from sample moisture and is reloased allover temperatures. IL a big analycal ‘advaniage ofthe RC612 to have the water signal logothor wih the Carbon signal. i) = rr) oO [4 & -¥ iS co x wi c 2 = © 2 ‘2 2 agCarbon / Water Signal ‘Temp. 100 - 100°C TOC : Water plus CO; H,0 Signal mites water Carbon Signal Timeins Figure 7 shows an environmental sample being heated up with a three step program to {elermine TOC, EC and TIC. Here only very small TOC peak and a major EC peaks is Shown beside some inorganic carbon. The water peak end proves the quality and ‘accuracy ofthe obtained data Ec Toc Te N = o [S} [4 a 2 = © x wi < S fe © A r-% 2 Pd Figur 7 Carbon plus Water anal ssdetonlifoatonLooking more closely into some analyzed data shows that for samples containing no ‘lomental carbon (EC) te obtained values fr the tradivonal method (acid treatment) ond the temperature method give the same results. A comparison fs given in table 2. The TOC and ‘TiC values ara in close agreemert for all samples, No matter # there are samples wth nesrly ‘ne TIC (Like sample 1 or 4) or samples with higher TIC values like sample 2 or 3. The big Advantage of the temperature method in this case i, that ro acid ealment has to be cone {and the analysis is running without aggressive acds or other chemicals, TOC, TIC and TC values ate obtained in ono run. The analysis here is started normally at 850°C and fs fished a1 1000°C. Inclucing the cool down time back fo §50°C 6 analysis per hour ae feasible For “TOC only determination a average runtime between 2 and 3 minutes can be obtained. For high throughput analysis an autosampler is available ‘The TOC determination according to this method ie used as a reference method for sols VD Lufa method A4.13.2 (Associaton of German Agricultural Analytic and Research instiites) | TC Total Carbon) | TOC (Acid) TOC (Temp Method) sample 1 673 654 649 [Sample 2 3.88 12 1.55 Samples «(8.10 2.40 2.38 Sample 4 7a 702 82 Sample § 358 [270 259 | ‘Sample 6 305 245 2.48 Carbon / Water Signal ‘Temp. 100 - 100°C H,0 Signal f\ TOC Application Example RC 612 Water plus CO, Carbon‘Comparison data for samples containing TOC, TIC and EC is shown in table 3. The problem ‘of not considering elomental Carbon (EC) Is especially obvious when looking to sample ‘waste 2. This sample does not contain TIC and only a very small amount of TOC. Most ofthe sample is elemental carbon EC, whic Is detected ertoneous as TOC withthe acid treatment ‘mathod, Also for samples waste 7 and Industrial sol the aflerence is cbviously. Here the ecessiy fora suitable EC reference method is given. This data shows imitations of acid Uteatment methods. For samples containing EC the temperature ramp method delivers more reliable results, TE | TOC |TOC(aciaj| ECTemp |ECchem | Tic (Temp) Waste 1 a6% | 455% | 843% | 305% | 376% | <01% Waste 2 322% | 244% | ar4% | 209% | >25% | <01% Soi 73% | 48% | 45% * * 27% Industial Sot | 120% | 29% | 86% | 55% - 35% Tie 3 Comparison dt fo TOC detention afr temperature a ai vestent meted and ROC (EC) Uaramae ® Hop Senet . Sol quality — Dsterminaon of eigen end tte 180 10694:1995(en) csc aher dry combust (elomentary anaes) Foreword 130 fre ination! Organ or Standrazan) i ortwte cern onto tanaka ies (8 meer tes) “Te wor cpap mienabee| Stands ermal cared oat oun 0 ei cnmtees sh manar hay eeiod Ing eect wha ecanel eres fas ba ested has a rho om represeneg ona cee inane Cnenaiee, ovement ard pangovermata, mao wih 80 st ee pan ne wor 0 colada keel wit he Imsreton Cetoteaweal Canmssen (EC) on a mates of chelate sanceoeaon Dra marstoa Stnsadeetptd nye tenes commits sf isd othe menbe: bee Ir voting Pubeafon aah Inert! Stara egures appeal y stat 7% ofthe meat tdies casing ne nsmaton Stand 0 105 was prepares by Tens Cortes IO.TE 180, So gosh Subconmtes SC 3, Chemis ‘Anseras Aan o rasa Sand arr ntomaton cry 4 Scope “Ts rtamatorl Sana ones ¢ method ore cermin el eon cont 0 te dy conbuston The ore Caen covert s acute Wom thant ater coreg fr carats ent ine sarge eabenates we emea Detrtans, meee can cris messes ores ‘Tris rstona Stands apical pas of atid so sampes 2 Normative references “Ta olowng sanded conta prove vin, gh lee i a, costae pronsins is eran Santis AL {etn of pubeaton