ROcky Mountain Atmospheric Nitrogen and Sulfur study (ROMANS)

Transcription

1 ROcky Mountain Atmospheric Nitrogen and Sulfur study (ROMANS) STATEMENT OF THE PROBLEM Rocky Mountain National Park (ROMO) is experiencing a number of deleterious effects due to atmospheric nitrogen and sulfur compounds. These effects include visibility degradation, changes in ecosystem function and surface water chemistry from atmospheric deposition, and human health concerns due to elevated ozone concentrations. The nitrogen compounds include both oxidized and reduced nitrogen. Emissions of nitrogen compounds need to be reduced to alleviate these deleterious effects. Various regulatory programs are underway to address emission reductions, many of which will be achieved from the most easily identified contributors to oxidized nitrogen related effects at the park.

2 NADP 24 Annual Summary Wet deposition patterns and trends N deposition hot spot in northern Colorado Rockies Current N deposition ~ 2x natural levels Nitrogen deposition increasing at high elevation sites Ammonium deposition increasing faster than nitrate Niwot Saddle NADP site Burns (23)

3 ROMANS OBJECTIVES Characterize the atmospheric concentrations of sulfur and nitrogen species in gaseous, particulate and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide (Organic Nitrogen?) GAS: NH 3, R-NH 2, NO X (NO+NO 2 ), NO Y (HNO 3, PAN, etc) PARTICLE: NH 4, NO 3, ORGANICS (reduced and oxidized)? WET (rain, snow, and clouds): NH 4, NO 3, ORGANICS (reduced and oxidized)? Identify the relative contributions to atmospheric sulfur and nitrogen species in RMNP from within and outside of the state of Colorado. Identify the relative contributions to atmospheric sulfur and nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado. Identify the relative contributions to atmospheric sulfur and nitrogen species from mobile sources, agricultural activities, large and small point sources within the state of Colorado.

4 The urban/industrialagricultural interface +hv NO x VOC Organic nitrogen? HNO 3 + NH 3 NH 4 NO 3 (p)

5 Apportionment Strategy If chemical transport models were perfect then all apportionment problems would best be addressed through the exercise of these models. BUT THEY ARE NOT! especially when addressing species other than ozone and sulfate.

6 Apportionment Strategy (Weight of Evidence) Concentration gradients. Which way is the wind coming from? Simple back trajectories. Frequency with which the air mass passes over source areas before it arrives at the receptor -residence time analysis. Trajectory receptor models. Receptor models. Chemical transport models. Hybrid Models.

7 STUDY DESIGN Grant, NE Dinosaur Timber Creek Loch Vale Beaver Meadows Brush Gore Pass Core Site Lyons Springfield

8 CORE SITE

9 Time series of PILS and IMPROVE sulfate and nitrate

10 Spring atmospheric scattering estimations bcm 22% blac 1% babsf 5% babsc % (NH4)2(SO4) 41% POM 15% NH4NO3 16% V r = 4 km

11 Summer atmospheric scattering estimations babs_fine babs_coarse 8% 2% BSCM 8% blac 2% SOIL 7% (NH4)2(SO4) 18% NH4NO3 5% POM 5% V r =27 KM

12 Comparison of visibility on clear day and a day with V r =25 km

13 Precipitation (mm) Precipitation (mm) Wet Concentration and Deposition (Spring) SO 4 NO 3 NH 4 DON mmprecip Concentration ( g N or S/L) 3/26 3/29 4/1 4/5 4/6 4/15 4/17 4/18 4/23 4/24 4/28 14 SO 4 NO 3 NH 4 DON mmprecip Wet Deposition N or S ( g/m 2 ) 3/26 3/29 4/15 4/17 4/18 4/23 4/24 4/28

14 Wet Concentration and Deposition (Summer) SO 4 NO 3 NH 4 DON mmprecip Precipitation (mm) Concentration ( g N or S/L) 8/1 8/11 8/6 8/5 8/3 7/3 7/31 7/23 7/24 7/25 7/26 7/2 7/19 7/17 7/15 7/11 7/6 7/7 7/8 7/9 14 SO 4 NO 3 NH 4 DON mmprecip Precipitation (mm) Wet Deposition N or S ( g/m 2 ) 8/1 8/11 8/7 8/5 8/3 7/3 7/31 7/23 7/24 7/25 7/26 7/19 7/2 7/17 7/15 7/11 7/6 7/7 7/8 7/9

15 Relative contributions of individual N deposition pathways to total measured N deposition ON wet 16.65% Spring HNO3 7.49% NO3 dry 1.8% NO3 wet 23.76% SPRING Total Dep=3326 ug/m2 NH4 wet 34.11% NH4 dry 3.15% NH % Summer ON wet 12.33% HNO3 7.5% NO3 dry.2% SUMMER Total Dep = 6228 ug/m2 NO3 wet 27.83% NH4 wet 34.24% NH4 dry 1.41% NH %

16 Concentration Gradients

17 Spring overview Concentrations lower in mountains Gases dominate at eastern and western sites Highest ammonia at Brush in NE Colorado Particles dominate in mountains

