3/30/2005 Linsey DeBell Cooperative Institute for Research in the Atmospheres
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3/30/2005 Linsey DeBell Cooperative Institute for Research in the Atmospheres Interagency Monitoring of Protected Visual Environments Colorado State University Data Validation Historical Report Soil Elements Data Start: March 1988 Data End: December 2003 Retrieved from the VIEWS Database on Various Dates: 11/2004-3/2005 Summary Some general observations based on this analysis: It seems that Al data has been particularly sensitive to analytical and data processing changes. The possibility that the PIXE system was contaminated with Titanium should be explored. Persistent offsets from nominal flow in the A module appear to have resulted in trends in absolute and relative SOIL concentrations. This could have significant impacts for trends analysis at sites where SOIL is a dominant fraction of the aerosol. The soil elements taken as an ensemble, but not as a composite variable such as SOIL, seem to be more revealing of analytical inconsistencies and problems than the rest of IMPROVE’s current data validation tests. Background With the exception of the collocated QC modules, there are no redundant measurements of the soil elements, so all validation efforts at this level focus on 1) internal consistency between the elements for a given sample and 2) consistency through time and, to a lesser extent space, for the elements individually and in relation to each other. Internal consistency between the soil elements is examined using soil enrichment factors (elemental ratio in aerosol/elemental ratio in average crustal rock), which roughly show if the soil elements in the aerosol sample are found in the same ratio as they would be in average crustal rock. Iron is the most stable element from the XRF systems, so it was selected as the reference element in calculating the enrichment factors. Individual samples are not examined for departures from the expected value of 1 for the enrichment factor; rather, the relative number of these samples and the typical value of the enrichment factor are monitored. Three panel time series charts are produced for each site for Al, Ca, Si, and Ti with the element of interest in the first, Fe in the second ,and the enrichment factor ((X/Feaerosol)/(X/Feaverage crustal rock)) for the element of interest in the third panel. The charts are examined primarily for changes in behavior in any of the three metrics over time that could indicate data quality problems. Additionally, the IMPROVE SOIL parameter is examined in relation to the A module cut point and RCFM. Time series of the three parameters are examined for trends in SOIL that appear related to changes in cut point rather than emissions patterns. Figures 5–9 are examples of the time series plots used to validate the SOIL parameter. Anomaly 1: At a select few sites, the trends in SOIL concentrations and/or relative SOIL contributions to reconstructed fine mass (SOIL/RCFM) look to be correlated to trends in the A module cut point. Obvious problems are fairly limited, which is surprising given the high degree of variability in cut point over time at many sites. Prominent problems are most noticeable at sites where SOIL concentrations are high and the cut point has been greater then 3 ug/m3 for a prolonged period of time. All sites are identified in the attached PowerPoint files with magenta rectangles. Affected Sites: Site Code AREN1 GRBA1 STAR1 IKBA1 PEFO1 TONT1 EVER1 CHIR1 BIBE1 SACR1 Site Name Arendtsville Great Basin NP Starkey Ike's Backbone Petrified Forest NP Tonto NM Everglades NP Chiricahua NM Big Bend NP Salt Creek Unaffected Regions: Alaska Region Boundary Waters Region California Coast Region Central Great Plains Region Central Rockies Region Colorado Plateau Region Columbia River Gorge