NASA/TMm2000-209891, Vol. 242

Technical Report Series on the

Boreal Ecosystem-Atmosphere Study (BOREAS)

Forrest G. Hall and Sara K. Conrad, Editors

Volume 242

BOREAS TGB-10 Oxidant Flux Data

over the SSA

Hal Westberg and Brad Hall, Washington State University, Pullman

Andrea V. Jackson, Lancaster University, UK

National Aeronautics and

Space Administration

Goddard Space Flight Center

Greenbelt, Maryland 20771

November 2000

https://ntrs.nasa.gov/search.jsp?R=20010022511 2018-05-14T19:05:21+00:00Z
The NASA STI Program Office ... in Profile

Since its founding, NASA has been dedicated to

the advancement of aeronautics and space

science. The NASA Scientific and Technical

Information (STI) Program Office plays a key

part in helping NASA maintain this important

role.

The NASA STI Program Office is operated by

Langley Research Center, the lead center for

NASA's scientific and technical information. The

NASA STI Program Office provides access to

the NASA STI Database, the largest collection of

aeronautical and space science STI in the world.

The Program Office is also NASA's institutional

mechanism for disseminating the results of its

research and development activities. These

results are published by NASA in the NASA STI

Report Series, which includes the following

report types:

• TECHNICAL PUBLICATION. Reports of

completed research or a major significant

phase of research that present the results of

NASA programs and include extensive data or

theoretical analysis. Includes compilations of

significant scientific and technical data and

information deemed to be of continuing

reference value. NASA's counterpart of

peer-reviewed formal professional papers but

has less stringent limitations on manuscript

length and extent of graphic presentations.

• TECHNICAL MEMORANDUM. Scientific

and technical findings that are preliminary or

of specialized interest, e.g., quick release

reports, working papers, and bibliographies

that contain minimal annotation. Does not

contain extensive analysis.

• CONTRACTOR REPORT. Scientific and

technical findings by NASA-sponsored

contractors and grantees.

CONFERENCE PUBLICATION. Collected

papers from scientific and technical

conferences, symposia, seminars, or other

meetings sponsored or cosponsored by NASA.

SPECIAL PUBLICATION. Scientific, technical, or historical information from NASA

programs, projects, and mission, often concerned with subjects having substantial public

interest.

TECHNICAL TRANSLATION.

English-language translations of foreign scientific and technical material pertinent to NASA's

mission.

Specialized services that complement the STI

Program Office's diverse offerings include creating custom thesauri, building customized databases, organizing and publishing research results...

even providing videos.

For more information about the NASA STI Prograin Office, see the following:

Access the NASA STI Program Home Page at

http://www, sti.nasa.gov/STI-homepage.html

E-mail your question via the Internet to

help@ sti.nasa.gov

Fax your question to the NASA Access Help

Desk at (301) 621-0134

• Telephone the NASA Access Help Desk at

(301) 621-0390

Write to:

NASA Access Help Desk

NASA Center for AeroSpace Information

7121 Standard Drive

Hanover, MD 21076-1320
NASA/TMm2000-209891, Vol. 242

Technical Report Series on the

Boreal Ecosystem-Atmosphere Study (BOREAS)

Forrest G. Hall and Sara K. Conrad, Editors

Volume 242

BOREAS TGB-10 Oxidant Flux Data

over the SSA

Hal Westberg and Brad Hall, Washington State University, Pullman

Andrea V. Jackson, Lancaster University, UK

National Aeronautics and

Space Administration

Goddard Space Flight Center

Greenbelt, Maryland 20771

November 2000
NASA Center for AeroSpace Information

7121 Standard Drive

Hanover, MD 21076-1320

Price Code: A17

Available from:

National Technical Information Service

5285 Port Royal Road

Springfield, VA 22161

Price Code: A10
BOREAS TGB-10 Oxidant Flux Data over the SSA

Hal Westberg, Brad Hall, Andrea V. Jackson

Summary

The BOREAS TGB-10 team collected several trace gas data sets in its efforts to determine the role of

biogenic hydrocarbon emissions with respect to boreal forest carbon cycles. This oxidant data set

contains measured peroxide (H202 and total organic peroxides (ROOH)) and ozone concentrations as

well as H202 and ROOH deposition velocities. These data were obtained at the SSA-OJP site during

the summer of 1994. Measurements were made from May to September 1994. The data are stored in

tabular ASCII files.

Some important results were:

• Ozone concentrations were consistently low, 20-30 ppb, during the summer of 1994.

• Peroxide concentrations showed a seasonal variation with highest concentrations occurring in

July (IFC-2).

• Midday H202 levels averaged around 1.4 ppb during IFC-2 and 0.4-0.5 ppb during IFC's 1

and 3.

• Midday organic peroxide concentrations were lower, averaging 0.8 ppb during IFC-2, and

0.4-0.5 ppb during IFC's 1 and 3.

• The rough pine forest canopy serves as a significant sink for H202.

• Midday H202 deposition velocities averaged 4-7 cm/s.

• Organic peroxide deposition velocities (measured as total ROOH) were approximately 40% as

large as those of H202.

Table of Contents

1) Data Set Overview

2) Investigator(s)

3) Theory of Measurements

4) Equipment

5) Data Acquisition Methods

6) Observations

7) Data Description

8) Data Organization

9) Data Manipulations

10) Errors

11) Notes

12) Application of the Data Set

13) Future Modifications and Plans

14) Software

15) Data Access

16) Output Products and Availability

17) References

18) Glossary of Terms

19) List of Acronyms

20) Document Information

Page 1
1. Data Set Overview

1.1 Data Set Identification

BOREAS TGB- 10 Oxidant Flux Data over the SSA

1.2 Data Set Introduction

The BOReal Ecosystem-Atmosphere Study (BOREAS) Trace Gas Biogeochemistry (TGB)-10

team collected oxidant flux data at the Southern Study Area (SSA) Old Jack Pine (OJP) site during the

growing season of 1994. Ambient hydrogen peroxide and organic peroxides concentrations were

determined by high performance liquid chromatography (HPLC) with fluorometric detection.

