Identification

Title

Observational constraints on the chemistry of isoprene nitrates over the Eastern United States

Abstract

The formation of organic nitrates during the oxidation of the biogenic hydrocarbon isoprene can strongly affect boundary layer concentrations of ozone and nitrogen oxides (NOx = NO + NO₂). We constrain uncertainties in the chemistry of these isoprene nitrates using chemical transport model simulations in conjunction with observations over the eastern United States from the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) field campaign during summer 2004. The model best captures the observed boundary layer concentrations of organic nitrates and their correlation with ozone using a 4% yield of isoprene nitrate production from the reaction of isoprene hydroxyperoxy radicals with NO, a recycling of 40% NOx when isoprene nitrates react with OH and ozone, and a fast dry deposition rate of isoprene nitrates. Simulated boundary layer concentrations are only weakly sensitive to the rate of photochemical loss of the isoprene nitrates. An 8% yield of isoprene nitrates degrades agreement with the observations somewhat, but concentrations are still within 50% of observations and thus cannot be ruled out by this study. Our results indicate that complete recycling of NOx from the reactions of isoprene nitrates and slow rates of isoprene nitrate deposition are incompatible with the observations. We find that ∼50% of the isoprene nitrate production in the model occurs via reactions of isoprene (or its oxidation products) with the NO₃ radical, but note that the isoprene nitrate yield from this pathway is highly uncertain. Using recent estimates of rapid reaction rates with ozone, 20-24% of isoprene nitrates are lost via this pathway, implying that ozonolysis is an important loss process for isoprene nitrates. Isoprene nitrates are shown to have a major impact on the nitrogen oxide (NOx = NO + NO₂) budget in the summertime U.S. continental boundary layer, consuming 15-19% of the emitted NOx, of which 4-6% is recycled back to NOx and the remainder is exported as isoprene nitrates (2-3%) or deposited (8-10%). Our constraints on reaction rates, branching ratios, and deposition rates need to be confirmed through further laboratory and field measurements. The model systematically underestimates free tropospheric concentrations of organic nitrates, indicating a need for future investigation of the processes controlling the observed distribution.

Resource type

document

Resource locator

Unique resource identifier

code

http://n2t.net/ark:/85065/d7mw2hd1

codeSpace

Dataset language

eng

Spatial reference system

code identifying the spatial reference system

Classification of spatial data and services

Topic category

geoscientificInformation

Keywords

Keyword set

keyword value

Text

originating controlled vocabulary

title

Resource Type

reference date

date type

publication

effective date

2016-01-01T00:00:00Z

Geographic location

West bounding longitude

East bounding longitude

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South bounding latitude

Temporal reference

Temporal extent

Begin position

End position

Dataset reference date

date type

publication

effective date

2007-05-08T00:00:00Z

Frequency of update

Quality and validity

Lineage

Conformity

Data format

name of format

version of format

Constraints related to access and use

Constraint set

Use constraints

Limitations on public access

None

Responsible organisations

Responsible party

contact position

OpenSky Support

organisation name

UCAR/NCAR - Library

full postal address

PO Box 3000

Boulder

80307-3000

email address

opensky@ucar.edu

web address

http://opensky.ucar.edu/

name: homepage

responsible party role

pointOfContact

Metadata on metadata

Metadata point of contact