the eos ndeatas wer vad AI Stns oe sabe rewsan tne pao ager based on Intenatena Stand are encourages ones epost ot appling te elses sone! he strcace ted bob ree of an ISO manana of otrany vanes Stance | 36961987, Wat tor naycl trates — Speoeaton atest mene 150 1008099, Sat gua — etemraton op 180 10608266), So uaty— Detention earorai contnt— Yaumaae mano. '80 1468996, So quaty— Peveatant of samples orpysie-nema anaes 10 514651659 Ser quay — Delamination ay mse ang war cont on ase Gas — Grane meio. ‘Oni itrmatve sections ot tancards are pubiey ava To ow he corny, you wl ned to purse he sandard ‘yanking onthe "by un.theme arena NAR Teed a“ zPe eerie en) : errr Pee reste eer) eect e)AGQCalifornia Environmental Protection Agency © Air Resources Board STANDARD OPERATING PROCEDURE (SOP) FOR THE ANALYSIS OF ANIONS AND CATIONS IN PMyo SAMPLES BY ION CHROMATOGRAPHY SOP MLD 068 Revision 0.0, Northern Laboratory Branch Monitoring and Laboratory Division Version 1.0 Approval Date: August 4,2015 Propared by: L6fo Withele Prstoe, Ar Potuton Specilat Bate Inorganies Laboratory Section Approved by: = S-4-1IS- Brenda Sadana, Manager Dale a {4s Date [7 bate DISCLAIMER: Merton of ay rade nme or commer produc ‘ons endoremat a ecormendon of is proal y Ine Standard Operating Posie dons ot - scutes Soar. Spocte mend names nd rere desotpins std in tne Stadara Operating Pocagir are er equomn ceedby fe At Resources Board iboratry. Ary uncon ex‘TABLE OF CONTENTS $0098 ‘Summary of Method. Interferences and Linitations Personnel Qualifications. = Safety Statement... Equipment and Procedures Data Handling uaity Contei. 10 SOP History... 11 References...MLD soP 068 Revision 0.0 August, 20°5 Page 1 of 14 ‘SOP MLD 068 STANDARD OPERATING PROCEDURE FOR THE ANALYSIS OF ANIONS AND CATIONS IN PM) SAMPLES BY 1ON CHROMATOGRAPHY Scope ‘This document descrites the methodology used by Monitoring and Laberatry Division (MLD) Inorganics Laboratory Section (ILS) staff to determine aniors (chlorée, nitrate, and sulfate) and cations (ammonium and potassium) colcted on {quartz microfiber ters exposed to pariculate mattor less than or equal fon imiocometers in aerodynamic diameter (PMc) ‘Summary of Method Method N1LD068 determines anions (chlosée, nitrate, and sulfate) and cations (ammonium and potassium) collected on & x 10 ineh quartz ine fiters exposed to PM, A quarter ofthe filters extracted in deionized water. tered, and stereo ‘overnight na etigarator. The extract fs analyzed by lon chromatography vsing @ {ual channel system with each channel containing the folowing componenis 3 uard column, anal column, sefsegonerating suppressor, eluent gonerator, ‘and a conductvly detector. Peak analysis is determined using Chromeleon Chromatography software, Interferences and Limitations 31 Co-hutioninerforonce can be caused by lone with retention imes tr are similar to and thus overiap those of the fons of interest, or by large amounts ‘of any one anion or cation that interferes wit the peak resolution of an lan ‘with closely matching retention tme. Sample diuton or a decrease 1 ‘eluent concentration can reduce these co-eluton Interterences. 3.2 Inlerferences may be caused by contaminants in the reagent water, reagents, classware, quartz fiber Fiters. and other sample processing ‘apparatus thal could lead to an elevated baseline or detectable concentrations of any of the fons of interest. A reagent water Clank, ‘exraction water blank, anda fiter blank are run with each set of samples to ‘monitor these possible sources of contamination, 33 Losses in retention time and resolution can be signs of column dteroration, Monitoring analyte retention times and column back pressure wil assist InMLD SOP ose Revision 0.0 August 4, 2015 Page 2of 14 18 Ma-em) Procedures iy G va 72 Preparation of Events 7.1.4 Anion and cation eluents are genorated by an eluent gendrator module ard requires no preparation other than keeping the, reservors filed wih nanopure water PProparation of Standards and Controls ‘The standard ané contol stock solitions both contain 1000 jigimL. nitrate, 1000 pgimL sufate, 220 pgm potsestum, 200 pgimL chloride, and 200ugimL ammoniim. Both standara and contol solitons are NIST- traceable In addition 6 