Formaldehyde monitoring was performed based on the reaction of formaldehyde with

dinitrophenylhydrazine (DNPH).

1.3 Objective/Purpose

Emission/deposition rates of biogenic hydrocarbons (or volatile organic carbon (VOC)) and

oxidants (hydrogen peroxide and ozone) were measured along with ambient concentrations of biogenic

hydrocarbons, hydrogen peroxide, and organic hydroperoxides. We will use these data to examine (a)

the role of biogenic hydrocarbon emissions with respect to carbon cycles in the boreal forest, (b) the

chemical fate of boreal biogenic emissions, (c) the hypothesis that biospheric VOC emissions

contribute to peroxide formation, and (d) the deposition rates of hydrogen peroxide and organic

peroxides.

1.4 Summary of Parameters

Investigations of tropospheric concentration gradients of hydrogen peroxide and organic

hydroperoxides in a boreal forest.

1.5 Discussion

None given.

1.6 Related Data Sets

BOREAS TGB-08 Monoterpene Concentration Data over the SSA

BOREAS TGB-08 Photosynthesis Data over the SSA

BOREAS TGB-08 Starch Data over the SSA

BOREAS TGB-09 Above Canopy Non-Methane Hydrocarbon Data over the SSA

BOREAS TGB-10 Oxidant Concentration Data over the SSA

BOREAS TGB-10 Volatile Organic Carbon Data over the SSA

2. Investigator(s)

2.1 Investigator(s) Name and Title

Dr. Hal Westberg

Washington State University

Dr. Nick Hewitt

Lancaster University

2.2 Title of Investigation

Measurement of Biogenic Hydrocarbon Fluxes

Page 2
2.3 Contact Information

Contact 1: Biogenic Hydrocarbon Emissions

Dr. Hal Westberg

Dept. of Civil and Environmental Engineering

Washington State University

Pullman, WA 99164-2710

(509) 335-1529

(509) 335-7632 (fax)

westberg@mail.wsu.edu

Contact 2: Deposition of Hydrogen Peroxide

Brad Hall

(Dr. Candis Claiborn)

Dept. of Civil and Environmental Engineering

Washington State University

Pullman, WA 99164-2710

(509) 335-5553

(509) 335-7632 (fax)

bhall@lar.ce.wsu.edu

claiborn@wsu.edu

Contact 3: Hydrogen Peroxide and Hydroperoxides

Andrea V. Jackson

(Dr. Nick Hewitt)

Environmental Science Division

Institute of Environmental and Biological Sciences

Lancaster University

Lancaster LA1 4QY

United Kingdom

(44-1524)-843854 (fax)

andrea@lec.leeds.ac.uk

n.hewitt@lancaster.ac.uk

Contact 4:

Jeffrey A. Newcomer

Raytheon ITSS

Code 923

NASA GSFC

Greenbelt, MD 20771

(301) 286-7858

(301) 286-0239 (fax)

Jeffrey.Newcomer@ gsfc.nasa.gov

3. Theory of Measurements

The deposition velocity (Vd) of hydrogen peroxide is found from the eddy exchange coefficient and

the normalized gradient.

Vd = K*(dC/dz)/C (m/s)

where concentration is measured in ppbV.

Page 3
RelaxedEddyAccumulation(REA)MethodCanopy-scalefluxesof biogenichydrocarbonswere

determinedby theREAmethodattheOldBlackSpruce(OBS)site.Thesemeasurementswerecarried

outin cooperationwith Dr. ElizabethPattey(BOREASTowerFlux (TF)-07team).In thismethod,air

is sampledat aconstantrateandpartitionedintooneof twocontainers,contingentuponwhetherthe

verticalvelocitycomponentwaspositive(upward)ornegative(downward).Theflux is computed

from thefollowingexpression:

F = b*sw*(C2 - C1) (gC/m2/s)

whereb (dimensionless)is aweakfunctionof stability(determinedby eddycorrelationmeasurements

of heat,watervapor,or CO2flux), sw(m/s)is thestandarddeviationof verticalwind speed,andC2

andC1(g C/ln3)aretheconcentrationsin the"upward"and"downward"containers,respectively.For

amorecompletedescriptionof theREAmethod,oneshouldconsulttheTF-07documentation.

HydrogenPeroxideandOrganicPeroxideMeasurementsAmbienthydrogenperoxideandorganic

peroxidesconcentrationsweredeterminedby HPLCwith fluorometricdetection.Thedetectionmethod

is similarto thatdescribedin theprevioussection.

FormaldehydeMonitoringThereactionof formaldehydewith DNPHwasthebasisfor the

measurementprocedureusedduringthisstudy.

4. Equipment

4.1 Sensor/Instrument Description

Hydrogen peroxide was measured by the dual-channel, enzyme-catalyzed, fluorometric method.

The instrument was constructed at Washington State University (WSU), following the procedure

outlined by K&K Instruments; Boulder, Colorado (Lazrus et al., 1986). Ozone was measured with a

Dasibi 1003-AH ozone sensor.

4.1.1 Collection Environment

Tower-based measurements were conducted under ambient atmospheric conditions.

4.1.2 Source/Platform

All peroxide and ozone measurements were made from ground- and tower-mounted systems.

4.1.3 Source/Platform Mission Objectives

The objective of these experiments was to obtain canopy-scale fluxes of peroxides and

branch-scale fluxes of biogenic VOCs in a boreal environment.

4.1.4 Key Variables

Emissions and/or ambient concentrations of the following trace gases were measured:

• isoprene

• alpha-pinene

• beta-pinene

• limonene

• monoterpenes

• hydrogen peroxide

• methylhydroperoxide

• hydroxymethlyhydroperoxide

• ozone

4.1.5 Principles of Operation

See Section 3.

