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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

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SLIDE 1

Low Level Low Level Low Level Low Level Detection of Detection of Detection of Detection of A i A i Ammonia Ammonia

Ne w Me thod Validate d F

  • llowing E

PA Guidanc e AT P Case #: N08 0004 AT 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

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SLIDE 2

A i ??? A i ??? Ammonia??? Ammonia???

Ionize d Un ionize d Ionize d Un-ionize d

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SLIDE 3

Ammonia Detection Ammonia Detection

2 NH3 H2SO4 (NH4)2SO4 Green Lavender

Titration

NH3 + H2O NH4

+ + OH
  • pH

Inside ISE

Reaction Inside the Ion Selective Electrode (ISE)

OH N OH O

  • NH3 + ClO
  • Colorless

Blue Color 1

+ 2

N O N O Blue Color 2

Berthelots (Phenate) Reaction Berthelots (Phenate) Reaction

2 K2(HgI4) + 2 NH3 NH2Hg2I3 + 4KI + NH4I Colorless Orange Brown

Nesslers Reaction

Inside Membrane NH3 + Caustic NH4

+ (Conductance)

Boric Acid

Reaction for Membrane Extraction/Conductance

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SLIDE 4

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

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SLIDE 5

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 d d P ti f D t i ti f P i i

  • Sta nda rd Pra c tic e s fo r De te rmina tio n o f Pre c isio n

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

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SLIDE 6
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SLIDE 7

60

4 Inch Membrane MDL

40 50 PPB 20 30 Ammonia 10

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SLIDE 8

12

10 Inch Membrane MDL

8 10 6 Ammonia PPB 2 4 6 9 10 Total Laboratories MDL Total Laboratories ML Reporting ML

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SLIDE 9

105.00%

4 inch LFB Average % Recovery

100.00% 95.00% 90 00% 90.00% 85.00% 80.00% 1 2 3 4 5 6 7 8 9 Total Laboratories

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SLIDE 10

98.00%

10 Inch LFB Average % Recovery

97.50% 96.50% 97.00% 95.50% 96.00% 95.00% 94.00% 94.50% 93.50% 6 9 10 Total Laboratories

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SLIDE 11

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

POT W

POT W P i Cl ifi E ffl t

  • POT

W Primar y Clarifie r E fflue nt:

  • 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

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 .

  • 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.

  • 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 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.

  • 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.
  • Cate gor

ic al Industr ial E fflue nt 40 CF R 442 Comme r c ial T r uc k Wash:

  • Cate gor

ic al Industr ial E fflue nt, 40 CF R 442 Comme r c ial T r 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.
  • 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.
  • 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

K je lda hl me tho d.

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SLIDE 12

LFM/LFMD Recoveries 4 Inch Membrane

130% 135% 140% 110% 115% 120% 125% 95% 100% 105% 110% LFM LFMD 80% 85% 90%

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SLIDE 13

4 Inch Membrane

30.00% 35.00%

4 Inch Membrane LFM/LFMD RPD

20.00% 25.00% 30.00% 10.00% 15.00% 0.00% 5.00%

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SLIDE 14

110%

LFM/LFMD Recoveries 10 Inch Membrane

105% 95% 100% LFM LFMD 85% 90% FM 80% POTW Receiving Watershed Metal Finisher Effluent POTW Eff‐Non Dis. Average

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SLIDE 15

20.00%

10 Inch Membrane LFM/LFMD RPD

15.00% 10.00% 5.00% 0.00% POTW Receiving Watershed Metal Finisher Effluent POTW Eff‐Non Dis. Average

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SLIDE 16

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

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SLIDE 17

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

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SLIDE 18

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);
  • (2) Me tho d De te c tio n L

imit (MDL );

  • (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;

  • (4) L

a b o ra to ry fo rtifie d b la nk (L F B), a lso re fe rre d to a s a spike d b la nk, o r ( ) y ( ), p , 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

(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 ) ( 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

(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);
  • (9) Co rre c tive a c tio n (ro o t c a use a na lyse s);
  • (10) QC a c c e pta nc e c rite ria ;
  • (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
  • (12) Spe c ify a minimum fre q ue nc y fo r c o nduc ting the se QC c he c ks.
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SLIDE 19

Initial Demonstration of Initial Demonstration of C bilit C bilit Capability Capability

  • 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.

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SLIDE 20

Continuing Calibration Continuing Calibration V ifi ti V ifi ti Verification Verification

  • 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 i l l t d d l t d f t is c a lc ula te d a nd e va lua te d fo r a c c e pta nc e .

  • 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 th d d h ll t d 90% 110 % me tho d a nd sha ll no t e xc e e 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 t l i t b f d ti 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.

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SLIDE 21

L b t R t Bl k L b t R t Bl k Laboratory Reagent Blank Laboratory Reagent Blank

  • 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 l b t h t d sa mple b a tc h re pe a te d.