Region Death Valley Region East Coast Region Hawaii Region Lone Peak Region Mid South Region Northeast Region Northern Region Great Plains Region Northern Rockies Region Northwest Region Ohio River Valley Region Oregon and Northern California Region Puget Sound Region Sierra Nevada Region Southern California Region Virgin Islands Region Washington DC Region State PA NV OR AZ AZ AZ FL AZ TX NM IMPROVE Region Appalachia Great Basin Hells Canyon Mongollon Plateau Mongollon Plateau Mongollon Plateau Southeast Southern Arizona West Texas West Texas Example: Figure 1. Increases in relative and total soil concentrations at SACR1 in 2003 are correlated to increases in the A module cut point. Legend: SOILfVAL: soil concentration calculated from the soil elements using the IMPROVE algorithm, [SOIL] in ug/m3 ACutPoint: A module cut point, aerodynamic diameter at which 50% of the particles are collected ( m) SOIL_RCFM: soil concentration divided by the reconstructed fine mass concentration calculated using the IMPROVE algorithm=[SOIL]/[RCFM] Anomaly 2. There were anomalously high Al detection counts from 1/1993-12/1994 at all sites across the network. Based on the network wide occurrence an analytical anomaly or change in sampling materials is the likely underlying cause. The high detection counts, if real, would provide higher quality Al data. However the isolated nature of the anomaly suggests that the conditions that lead to the improvement were difficult to maintain or that the high detection counts were an artifact of data processing changes. It was suggested by Crocker Nuclear Laboratory (CNL) at the time to be due to an improvement in the PIXE detector. If this is the case then something changed in 1995 to reverse the positive improvement. All sites are identified in the attached PowerPoint files with royal blue rectangles. Affected Sites: entire network Example: Figure 2. The numbers of samples with Al concentrations above detection limit were significantly higher from 1993-1994 compared to all other years of operation. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 3. There were anomalously high Al detection counts in 1995 similar to 1993 and 1994 but only at 9 sites. All sites are identified in the attached PowerPoint files with sky blue rectangles. Affected Sites: Site Code GRSM1 State TN IMPROVE Region Appalachia CO Central Rockies PEFO1 ACAD1 BADL1 Site Name Great Smoky Mountains NP Great Sand Dunes NM Petrified Forest NP Acadia NP Badlands NP AZ ME SD BLIS1 Bliss SP (TRPA) CA SAGO1 San Gorgonio Wilderness Big Bend NP Guadalupe Mountains NP CA Mongollon Plateau Northeast Northern Great Plains Oregon and Northern California Southern California TX TX West Texas West Texas GRSA1 BIBE1 GUMO1 Unaffected Regions: Alaska Region Boundary Waters Region California Coast Region Central Great Plains Region Colorado Plateau Region Columbia River Gorge Region Death Valley Region East Coast Region Great Basin Region Hawaii Region Hells Canyon Region Lone Peak Region Mid South Region Northern Rockies Region Northwest Region Ohio River Valley Region Puget Sound Region Sierra Nevada Region Southern Arizona Region Southeast Region Virgin Islands Region Washington DC Region Example: Figure 3. The numbers of samples with Al concentrations above detection limit were significantly higher during 1995 compared to all other years of operation at a select number of sites. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 4. There were low above detection counts for Al at MOOS1 in 1999. Fe concentrations show no significant decrease during the same period indicating that soil concentrations were typical during this period, assuming a soil source for the Fe. The site is identified in the attached PowerPoint files with a royal blue rectangle. Affected Site: Site Code MOOS1 Site Name Moosehorn NWR State ME IMPROVE Region Northeast Example: Figure 4. The numbers of samples with Al concentrations above detection limit were significantly lower for 1999 compared other years of operation at MOOS1. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 5. There were low above detection counts for Al at a number of sites in 2000. Fe concentrations show no significant decrease during the same period indicating that soil concentrations were typical during this period, assuming a soil source for the Fe. There was not a set block of time affected at all sites. All sites are identified in the attached PowerPoint files with royal blue rectangles. Affected Sites: Site Code Site Name State GRSM1 Great Smoky Mountains NP James River Face Wilderness Linville Gorge Shenandoah NP Isle Royale NP Seney TN IMPROVE Region Appalachia VA Appalachia NC VA Appalachia Appalachia MI MN PINN1 Voyageurs NP #2 Pinnacles NM RAFA1 San Rafael CA BRLA1 Brooklyn Lake Great Sand Dunes NM White River NF Bandelier NM WY Bryce Canyon NP Canyonlands NP Capitol Reef NP Indian Gardens Mesa Verde NP UT Boundary Waters Boundary Waters Boundary Waters California Coast California Coast Central Rockies Central Rockies Central Rockies Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau JARI1 LIGO1 SHEN1 ISLE1 SENE1 VOYA2 GRSA1 WHRI1 BAND1 BRCA1 CANY1 CAPI1 INGA1 MEVE1 MI CA CO CO NM UT UT AZ CO SAPE1 San Pedro Parks Zion NM Great Basin NP Haleakala NP Craters of the Moon NM Sawtooth NF Starkey Bosque del Apache Gila Wilderness Sierra Ancha NV Colorado Plateau Colorado Plateau Great Basin HI ID Hawaii Hells Canyon ID OR NM NH VT Northeast BADL1 Great Gulf Wilderness Lye Brook Wilderness Badlands NP Hells Canyon Hells Canyon Mongollon Plateau Mongollon Plateau Mongollon Plateau Northeast SD LOST1 Lostwood ND MELA1 MT ULBE1 Medicine Lake Theodore Roosevelt UL Bend WICA1 Wind Cave SD BRID1 WY MONT1 Bridger Wilderness Monture SULA1 Sula Peak MT YELL2 Yellowstone NP 2 Snoqualmie Pass White Pass Mammoth Cave NP WY Northern Great Plains Northern Great Plains Northern Great Plains Northern Great Plains Northern Great Plains Northern Great Plains Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northwest ZION1 GRBA1 HALE1 CRMO1 SAWT1 STAR1 BOAP1 GICL1 SIAN1 GRGU1 LYBR1 THRO1 SNPA1 WHPA1 MACA1 UT NM AZ ND MT MT WA WA KY Northwest Ohio River Valley MING1 Mingo MO BLIS1 Bliss SP (TRPA) CA KALM1 Kalmiopsis OR LABE1 Lava Beds NM CA MOHO1 Mount Hood OR THSI1 Three Sisters Wilderness OR DOME1 CA SEQU1 Dome Lands Wilderness Sequoia NP YOSE1 Yosemite NP CA JOSH1 Joshua Tree NP Virgin Islands NP Big Bend NP Guadalupe Mountains NP CA VIIS1 BIBE1 GUMO1 Unaffected Regions: Alaska Region Central Great Plains Region Columbia River Gorge Region Death Valley Region East Coast Region Lone Peak Region Mid South Region Puget Sound Region Southern Arizona Region Southeast Region Washington DC Region VI Ohio River Valley Oregon and Northern California Oregon and Northern California Oregon and Northern California Oregon and Northern California Oregon and Northern California Sierra Nevadas Sierra Nevadas Sierra Nevadas Southern California Virgin Islands TX TX West Texas West Texas CA Example: Figure 5. The numbers of samples with Al concentrations above detection limit were significantly lower for various periods during 2000 compared to other years of operation at a large number of sites. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 6. There were low above detection counts for Al at a large number of sites in 2001. Fe concentrations show no significant decrease during the same period indicating that soil concentrations were typical during this period, assuming a soil source for the Fe. There was not a set block of time affected at all sites. All sites are identified in the attached PowerPoint files with royal blue rectangles. Affected Sites: Site Code Site Name State DENA1 TRCR1 AREN1 COHU1 DOSO1 Denali NP Trapper Creek Arendtsville Cohutta Dolly Sods Wilderness Great Smoky Mountains NP James River Face Wilderness Linville Gorge Shenandoah NP Shining Rock Wilderness Boundary Waters Canoe Area Seney AK AK PA GA WV IMPROVE Region Alaska Alaska Appalachia Appalachia Appalachia TN Appalachia VA Appalachia NC VA NC Appalachia Appalachia Appalachia MN Boundary Waters MI MN PINN1 Voyageurs NP #2 Pinnacles NM RAFA1 San Rafael CA BOND1 Bondville IL BRLA1 Brooklyn Lake WY MOZI1 Mount Zirkel Wilderness Rocky Mountain NP CO Boundary Waters Boundary Waters California Coast California Coast Central Great Plains Central Rockies Central Rockies Central Rockies GRSM1 JARI1 LIGO1 SHEN1 SHRO1 BOWA1 SENE1 VOYA2 ROMO1 CA CO WHPE1 Wheeler Peak WHRI1 White River NF CO BAND1 Bandelier NM NM BRCA1 UT INGA1 Bryce Canyon NP Canyonlands NP Capitol Reef NP Hance Camp at Grand Canyon NP Indian Gardens MEVE1 Mesa Verde NP CO SAPE1 San Pedro Parks Weminuche Wilderness Zion NM Columbia Gorge #1 Columbia River Gorge Brigantine NWR Swanquarter Great Basin NP Jarbidge Wilderness Haleakala NP Craters of the Moon NM Hells Canyon Sawtooth NF Starkey HerculesGlades Sikes Upper Buffalo WA CANY1 CAPI1 GRCA2 WEMI1 ZION1 COGO1 CORI1 BRIG1 SWAN1 GRBA1 JARB1 HALE1 CRMO1 HECA1 SAWT1 STAR1 HEGL1 SIKE1 UPBU1 NM UT UT AZ AZ Central Rockies Central Rockies Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau NJ Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau Colorado Plateau Columbia River Gorge Columbia River Gorge East Coast NC NV NV East Coast Great Basin Great Basin HI ID Hawaii Hells Canyon OR ID OR MO Hells Canyon Hells Canyon Hells Canyon Mid South LA AR Mid South Mid South CO UT WA BALD1 Wilderness Wichita Mountains Mount Baldy GICL1 Gila Wilderness NM HILL1 Hillside AZ PEFO1 Petrified Forest NP Sierra Ancha AZ Sycamore Canyon Tonto NM AZ ME NY ME ME MA NY Northeast Northeast Northeast Northeast NH Northeast VT Northeast ME Northeast ME ME MA Northeast Northeast Northeast BADL1 Acadia NP Addison Pinnacle Bridgton Casco Bay Cape Cod Connecticut Hill Great Gulf Wilderness Lye Brook Wilderness Moosehorn NWR Old Town Presque Isle Quabbin Summit Badlands NP Mongollon Plateau Mongollon Plateau Mongollon Plateau Mongollon Plateau Mongollon Plateau Mongollon Plateau Mongollon Plateau Northeast Northeast SD LOST1 Lostwood ND MELA1 Medicine Lake MT THRO1 Theodore Roosevelt UL Bend ND Northern Great Plains Northern Great Plains Northern Great Plains Northern Great Plains Northern Great Plains WIMO1 SIAN1 SYCA1 TONT1 ACAD1 ADPI1 BRMA1 CABA1 CACO1 COHI1 GRGU1 LYBR1 MOOS1 OLTO1 PRIS1 QURE1 ULBE1 OK Mid South AZ AZ AZ MT WICA1 Wind Cave SD BRID1 WY GLAC1 Bridger Wilderness Cabinet Mountains Gates of the Mountains Glacier NP MONT1 Monture MT NOAB1 North Absaroka WY SULA1 Sula Peak MT YELL2 WY SPOK1 WHPA1 CADI1 Yellowstone NP 2 Mount Rainier NP Pasayten Snoqualmie Pass Spokane Res. White Pass Cadiz LIVO1 Livonia IN MACA1 MING1 Mammoth Cave KY NP Mingo MO MKGO1 M.K. Goddard PA QUCI1 Quaker City OH BLIS1 Bliss SP (TRPA) CA KALM1 Kalmiopsis OR LABE1 Lava Beds NM CA CABI1 GAMO1 MORA1 PASA1 SNPA1 WA Northern Great Plains Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northwest WA WA Northwest Northwest WA WA KY Northwest Northwest Ohio River Valley Ohio River Valley Ohio River Valley Ohio River Valley Ohio River Valley Ohio River Valley Oregon and Northern California Oregon and Northern California Oregon and Northern California MT MT MT LAVO1 Lassen Volcanic NP CA MOHO1 Mount Hood OR THSI1 Three Sisters Wilderness OR TRIN1 Trinity CA PHOE1 PUSO1 DOME1 AZ WA CA KAIS1 Phoenix Puget Sound Dome Lands Wilderness Kaiser SEQU1 Sequoia NP CA YOSE1 Yosemite NP CA CHAS1 FL FL GA Southeast Southeast SC Southeast QUVA1 Chassahowitzka NWR Everglades NP Okefenokee NWR Cape Romain NWR Queen Valley Oregon and Northern California Oregon and