Page 4
4.1.6 Sensor/Instrument Measurement Geometry

Enclosure Sampling The instruments used for enclosure sampling were mounted on a

battery-powered portable cart. The bag enclosure was mounted on a tripod base, allowing access to

branches 1-3 meters from the ground.

Gradient Sampling Inlets were located on beams protruding 1 m off the west sides of the TF

towers. With winds predominately from the south, west, or north, the samples usually contained

unperturbed air. The inlet heights (above the forest floor) are summarized below.

OJP 16.5 m and 23.8 m Intensive Field Campaign (IFC)-I, IFC-2

OJP 17 .2 m and 23.8 m IFC-3

The lower inlet at the OJP site was raised prior to IFC-3 to alleviate possible influences of the

roughness sublayer.

4.1.7 Manufacturer of Sensor/Instrument

HP5890 gas chromatograph:

Hewlett Packard

15815 SE 37th St.

Bellevue, WA 98006

Dasibi 1003-AH ozone analyzer:

Dasibi Environmental

616 E. Colorado St.

Glendale, CA 91205

HP-3396A integrator:

Hewlett Packard

15815 SE 37th St.

Bellevue, WA 98006

The hydrogen peroxide system was custom-built at WSU:

WSU Technical Services

Washington State University

Pullman, WA 99164-2801

HPLC system:

Merck Ltd.

Merck House

Poole, Dorset

BH15 1TD, England

Data handling systems:

Labtech

400 Research Dr.

Wilmington, MA 01887

VG Data Systems

St. Georges Court

Hanover Business Park

Altrincham, Cheshire

WA14 5UG England

Page 5
4.2 Calibration

FormaldehydeHigh-purityformaldehyde-hydrazonewaspreparedby conventional methods for

use as a master standard. The master standard was diluted to concentrations of 0.2, 0.5, 1.0, 2.0, and

5.0 ppm to establish calibration curves.

Sensors for the peripheral environmental measurements were calibrated at WSU prior to the field

sampling program. Mass flow meters were tested against a precision wet-test meter at several flow

rates. The thermocouples and amplifiers were calibrated against a National Institute for Standards and

Technology (NIST) traceable mercury thermometer by measuring the response with all sensors

immersed in a stirred ice-water bath slowly warmed to approximately 45 °C. The humidity sensor was

compared to calculated values for air passed through a temperature-controlled water bath. All of the

sensor calibrations were performed using the PC laptop data system employed in the field.

Hydrogen peroxide The continuous hydroperoxide system was calibrated twice daily with liquid

standards of hydrogen peroxide in deionized water. The standards were prepared at the 10-8 M level

by serial dilution of a 30% H:O: reagent (Fisher). The concentration of the primary reagent was

determined by titration against KMnO4, which was then titrated against a NIST-traceable sodium

oxalate solution.

Line losses through the PFA Teflon tubing were measured before and after each IFC. A gas-phase

H202 generation system was used to produce a sample stream with near-ambient levels of H202. Line

losses were determined by sampling this stream with and without the tower sampling line. A critical

aspect of the peroxide gradient system is the potential for bias introduced in the two separate inlet

sections. Care was taken to ensure that bias introduced by the valve and 4-m inlet sections was

well-known and correctable. Relative bias was determined every few days by placing both inlets at the

same height and sampling ambient air for several hours. Subsequent gradients were corrected for bias,

which ranged from - 1 to 9%. When the bias surpassed 7%, samples were rejected and the valve and

sample lines were cleaned with methanol, deionized water, and peroxide-free air. After cleaning, bias

was reduced to a nondetectable level.

Hydroperoxides Peak identities were confirmed by comparison with retention times of authentic

standards. Quantification was based on system response to hydrogen peroxide, as the same fluorescent

dimer is formed for all hydroperoxides. Calibration was carried out twice daily and was found to be

linear over the range 8x10 8 M to 5x10 6 M. The limit of detection has been determined to be less than

50 pptv.

Ozone The Dasibi ozone monitor was calibrated against a Dasibi ozone source/monitor model

1008-PC (serial #3226).

4.2.1 Specifications

Hydrogen Peroxide The H202 gradient measurements were occasionally subject to bias. It was

extremely difficult to maintain clean sampling conditions at all times. Inlet filters cannot be used due to

the potential for severe H202 loss on filter surfaces. Periods of unacceptable bias were encountered

during the first IFC when the jack pine trees were pollinating, and occasionally during IFC-2 and

IFC-3 when bugs would collect in the sample lines. The sample lines were sequentially flushed with

methanol, water, and dry air periodically to remove dirt, pollen, and bugs.

Ozone The source instrument was recently compared to other instruments at the University of

Idaho, and was found to agree within 1-2 ppb.

4.2.1.1 Tolerance

None given.

4.2.2 Frequency of Calibration

Calibrations were performed before and after each IFC. Bias checks for peroxide gradients were

performed every few days during IFC-2 and IFC-3. No bias checks were performed during IFC-1.

4.2.3 Other Calibration Information

None given.

Page 6
5. Data Acquisition Methods

Hydrogen Peroxide and Organic Peroxide Measurements Air was drawn at 4 L/min from the inlet (24

m height) on the TF tower through 1/4" TFE Teflon tubing to the tower base, where a gas-phase

scrubber was used to scrub peroxides from the air stream. Samples were collected in 5 mL deionized

water. HPLC analysis was performed immediately after sample collection.