18 Summer overview Concentrations higher than in spring Highest concentrations again east of RMNP Increasing N gas importance in mountains

19 Concentration Gradient Across Monitoring Network DI GP TC BM MS LY BR NE [HNO3 +NO3 - ] ( g/m 3 ) [NH3 + NH4 + ] ( g/m 3 ) 3/25 3/26 3/27 3/28 3/29 3/3 3/31 4/1 4/2 4/3 4/4 4/5 4/6 4/7 4/8 4/9 4/1 4/11 4/12 4/13 4/14 4/15 4/16 4/17 4/18 4/19 4/2 4/21 4/22 4/23 4/24 4/25 4/26 4/27 4/28 3/25 3/26 3/27 3/28 3/29 3/3 3/31 4/1 4/2 4/3 4/4 4/5 4/6 4/7 4/8 4/9 4/1 4/11 4/12 4/13 4/14 4/15 4/16 4/17 4/18 4/19 4/2 4/21 4/22 4/23 4/24 4/25 4/26 4/27 4/28

20 Concentration Gradient Across Rocky Mt NP GP BM MS [NH3 + NH4 + ] ( g/m 3 ) [NH3 + NH4 + ] ( g/m 3 ) 7/6 7/7 7/8 7/9 7/1 7/11 7/12 7/13 7/14 7/15 7/16 7/17 7/18 7/19 7/2 7/21 7/22 7/23 7/24 7/25 7/26 7/27 7/28 7/29 7/3 7/31 8/1 8/2 8/3 8/4 8/5 8/6 8/7 8/8 8/9 8/1 3/25 3/26 3/27 3/28 3/29 3/3 3/31 4/1 4/2 4/3 4/4 4/5 4/6 4/7 4/8 4/9 4/1 4/11 4/12 4/13 4/14 4/15 4/16 4/17 4/18 4/19 4/2 4/21 4/22 4/23 4/24 4/25 4/26 4/27 4/28

21 Colorado Front Range Upslope Events Easterly Winds Transport Airmasses from Front Range and Further East to Rocky Mountain

22 Wind Direction for a Major Episode

23 WIND DIRECTION AND PARTICLE CONCENTRATIONS neq /m Rain W D ( Deg ree ) 4/2 4/21 4/22 4/23 4/24 4/25 4/26 4/27 Date SO4= NO3- NH4+ WD 3 per. Mov. Avg. (WD)

24 Simple Trajectory Analysis

25 Nitrate Wet Deposition Flux [ug/m2/day] /17 8/18 8/19 8/2 8/21 8/22 8/23 9/6 9/8 MS1 MS2 BM LV HV RB RK AC LI Rocky Mountain National Park Beginning Sep. 8, 25 hr (jd 251) Started During Next 24 Hrs, 5 Day Length However, most of the upslope events were associated with precipitation events accounts for between 8-9% of the deposition. Upslope trajectories occurred: Aug 2-22, Sept 2-3, 6, 8 Start Height (m) height(km) hours

26 Statistical Analysis of Many Trajectories (Residence Time)

27 NH3 Spring NOx Spring NH3 Summer NH3 Summer

28 Apportionment of Gas/Particle Species Using Modeled Tracer

29 Existing CAMx 36 km and 12 km nested grids, and approximate location of 4 km grid d2 d3 d1 National Park Service U.S. Department of the Interior Cooperative Institute for Research in the Atmosphere Colorado State University

30 SOURCE REGIONS for CAMX RUNS NH 3 NO x SO 2

31 Where C ki = j a kj S k = 1... m, the number of observations, i = 1... n, the number of sources contributing to receptor, j = 1... N, the number of source region vectors, C ki = concentrations of ammonia from source i for time period k, a kj = time weighting functions, and S ji = source vectors. = error term including random and lack of fit error. ε ik The receptor model ji ( C) = α Φ k j jk C k = the measured hourly aerosol concentrations Α jk = the regression coefficients Φ jk = the average of modeled concentrations arriving at the receptor from sources areas grouped according to eigenvectors, v + jk ε ik

32 Grouping of Source Regions Spring NH 3 /NH 4 Northeast Region Spring NH 4 Region 7 Spring NH 3 /NH 4 Region 8 Spring NO X Region 2

33 Ammonia 4/4 4/5 4/6 4/7 4/9 4/1 4/11 4/12 4/13 4/14 4/16 4/17 4/18 4/19 4/2 4/21 4/23 4/24 4/25 4/26 4/27 4/28 Date Ammonia Other East WY Local SW WY NW CO Four Corn NGS S Neveda Calif Western CO Estes Denver Other East WY Local SW WY NW CO Four Corn NGS S Neveda Calif Western CO Estes Denver 4/2 4/3 4/4 4/5 4/6 4/7 4/9 4/1 4/11 4/12 4/13 4/14 4/16 4/17 4/18 4/19 4/2 4/21 4/23 4/24 4/25 4/26 4/27 4/28 4/3 3/3 3/31 4/2 1% 8% 6% 4% 2% % APPORTIONMENT TO SOURCE REGIONS (NH 3 SPRING) Date 3/3 3/31 Percentage Concentration (ug/m3)