each having siferent lot aumbers, All standard and conto solutions are stored in he refrigerator untlraedy for use. Stock solutions are not used past the expiration date listed by tho manufacturer, 7.2.4 Working standards: The stock solution is diuted to give working standards for nitrate and sulfate from 2.0 ygimL. to 60.0 ull, for Chloride and ammonium from 0.4 wpm to 12.0 poll, and for Potassium from 0.44 ugiml to 13.2 ugimL. All tions ere made Using nanopure deiorized water. Store the working standard in polvothylene bots in tho refrigerator. Standards should be labeled withthe date they wore prepared ang the ital ofthe Dreparer. Working standards are usable for upto 30 days before they must be prepsred again from the stock solution,MUD soP 068 Revision 0.0 August, 2015 Page Sof 14 7244 Table 7.2.1.1 shows the concentrations of the woking standards sed forthe callbration curve. Standart 5s also used as the check standard Tobie 7.2.1.1, ‘anaie Sat | Sez | SUS | Sea | Sas) See NOy Sandan zo | 60 | 1s | 20) a0 eo Concentration (yon) ‘SOF Sanda Z| 80 | oe | wo | wo | eae ‘Concentration (um) [or Standard de Concentration (ign) } | WHS Siandad a [Concentration (gmt) we Siandare a CConconiaton (uo) 7.242 Table 72.1.2 shows the volume of stock standard needed to produce the working standards shown in Table 7.2.1.1. Working standards are disted toe volume of 200 mL with the exception of Standard 5 whict is diluted to 500 mL. To prepare each standard, uss the amount of the stock solution indicated in Table 72.1.2 bolow and diute tothe line etched inthe volumetic flask vith nanopure water. Toble 7.2.1.2 Sat [Sw2 [sas [Sis [SWS [sa6 Voume oF oa} 0] 20 | 40-1 200] 120 ‘Stock needed {mt _ 7.2.2 Controls: The controls aro prepared from a secondary soutve stock standard. The contol concentrations are 20.0 gil. for nfrate and73 MLD SOP 068 Revision 0.0 ‘August 4, 2015 Page Gof 14 sult, 4.0 pg/ml for chloride and ammonium, and 4.4 yall for potassium. ‘To prepare use 4.0 mi. ofthe contrl stock solution and lute tothe Ine etched inthe volumetic flask with nanopure water jn. 200 mL volumotc flask. Store the contol in polyethylene ‘ota in te refrigerator. Controls should be labeled wit the date they were prepared and he inais ofthe preparer. Contols are usable for up to 30 days before they must be prepared again from the stock solution, Fillr Extraction 73. 732 733 734 738 Pint out an IC works from LIMS of eames tobe analyzed. ‘Samples should be extracted within 20 business days eer receipt Inthe laboratory 7.3.4.1 Samples not extracted within 20 business days wil be flagged, Create a set of extraction labels withthe barcodes thet correspond to the extraction workist. Include labels fer an exiraction water Dian, a fier Blank, a spike, and duplicstes. 7.3.2.1 Duplicates need to be logged into LINS prior to extraction. The duplicate percentaga must be = 10%, ‘Aff extraction labels to Erlenmeyer asks, Using 2 clean, dry laboratory wipe, thoroughly lean the cuting board blade and scissors. Place clean, cry laboratory wipes ‘around the immaciate cutting area to prevent contamination. Wear loves throughout the entire outing process fo prevent Contamination. Be careful not to touch the sampled portion ofthe fier. Use the cuttng board to cuta 4” x 5 section of each fiter. Remove after from is menila envelope and place it lengthwise on the ‘uting Board, exposad-eide up, with the fectory-otamped number ‘on the right side. Line the lot margin ofthe expoeed area up with the 5" Ine ofthe cuting bosrd and cut the fiter. Rotate the lat half the fiter 80 degrees counter-lockwise, line the left margin of the ‘exposed area up with the 4” line ofthe cuting board and cut the fier. These two cuts will produce a section of iter cantaning one.736 737 738 739 73.41 73.12 73.13 MUD SOP 068 Revision 0.0 August 4, 2018 Pace 7 of 14 {quarter ofthe orignal exposed area. Place the remaining free {quarters of the fiter back into the glassine envelope. Fold the 4” x 5° section in half withthe exposed area facing Inwards. Roll the section of fiter nto roughly eyindcal nape. Using the long-adge scissors, cut the fier into approximately ‘equal sized ploces directly into the appropriate Exienmayer flask. For duplicate samples, use the addtional quarter piece of titer created in stop 7:35. For the fiter blank and spike, there are unexposed fit quarters located inthe extraction lab that aro used as background media. Repeat step 7.9.6 for te fter blank and spke using these unexposed fiter quarters, Verity thatthe Wheaton Unispense is delivering the approrrs ‘amount of water by weighing on an analytical balance. 