HPLC separation was achieved on an Absorbosphere MF Plus C18 column (Altech) using an

eluent of 0.001 M sulfuric acid and 0.0001 M EDTA delivered by a Merck-Hitachi L-6200 Intelligent

HPLC pump at a flow rate of 0.6 mL/min. After separation, the peroxides were derivatized by addition

of 0.026 M p-hydroxyphenylacetic acid with 10,000 units/L of horseradish peroxidase (type II Sigma

Chemical) in 0.5 M potassium hydrogen phthalate buffer at pH 5.8. The reaction of the fluorescence

reagent with the separated hydroperoxides takes place in a Teflon coil to ensure adequate mixing. The

pH of the resulting solution is raised to above 10 to convert the dimer to its fluorescent anionic form

using a membrane reactor constructed of Nation (DuPont) tubing immersed in 30% ammonium

hydroxide solution. Fluorescence measurements were made using a Merck-Hitachi spectrophotometer

with excitation and emission wavelengths of 310 and 405 nm, respectively. The HPLC analytical

system was located in the instrument hut.

Formaldehyde Monitoring The reaction of formaldehyde with DNPH was the basis for the

measurement procedure used during this study. A DNPH/silica cartridge was connected to the inlet end

of a 1/4" stainless steel tube extending to 3 m above the ground. The sample flow (1 L/min) was

generated with a small pump and monitored with a Matheson flow meter. A calibrated Tylan digital

totalizer was used to record the total volume sampled. The cartridges were exposed to the ambient air

for nominal durations of 2, 4, or 6 hours. Cartridges were brought back to WSU for analysis.

Sample and blank cartridges were eluted with 3 mL acetonitrile. Hydrazone concentrations in the

eluent were determined by reverse-phase HPLC. The HPLC analysis was performed using an LKB

modular system consisting of two pumps (LKB #2150), a 190-600 nm ultraviolet/visible wavelength

detector (LKB #2151) operated at 360 nm, and an LC gradient controller (LKB # 2152). A

Brownlee-Rainln 10-cm OD-MPS column (or comparable) with a hydrophobic, nonpolar stationary

phase (bonded on 5-micrometer spheres), preceded by a similar guard column was used for peak

separation. A gradient elution, beginning with a 50:50 water:acetonitrile ratio was used, changing to a

30:70 water:acetonltrile ratio over a period of 21 minutes. The column flow rate was 0.5 mL/min, and

the sample loop volume was 20 microliters.

Signals from the hydrogen peroxide and ozone instruments were stored as 1-minute averages via

PC. Data acquisition software from Labtech was used to record signals (voltages). The gas

chromatograph was interfaced to a pair of HP-3396A integrators for peak integration. Raw signals

were also stored via PC for data reprocessing. The HPLC system for hydroperoxides was interfaced

with a VG Data Systems Minlchrom data acquisition system for chromatography. The connection of

the HPLC to the data system was achieved using a chromatography server.

6. Observations

6.1 Data Notes

Hydrogen peroxide

Periods of unacceptable bias were encountered during the first IFC, when the jack pine trees were

pollinating, and occasionally during IFC-2 and IFC-3 when bugs would collect in the sample lines.

Ozone

Some problems with the electronic zero were detected during IFC- 1. An offset of -6 ppb relative to

the data acquisition system was discovered. This offset was easily measured on a daily basis, and

remained essentially unchanged throughout the experiment.

Page 7
6.2 Field Notes

Peroxide data were deemed questionable (QC = 2) or unacceptable (QC = 3) during the following

periods:

C *** QUALITY CONTROL (based local TIME and DAY)

25-May-1994 QC = 2 poor calibration

26-May-1994 QC = 2 poor calibration

27-May-1994 QC : 2 poor calibration

04-Jui-1994 QC : 3 extreme pollen event

05-Jui-1994 QC : 3 extreme pollen event

06-Jui-1994 QC : 2 moderate pollen event

09-Jui-1995 QC : 2 bias unknown

25-Jui-1994 QC : 2 poor calibration

31-Jui-1994 QC : 3 high noise level

04-Aug-1994 QC : 2 smoke

05-Aug-1994 QC : 2 smoke

06-Aug-1994 QC : 3 rain

01-Sep-1994 QC : 2 lost signal

02-Sep-1994 QC : 3 suspect line loss

7. Data Description

7.1 Spatial Characteristics

7.1.1 Spatial Coverage

Peroxide and ozone concentrations were measured at the OJP site only. The North American

Datum of 1983 (NAD83) coordinates for the site are:

SSA-OJP 53.98717N, I05.11779W

7.1.2 Spatial Coverage Map

Not available.

7.1.3 Spatial Resolution

The data represent point source values at the locations given.

7.1.4 Projection

Not applicable.

7.1.5 Grid Description

Not applicable.

7.2 Temporal Characteristics

7.2.1 Temporal Coverage

Measurements were taken at SSA-OJP from 25-May-1994 to 09-Sep-1994.

7.2.2 Temporal Coverage Map

None given.

Page 8
7.2.3 Temporal Resolution

Peroxide and ozone concentrations were measured continuously during daylight hours. In

addition, many overnight sampling periods were obtained. No regular intervals of data collection were

made at the site; however, data were collected on several days during the growing season of 1994.

7.3 Data Characteristics

7.3.1 Parameter/Variable

The parameters contained in the data files on the CD-ROM are:

Column Name

SITE NAME

SUB SITE

DATE OBS

TIME OBS

H202 CONC

ROOH CONC

H202 CONC GRAD

ROOH CONC GRAD

EDDY DIFF

MEAN H202 DEP VELOC

SDEV H202 DEP VELOC

MEAN ROOH DEP VELOC

SDEV ROOH DEP VELOC

QUALITY CODE

CRTFCN CODE

REVISION DATE

7.3.2 Variable Deseription/Definition

The descriptions of the parameters contained in the data files on the CD-ROM are:

Column Name Description

SITE NAME

SUB SITE

DATE OBS

TIME OBS

H202 CONC

ROOH CONC

H202 CONC GRAD

ROOH CONC GRAD

EDDY DIFF

The identifier assigned to the site by BOREAS, in

the format SSS-TTT-CCCCC, where SSS identifies the

portion of the study area: NSA, SSA, REG, TRN, and

TTT identifies the cover type for the site, 999 if

unknown, and CCCCC is the identifier for site,

exactly what it means will vary with site type.

