IMPROVE Steering Committee Meeting Petaluma, California 2019 Tracy - - PowerPoint PPT Presentation

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IMPROVE Steering Committee Meeting

Petaluma, California 2019

Tracy Dombek, Ions Report

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Minimum Detection Limits

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• Calibrate systems daily
• Quality Controls before and after every ten samples analyzed.
• Duplicates at a rate of 3 per batch of 50.
• Instrument and Method Blanks every batch extracted and analyzed.
• Random reanalysis of 5% of the sample total.
• Re-extraction of filters to evaluate extraction efficiencies.

Chloride Nitrite Nitrate Sulfate

2019 0.005 ppm 0.010 ppm 0.008 ppm 0.011 ppm

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Quality Control Standards

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Average Recovery Chloride Average Recovery Nitrite Average Recovery Nitrate Average Recovery Sulfate

QC-Low

n= 587

101% 97.2% 98.7% 99.2%

QC-Med

n=901

101% 98.8% 99.4% 99.7%

QC-Med-HI

n=560

101% 100% 99.9% 99.8%

QC-High

n-= 297

101% 102% 100% 101%

Instrument Control Charts

170 180 190 200 210 220 230

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Low QC - Cl

350 360 370 380 390 400 410 420 430 440 450

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Low QC - NO2

1070 1120 1170 1220 1270 1320

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Low QC - SO4

520 540 560 580 600 620 640 660 680

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Low QC - NO3

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Instrument Control Charts

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425 445 465 485 505 525 545 565

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration (ug/L) Analysis Date

Instrument MED QC - Cl

850 900 950 1000 1050 1100 1150

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument MED QC - NO2

1325 1375 1425 1475 1525 1575 1625 1675

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration (ug/L) Analysis Date

Instrument Med QC - NO3

2675 2775 2875 2975 3075 3175 3275

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Med QC - SO4

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Instrument Control Charts

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890 940 990 1040 1090

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration (ug/L) Analysis Date

Instrument Med-HI QC - Cl

1750 1800 1850 1900 1950 2000 2050 2100 2150 2200 2250

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Med-Hi QC – NO2

2690 2790 2890 2990 3090 3190 3290

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Med-Hi QC - NO3

5390 5590 5790 5990 6190 6390 6590

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

Instrument Med-Hi QC - SO4

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25th, 50th,& 75th Percentile Chloride

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Approximate Air Concentrations 25th Chloride - 0.016 ug/m3 50th Chloride – 0.031 ug/m3 75th Chloride - 0.061 ug/m3

15 17 19 21 23 25 27 29 31 33 35

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA25 25th Percentile Concentration Chloride

25 30 35 40 45 50 55 60 65 70 75

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA50 50th Percentile Concentration Chloride

85 90 95 100 105 110 115 120 125 130 135

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA75 75th Percentile Concentration Chloride

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25th , 50th , & 75th Percentile Nitrite

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7 9 11 13 15 17

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA25 25th Percentile Concentration Nitrite

12 14 16 18 20 22 24 26 28 30 32

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA50 50th Percentile Concentration Nitrite

25 30 35 40 45 50 55 60 65

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA75 75th Percentile Concentration Nitrite

Approximate Air Concentration 25th Nitrite – 0.007 ug/m3 50th Nitrite – 0.013 ug/m3 75th Nitrite – 0.026 ug/m3

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25th, 50th , & 75th Percentile Nitrate

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Approximate Air Concentration 25th Nitrate – 0.092 ug/m3 50th Nitrate – 0.18 ug/m3 75th Nitrate – 0.36 ug/m3

130 135 140 145 150 155 160 165 170

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA25 25th Percentile Concentration Nitrate

530 550 570 590 610 630 650 670

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA75 75th Percentile Concentration Nitrate

260 270 280 290 300 310 320 330 340

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA50 50th Percentile Concentration Nitrate

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25th, 50th, & 75th Percentile Sulfate

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Approximate Air Concentration 25th Sulfate – 0.30 ug/m3 50th Sulfate – 0.60 ug/m3 75th Sulfate – 1.2 ug/m3

1775 1825 1875 1925 1975 2025 2075 2125 2175 2225

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA75 75th Percentile Concentration Sulfate

425 445 465 485 505 525 545 565

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA25 25th Percentile Concentration Sulfate

425 445 465 485 505 525 545 565

12/16/18 2/4/19 3/26/19 5/15/19 7/4/19 8/23/19 10/12/19

Concentration ug/L Analysis Date

QA50 50th Percentile Concentration Sulfate

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Duplicate Precision

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Chloride Percent Differences Average = -0.28% Median = 0.03% Maximum = 35.3% Minimum = -130.% Count = 789 Failures 0.3% Nitrite Percent Differences Average = 4.2% Median = 0% Maximum = 200% Minimum = -200 % Count = 789 Failures 0%

y = 1.0006x + 0.3519 R² = 0.9988 500 1000 1500 2000 2500 3000 3500 4000 4500 1000 2000 3000 4000 5000

Duplicate Sample Concentration (ug/L) Sample Concentration (ug/mL)

2019 Chloride Duplicate Precision

y = 1.0046x - 0.1333 R² = 0.9856

• 50

50 100 150 200 250 50 100 150 200 250

Duplicate Sample Concentration (ug/L) Sample Concentration (ug/mL)

2019 Nitrite Duplicate Precision

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Duplicate Precision

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Nitrate Percent Differences Average = 0.10% Median = 0.07% Maximum = 38% Minimum = -38 % Count = 789 Failures 0% Sulfate Percent Differences Average = 0.19% Median = 0.06% Maximum = 200% Minimum = -146% Count = 789 Failures 0%

y = 0.9995x + 0.0247 R² = 1 5000 10000 15000 20000 25000 5000 10000 15000 20000 25000

