Improved AntimonyRecoveries in Soil Matrices

by 3050B/6010B

DataChem Laboratories, Inc.Robert P. Di Rienzo

Jeffery S. WardJohn T. Kershisnik

Agenda� Past Method Performance for Antimony

� Current Method Performance for Antimony

� Method 3050B and procedure change

� Method 3050B effect on other elements

� Conclusions

Past LCS PerformanceAntimony Soil LCS Recovery

3050 Before May 4, 2004

60

80

100

120

140

1/28/2

0023/2

8/2002

5/28/2

0027/2

8/2002

9/28/2

00211

/28/200

21/2

8/2003

3/28/2

0035/2

8/2003

7/28/2

0039/2

8/2003

11/28

/2003

1/28/2

0043/2

8/2004

Date Analyzed

Perc

ent R

ecov

ery Recovery

MeanLCLUCL

Past MS/MSD PerformanceAntimony Soil Matrix Spike Recovery

3050 Before May 4, 2004

020406080

100120140

1/28/2

002

3/28/2

002

5/28/2

002

7/28/2

002

9/28/2

002

11/28

/2002

1/28/2

003

3/28/2

003

5/28/2

003

7/28/2

003

9/28/2

003

11/28

/2003

1/28/2

004

3/28/2

004

Date Analyzed

Perc

ent R

ecov

ery

RecoveryMeanLCLUCL

Soil LCSLCS Soil

Current LCS PerformanceAntimony Soil LCS Recovery

3050 After May 4, 2004

80

100

120

140

160

5/4/2004

5/9/2004

5/14/2004

5/19/2004

5/24/2004

5/29/2004

6/3/2004

6/8/2004

6/13/2004

6/18/2004

6/23/2004

6/28/2004

7/3/2004

7/8/2004

7/13/2004

7/18/2004

Date Analyzed

Perc

ent R

ecov

ery

RecoveryMeanLCLUCL

Current MS/MSD PerformanceAntimony Soil Matrix Spike Recovery

3050 After May 4, 2004

406080

100120

5/4/200

45/9

/2004

5/14/2

004

5/19/2

004

5/24/2

004

5/29/2

004

6/3/200

46/8

/2004

6/13/2

004

6/18/2

004

6/23/2

004

6/28/2

004

7/3/200

47/8

/2004

7/13/2

004

7/18/2

004

Date Analyzed

Perc

ent R

ecov

ery

RecoveryMeanLCLUCL

Overall LCS PerformanceAntimony Soil LCS Recovery

6080

100

120140160

1/28/2002

3/28/2002

5/28/2002

7/28/2002

9/28/2002

11/28/2002

1/28/2003

3/28/2003

5/28/2003

7/28/2003

9/28/2003

11/28/2003

1/28/2004

3/28/2004

5/28/2004

Date Analyzed

Perc

ent R

ecov

ery

RecoveryMeanLCLUCL

Overall MS/MSD PerformanceAntimony Soil Matrix Spike Recovery

020406080

100120140

1/28/2

002

3/28/20

025/28

/2002

7/28/20

029/2

8/200

211

/28/200

21/2

8/200

33/2

8/2003

5/28/200

37/2

8/200

39/2

8/200

311

/28/20

031/28

/2004

3/28/2

004

5/28/2

004

Date Analyzed

Perc

ent R

ecov

ery

RecoveryMeanLCLUCL

Method 3050BProcedure

7.1

7.2

7.2

7.3

7.4

Start Mix sample, weigh a 1-gportion of each sample

for preparation.

Add HNO3 and reflux;repeat.

Evaporate solution to~5 mL

Add ASTM Type II water andH2O2; warm for peroxide react.