The identifier assigned to the sub-site by BOREAS,

in the format GGGGG-IIIII, where GGGGG is the

group associated with the sub-site instrument,

e.g. HYD06 or STAFF, and IIIII is the identifier

for sub-site, often this will refer to an

instrument.

The date on which the data were collected.

The Greenwich Mean Time (GMT) when the data were

collected.

The hydrogen peroxide concentration.

The organic peroxide concentration.

Hydrogen peroxide concentration gradient.

The organic peroxide concentration gradient.

Eddy diffusivity for heat.

Page 9
MEAN H202 DEP VELOC

SDEV H202 DEP VELOC

MEAN ROOH DEP VELOC

SDEV ROOH DEP VELOC

QUALITY CODE

CRTFCN CODE

REVISION DATE

The mean deposition velocity of hydrogen peroxide.

The standard deviation of the deposition velocity

of hydrogen peroxide.

The mean deposition velocity of organic peroxides.

The standard deviation of the deposition velocity

of organic peroxides.

l:good data: normal operation, 2:good data: normal

operation, but uncertainties are greater due to

non-ideal sampling condition or equipment

function, 3:data questionable or possible

instrument malfunction

The BOREAS certification level of the data.

Examples are CPI (Checked by PI), CGR (Certified

by Group), PRE (Preliminary), and CPI-??? (CPI but

questionable).

The most recent date when the information in the

referenced data base table record was revised.

7.3.3 Unit of Measurement

The measurement units for the parameters contained in the data files on the CD-ROM are:

Column Name Units

SITE NAME

SUB SITE

DATE OBS

TIME OBS

H202 CONC

ROOH CONC

H202 CONC GRAD

ROOH CONC GRAD

EDDY DIFF

MEAN H202 DEP VELOC

SDEV H202 DEP VELOC

MEAN ROOH DEP VELOC

SDEV ROOH DEP VELOC

QUALITY CODE

CRTFCN CODE

REVISION DATE

[none]

[none]

[DD-MON-YY]

[HHMM GMT]

[parts per billion]

[parts per billion]

[parts per billion] [meter^-l]

[parts per billion] [meter^-l]

[meters^2] [second^-l]

[millimeters] [second^-l]

[millimeters] [second^-l]

[millimeters] [second^-l]

[millimeters] [second^-l]

[unitless]

[none]

[DD-MON-YY]

7.3.4 Data Source

The sources of the parameter values contained in the data files on the CD-ROM are:

Column Name Data Source

SITE NAME

SUB SITE

DATE OBS

TIME OBS

H202 CONC

ROOH CONC

H202 CONC GRAD

ROOH CONC GRAD

EDDY DIFF

Not applicable

Not applicable

Investigator

Investigator

Gas chromatograph

Gas chromatograph

Gas chromatograph

Gas chromatograph

PL Gas chromatograph

Page 10
MEAN H202 DEP VELOC

SDEV H202 DEP VELOC

MEAN ROOH DEP VELOC

SDEV ROOH DEP VELOC

QUALITY CODE

CRTFCN CODE

REVISION DATE

Gas chromatograph]

Gas chromatograph

Gas chromatograph

Gas chromatograph

Investigator

Not applicable

Not applicable

7.3.5 Data Range

The following table gives information about the p_ameter values found in the data files on the

CD-ROM.

Minimum Maximum Missng Unrel Below Data

Data Data Data Data Detect Not

Column Name Value Value Value Value Limit Cllctd

SITE NAME SSA-OJP-FLXTR SSA-OJP-FLXTR None None None None

SUB SITE TGBI0-FLX01 TGBI0-FLX01 None None None None

DATE OBS 25-MAY-94 09-SEP-94 None None None None

TIME OBS 0 2358 None None None None

H202 CONC -.01 3.55 None None None None

ROOH CONC -.03 1.55 None None None None

H202 CONC GRAD -.1088 .1799 None None None None

ROOH CONC GRAD -.0199 .0618 None None None None

EDDY DIFF -i 10.64 None None None None

MEAN H202 DEP VELOC -195.6 278.4 -999 None None None

SDEV H202 DEP VELOC 0 34.1 -999 None None None

MEAN ROOH DEP VELOC -139.6 286.5 -999 None None None

SDEV ROOH DEP VELOC 0 20.3 -999 None None None

QUALITY CODE 1 3 None None None None

CRTFCN CODE CPI CPI None None None None

REVISION DATE 24-OCT-96 24-OCT-96 None None None None

Minimum Data Value -- The minimum value found in the column.

Maximum Data Value -- The maximum value found in the column.

Missng Data Value -- The value that indicates missing data. This is used to

indicate that an attempt was made to determine the

parameter value, but the attempt was unsuccessful.

Unrel Data Value -- The value that indicates unreliable data. This is used

to indicate an attempt was made to determine the

parameter value, but the value was deemed to be

unreliable by the analysis personnel.

Below Detect Limit -- The value that indicates parameter values below the

instruments detection limits. This is used to

indicate that an attempt was made to determine the

parameter value, but the analysis personnel determined

that the parameter value was below the detection

limit of the instrumentation.

Data Not Cllctd -- This value indicates that no attempt was made to

determine the parameter value. This usually

indicates that BORIS combined several similar but

not identical data sets into the same data base table

but this particular science team did not

measure that parameter.

Page 11
Blank -- Indicates that blank spaces are used to denote that type of value.

N/A -- Indicates that the value is not applicable to the respective column.

None -- Indicates that no values of that sort were found in the column.

7.4 Sample Data Record

The following are wrapped versions of data record from a sample data file on the CD-ROM.