7.39.1 The acceptable volume ranges 99.5 — 100.5 ml. Dispense 100.0 ml of nanopure water ito each Erienmeyar ask ‘and seal it with a ground glass stopper. For spikes, use the micropipettor to remove 4.0 mL of wate fram the flask and add 1.0 mL ofthe stock standard soliton. 7.3.11.4 The target spike concentrations are as follows: 2.0 gm for chiride and ammonium, 10.0 ygimL. for nitrate land sulfate, and 2.20 ygiml. for potassium, ‘Socure the stonpared Erienmoyer flasks on the shaker tabe and shake them for 60 minutes st low speed (approximataly 12) ‘excursionsiminute) Alter the samples, blanks, ané spike have sheken for 60 minutes, the extraction sokitions ere vacuum fitered. Gioves shoul be \worn throughout the vacuum fitration process In order to prevent contamination. 7.3.18. Thoroughly rinse the magnetifller funnel wh ranepure water. With the vacuum on, ingert the bottom piesa of the ‘magnetic fier funne! into the fiter dome, Then add ther3a4 MUD SOP 068 Revision 0.0 ‘August 4, 2015, Page bof 14 fitration membrane and the top piece ofthe fiter funnel Pour approximately 75- 100 mi of nanopure water into the funnel fo wet and nse the surface of the membrane Ensure tht allrinse water ls removed by breaklng the ‘vacuum and re-spplying it one or more tines 2s ‘necessary. Discard tha rinse water cov the drain 7.3.18.2.Immediataly prot to ftering, transfer the label trom the ‘samples’ Erlonmayer flask directly othe individual ‘sample bottle into vhich the fivate wil be stored. Place the labeled botle underneath th ft funnel 78.183. Swi the contents ofthe flask and then pour the solution Into the fiter funn. Let the vacuum pull the quid through the membrane into the samp botle, 7.3.13.4_ After the liquid has been puted through, disconnect the ‘apparatus cersuly and seal the labeled bot with a ean lc 7.3.435 Discard the used membrane and rinse both parts ofthe fiter funnel thoroughly wth nanopure watorn order to remove any fit residue or partces. 78.136 Ropeat Soctions 7.3.18. through 7.8.18. forthe remaining fates, ‘Alter extraction, fter samples are stored n a refrigerator at 4° ntl analy 7.3.14 Fiter extracts do not have @ holding te, but should be analyzed as soon as possible to aveld cégging the instrumentation. 74 Fiter Anais TAs PPropare an aneiytical run sequence on the Chremeleon software, TAAA The sequence begins with a wator rinse, than the calibration standards inorder of increasing concentration, ‘olowed by a control and a check standard, 7.44.2. Follow these with th list of samples, Including atleast 10% duplicates, at inast 10% replicates ané, aor each18 78 MLD SOP 068 Refision 0.0 August 4, 2015, Page Sof 14 410 analyses, another check standard. An extraction water blank’after blank, and a spice must also be Included and analyzed. ‘The lat analysis ofeach run is another check standard 7.4.2 Transfer approximately 3 mL of working standards, controls, check Standards blanks, spike, and extracted samples to f0nL ‘autosampler vials Place a cap with @ red septa onto each vial and place them into the autosampler tray. Place the autosamper tray Into the autosampler and begin the analyels 7.4.3. After analysis, the samplos are stored in a refrigerator for es long fas the chemist deme necessary, Preventative Maintenance and Repairs 7.5.1 The IC system should be covered by a contract with a certfied vendor that includes preventative maintenance and repairs 7.5.1.4 Preventative maintenance should be performed annually (on the IC system and autosampler. 