Duplicate Sample Concentration (ug/L) Sample Concentration (ug/mL)

2019 Nitrate Duplicate Precision

y = 0.9987x + 0.7877 R² = 0.9999 5000 10000 15000 20000 25000 5000 10000 15000 20000 25000

Duplicate Sample Concentration (ug/L) Sample Concentration (ug/mL)

2019 Sulfate Duplicate Precision

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Blank Analyses

2 4 6 8 10 12 14 16 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Chloride Concentration (ug/L) Analysis Date

2019 Chloride Instrument Blanks

5 10 15 20 25 30 35 40 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Chloride Concentration (ug/L) Analysis Date

2019 Chloride Method Blanks

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Nitrite Concentration (ug/L) Analysis Date

2019 Nitrite Instrument Blanks

5 10 15 20 25 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Nitrite Concentration (ug/L) Analysis Date

2019 Nitrite Method Blanks

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Blank Analyses

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Blank Analyses

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Nitrate Concentration (ug/L) Analysis Date

2019 Nitrate Instrument Blanks

2 4 6 8 10 12 14 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Nitrate Concentration (ug/L) Analysis Date

2019 Nitrate Method Blanks

5 10 15 20 25 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Sulfate Concentration (ug/L) Analysis Date

2019 Sulfate Instrument Blanks

5 10 15 20 25 12/16/2018 2/4/2019 3/26/2019 5/15/2019 7/4/2019 8/23/2019 10/12/2019

Sulfate Concentration (ug/L) Analysis Date

2019 Sulfate Method Blanks

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Reanalysis

Chloride Nitrite Nitrate Sulfate 2019 median RPD 0.03% 0%

• 0.59%

0.01% 2019 Average RPD 0.26%

• 0.51%

0.21% 0.52%

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Routine Filter Re-Extraction

• Extraction efficiencies were evaluated on nearly 200 samples
• Efficiency is determined by dividing the result measured on the

re-extracted filter by the sum of the original and re-extracted results.

Chloride Nitrite Nitrate Sulfate 98.0% 95.5% 99.9%

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Comparison of Nitrate Measured in Field Blanks

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Quartile Concentrations

Year Q1 ug/mL Q1 air concentration ug/m3 Q2 ug/mL Q2 air concentration ug/m3 Q3 ug/mL Q3 air concentration ug/m3 2009 0.039 0.024 0.045 0.028 0.050 0.031 2010 0.048 0.029 0.058 0.035 0.072 0.044 2011 0.023 0.014 0.028 0.017 0.038 0.023 2012 0.023 0.014 0.029 0.018 0.037 0.022 2013 0.000 0.000 0.017 0.010 0.024 0.015 2014 0.011 0.007 0.018 0.011 0.024 0.015 2015 0.000 0.000 0.014 0.009 0.030 0.018 2016 0.000 0.000 0.000 0.000 0.009 0.005 2017 0.000 0.000 0.000 0.000 0.012 0.007 2018 0.000 0.000 0.009 0.006 0.017 0.010 2019 0.000 0.000 0.007 0.004 0.014 0.009

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Update for Detection of Organic Sulfur in IMPROVE Extracts

• Collaborating with Dr. Jason Surratt (UNC

Chapel Hill) and Yuzhi Chen (Doctoral Candidate)

• Using HILIC Method to Separate Species and

Mass Spectrometry to identify species observed in extracts.

• Our goal is to identify if OS is in our extracts
• Identify a method for quantification.

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Update for Detection of Organic Sulfur in IMPROVE Extracts

Name [M-H]- m/z Precursor

methanesulfonic acid CH3O3S- 94.98 Dimethylsulfide (DMS) methyl sulfate CH3O4S- 110.976 Hydroxyacetone sulfate C3H5O5S- 152.986 Hydroxyaceton e/ Methacrolein (MACR)/ Methyl vinyl ketone (MVK) C2H3O6S- 154.97 Glycolic acid/ MVK C3H7O5S- 155.0022 unknown C3H5O6S- 168.981 Isoprene/Green Leaf Volatile (GLV) C4H7O6S- 182.997 Isoprene/MACR /MVK C5H9O6S- 197.013 Isoprene methylglyceric acid sulfate C4H7O7S- 198.992 Isoprene C5H11O6S- 199.028 MBO/ Isoprene C5H7O7S- 210.992 isoprene C5H9O7S- 213.007 isoprene

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Update for Detection of Organic Sulfur in IMPROVE Extracts

methyltetrol sulfate C5H11O7S- 215.023 isoprene C6H9O7S- 225.007 GLV/Isoprene C8H13O6S- 237.044 MVK C7H11O7S- 239.023 MACR/MVK C9H13O6S- 249.044 Limonene C8H11O7S- 251.023 α-pinene C8H13O7S- 253.039 Terpinolène C5H10NO9S- 260.008 isoprene C12H24O4S- 265.148 Diesel and biodiesel fuel C10H15O7S- 279.054 α-/β-pinene; terpinenes/Lim

• nene

C10H17O7S- 281.07 α- terpinene/Limo nene C10H16NO7S- 294.065 α-/β-pinene C10H15N2O9S- 342.05 α-/β-pinene / α-terpinene

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Update for Detection of Organic Sulfur in IMPROVE Extracts

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 ng S

Winter

methyltetrol sulfates methyl sulfates lactic acid sulfate

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Update for Detection of Organic Sulfur in IMPROVE Extracts

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 ng S

Summer

methyltetrol sulfates methyl sulfates lactic acid sulfate

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Next Steps

• Verify with secondary analyses.
• Calculate amount present in composited

samples

• Utilize this data as pilot to write up a proposal to

request funding.

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Name Tracy Dombek Email tdombek@rti.org Phone Number 919-541-5934

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