Low Level Low Level Low Level Low Level Detection of Detection of - PowerPoint PPT Presentation

Low Level Low Level Low Level Low Level Detection of Detection of Detection of Detection of Ammonia Ammonia A A i i Ne w Me thod Validate d F ollowing E PA Guidanc e AT AT P Case #: N08 0004 P Case #: N08-0004 E dwa rd F Aske w PhD Aske w Sc ie ntific Co nsulting Aske w Sc ie ntific Co nsulting

A A Ammonia??? Ammonia??? i ??? i ??? Ionize d Ionize d Un ionize d Un-ionize d

Ammonia Detection Ammonia Detection H 2 SO 4 2 NH 3 (NH 4 ) 2 SO 4 Lavender Green Titration Inside ISE + + OH - NH 3 + H 2 O NH 4 pH Reaction Inside the Ion Selective Electrode (ISE) OH - O OH N N - NH 3 + ClO N + 2 O O Colorless Blue Color 1 Blue Color 2 Berthelots (Phenate) Reaction Berthelots (Phenate) Reaction NH 2 Hg 2 I 3 + 4KI + NH 4 I 2 K 2 (HgI 4 ) + 2 NH 3 Orange Brown Colorless Nesslers Reaction Inside Membrane + (Conductance) NH 3 + Caustic NH 4 Boric Acid Reaction for Membrane Extraction/Conductance

Timberline TL series Timberline TL series Timberline TL series Timberline TL series

New Method Validation References New Method Validation References • Pro to c o l fo r E PA Appro va l o f Ne w Me tho ds fo r pp Org a nic a nd I no rg a nic Ana lyte s in Wa ste wa te r a nd Drinking Wa te r, Ma rc h 1999, E PA 821-B-98-003 • St Sta nda rd Pra c tic e s fo r De te rmina tio n o f Pre c isio n d d P ti f D t i ti f P i i a nd Bia s o f Applic a b le T e st Me tho ds o f Co mmitte e D19 o n Wa te r, AST M D2777-06 • Sta nda rd me tho ds fo r the E xa mina tio n o f Wa te r a nd Wa ste wa te r, Pa rts 1000 a nd 4000, Online

4 Inch Membrane MDL 60 50 40 PPB Ammonia 30 20 10 0

10 Inch Membrane MDL 12 10 8 Ammonia PPB 6 4 2 0 6 9 10 Total Laboratories MDL Total Laboratories ML Reporting ML

4 inch LFB Average % Recovery 105.00% 100.00% 95.00% 90 00% 90.00% 85.00% 80.00% 1 2 3 4 5 6 7 8 9 Total Laboratories

10 Inch LFB Average % Recovery 98.00% 97.50% 97.00% 96.50% 96.00% 95.50% 95.00% 94.50% 94.00% 93.50% 6 9 10 Total Laboratories