34 Ammonia 7/16 7/17 7/18 7/19 7/2 7/22 7/23 7/24 7/25 7/26 7/27 7/29 7/3 7/31 8/1 8/2 8/3 8/5 8/6 8/7 8/8 8/9 8/1 Date Ammonia Other East WY Local SW Wy NW CO Four Corners NGS S Neveda Calif Western CO Estes Denver Northeast CO 7/15 7/16 7/17 7/18 7/19 7/2 7/22 7/23 7/24 7/25 7/26 7/27 7/29 7/13 7/15 7/12 7/13 7/11 7/1 7/11 7/12 1% 8% 6% 4% 2% % APPORTIONMENT TO SOURCE REGIONS (NH 3 SUMMER) 7/3 7/31 8/1 8/2 8/3 8/5 8/6 8/7 8/8 8/9 8/1 Date Other East WY Local SW Wy NW CO Four Corners NGS S Neveda Calif Western CO Estes Denver Northeast CO 7/1 Percentage Concentration(ug/m3)

35 Nitric Acid 4/4 4/5 4/6 4/7 4/9 4/1 4/11 4/12 4/13 4/14 4/16 4/17 4/18 4/19 4/2 4/21 4/23 4/24 4/25 4/26 4/27 4/28 Date Nitric Acid Other East WY Local SW WY NW CO Four Corn NGS S Neveda Calif Western CO Estes Denver Northeast CO 4/3 4/4 4/5 4/6 4/7 4/9 4/1 4/11 4/12 4/13 4/14 4/16 4/17 4/18 4/19 4/2 4/21 4/23 4/24 4/25 4/26 4/27 4/28 4/2 4/3 4/2 3/3 3/31 1% 8% 6% 4% 2% % APPORTIONMENT TO SOURCE REGIONS (HNO 3 SPRING) Date Other East WY Local SW WY NW CO Four Corn NGS S Neveda Calif Western CO Estes Denver Northeast CO 3/3 3/31 Percentage Concentration(ug/m3)

36 Average Apportionments (gas/particle concentrations) Fraction From Colorado (Spring) Fraction From Colorado (Summer) Fraction.6.4 Other Colorado Fraction.6.4 Other Colorado.2.2. NH3 NH4 NOx HNO3 NO3 SO2 SO4 NH3 NH4 NOx HNO3 NO3 SO2 SO4 Species Species Fraction Spring Average Fractional Contribution NH3 NH4 NOx HNO3 NO3 SO4 SO2 Species Other East WY SW WY Four Corners NGS S Nevada Calif NW CO Local Estes Western CO Denver Northeastern CO Fraction Summer Average Fractional Contribution NH3 NH4 NOx HNO3 NO3 SO4 SO2 Species Other East WY SW WY Four Cornersers NGS Nevada South Calif NW CO Local Estes Western CO Denver Northeastern CO

37 Spring Average Wet NH4 Fractional Contribution Average Spring Apportionments (wet deposition) East WY 8% Calif 2% local 4% Estes 3% Other 14% Denver 25% Western CO % Four Corners 1% S Nevada 3% East WY 1% Spring Average Wet SO4 Fractional Other Deposition 15% Calif 6% Denver 26% Western CO 1% Northeastern CO 44% Spring Average Wet NO3 Fractional Deposition Calif 1% NW CO 2% Four Corners East WY 1% 7% Estes 11% Other 5% Denver 51% local 4% Northeastern CO 34% Northeastern CO 22% Western CO %

38 Average Summer Apportionments (wet deposition) Summer Average SO4 Fractional Wet Deposition East WY 1% SW WY 5% Summer Average NH4 Fractional Wet Deposition Calif 5% Other 25% Denver 1% Local 29% Western CO 24% Northeastern CO 6% Estes 4% East WY 2% Four Corners 14% NGS 1% S Nevada 3% Other 13% DenverWestern CO 2% 5% Estes 7% Calif 36% Local 14% NW CO 3% Summer Average NO3 Fractional Wet Deposition Denver 7% East WY 3% SW WY 2% Other 3% Four Corners 9% NGS 1% S Nevada 9% Calif 14% Western CO 12% Este 2% Loca 6% NW CO 5%

39 SUMMARY A substantial portion of ammonia, ammonium, nitrate, and nitric acid originates in the state of Colorado. Sulfur species tend to more associated with longer range transport and come from outside the state. More sources contribute during the summer than spring. Natural emissions of ammonia appear to contribute significantly to ammonia and ammonium concentrations and deposition. During the Spring during upslope conditions northeastern Colorado contributes most of the ammonia and wet deposited ammonium. The town of Estes Park appears to contribute significantly to nitric acid and nitrate during the spring time frame. During the summer sources in California and off the coast of California contribute significantly.

40 END

41 FOOD FOR THOUGHT?