7.52 Consumables (Le, colurons, suppressors, ale) are replaced as needed, ‘Troubleshooting 7.6.1 Increased noise in the baseline may indicate a problem wit the ‘suppressor, 7.6.2. Decreasing peak retonton times may indicate deterioration ofthe colurmns, 1.83 An increase n system pressure may indicate a blockage inthe system, 7.64 The analyst may call the technical essstance line ofthe contracted vendor for more complex problems that may aleeMLD SOP 06a Rovision 0.0 August 4, 2015, Page 10 of 14 Data Handling 8.1 Data handling for thie method assumes a famiiay withthe operation of both Chromeleon lon Chromatography software and the Laboratory Information Management System (LIMS). 82 Extraction datos are transfered into LIMS using the Instrument Design Module IDM) LimsLik, 8.3 Analytes are identfied and quantited by the Chromeleon lon Chromatography software, 8.4 After each analysis run, tepots are printed from Chrorteleon which include ‘summary, calbration curves fo each analyte, and a chromatogrem for ‘9ach sample analyzed. This reportis reviewed by the analyst an a copy is archived for three years 8.5 After samples are analyzed and the deta has been reviewed by he analyst, {an excel fie containing the data results is created from Chromeleon. Any samples thal should not be report ta LIMS are removed from this fle betore.a csv flo's created. ‘The .osv lo Is transfrred Into LIMS using IDM LimsLink 8.6 When samplas havo boon transferred tho analyst generates a summary fopor from LIM which Is reviewed, inialed and dated by the analyst ‘This surtmary report is archived with the comtesponding copor fom Chromelon, 8.7 paper copy ofthe raw datas stored inthe laboratory. An electronic copy of the raw data ls stored on the Instumént controler. 8.8 Data Is compiled into monthly reports which ar reviewed at multiple levels in accordance ‘wih elena stated inthe NLB Qualty Conte! Manual Quality Control 9.1 Each year, the Limit of Detection (LOD) for the mathod must be verified. ‘The LOD is detined as the minmum concentration of@ substance that can bbe measured and reported with 29% confidence that the analyte Concontratlon is greater than zero and statistically different from a blank ‘The caleulated limit of detection forthe method is determined from analysis cof sample in a given matrix (including the sampling media) containing the ‘nave of intrest seven tes according to 40 CFR, Appendbc B, as fellows: LOD = Tynes 68)92 93 94 95 MLD SOP 062 Revision 0.0 August 4, 2015, Page 11 of 14 ‘where (ed) I the standard deviation and is caloulated forthe seve rephcates. Tis the Students T-value atthe 69% confidence level fora Particular numberof replicates. The standard numberof replicates used ‘or this methed is 7, which equates to a Tvalue of 3.143, ‘The Limit of Quantitation (LOA) isthe minimum concentration or amount of| ‘an analyte that amethod can measure with a degree of precision. The LOQ is based on the calculated LOD and the chemists experience of the ‘method and insttument anc takes into account vataton of istrument performance over ime. An annual check of he LOD vervies that he LOO Fomaine acceptable, ‘The vetiied LOD = 3.143 x standard devietion and the LO@= 10 x standard deviation. The verifed LOD and LOG values are roundes off to the nearest hundred (0.01) ugimL. ‘The concentration ofthe analytes of inorestin each ofthe 7 samples used for tve annual LOD verification must be no greator than five times the Vale ofthe LOQ.Thernew verified LOD must also be lees than the Loa, 9.1.4. Ifthe LOQis lower than the lowest standard used for the calbration,& reporting limit (RL) wil be applied equal tothe value ofthe lowest standarc, Data wil rot be reported below this it. All standards, benks, spikes, replicates, cupfcates, and samples are analyzed using the same analyleal method In order forthe calbration curve to be acceptable, the correlation coefficient must be greater than or equal 00.980, If the correlation coefficients less than 0.980, the standards are re-analyzed. ‘A contol is analyzed efter the calibration is complete, The allowable GC critera are 8% forthe waxing its end 10% for conta iis fom the target value I the control value fs out ofthe acceptable limits, the instrument is ‘evaluated for problems and a contol reanalyzed suecassully before ‘samples are analyzed, Ifthe contro value limits nees to be adjusted, the changes should be documented and approved by the Laboratory Supervisor. ‘The check stenderd is analyzed before any samples, again after each