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SLIDE 22

Laboratory Fortified Laboratory Fortified Bl k Bl k Blank Blank

  • L

a b o ra to ry F

  • rtifie d Bla nk: A L

F B with a c o nc e ntra tio n o f a mmo nia b e twe e n 10% a nd 50% o f the dyna mic ra ng e is a na lyze d a t le a st o nc e pe r b a tc h. T he L F B 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 : L

F B pe rc e nt re c o ve 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 87%-104 %.

  • Co rre c tive Ac tio n: I

f the L F B 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 ti t k ll fi di d d d th l 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.

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SLIDE 23

y Sample Matrix Spikes Sample Matrix Spikes (LFM LFM/LFMD LFMD) (LFM LFM/LFMD LFMD)

  • L

a b o ra to ry F

  • rtifie d Sa mple Ma trix Spike s (L

F M/ L F MD): A duplic a te se t o f a mmo nia o r K je lda hl sa mple s a re spike d with a kno wn a mo unt o f a mmo nia with a c o nc e ntra tio n tha t is b e twe e n 10% a nd 50% o f the dyna mic ra ng e

  • Ac c e pta nc e Crite ria : T

he L F M/ L F MD pe rc e nt re c o ve 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 84%-115 %. T he re la tive pe rc e nt diffe re nc e (RPD) h ll t d 20% (RPD) sha ll no t e xc e e d 20%.

  • Co rre c tive Ac tio n: I

f the L F M a nd L F MD pe rc e nt re c o ve ry o r the RPD fa ll o utside o f the se limits, the b a tc h i j d d t b t f t l A t l i 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.

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SLIDE 24

Ongoing Demonstration Ongoing Demonstration f C bilit ( f C bilit (ODC ODC)

  • f Capability (
  • f Capability (ODC

ODC)

  • Ong o ing De mo nstra tio n o f Ca pa b ility (ODC): A L

F B with a c o nc e ntra tio n o f a mmo nia b e twe e n 10% a nd 50% o f the dyna mic ra ng e is a na lyze d a t le a st o nc e pe r b a tc h. T he L F B pe rc e nt re c o ve ry will b e c ha rte d b y c o ntro l c ha rts a nd b l t d f t b e e va lua te d fo r a c c e pta nc e .

  • Ac c e pta nc e Crite ria : L

F B pe rc e nt re c o ve ry must sta y within the c o ntro l limits c a lc ula te d fo r the c o ntro l c ha ts.

  • Co rre c tive Ac tio n: I

f the L F B pe rc e nt re c o ve ry fa lls

  • utside o f the se c o ntro l limits, the b a tc h is judg e d to b e
  • ut o f c o ntro l. A ro o t c a use a na lysis must b e pe rfo rme d,

ti ti t k ll fi di d d d th 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.

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SLIDE 25

Sample Analysis Sample Analysis Sequence Sequence

  • Sa mple Ana lysis Se q ue nc e : T

ypic a l sa mple a na lysis se q ue nc e

  • I

nstrume nt Sta rt Up

  • Ca lib ra tio n ze ro
  • Ca lib ra tio n sta nda rds, 1-5
  • L

RB

  • L

F B

  • Sa mple use d fo r L

F M/ L F MD

  • L

F M

  • L

F MD

  • Sa mple s (F

irst ha lf o f b a tc h)

  • CCV
  • Sa mple s (Se c o nd ha lf o f b a tc h)

p ( )

  • Re pe a t CCV (Optio na l)
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SLIDE 26

I iti l C lib ti I iti l C lib ti Initial Calibration: Initial Calibration:

  • I

nitia l Ca lib ra tio n:

  • I

nitia l c a lib ra tio n is pe rfo rme d a t the b e g inning o f e a c h b a tc h.

  • Ca lib ra te instrume nt with c a lib ra tio n ze ro a nd five c a lib ra tio n

t d d f i sta nda rds o f a mmo nia .

  • Apply line a r o r po lyno mia l c urve -fitting sta tistic s, a s

a ppro pria te , to a na lyze the c o nc e ntra tio n–instrume nt re spo nse re la tio nship re spo nse re la tio nship.

  • Ac c e pta nc e Crite ria : T

he line a r o r no nline a r c o rre la tio n c o e ffic ie nt fo r sta nda rd c o nc e ntra tio n-to -instrume nt re spo nse sha ll b e g re a te r tha n o r e q ua l to 0.995.

  • Co rre c tive Ac tio n: I

f the c o rre la tio n c o e ffic ie nt fa lls

  • utside o f the limit, the initia l c a lib ra tio n is judg e d to b e
  • 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 c o rre c tive a c tio n ta ke n, a ll finding s re c o rde d a nd the initia l c a lib ra tio n re pe a te d.

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SLIDE 27

Standard Standard B k B k C l l ti l l ti Back Back Calculation alculation

  • Ba c k c a lc ula te the sta nda rd c o nc e ntra tio n o f e a c h

c a lib ra tio n po int using the c a lib ra tio n e q ua tio n de te rmine d b y the c urve fitting sta tistic s.

  • Ac c e pta nc e Crite ria : T

he b a c k-c a lc ula te d a nd true c o nc e ntra tio ns sho uld a g re e within ± 10% a nd c a nno t e xc e e d ± 15%.