Northern California Oregon and Northern California Oregon and Northern California Phoenix Puget Sound Sierra Nevadas Sierra Nevadas Sierra Nevadas Sierra Nevadas Southeast AZ SAGU1 Saguaro NM AZ AGTI1 Agua Tibia CA JOSH1 Joshua Tree NP CA SAGO1 San Gorgonio Wilderness Virgin Islands NP Washington D.C. Salt Creek CA Southern Arizona Southern Arizona Southern California Southern California Southern California Virgin Islands EVER1 OKEF1 ROMA1 VIIS1 WASH1 SACR1 CA VI DC NM Washington D.C. West Texas Unaffected Regions: Death Valley Region Lone Peak Region Example: Figure 6. The numbers of samples with Al concentrations above detection limit were significantly lower for various periods during 2001 compared to other years of operation at a large number of sites. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE or XRF, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 7. There were low above detection counts for Al at a large number of sites in 2002. Fe concentrations show no significant decrease during the same period indicating that soil concentrations were typical during this period, assuming a soil source for the Fe. There was not a set block of time affected at all sites. In almost all cases the problem persisted from 2001 into early 2002, but the exact duration varied from site to site. All sites are identified in the attached PowerPoint files with royal blue rectangles. Affected Sites: Site Code Site Name State DENA1 TRCR1 LIGO1 SHEN1 SHRO1 Denali NP Trapper Creek Linville Gorge Shenandoah NP Shining Rock Wilderness Boundary Waters Canoe Area Seney AK AK NC VA NC BOWA1 SENE1 VOYA2 ROMO1 WHRI1 BRCA1 CANY1 COGO1 BRIG1 SWAN1 CRMO1 SAWT1 STAR1 HEGL1 SIKE1 BRMA1 MN Boundary Waters MI NJ Boundary Waters Boundary Waters Central Rockies Central Rockies Colorado Plateau Colorado Plateau Columbia River Gorge East Coast NC ID East Coast Hells Canyon ID OR MO Hells Canyon Hells Canyon Mid South LA ME Mid South Northeast Voyageurs NP MN #2 Rocky CO Mountain NP White River NF CO Bryce Canyon NP Canyonlands NP Columbia Gorge #1 Brigantine NWR Swanquarter Craters of the Moon NM Sawtooth NF Starkey HerculesGlades Sikes Bridgton IMPROVE Region Alaska Alaska Appalachia Appalachia Appalachia UT UT WA GRGU1 Great Gulf Wilderness Lye Brook Wilderness Old Town UL Bend NH Northeast VT Northeast ME MT WY GLAC1 Bridger Wilderness Cabinet Mountains Gates of the Mountains Glacier NP MONT1 Monture MT NOAB1 North Absaroka WY SULA1 Sula Peak MT YELL2 WY WA WA WA WA Northwest Northwest Northwest SPOK1 WHPA1 KALM1 Yellowstone NP 2 Mount Rainier NP Olympic Pasayten Snoqualmie Pass Spokane Res. White Pass Kalmiopsis Northeast Northern Great Plains Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northern Rockies Northwest WA WA OR MOHO1 Mount Hood OR THSI1 Three Sisters Wilderness OR SEQU1 Sequoia NP CA SAGO1 San Gorgonio Wilderness Virgin Islands NP CA Northwest Northwest Oregon and Northern California Oregon and Northern California Oregon and Northern California Sierra Nevadas Southern California Virgin Islands LYBR1 OLTO1 ULBE1 BRID1 CABI1 GAMO1 MORA1 OLYM1 PASA1 SNPA1 VIIS1 MT MT MT VI Unaffected Regions: California Coast Region Central Great Plains Region Death Valley Region Great Basin Region Hawaii Region Lone Peak Region Mongollon Plateau Region Ohio River Valley Region Phoenix Region Puget Sound Region Southeast Region Southern Arizona Region Washington DC Region West Texas Region Example: Figure 7. The numbers of samples with Al concentrations above detection limit were significantly lower for various periods during 2002 compared to other years of operation at a large number of sites. The analysis method mentioned below applies to the time period of interest shown in the figure. AlfVal: Aluminum concentration as measured by XRF, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 8. Low Al above detection counts