MARGA Field Performance Evaluation

Update: April 2012

The two MARGA systems (MARGA-1 and MARGA-2) were installed at the BEL116 CASTNET site at the end of 2011 and have been undergoing maintenance and replacement of the analytical modules. As of April 1, MARGA-2 is collecting ambient concentration measurements and the results are being evaluated for consistency and stability. Additional parts are needed for MARGA-1, but it is expected to be operational by the end of April.

ORD continues to assess the applicability of the MARGA 2S, a direct flux measurement system, at the Duke Forest research site in NC. An update on the status of the MARGA 2S field project will be given at the Total Deposition Science Committee meeting (April 23^rd, Portland, OR).

Update: December 2011

Installation of the two MARGA systems at the BEL116, MD site has been completed. Internet access was connected to the instrument laptops for real time, remote data access. A laboratory space was created at a nearby facility for preparing solutions and washing the glassware. Performance quality solutions have been prepared at the lab and transported to the site, where quality assurance tests using the manufacturer's recommended data quality objectives are currently in progress. The first step is to test the analytical response of the MARGAs with an internal standard solution and standards of ammonium sulfate ((NH₄)₂SO₄), potassium chloride (KCl), and ammonium nitrate (NH₄NO₃) in concentrations assumed to bracket typically observed atmospheric concentration levels. The next steps will be for the MARGAs to undergo a field performance evaluation.

The objectives of the Field Performance Evaluation are:

• to re-establish the operational performance of the MARGAs observed in the ETV,
• to make improvements in the MARGA performance especially with regards to the quanitification of ammonia (NH₃) and ammonium (NH₄⁺) and nitrate (NO₃^-) and nitric acid (HNO₃),
• to better characterize the MARGA performance by evaluation with different reference methods including weekly CASTNET filterpack measurements and hourly trace-gas concentrations for SO₂ and NO_y,
• to characterize operational issues and time-demand associated with routine maintenance and troubleshooting in determining implementation of the MARGA in future monitoring efforts.

Current collaborators in this project include:

• U.S. EPA Office of Research and Development
• U.S. Department of Agriculture/Agricultural Research Service

Update: October 2011

The Monitor for AeRosols and GAses (MARGA) is a multi-pollutant semi-continuous instrument being tested for use in routine network operations at the Beltsville, MD CASTNET site (BEL116).

Installation of two MARGA systems at BEL116 is almost complete. The MARGA systems were moved to the site from EPA's ORD monitoring station in RTP, NC. The next steps for the MARGA include:

• Calibrating the instruments using internal and external standards,
• setting up an internet connection to get real-time measurements from the site,
• and comparing the MARGA results with the trace gas SO2 monitor and CASTNET filterpack measurements from the BEL116 site.

Updates on the MARGA study will continue to be provided on this site periodically.

CASTNET Ammonia Special Study (ACCS)

Update: March 2013

The ACCS began in August 2010 and the last sample was collected in October 2011. Final data, including ambient NH₃ concentrations and laboratory and field blanks, have been submitted to EPA. Preliminary results from the AMoN Radiello samplers versus duplicate annular denuders (reference method) from the five sites are described below.

The mean absolute relative percent difference (MARPD) between the passive samplers and the annular denuders from the five sites was 20%. MARPDs between individual sites ranged from 11% (Palo Duro, TX) to 46% (Connecticut Hill, NY). The left figure below shows the bi-weekly NH₃ concentrations as measured by AMoN and the average concentrations over the 2 one-week denuder sampling periods for each site. Concentrations ranged from less than 0.5 ug/m³ (Connecticut Hill, NY and Rocky Mountain National Park, CO) to 4.5 ug/m³ (Palo Duro, TX). The figure to the right shows the 2-week average NH₃ concentrations from AMoN versus the annular denuders for the 5 ACCS sites. There is good correlation (0.96) between the two sampling methods for the range of concentrations measured during the year sampling period.

The precision of the duplicate denuder systems at the five sites was 10%. Triplicate Radiello passive samplers were deployed at the five AMoN sites during the ten ACCS sampling periods. The precision of the triplicate samplers was 12% and comparable to previous quality control studies performed by the NADP.

Update: April 2012

Preliminary results from the ACCS were presented at the NADP Total Deposition Science Committee Meeting in Providence, RI (Oct. 2011). The preliminary results showed AMoN samplers compared well with the URG annular denuders, while the Super SASS mini-parallel plate denuders were likely biased low at CHE185 and ROM206.