group of ten analyses, and finaly t the end of the analy's. The ‘coeptable limits forthe check standards + 20% of the expected value96 or 98 29 MLD SOP o¢a Revision 0.0 ‘August 4, 2015, Pace 12 of 14 Ifthe check standard Is not within acceptable fits, the inirument Is ‘valatod for problome and a control sample is reanalyzod euscosstlly before samples are analyzed. Extraction water blanks and fiter blanks are analyzed with each sat of ‘extracted fils. Blank lvels are monitored to aseure that contamination {tom reagonts or fom sampling processing techniques are no affecting ‘sample results 8.6.1 Ifthe blank result is greater than the LOQ or reporting Kit, the blank shouldbe reanalyzed to very the high value, Once verted, the folowing corrective action crtora apply 8.6.1.4 If tho sample resuits are at least ton times higher than the blank result, no acon is taken. 9.6.1.2. Ifthe sample resuts are oss than ten times higher than the blank result, the analysis result should be invalidated for those samplos associatod with the blank. Spikes ae run to measure the accuracy ofthe entire process. Spikes are Prepared from unexposed fits and extraction water with #.0 mL of Standard stock solution added. A spike is extracted and analyzed with ‘each sample sot. The spike recover ints are + 20% of the expected value, 8.7.1 Ifthe spike value is outside of the recovery limits, the spike should be reanalyzed to verify the value. Once verified the samples associated withthe spike should be invalidated for he analyte) that were ouside ofthe acceptable range. Duplicates are made from two separate quarters of the PMAO ftor and aro run ata equency of atleast 10%. The relave porcent difference (RPD) is Cealculated viten both of the cupicate samples are above the RL or LOQ, lehichever Ie greeter. The RPD between cupleates ehould be lase than 20%. Duplicate samples are used to assess variance ofthe total method inekding sampling and analysis. 9.8.1 Since duplicate results are impacted by the sampling process, there fr9 no corrective actions for duplicate results that exceed the percent diference crteia. However, the site opetator should be holiied of duplicates that exceed the teria, Replcates aro an addtional analysis of the same sample extract and are run ata frequency of atleast 10%. The sample extract used for replicateMLD SOP 088 Revision 0.0 August 4, 2015 Page 13 of 14 ‘analyses must be chosen at random. The RPO between replcates is Calealated when both ofthe replicate samples concentvation values are above the RL or LOQ, whichever is greater. The RPD shoud be lass than 10% for samples whose concontration is mace than twenty tmes ebove fhe RL or LOG, whichever is greater, and ess than 25% for samples whose ‘concentrations tess than twonty times the RL or LOG, whicheveris ‘greater. Replicate analyses results are Used fo evaluate anelyteal Precision. 9.8.1 Ifthe replicate results do not meet spect QC criteria, the ‘sompies in the associated batch should be reanalyzed, or ‘invalidated for the analytes that are out of range if reanalysis not possible. 10 SOP History 104 ‘This method combines MLD 007, MLD 028, and the extraction procedure from MLD 016,MLD SOP 068 Revision 0.9 ‘August 4, 2015, Page 14 of 14 11 References 1 Method MLD007 Standard Operating Procedure forthe Determination of Sulfate, Nirete, and Chioide Using ion Chromatography, Norther, Laboratory ranch, Monitoring and Laborstory Branch, Revision 41 Method MLD023 Standard Operating procedure for the Daterminaiion of ‘Ammonium Using lon Chromatograpty, Northom Laboretary Branch, Monitoring and Laboratory Divsion, Revision 1.0. Laboratory Quality Control Manual, Norther Laboratory Branch, Nonitoring and Laboratory Division, Revision 3.0. ‘Chemical Hygiene Plan for 13” & T Facility, Monitoring and Laboratory Division, July 2006. Laboratory Information Management System Standard Operating Procedure, Northem Laboratory Branch, Monitoring and Laborstory Division, 2014 ICS-3000 fon Chromatography System Operators Manual, Revision 4.0, sianuary 2008 Method MLOO16 Standard Operating Procedure forthe Mass Analysis and ‘Subsequent Extraction of SSi-Sampled PMs from Exposed Quartz, Microfoer Fiters, Revision 6.0, January 2002,