  • Co rre c tive Ac tio n: I

f the sta nda rd b a c k c a lc ula tio ns fa ll o utside o f the limits, the initia l c a lib ra tio n 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 fi di d d d th i iti l lib ti finding s re c o rde d a nd the initia l c a lib ra tio n re pe a te d.

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SLIDE 28

Continuing Calibration Continuing Calibration V ifi ti V ifi ti Verification Verification:

  • Co ntinuing Ca lib ra tio n Ve rific a tio n:
  • A CCV is a na lyze d a t the midpo int o f the b a tc h sa mple

se t. T he CCV is pre pa re d fro m a diffe re nt so urc e (c he mic a l lo t) tha n tha t use d fo r the c a lib ra tio n sta nda rds.

  • 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 %.

  • Co rre c tive Ac tio n: I

f the CCV re c o ve ry fa lls o utside

  • 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 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.

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SLIDE 29

Ongoing Demonstration Ongoing Demonstration f C bilit f C bilit

  • Ong o ing De mo nstra tio n o f Ca pa b ility Ana lyst
  • f Capability
  • f Capability

Pro fic ie nc y: A L F B is a na lyze d using the sa me instrume nta l c o nditio ns a nd pro c e dure s use d to a na lyze sa mple s a t le a st o nc e pe r b a tc h. T he L F B pe rc e nt ill b h t d b t l h t d b re c o ve ry will b e c ha rte d b y c o ntro l c ha rts a nd b e e va lua te d fo r a c c e pta nc e .

  • Ac c e pta nc e Crite ria : L

F B pe rc e nt re c o ve ry must t ithi th t l li it l l t d f th sta y within the c o ntro l limits c a lc ula te d fo r the c o ntro l c ha ts.

  • Co rre c tive Ac tio n: I

f the L F B pe rc e nt re c o ve ry fa lls t id f th t l li it th b t h i j d d t

  • utside o f the se c o ntro l 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 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 re c o rde d a nd the sa mple b a tc h re pe a te d .

slide-30
SLIDE 30

Corrective Action Corrective Action (R t C A l i R t C A l i ) (Root Cause Analysis Root Cause Analysis)

  • Co rre c tive Ac tio n (Ro o t Ca use Ana lysis): T

he la b o ra to ry a na lyst(s) a nd la b o ra to ry ma na g e me nt will pe rfo rm a ro o t c a use a na lysis fo r a ny QC la b o ra to ry ma na g e me nt will pe rfo rm a ro o t c a use a na lysis fo r a ny QC fa ilure s. T he a na lysis will ha ve a t a minimum the fo llo wing a re a s de sc rib e d in de ta il:

  • I

de ntify the pro b le m: I de ntify the QC fa ilure . I nc lude instrume nt, re a g e nt, sa mpling , pe rso nne l a nd a ny o the r pro b le ms. I ti t t id tif th t D t i h h b l

  • I

nve stig a te to ide ntify the ro o t c a use : De te rmine ho w e a c h pro b le m ide ntifie d inte ra c te d with e a c h o the r to c re a te the QC pro b le m.

  • Co me up with the so lutio n: De ve lo p a n e nc o mpa ssing so lutio n to

a ddre ss a ll pro b le ms tha t c re a te d the QC fa ilure .

  • I

mple me nt the so lutio n: De ve lo p a n imple me nta tio n pla n tha t I mple me nt the so lutio n: De ve lo p a n imple me nta tio n pla n tha t inc lude s a ll c o mpo ne nts o f the de ve lo pe d so lutio n a nd ha ve la b o ra to ry ma na g e me nt imple me nt it.

  • Do c ume nt the so lutio n: Do c ume nt a ll c o rre c tive a c tio n ste ps ta ke n

unde r la b o ra to ry ma na g e me nt imple me nta tio n o f the c o rre c tive a c tio n a c tio n.

  • Co mmunic a te the so lutio n: De ve lo p tra ining a nd ma na g e me nt

pro g ra ms to c o mmunic a te a nd e va lua te a ll pe rso nne l inc lude d in the c o rre c tive a c tio n so lutio n.

  • E

va lua te the e ffe c tive ne ss o f the so lutio n: Do c ume nt QC re sults in tre nd c ha rts a nd la b o ra to ry sta ff pe rfo rma nc e to va lida te c o rre c tive a c tio n so lutio n.

slide-31
SLIDE 31

I C l i I C l i In Conclusion In Conclusion

  • We binar

:

  • We binar

:

  • De te r

mination of Inor ganic Ammonia by Continuous F low Gas Diffusion and Conduc tivity Ce ll Analysis, We dne sday, August 24, 2011, 2:00 PM - 3:00 PM E DT

  • Ple a se c o nta c t Sa ra Bury a t awtimbe r

@t-line .c om

fo r furthe r info rma tio n o n the we b ina r.

  • Re g iste r a t:
  • Re g iste r a t:

https:/ / www3.g o to me e ting .c o m/ re g iste r/ 662000630

slide-32
SLIDE 32

Q i ??? Q i ??? Questions ??? Questions ???