at all sites in spring 2003. Fe concentrations show no significant decrease during the same period indicating that soil concentrations were typical during this period, assuming a soil source for the Fe. The missing Al has been attributed by CNL to a failing detector on the XRF system. The problem is not obvious at all sites, but is assumed to have affected all sites to varying degrees. All sites are identified in the attached PowerPoint files with royal blue rectangles. Affected Sites: entire network Example: Figure 8. The numbers of samples with Al concentrations above detection limit were significantly lower during spring 2003 compared to other years of operation at most sites. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by XRF, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 9. Seasonality of the Ca/Fe, Si/Fe, Ti/Fe and to a lesser degree Al/Fe enrichment factors (e.g. [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock) is present to varying degrees at all sites. The seasonality in the enrichment factors may be a reflection of natural shifts in aerosol source. However, the seasonality of the SO4/S ratio and the soil element enrichment factors seems to imply a potential analytical problem related to the XRF and PIXE systems. The affected sites are not identified in the attached PowerPoint files. Affected Sites: entire network Examples: Figure 9 a-d. The seasonality in the enrichment factors can be very pronounced for some soil elements at some sites. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE or XRF, [Al] in ug/m3 SifVal: Silicon concentration as measured by PIXE or XRF, [Si] in ug/m3 TifVal: Titanium concentration as measured by PIXE or XRF, [Ti] in ug/m3 CafVal: Calcium concentration as measured by PIXE or XRF, [Ca] in ug/m3 FefVal: Iron concentration as measured by PIXE or XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Si EF: Silicon Enrichment Factor, Si EF = [Si]/[Fe] aerosol / [Si]/[Fe] average crustal rock Ti EF: Titanium Enrichment Factor, Ti EF = [Ti]/[Fe] aerosol / [Ti]/[Fe] average crustal rock Ca EF: Calcium Enrichment Factor, Ca EF = [Ca]/[Fe] aerosol / [Ca]/[Fe] average crustal rock Anomaly 10. There is decreased range and variability in the Ti enrichment factor with the introduction of XRF. The period 95-late 01 seems to be particularly noisy at all sites and 93-95 at a smaller number of sites. Increased Ti concentrations are also present during this period at a number of sites, but not all. There were apparently a number of changes in PIXE hardware and operating procedures which may be responsible for the observed noisiness in the Ti data during that period. Changes included updating the data acquisition hardware, changes in the energy setting on the PIXE beam and a failing PIXE detector. Another possible explanation could be variable Ti contamination of either the PIXE system or the sampling media The affected sites are identified in the attached PowerPoint files with pink rectangles. Affected Sites: Entire network Examples: Figure 10 a-b. The increased range and variability of the Ti enrichment factor and increased Ti concentrations during the period 1993-2001 can be seen at WASH1. Ti measured by XRF has much less variability in its relative concentration compared to Fe than does Ti measured by PIXE. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: TifVal: Titanium concentration as measured by PIXE or XRF, [Ti] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Ti EF: Titanium Enrichment Factor, Ti EF = [Ti]/[Fe] aerosol / [Ti]/[Fe] average crustal rock Anomaly 11. There was increased range and variability in the Si enrichment factor from approximately late 1994 through 2000 at a select few sites. The very limited spatial distribution suggests that this anomaly could be real. The affected sites are identified in the attached PowerPoint files with green rectangles. Affected Sites: Site Code Site Name State PORE1 Point Reyes National Seashore Mount Rainier NP Crater Lake NP CA Redwood NP CA MORA1 CRLA1 REDW1 IMPROVE Region California Coast WA Northwest OR Oregon and Northern California Oregon and Northern California Example: Figure 11. The increased range and variability of the Si enrichment factor during the period late 1994-1999 can be seen at MORA1. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: SifVal: Silicon concentration as measured by PIXE, [Si] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Si EF: Silicon Enrichment Factor, Si EF = [Si]/[Fe] aerosol / [Si]/[Fe] average crustal rock Anomaly 12. There was increased range and variability in the Si enrichment factor from approximately early 2001 or mid 2002 through 2003 at a limited number of sites. The affected sites are identified in the attached PowerPoint files with red rectangles. Affected Sites early 2001-2003 Site Code Site Name State DOSO1 Dolly Sods Wilderness Hawaii Volcanoes NP Upper Buffalo Wilderness Mammoth Cave NP Chassahowitzka NWR Okefenokee NWR WV IMPROVE Region Appalachia HI Hawaii AR Mid South KY FL Ohio River Valley Southeast GA Southeast HAVO1 UPBU1 MACA1 CHAS1 OKEF1 Affected Sites mid 2002-2003 Site Code Site Name State COHU1 GRSM1 Cohutta Great Smoky Mountains NP Linville Gorge Shenandoah NP Shining Rock Wilderness Sipsy Wilderness Brigantine NWR Swanquarter Caney Creek Everglades NP Cape Romain NWR St. Marks GA TN IMPROVE Region Appalachia Appalachia NC VA Appalachia Appalachia NC Appalachia AL Appalachia NJ East Coast NC AR FL East Coast Mid South Southeast SC Southeast FL Southeast LIGO1 SHEN1 SHRO1 SIPS1 BRIG1 SWAN1 CACR1 EVER1 ROMA1 SAMA1 WASH1 Washington D.C. DC Unaffected Regions Alaska Region Boundary Waters Region California Coast Region Central Great Plains Region Central Rockies Region Colorado Plateau Region Columbia River Gorge Region Death Valley Region Great Basin Region Hells Canyon Region Lone Peak Region Mongollon Plateau Region Northeast Region Northern Great Plains Region Northern Rockies Region Northwest Region Oregon and Northern California Region Phoenix Region Puget Sound Region Sierra Nevada Region Southern California Region Southern Arizona Region Virgin Islands Region West Texas Region Washington D.C. Examples: Figure 12 a-b. The increased range and variability of the Si enrichment factor during the period 2001-2003 can be seen at DOSO1 and 2002-2003 at SIPS1. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: SifVal: Silicon concentration as measured by PIXE or XRF, [Si] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Si EF: Silicon Enrichment Factor, Si EF = [Si]/[Fe] aerosol / [Si]/[Fe] average crustal rock Anomaly 13. Three east coast sites, CHAS1, ROMA1, and SWAN1, had extremely poor agreement between SO4 and S measurements and reconstructed fine mass with measured fine mass during mid-late 2003. During the same period the Al concentrations are low relative to the Fe concentrations. It is suspected that sampling problems were responsible for the decreasing concentrations of all parameters sampled on module A at CHAS1 and SWAN1. Sampling problems may also exist for one or more of the modules at the other sites. In trying to find the cause of the anomalously high SO4/ S ratios at these sites, it was discovered that the samplers had clogged inlet(s). Flow rates were unaffected, so it appears that the clogging material was filtering out the aerosols. The clogged inlets at CHAS1 and SWAN1 were replaced. The clogged inlets have been returned to the laboratory and are being used to investigate the problem. Results from these studies as well as a full listing of affected sites are not currently available. The data for CHAS1 and SWAN1 are being withheld pending further review from 3/2003 and 8/2003 forward