SITE NAME,SUB SITE,DATE OBS,TIME OBS,H202 CONC,ROOH CONC,H202 CONC GRAD,

ROOH CONC GRAD,EDDY DIFF,MEAN H202 DEP VELOC,SDEV H202 DEP VELOC,

MEAN ROOH DEP VELOC,SDEV ROOH DEP VELOC QUALITY CODE

'SSA-OJP-FLXTR', 'TGBI0-FLX01',25-MAY-94 609, .59, .42,

-999.0,-999.0,2, 'CPI',24-OCT-96

'SSA-OJP-FLXTR', 'TGBI0-FLX01',25-MAY-94

-999.0,-999.0,-999.0,2, 'CPI',24-OCT-96

'SSA-OJP-FLXTR', 'TGBI0-FLX01',25-MAY-94

-999.0,-999.0,-999.0,2, 'CPI',24-OCT-96

'SSA-OJP-FLXTR', 'TGBI0-FLX01',25-MAY-94

-999.0,-999.0,-999.0,2, 'CPI',24-OCT-96

CRTFCN CODE,REVISION DATE

0145,0.0,-1.0,-999.0,-999,

650,.56,.42, 0153,-.0006,-1.0,-999.0,

730,.49,.4,.0074,.0022,-1.0,-999.0,

803,.44,.37,.0229,.0193,-1.0,-999.0,

8. Data Organization

8.1 Data Granularity

The smallest unit of data tracked by the BOREAS Information System (BORIS) was oxidant

concentrations measured on a particular day at a particular site.

8.2 Data Format(s)

The Compact Disk-Read-Only Memory (CD-ROM) files contain American Standard Code for

Information Interchange (ASCII) numerical and character fields of varying length separated by

commas. The character fields are enclosed with single apostrophe marks. There are no spaces between

the fields.

Each data file on the CD-ROM has four header lines of Hyper-Text Markup Language (HTML)

code at the top. When viewed with a Web browser, this code displays header information (data set

title, location, date, acknowledgments, etc.) and a series of HTML links to associated data files and

related data sets. Line 5 of each data file is a list of the column names, and line 6 and following lines

contain the actual data.

9. Data Manipulations

9.1 Formulae

The peroxide gradient was computed from three successive measurements of peroxide

concentration at two levels (10-18 minutes at each level).

Peroxide_gradient = (C2 - 0.5*(Cl+C3))/delta_Z

where: C 1 = concentration measured at lower level (period t)

C2 = concentration measured at upper level (period t+ 1)

C3 = concentration measured at lower level (period t+2)

Page 12
Specialnote:If thestandarderrorassociatedwith C1,C2,orC3wasgreaterthan0.05%,theperoxide

gradientwasdeemedunacceptable.Thisprocedurewasperformedin orderto screenperiodsof highly

variableconcentration,whichmight suggestunsteady-stateconditions(gustsorlargeeddies)which

arenotconducivetoK-theory.Thisdatascreeningprocedurehelpseliminatemanyunrealistic

depositionvelocities,butdoesnotaffecttheoverallconclusions.

Peroxide_depositionvelocity= (peroxide_gradient)/(C_avg)*(eddy_diffusivity)

where: C_avg= averageperoxideconcentration(overbothlevels)

9.1.1 Derivation Techniques and Algorithms

None given.

9.2 Data Processing Sequence

9.2.1 Processing Steps

None given.

9.2.2 Processing Changes

None given.

9.3 Calculations

Emission rate:

E = C*Q/B

where: C is the concentration of a specific VOC

Q is the flow rate of air through the chamber

B is the dry leaf (needle) biomass of the enclosed branch

Deposition velocity (Vd):

Vd = K*(dC/dz)/C

9.3.1 Special Corrections/Adjustments

Peroxide Bias adjustment: C1 = Cl*fb C3 = Cl*fb

where: fb = bias relative to upper sampling level

(range 0.99 to 1.07 for H202, 0.99 to 1.02 for ROOH)

9.3.2 Calculated Variables

None given.

9.4 Graphs and Plots

None.

Page 13
10. Errors

10.1 Sources of Error

Hydroperoxides:

• Fluctuations in air flow rate.

• Error in preparing sample volume.

• Fluctuations in sample collection efficiency with temperature.

• Possible condensation in sample lines.

• Interference due to smoke particles.

• Error associated with the serial dilution of H202 standards.

10.2 Quality Assessment

10.2.1 Data Validation by Source

None given.

10.2.2 Confidence Level/Accuracy Judgment

Hydrogen peroxide concentrations are good to approximately 30%. Total organic peroxide

concentrations have not been corrected for collection efficiency. Reported total organic peroxide

concentration may be underestimated by as much as 60%. Individual deposition velocity measurements

are subject to 50-80% uncertainty due to uncertainties in the measured gradient, the measured eddy

diffusivity, and the natural variability of a turbulent atmosphere. Ozone concentrations are good to +/-

5 ppb for IFC-1, and +/- 3 ppb for IFC-2 and IFC-3.

10.2.3 Measurement Error for Parameters

None given.

10.2.4 Additional Quality Assessments

None.

10.2.5 Data Verification by Data Center

BORIS processed the data by:

• Reviewing the initial data files and loading them online for BOREAS team access.

• Designing relational data base tables to inventory and store the data.

• Loading the data into the relational data base tables.

• Performing the conversions on measurements into System International (SI) units.

• Extracting the standardized data into logical files.

11. Notes

11.1 Limitations of the Data

Peroxide deposition velocities at OJP are subject to some uncertainty (factor of 2) simply because

we do not know for certain that the application of Kh is appropriate for peroxide transport. The eddy

diffusivity for water vapor over OJP was lower than that of heat. Therefore, average peroxide

deposition velocities should probably be taken as an upper limit.

11.2 Known Problems with the Data

None given.

Page 14
11.3 Usage Guidance

Peroxide deposition rates are extremely difficult to measure in the field. Individual measurements

of peroxide deposition velocity hold little significance due to the uncertainties mentioned in Section

10.2. However, because of the large amount of data collected, these deposition rates are a valuable

component of the peroxide budget. Vd data should be used to assess average deposition rates to a

rough, boreal pine forest.