Add H2O2 and warm untileffervescence is minimal

A

A

Type Analysis

7.5

ICP analysis of As and Se,flame AA or ICP analysis of Ag, A1,Ba, Be, Ca, Cd, Cr, Co, Cr, Cu,Fe, Pb, Mg, Mn, Mo, Ni, K, Na, SbT1, V, and Zn

Furnace analysis of As, Be,Cd, Cr, Co, Pb, Fe, Mo,Se, TI, and V

7.6

Continue heating andreduce volume

Cool; dilute with ASTM Type IIwater; allow particulatesin the digestate to settle

7.6

Add concentrated HC1 andASTM Type II water; reflux

7.5

7.5

Cool; dilute with ASTM Type IIwater; allow particulates in

the digestate to settle

Digestatenow readyfor analysis

Method 3050BProcedure

Method 3050B OptionsNOTE: Section 7.5 may be used to improve the solubilitiesand recoveries of antimony, barium, lead, and silver whennecessary. These steps are optional and are not requiredon a routine basis.

7.5 Add 2.5 mL conc. HNO and 10 mL conc. HCl to a 1-2 gsample (wet weight) or 1 g sample (dry weight) and coverwith a watchglass or vapor recovery device. Place the sampleon/in the heating source and reflux for 15 minutes.

Method 3050B Options7.5.1 Filter the digestate and collect filtrate in a 100-mLvolumetric flask. Wash the filter paper, while still in the funnel,with no more than 5 mL of hot (~95oC) HCl, then with 20 mLof hot (~95oC) reagent water.Collect washings in the same 100-mL volumetric flask.

Method 3050B Options

7.5.2 Remove the filter and residue from the funnel, and placethem back in the vessel. Add 5 mL of conc. HCl, place thevessel back on the heating source, and heat at 95oC ± 5oC untilthe filter paper dissolves. Remove the vessel from the heatingsource and wash the cover and sides with reagent water. Filterthe residue and collect the filtrate in the same 100-mLvolumetric flask. Allow filtrate to cool, then dilute to volume.

Method 3050B Options

7.5.3 If a precipitate forms on the bottom of a flask, add up to10 mL of concentrated HCl to dissolve the precipitate. Afterprecipitate is dissolved, dilute to volume with reagent water.Analyze by FLAA or ICP-AES.

NewProcedure

Mix sample, weigh a 1-gportion of each sample

for preparation.

Start

Add 2.5 mL HNO3 and 10 mL HCL

and reflux for 15 minutes.

Analysis by ICPBring to Volume with ASTM Type II water

Prewet filter paper in funnel with several mLs of Hot ASTM

Type II water.Filter digest into 100 mL

volumetric flask.

Rinse the digestion vessel and wash filter paper using 5 mL Hot HCl

and 20 mL of Hot ASTM Type II water.Collect washing in same 100 mL volumetric

flask.

New Procedure

New Procedure

New Procedure

New Procedure

New Procedure

New Procedure

New Procedure

New Procedure

New Procedure

New Procedure

Change in Performance – All ElementsAll Elements LCS Average Recovery

6080

100120140

Aluminu

mAnti

mony

Arsenic

Barium

Berylliu

mCad

miumCalc

iumChro

miumCob

altCop

per

Iron

Lead

Magnes

iumMan

ganes

eNick

elSele

nium

Silver

Thalliu

mVan

adium Zinc

Element

Ave

rage

Rec

over

y

Change in Performance – All ElementsAll Elements MS/MSD Average Recovery

60708090

100110

Antimony

ArsenicBariu

m

Beryllium

Cadmium

ChromiumCobalt

CopperLead

ManganeseNicke

l

SeleniumSilver

Vanadium Zinc

Element

Perc

ent R

ecov

ery

Conclusions

Everything should be made as simple as possible, but not simpler.

--- Albert Einstein

Conclusions

Conclusions

A new scientific truth does not triumph by convincing its opponents and making them see the light,

but rather because its opponents eventually die, and a new generation grows up that is familiar with it.

--- Max Planck

Thank You

Questions???DataChem Laboratories, Inc.

Robert P. Di RienzoJeffery S. Ward

John T. Kershisnik(801) 266-7700