Matrixes Matrixes • Raw POT W Influe nt: Ra w do me stic a nd industria l wa ste wa te r tha t is re c e ive d a t the he a dwo rks o f a o POT W • POT POT W P i W Primar y Clarifie r E Cl ifi E ffl fflue nt: t Wa ste wa te r tha t is disc ha rg e d fro m the prima ry c la rifie r a t the POT W. Co nta ins o disso lve d a nd suspe nde d so lids. • POT W Re tur n Waste Ac tivate d Sludge Ce ntr ifugation L iquor : Hig h stre ng th a mmo nia wa ste wa te r fro m the POT W a c tiva te d sludg e c e ntrifug e . o • F inal POT W E fflue nt, Non Disinfe c te d: F ina l e fflue nt fro m the POT W tha t ha s no t b e e n disinfe c te d. o • F inal POT W E fflue nt, De c hlor inate d: F ina l e fflue nt fro m the POT W tha t ha s b e e n disinfe c te d with c hlo rine a nd o de c hlo rina te d with a sulfur b a se d c o mpo und. p • POT W Re c e iving Wate r she d: Surfa c e wa te r tha t re c e ive s the POT W fina l de c hlo rina te d e fflue nt. o • Cate gor ic al Industr ial E fflue nt, 40 CF R 433 Me tal F inishe r : Ra w industria l wa ste wa te r disc ha rg e to a po int in the c o lle c tio n syste m. o • • Cate gor Cate gor ic al Industr ic al Industr ial E ial E fflue nt 40 CF fflue nt, 40 CF R 442 Comme r R 442 Comme r c ial T c ial T r r uc k Wash: uc k Wash: Ra w industria l wa ste wa te r disc ha rg e to a po int in the c o lle c tio n syste m. o • Cate gor ic al Industr ial E fflue nt, 40 CF R 430 Pulp and Pape r Mill: Wa ste wa te r fro m a pa pe r pulp mill tre a tme nt pro c e ss. o • Signific ant Industr ial E fflue nt Kje ldahl Dige stant: Wa ste wa te r la g o o n (liq uid ma nure ) tha t ha s b e e n dig e ste d b y a n a ppro ve d o K je lda hl me tho d.

LFM/LFMD Recoveries 4 Inch Membrane 140% 135% 130% 125% 120% 115% 110% 110% 105% 100% LFM LFMD 95% 90% 85% 80%

4 Inch Membrane 4 Inch Membrane LFM/LFMD RPD 35.00% 30.00% 30.00% 25.00% 20.00% 15.00% 10.00% 5.00% 0.00%

LFM/LFMD Recoveries 10 Inch Membrane 110% 105% 100% 95% LFM LFMD FM 90% 85% 80% POTW Receiving Watershed Metal Finisher Effluent POTW Eff ‐ Non Dis. Average

10 Inch Membrane LFM/LFMD RPD 20.00% 15.00% 10.00% 5.00% 0.00% POTW Receiving Watershed Metal Finisher Effluent POTW Eff ‐ Non Dis. Average

Summary Single Operator Standard Deviation and %RSD – 4 Inch Membrane Youden Pair Youden Pair Youden 1 Youden 1 Youden 2 Youden 2 Youden 3 Youden 3 Single Operator So (Standard Deviation) 0.24 0.0049 0.049336281 Single Analyst %RSD 4.08% 0.22% 1.63%

Summary Single Operator Standard Deviation and %RSD – 10 Inch Membrane Youden Pair Youden Pair Youden Pair 1 Youden Pair 1 Single Operator So (Standard Deviation) 0.07 Single Analyst %RSD 0.06%

New Method Improvements New Method Improvements New Method Improvements New Method Improvements • 40 CF R Pa rt 136.7 (1) De mo nstra tio n o f Ca pa b ility (DOC); o (2) Me tho d De te c tio n L imit (MDL ); o (3) L a b o ra to ry re a g e nt b la nk (L RB), a lso re fe rre d to a s me tho d b la nk; o (4) L ( ) a b o ra to ry fo rtifie d b la nk (L y ( F B), a lso re fe rre d to a s a spike d b la nk, o r ), p , o la b o ra to ry c o ntro l sa mple (L CS); (5) Ma trix spike , ma trix spike duplic a te , o r la b o ra to ry fo rtifie d b la nk duplic a te o (L F BD) fo r suspe c te d diffic ult ma tric e s; (6) I ( ) nte rna l sta nda rds, surro g a te sta nda rds (fo r o rg a nic a na lysis) o r tra c e rs (fo r , g ( g y ) ( o ra dio c he mistry); (7) Ca lib ra tio n (initia l a nd c o ntinuing ), initia l a nd c o ntinuing pe rfo rma nc e o (I CP) so lutio n a lso re fe rre d to a s initia l c a lib ra tio n ve rific a tio n (I CV) a nd c o ntinuing c a lib ra tio n ve rific a tio n (CCV); (8) Co ntro l c ha rts (o r o the r tre nd a na lyse s o f q ua lity c o ntro l re sults); o (9) Co rre c tive a c tio n (ro o t c a use a na lyse s); o (10) QC a c c e pta nc e c rite ria ; o (11) De finitio ns o f a b a tc h (pre pa ra tio n a nd a na lytic a l); a nd (11) De finitio ns o f a b a tc h (pre pa ra tio n a nd a na lytic a l); a nd o o (12) Spe c ify a minimum fre q ue nc y fo r c o nduc ting the se QC c he c ks. o