11.4 Other Relevant Information

None given.

12. Application of the Data Set

The data can be used to examine (a) the role of biogenic hydrocarbon emissions with respect to carbon

cycles in the boreal forest, (b) the chemical fate of boreal biogenic emissions, (c) the hypothesis that

biospheric VOC emissions contribute to peroxide formation, and (d) the deposition rates of hydrogen

peroxide and organic peroxides.

None.

13. Future Modifications and Plans

14. Software

14.1 Software Description

All software programs used to gather data were standard scientific packages.

14.2 Software Access

None given.

15. Data Access

The TGB- 10 oxidant flux data are available from the Earth Observing System Data and Information

System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center

(DAAC).

15.1 Contact Information

For BOREAS data and documentation please contact:

ORNL DAAC User Services

Oak Ridge National Laboratory

P.O. Box 2008 MS-6407

Oak Ridge, TN 37831-6407

Phone: (423) 241-3952

Fax: (423) 574-4665

E-mail: ornldaac@ornl.gov or ornl@eos.nasa.gov

Page 15
15.2 Data Center Identification

Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory

(ORNL) Distributed Active Archive Center (DAAC) for Biogeochemical Dynamics

http://www-eosdis.ornl.gov/.

15.3 Procedures for Obtaining Data

Users may obtain data directly through the ORNL DAAC online search and order system

[http://www-eosdis.ornl.gov/] and the anonymous FTP site [ftp://www-eosdis.ornl.gov/data/] or by

contacting User Services by electronic mail, telephone, fax, letter, or personal visit using the contact

information in Section 15.1.

15.4 Data Center Status/Plans

The ORNL DAAC is the primary source for BOREAS field measurement, image, GIS, and

hardcopy data products. The BOREAS CD-ROM and data referenced or listed in inventories on the

CD-ROM are available from the ORNL DAAC.

16. Output Products and Availability

16.1 Tape Products

None.

16.2 Film Products

None.

16.3 Other Products

These data are available on the BOREAS CD-ROM series.

17. References

17.1 Platform/Sensor/Instrument/Data Processing Documentation

None given.

17.2 Journal Articles and Study Reports

Guenther, A. 1996. Isoprene fluxes measured by enclosure, relaxed eddy accumulation, surface layer

gradient, mixed layer gradient, and mixed layer mass balance techniques. Journal of Geophysical

Research, 101, 18,555-18,567.

Hall, B.D. and C.S. Claiborn. 1997. Measurements of the dry deposition of peroxides to a Canadian

boreal forest. Journal of Geophysical Research 102(D24):29,343-29,353.

Lazrus, A.L, G.L. Kok, S.N. Gitlin, J.A. Lind, B.G. Heikes, and R.E. Shetter. 1986. Automated

fluorometric method for hydrogen peroxide in air. Anal. Chem. 58, 594-597.

Kok, G.L., S.E. McLaren, and T.A. Staffelbach. 1995. HPLC determination of atmospheric organic

hydroperoxides. J. Atmos. Ocean Tech., 12, 282-289.

Newcomer, J., D. Landis, S. Conrad, S. Curd, K. Huemmrich, D. Knapp, A. Morrell, J. Nickeson,

A. Papagno, D. Rinker, R. Strub, T. Twine, F. Hall, and P. Sellers, eds. 2000. Collected Data of The

Boreal Ecosystem-Atmosphere Study. NASA. CD-ROM.

Page 16
Sellers,P.andF.Hall. 1994.BorealEcosystem-AtmosphereStudy:ExperimentPlan.Version

1994-3.0,NASA BOREASReport(EXPLAN 94).

Sellers,P.andF.Hall. 1996.BorealEcosystem-AtmosphereStudy:ExperimentPlan.Version

1996-2.0,NASA BOREASReport(EXPLAN 96).

Sellers,P.,F. Hall, andK.F. Huemmrich.1996.BorealEcosystem-AtmosphereStudy:1994

Operations.NASA BOREASReport(OPSDOC94).

Sellers,P.,F. Hall, andK.F. Huemmrich.1997.BorealEcosystem-AtmosphereStudy:1996

Operations.NASA BOREASReport(OPSDOC96).

Sellers,P.,F. Hall, H. Margolis,B. Kelly, D. Baldocchi,G. denHartog,J.Cihlar, M.G. Ryan,B.

Goodison,P.Crill, K.J.RansomD. Lettenmaier,andD.E. Wickland. 1995.Theboreal

ecosystem-atmospherestudy(BOREAS):anoverviewandearlyresultsfrom the1994field year.

Bulletinof theAmericanMeteorologicalSociety.76(9):1549-1577.

Sellers,P.J.,F.G.Hall, R.D.Kelly, A. Black, D. Baldocchi,J. Berry, M. Ryan,K.J. Ranson,P.M.

Crill, D.P.Lettenmaier,H. Margolis,J.Cihlar, J.Newcomer,D. Fitzjarrald,P.G.Jarvis,S.T.

Gower,D. Halliwell, D. Williams, B. Goodison,D.E.Wickland, andF.E.Guertin.1997.BOREAS

in 1997:ExperimentOverview,ScientificResultsandFutureDirections.Journalof Geophysical

Research102(D24):28,731-28,770.

17.3 Arehive/DBMS Usage Documentation

None.

None.

