Passive Diffusion Monitoring for Ammonia in the US U.S. Lear, G. 1, C. Sweet 2,3, M. Caughey 3, C. Lehmann 2,3, T. Dombek 2,3, and D. Gay 2,3 1 U.S. Environmental Protection Agency Clean Air Markets Division 2 National Atmospheric Deposition Program, U of Illinois 3 Illinois i State Water Survey, U of Illinois i NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 1
Monitoring Goals Determining the spatial distribution of ammonia concentrations, Determine the seasonality of these concentrations, Help in meeting air quality goals, and improve modeling, CMAQ Ammonia Concentrations, 2001 Provide information for other scientific and policy needs. Cost efficient Network NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 2
Goals of This Project Test the Passive Samplers for Performance Develop a cost efficient Network procedures sites Measurement of Ammonia Concentrations NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 3
Passive Diffusion Sampler Alternatives Radiello Ogawa I Alpha E F C All vs. Denuders ( standard method ) NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 4
Radiello NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 5
Results of the Diffusive Samplers Blanks Accuracy Laboratory Blanks Travel Blanks vs. denuderd Repeatability Ti Triplicate samples Reporting limit NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 6
Radiello Ammonium Lab Blanks With Time 0.080 mg g/liter 0.060 0.040 0.020 0.000 Median Lab Blank=0.015 015 mg/l -0.020-0.040 ph Imbalance w/instrument Oct-07 Dec-07 Feb-08 Apr-08 Jun-08 Aug-08 Dist. Water Oct-08 Lab Blank NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 7
Radiello Ammonium Travel Blanks With Time 0.800 Contaminated 0.700 248 valid travel blanks 0.600 Shipping Containers mg/liter 0.500 0.400 0.300 0.200 0.100 0.000 Oct-07 Dec-07 Feb-08 Apr-08 Jun-08 Aug-08 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 8
Radiello Accuracy Radiello vs Denuder Ammonia Concentrations 10.00 ppb Ammon nia 8.00 6.00 4.00 2.00 0.00 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 IL11 Con IL11 Avg Oct-08 Denud NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 9
Alpha Accuracy Accuracy: Alpha vs. Denuder Ammonia Con. ppb Ammonia 6.0 5.0 4.0 3.0 2.0 1.0 0.0 Feb-08 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Alpha Alpha Avg Sep-08 Denud NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 10
Ogawa Accuracy Accuracy: Ogawa vs Denuder Concentrations 10 ppb Am mmonia 8 6 4 2 0 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08 Jun-08 Oga Con Oga Avg Jul-08 Denud NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 11
Repeatability of Passives Repeatability: Difference From the Mean ppbv Diff ference 300 3.00 2.00 1.00 0.00-1.00-2.00-3.00 Rad ddiff Oga Diff Alpha Diff Sep-07 Nov-07 Jan-08 Feb-08 Apr-08 Jun-08 Jul-08 Sep-08 Oct-08 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 12
Repeatability Comparison Comparisons ppbv units Measure Radiello Alpha Ap Ogawa a Repeatability Removed From consideration median difference (vs avg) 0.00 0.01 0.15 maximum difference (vs avg) 073 0.73 079 0.79 204 2.04 Standard Dev. Of difference 0.19 0.33 0.89 75th perc. Difference 0.07 0.11 0.52 25th perc. Difference -0.05-0.08-0.48 interquartile range 0.12 0.18 1.00 n 63 39 42 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 13
Radiello x Alpha Accuracy Radiello vs Denuder Ammonia Concentrations 9.0 8.0 7.0 Alpha Denud IL11 ppb Amm monia 6.0 50 5.0 4.0 3.0 2.0 1.0 0.0 Feb-08 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 14
Radiello x Alpha, Cost Comparisons Costs Measure Radiello Alpha Costs Body ($) $8.00 $23.00 no. of body uses 10 100 ++ Replaceable "core"/filter ($) $11.00 42 replaceable membrane $2.10 1 year, triplicate samples $874 $60 cleaning (hrs) minimal minimal preperation little somewhat more Alphas are English ( to $ conversion) NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 15
Radiello vs. Alpha Travel Blanks Radiello and Alpha Travel Blanks @ IL11 0.400 0.350 0.300 Radiello TB Alpha TB mg/lite er 0.250 0.200 0.150 0.100 0.050 0.000 Oct-07 Dec-07 Feb-08 Apr-08 Jun-08 Aug-08 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 16
Low Bias for Passive Diffusion Samplers Consistently below the denuders Average Median ppbv ppbv % Abs % Denuder 2.56 2.30 Radiello 2.02 1.61 Alpha 178 1.78 160 1.60 Radiello - Den Difference -0.54-0.75-34% 37% Alpha - Den Difference -0.80-0.99-35% 35% March to Sept 2008 measurements only Denuders flow checks to two separate mass flow devices Lab blanks and travel blanks are clean 2 sequential denuders; no breakthrough to 2 nd denuder Agree with monitor (Nitrolux 200) Radiellos & Alphas Generally agree Limited observations, particularly for winter NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 17