In addition to the ammonia analysis, ion concentrations measured with the CASTNET filter pack were compared with those measured with the Super SASS ion canisters (routinely used in the Chemical Speciation Network). Preliminary results showed good agreement for gasesous SO₂ between the filter pack and the ion canisters, but comparison for the particulates (NO₃^- and NH₄⁺) showed the ion canisters was biased low when compared to the filter pack. We believe this bias may be attributable to the cut-point. The Super SASS uses a Teflon cyclone with a 2.5μm cut-point while the filter pack is an open-faced surface, which likely allows larger particles to collect on the filters.

Final results will be published in two journal articles, one providing the results from the ammonia study and the other showing the results from the ion comparison.

The presentation with the preliminary results from both the ammonia and ion studies can be found on the NADP website here.

Update: November 2011

Ambient ammonia (NH₃) concentrations are not routinely measured at CASTNET, Chemical Speciation Network (CSN) or NCore sites, which results in a significant gap in our understanding of the total nitrogen budget. In some areas, NH₃ dry deposition is estimated to be approximately 30% of the total deposited nitrogen (eg. Rocky Mountain NP). The Ammonia Monitoring Network (AMoN), a newly formed sub-network within the NADP, measures ambient NH₃ concentrations at approximately 50 sites throughout the US.

This study was developed to validate the passive Radiello samplers deployed in the AMoN, to characterize the sulfur and nitrogen species collected on the CASTNET filter pack and the ion canisters from the Super SASS (used in the CSN), and evaluate a newly developed mini-parallel plate denuder (MPPD) for measuring NH₃ in one of the channels of the Super SASS. To accomplish these goals, a five site study (site locations indicated on the map below) plan was developed. The first sampling period began in August 2010, and the study was completed in September 2011. To stay within budget, two week sample deployments occurred every 6 weeks for a total of 10 sampling time periods. Each site was collocated with AMoN, which provided a two week NH₃ concentration. All AMoN samplers were prepared, shipped and analyzed by NADP’s Central Analytical Laboratory. AMoN data are processed and posted to the NADP AMoN website routinely. In addition to the passive samplers, each of the five sites also deployed two consecutive 1-week annular denuders systems (ADS) as the reference method. Three sites deployed two consecutive 1-week MPPDs housed within the Super SASS module and two consecutive 1-week ion canisters. The MPPDs are being tested for routine use in the CSN for capturing 24-hour NH₃ concentrations. The dual ADS systems were analyzed for a full suite of anions and cations for comparison to the CASTNET filter pack and Super SASS ion measurements. The ion canisters were analyzed by RTI for the non-NH₃ analytes. A summary of the study sites are shown in the table below.

Preliminary results show a good comparison between the ADS and AMoN samplers. Comparisons between the MPPDs and the ADS are variable, but this may be a result of invalid flow at the Rocky Mountain NP (ROM206/406) site. Updates will be provided here and the final results will be published in peer-reviewed journal articles.

Funding for this study was provided by EPA’s Office of Research and Development, Clean Air Markets Division and Office of Air Quality Planning and Standards (OAQPS). The Super SASS systems were provided by OAQPS.

Ameriflux Deposition Study

Update: October 2011

CASTNET will be conducting a direct deposition study at the Howland, ME Ameriflux site. The study includes two filterpacks installed above and below the forest canopy at sampling heights of 20.5 and 2 m, respectively, and a multi-stage, solenoid-switch ozone sampling system with inlets at eight different heights; 28, 23.5, 20.5 (just above canopy), 17 (just below canopy), 14.5, 10, 6 and 2 m. The heights were chosen based on the vegetation in the area, represented by Leaf Air Index (LAI) and is represented in the figure below.

The objective of the study is the monitor differences at various heights presumably due to dry deposition on an hourly basis for ozone and on a weekly basis for the suite of pollutants sampled with the filterpack. The study is being coordinated by CAMD, EPA's Office of Research and Development (ORD), Mactec and the State of Maine. In addition to the direct deposition study, a comparison between the current CASTNET site (HOW132) and the Ameriflux site (HOW191) will run from September 2011 - September 2012 to determine if any biases would be introduced if the HOW132 site is permanently moved to the Ameriflux site. Additional information about the Howland Ameriflux site can be found here: Ameriflux at Howland, ME

Differences in ozone concentrations will be calculated at the different inlet heights to estimate the deposition flux, above and below the canopy. In addition, CASTNET filterpacks will be deployed on the normal Tuesday - Tuesday CASTNET schedule.