18. Glossary of Terms

ASCII

BOREAS

BORIS

CD-ROM

DAAC

DNPH

EOS

EOSDIS

GIS

GMT

GSFC

HPLC

HTML

IFC

NAD83

NASA

NIST

NMHC

NSA

OA

19. List of Acronyms

- American Standard Code for Information Interchange

- BOReal Ecosystem-Atmosphere Study

- BOREAS Information System

- Compact Disk-Read-Only Memory

- Distributed Active Archive Center

- dinitrophenylhydrazine

- Earth Observing System

- EOS Data and Information System

- Geographic Information System

- Greenwich Mean Time

- Goddard Space Flight Center

- High Performance Liquid Chromatography

- Hyper-Text Markup Language

- Intensive Field Campaign

- North American Datum of 1983

- National Aeronautics and Space Administration

- National Institute for Standards and Technology

- Non-Methane Hydrocarbon

- Northern Study Area

- Old Aspen

Page 17
OBS Old Black Spruce

OJP - Old Jack Pine

ORNL - Oak Ridge National Laboratory

PANP - Prince Albert National Park

REA - Relaxed Eddy Accumulation

SI - System International

SSA - Southern Study Area

TF - Tower Flux

TGB - Trace Gas Biogeochemistry

URL - Uniform Resource Locator

VOC - Volatile Organic Compound (or

WSU - Washington State University

Carbon)

20. Document Information

20.1 Document Revision Dates

Written: 17-Nov- 1994

Last Updated: 16-Jul- 1999

20.2 Document Review Dates

BORIS Review: 12-Jun-1998

Science Review:

20.3 Document ID

20.4 Citation

When using these data, please contact the personnel listed in Section 2.3 and cite any relevant

papers in Section 17.2.

If using data from the BOREAS CD-ROM series, also reference the data as:

Westberg, H. and N. Hewitt, "Measurement of Biogenic Hydrocarbon Fluxes." In Collected Data

of The Boreal Ecosystem-Atmosphere Study. Eds. J. Newcomer, D. Landis, S. Conrad, S. Curd, K.

Huemmrich, D. Knapp, A. Morrell, J. Nickeson, A. Papagno, D. Rinker, R. Strub, T. Twine, F.

Hall, and P. Sellers. CD-ROM. NASA, 2000.

Also, cite the BOREAS CD-ROM set as:

Newcomer, J., D. Landis, S. Conrad, S. Curd, K. Huemmrich, D. Knapp, A. Morrell, J.

Nickeson, A. Papagno, D. Rinker, R. Strub, T. Twine, F. Hall, and P. Sellers, eds. Collected Data of

The Boreal Ecosystem-Atmosphere Study. NASA. CD-ROM. NASA, 2000.

20.5 Document Curator

20.6 Document URL

Page 18
REPORT DOCUMENTATION PAGE FormApproved

OMB No. 0704-0188

Public reporting burden for this collection of informationis estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources,

gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this

collection of information, including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson

Davis Highway, Suite 1204, Arlington, VA 22202-4302, and to the Office of Management and Budget, Paperwork Reduction Project (0704-0188), Washington, DC 20503.

1. AGENCY USE ONLY (Leave blank) 2. REPORT DATE 3. REPORT TYPE AND DATES COVERED

November 2000 Technical Memorandum

4. TITLE AND SUBTITLE

Technical Report Series on the Boreal Ecosystem-Atmosphere Study (BOREAS)

BOREAS TGB-10 Oxidant Flux Data over the SSA

6. AUTHOR(S)

Hal Westberg, Brad Hall, and Andrea V. Jackson

Forrest G. Hall and Sara K. Conrad, Editors

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS (ES)

Goddard Space Flight Center

Greenbelt, Maryland 20771

9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS (ES)

National Aeronautics and Space Administration

Washington, DC 20546-0001

5. FUNDING NUMBERS

923

RTOP: 923-462-33-01

8. PEFORMING ORGANIZATION

REPORT NUMBER

2000-03136-0

10. SPONSORING / MONITORING

AGENCY REPORT NUMBER

TM--2000-209891

Vol. 242

11. SUPPLEMENTARY NOTES

H. Westberg and B. Hall: Washington State University, Pullman; A.V. Jackson: Lancaster University,

UK; S.K. Conrad: Raytheon ITSS

12a. DISTRIBUTION / AVAILABILITY STATEMENT

Unclassifie_Unlimited

Subject Category: 43

Report available from the NASA Center for AeroSpace Information,

7121 Standard Drive, Hanover, MD 21076-1320. (301) 621-0390.

12b. DISTRIBUTION CODE

13. ABSTRACT (Maximum 200 words)

The BOREAS TGB-10 team collected several trace gas data sets in its efforts to determine the role of biogenic

hydrocarbon emissions with respect to boreal forest carbon cycles. This oxidant data set contains measured

peroxide (H202 and total organic peroxides (ROOH)) and ozone concentrations as well as H202 and ROOH

deposition velocities. These data were obtained at the SSA-OJP site during the summer of 1994. Measurements

were made from May to September 1994. The data are stored in tabular ASCII files. Some hnportant results were:

• Ozone concentrations were consistently low, 20-30 ppb, during the summer of 1994.

• Peroxide concentrations showed a seasonal variation with highest concentrations occurring in July

(IFC-2).

• Midday H202 levels averaged around 1.4 ppb during IFC-2 and 0.4-0.5 ppb during IFC's 1 and 3.

• Midday organic peroxide concentrations were lower, averaging 0.8 ppb during IFC-2, and 0.4-0.5 ppb

during IFC's 1 and 3.

• The rough pine forest canopy serves as a significant sink for H202.

• Midday H202 deposition velocities averaged 4-7 cm/s.

• Organic peroxide deposition velocities (measured as total ROOH) were approximately 40% as large as

those of HaOa.

14. SUBJECT TERMS

BOREAS, trace gas biogeochemistry.

17. SECURITY CLASSIFICATION

OF REPORT

Unclassified

NSN 7540-01-280-5500

18. SECURITY CLASSIFICATION

OF THIS PAGE

Unclassified

19. SECURITY CLASSIFICATION

OF ABSTRACT

Unclassified

15. NUMBER OF PAGES

18

16. PRICE CODE

20. LIMITATION OF ABSTRACT

UL

Standard Form 298 (Rev. 2-89)

Prescribed by ANSI Std. Z39.18

298-102