Radiello Method Detection Limit With a two-weekweek sample, Average lab blank of 0.014 mg/l Standard ddeviation i of +0.016 016 mg/l, and Method Detection Limit = (L blank +2 std) Method Detection Limit of 0.15 ppbv NH 3 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 18
Summary Ogawa No longer being considered d High variation within triplicates (wind orientation likely) Radiello Generally good agreement with denuders Relatively low bias Low variation between replicates Good blanks Expensive Alpha Blanks seem to be as good as Radiello Generally good agreement with denuders Relatively low bias Low variation between replicates LOW cost Considering for adoptions NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 19
Ammonia Monitoring Network (AMoN) 21 Sites operating (as of Sep 2008) Two-week samples in triplicate Radiello Sampler Sampling began Oct 30, 2008 393 triplicate icate measurements e e (9/2/08) /08) NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 20
Network Sites NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 21
Measurement Results General stats Max, min, etc overall sites Time lines by site or state or region Median, range max min weekly standev about mean, n= NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 22
Concentrations: New York 67 (Connecticut Hill) Ammonia (p ppb) 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 02 0.2 0.0 likely contamination below reporting limit NY67 Sep-07 Nov-07 Jan-08 Feb-08 Apr-08 Jun-08 Jul-08 Sep-08 Median 0.34 95 Perc 1.30 5th Perc 0.0606 Maximum 1.66 Minimum 0.03 Average 0.50 St. Deviation 0.44 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 23
Concentrations: Kansas 24 (Coffeeville) Ammonia (ppb) 18.0 16.0 14.0 12.0 10.0 8.0 6.0 4.0 2.0 0.0 likely contamination Sep-07 Nov-07 Jan-08 Feb-08 Apr-08 Jun-08 Jul-08 Sep-08 Median 8.12 95 Perc 14.68 5th Perc 2.24 Maximum 15.68 Minimum 1.57 Average 818 8.18 St. Deviation 3.98 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 24
Concentrations: Illinois 11 (Bondville) Ammonia (p ppb) 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 10 1.0 0.0 possible contamination Sep-07 Nov-07 Jan-08 Feb-08 Apr-08 Jun-08 Jul-08 Sep-08 Oct-08 Median 1.35 95 Perc 5.29 5th Perc 0.19 Maximum 8.19 Minimum 0.00 Average 1.74 St. Deviation 1.84 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 25
Fall Concentrations November 2007 Concentrations Gaseous Ammonia ppb pp 2.5 2.5-5.0 5.0-7.5 7.5-10.0 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 26 >10.0
Fall Concentrations November 2007 Concentrations Gaseous Ammonia ppb 2.5 2.5-5.0 5.0-7.5 7.5-10.0 >10.0 Precip. Ammonium /L 0.20 0.20-0.25 0.25-0.30 0 30-0 35 mg/l 0.30-0.35 0.35-0.40 0.40-0.45 0.45-0.50 0 50-0 55 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 27 0.50-0.55 0.55-0.60 0.60-0.65 >0.65
Winter Concentrations December 2007 February 2008 Concentrations Gaseous Ammonia ppb pp 2.5 2.5-5.0 5.0-7.5 7.5-10.0 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 28 >10.0
Winter Concentrations December 2007 February 2008 Concentrations Gaseous Ammonia ppb 2.5 2.5-5.0 5.0-7.5 7.5-10.0 >10.0 Precip. Ammonium /L 0.20 0.20-0.25 0.25-0.30 0 30-0 35 mg/l 0.30-0.35 0.35-0.40 0.40-0.45 0.45-0.50 0 50-0 55 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 29 0.50-0.55 0.55-0.60 0.60-0.65 >0.65
Spring Concentrations March 2008 May 2008 Concentrations Gaseous Ammonia ppb pp 2.5 2.5-5.0 5.0-7.5 7.5-10.0 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 30 >10.0
Spring Concentrations March 2008 May 2008 Concentrations Gaseous Ammonia ppb 2.5 2.5-5.0 5.0-7.5 7.5-10.0 >10.0 Precip. Ammonium /L 0.20 0.20-0.25 0.25-0.30 0 30-0 35 mg/l 0.30-0.35 0.35-0.40 0.40-0.45 0.45-0.50 0 50-0 55 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 31 0.50-0.55 0.55-0.60 0.60-0.65 >0.65
Next Steps Funding through October 2009 Seek additional sponsors Reduce costs of Radiellos Determine optimum number of replicates Decision on elimination by January 2009 Field blank corrections Still too much contamination Goal: 0.2 ppbv correction (limit) Prep, removal, analysis all in one hood New glass shipping tubes (into ISWS next week) NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 32
Next Steps Additional denuder comparisons NC sites Environment Canada a a Additional alphas at CO and TX sites Make preliminary data available by January 2009 Meeting of interested parties Thursday afternoon NADP Spring 2009 NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 33
Acknowledgements Additional financial support from the Lake Michigan Air Directors Consortium (LADCO), Chicago IL NADP Fall Meeting 2008, Madison WI, Oct 14-16, 2008, Slide 34