Initial Demonstration of Initial Demonstration of C C Capability Capability bilit bilit o I nitia l De mo nstra tio n o f Ca pa b ility: A la b o ra to ry fo rtifie d b la nk who se c o nc e ntra tio n is b e twe e n the 10% a nd 50% o f the dyna mic ra ng e is a na lyze d fo ur time s. T he me a n re c o ve ry a nd sta nda rd de via tio n a re c a lc ula te d a nd e va lua te d fo r a c c e pta nc e . a c c e pta nc e • Ac c e pta nc e Crite ria : I DC c o ntro l limit fo r the la b o ra to ry is b a se d o n the limits de te rmine d in this me tho d a nd sha ll no t e xc e e d 82%-110 % with a pe rc e nt Re la tive Sta nda rd De via tio n le ss tha n 8%. • Co rre c tive Ac tio n: I f the I DC re c o ve ry fa lls o utside o f the se limits, the a na lyst o r instrume nt is judg e d to b e o ut o f c o ntro l. A ro o t c a use a na lysis must b e pe rfo rme d c o rre c tive a c tio n A ro o t c a use a na lysis must b e pe rfo rme d, c o rre c tive a c tio n ta ke n, a ll finding s re c o rde d a nd the I DC re pe a te d until pa sse d.

Continuing Calibration Continuing Calibration V V Verification Verification ifi ifi ti ti o Co ntinuing Ca lib ra tio n Ve rific a tio n: At le a st o ne CCV sta nda rd will b e pre pa re d so a s to ha ve a c o nc e ntra tio n in the dyna mic ra ng e o f the instrume nt. T he CCV will b e run a t le a st o nc e pe r e a c h b a tc h. T he CCV pe rc e nt re c o ve ry is c a lc ula te d a nd e va lua te d fo r a c c e pta nc e . i l l t d d l t d f t • Ac c e pta nc e Crite ria : CCV c o ntro l limit fo r the la b o ra to ry is b a se d o n the limits de te rmine d in this me tho d a nd sha ll no t e xc e e d 90%-110 %. th d d h ll t d 90% 110 % • Co rre c tive Ac tio n: I f the CCV re c o ve ry fa lls o utside o f the se limits, the b a tc h is judg e d to b e o ut o f c o ntro l. A ro o t c a use a na lysis must b e pe rfo rme d, c o rre c tive t l i t b f d ti a c tio n ta ke n, a ll finding s re c o rde d a nd the sa mple b a tc h re pe a te d.

L b Laboratory Reagent Blank Laboratory Reagent Blank L b t t R R t Bl t Bl k k o L a b o ra to ry Re a g e nt Bla nk: A L RB is a na lyze d a s a sa mple a t le a st o nc e pe r b a tc h. T he L RB c o nc e ntra tio n re sult will b e e va lua te fo r a c c e pta nc e . • Ac c e pta nc e Crite ria : T he L RB c o nc e ntra tio n re sult will b e b e lo w the lo we st c a lib ra tio n sta nda rd in the dyna mic ra ng e . • Co rre c tive Ac tio n: I f the L RB fa lls o utside o f the a c c e pta nc e limit, the b a tc h is judg e d to b e o ut o f c o ntro l. A ro o t c a use a na lysis must b e pe rfo rme d, c o rre c tive a c tio n ta ke n, a ll finding s re c o rde d a nd the sa mple b a tc h re pe a te d. l b t h t d