respectively. The data from the other sites listed here will continue to be available unless continued testing indicates that it should be invalidated. The affected sites are identified in the attached PowerPoint files with yellow rectangles. Affected Sites: Site Code Site Name SWAN1 CHAS1 ROMA1 State Swanquarter NC Chassahowitzka FL NWR Cape Romain SC NWR IMPROVE Region East Coast Southeast Southeast Examples: Figure 13. CHAS1, SWAN1, and ROMA1 all had very disagreements between SO4 and S and RCFM and FM during 2003. Al data also looks to be questionable during this period. Legend: AlfVal: Aluminum concentration as measured by PIXE or XRF, [Al] in ug/m3 FefVal: Iron concentration as measured by PIXE or XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 14. There were low above detection counts for Al at two coastal northern California sites from 6/1996-12/2001. Fe concentrations show no significant decrease during the same period indicating that soil concentrations were typical during this period, assuming a soil source for the Fe. Total and relative Ca concentrations are normal during this period supporting the supposition that soil concentrations were normal. Ti and Si relative concentrations were elevated during this period, but those issues were not limited to these two sites (see anomalies 10 and 11). All sites are identified in the attached PowerPoint files with bright green rectangles. Affected Sites: Site Code PORE1 REDW1 Site Name Point Reyes National Seashore Redwood NP State CA IMPROVE Region California Coast CA Oregon and Northern California Example: Figure 14. The numbers of samples with Al concentrations above detection limit were significantly lower from 1996-2001 compared to all other years of operation at PORE1 and REDW1. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 15. There was an increase in Al relative to Fe at CRLA1 from 4/1999-2/2000. The site is identified in the attached PowerPoint files with a violet rectangle. Affected Site: Site Code CRLA1 Example: Site Name State Crater Lake NP OR IMPROVE Region Oregon and Northern California Figure 15. The Al concentrations relative to Fe concentrations were significantly higher from 4/1999-2/2000 at CRLA1. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE, [Al] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Anomaly 16. There was reduced range in the Fe concentrations from 8/2000-12/2003 without a corresponding decrease in range in Al, CA, Ti or Si concentrations at BOWA1. The site is identified in the attached PowerPoint files with an orange rectangle. Affected Site: Site Code BOWA1 Examples: Site Name State Boundary Waters Canoe Area MN IMPROVE Region Boundary Waters Figure 16 a-d. The Fe concentrations relative to Al, Ca, Si, and Ti concentrations were significantly reduced in variability from late 2000 through 2003 at BOWA1. The analysis method mentioned below applies to the time period of interest shown in the figure. Legend: AlfVal: Aluminum concentration as measured by PIXE or XRF, [Al] in ug/m3 SifVal: Silicon concentration as measured by PIXE or XRF, [Si] in ug/m3 TifVal: Titanium concentration as measured by PIXE or XRF, [Ti] in ug/m3 CafVal: Calcium concentration as measured by PIXE or XRF, [Ca] in ug/m3 FefVal: Iron concentration as measured by XRF, [Fe] in ug/m3 Al EF: Aluminum Enrichment Factor, Al EF = [Al]/[Fe] aerosol / [Al]/[Fe] average crustal rock Si EF: Silicon Enrichment Factor, Si EF = [Si]/[Fe] aerosol / [Si]/[Fe] average crustal rock Ti EF: Titanium Enrichment Factor, Ti EF = [Ti]/[Fe] aerosol / [Ti]/[Fe] average crustal rock Ca EF: Calcium Enrichment Factor, Ca EF = [Ca]/[Fe] aerosol / [Ca]/[Fe] average crustal rock Attachments For individual charts for each site please refer to the following associated files: Al_88-03.ppt Al_98-03.ppt Ca_88-03.ppt Ti_88-03.ppt Si_88-03.ppt Soil_88-03.ppt
