uid=HFR,o=lter,dc=ecoinformatics,dc=org all public read doi:10.6073/pasta/b535566978c98d5471072efeb7c1211d Roisin Commane https://orcid.org/0000-0003-1373-1550 Steven Wofsy https://orcid.org/0000-0002-3133-2089 Richard Wehr https://orcid.org/0000-0002-0806-9390 2023 English

Carbonyl sulfide (OCS), the most abundant sulfur compound in the atmosphere, controls the sulfur budget and aerosol loading of the stratosphere in times of low volcanic activity. OCS is also closely tied to the vegetative carbon cycle and may provide an independent measure of the photosynthetic uptake of carbon. However, the detailed nature of the biogeochemical cycling of OCS throughout the seasons in terrestrial ecosystems has not been thoroughly explored. We measured the seasonal response of the ecosystem flux of OCS above a deciduous temperate forest using an infrared laser absorption spectrometer at Harvard Forest (MA, USA) in 2011. Fluxes were calculated using two complementary approaches: gradient – flux (also known as flux – gradient; January – July, 2011) and eddy covariance flux (August – December, 2011), which agreed within the combined error for a period with both measurements. Strong uptake of OCS by the forest was observed during most of the growing season, but significant uptake also occurred when the deciduous leaves were not present. A strong diel cycle of mid-day OCS uptake was observed in May/June and August/September, consistent with OCS uptake by processes parallel to CO2 photosynthetic uptake, at the ecosystem scale, for these months. The results show that while overall OCS and CO2 both show evidence of vegetative uptake, the OCS flux cannot be explained by this process alone and the relationship between OCS and CO2 changes throughout the year above this mixed deciduous forest. The data imply that terrestrial uptake of OCS, and hence the stratospheric sulfur cycle, are potentially quite sensitive to extremes in temperature and soil moisture.

biogeochemistry eddy covariance sulfide LTER controlled vocabulary primary production inorganic nutrients LTER core area Harvard Forest HFR LTER USA HFR default

This dataset is released to the public under Creative Commons CC0 1.0 (No Rights Reserved). Please keep the dataset creators informed of any plans to use the dataset. Consultation with the original investigators is strongly encouraged. Publications and data products that make use of the dataset should include proper acknowledgement.

Creative Commons Zero v1.0 Universal https://spdx.org/licenses/CC0-1.0.html CC0-1.0 https://harvardforest.fas.harvard.edu/exist/apps/datasets/showData.html?id=hf214 Prospect Hill Tract (Harvard Forest). Coordinates based on WGS84 datum. -72.171478 -72.171478 +42.537755 +42.537755 340 340 meter 2010 2013 complete Information Manager Harvard Forest

324 North Main Street Petersham MA 01366 USA

(978) 724-3302 hf-im@lists.fas.harvard.edu Harvard Forest

324 North Main Street Petersham MA 01366 USA

(978) 724-3302 (978) 724-3595 https://harvardforest.fas.harvard.edu

OCS and CO2 were measured using a Tunable Infra-red Laser Direct Absorption Spectrometer (TILDAS, Aerodyne Research Inc.). OCS fluxes were measured by eddy covariance and gradient fluxes.

OCS, CO2, and meteorological data were collected during deployment of the 2nd-generation OCS quantum cascade laser spectrometer at the HF-EMS tower (years 2012 and 2013). Fluxes for which the sonic anemometer data were erroneous have been excluded. The CO2 and temperature cospectra used to correct for high-frequency signal attenuation are found in Harvard Forest Data Archive HF209. The OCS spectrometer sampled the same gas flow as the CO2 isotope spectrometer in record HF209, in series, and should be subject to the same tube-transit signal attenuation. The CO2 fluxes are from Harvard Forest Data Archive record HF209. The data for air temperature, pressure, relative humidity, dry air concentration, and PAR are from Harvard Forest Data Archive record HF004.

OCS and CO2 molar mixing ratios (to dry air) were measured at the indicated heights on the EMS flux tower by the 2nd-generation OCS quantum cascade laser spectrometer at the HF-EMS tower (years 2012 and 2013).

Harvard Forest

324 North Main Street Petersham MA 01366 USA

(978) 724-3302 (978) 724-3595 https://harvardforest.fas.harvard.edu https://ror.org/059cpzx98 pointOfContact The Harvard Forest Long-Term Ecological Research (LTER) program examines ecological dynamics in the New England region resulting from natural disturbances, environmental change, and human impacts. National Science Foundation LTER grants: DEB-8811764, DEB-9411975, DEB-0080592, DEB-0620443, DEB-1237491, DEB-1832210. hf214-01-ocs-flux-2011.csv carbonyl sulfide flux in 2011 using the prototype OCS spectrometer hf214-01-ocs-flux-2011.csv 1607919 3c44df793c74f36b2a4bb8b22ad2f7ba 1 \r\n column , https://harvardforest.fas.harvard.edu/data/p21/hf214/hf214-01-ocs-flux-2011.csv datetime date and time stamp, mean value for the eddy flux integration period YYYY-MM-DDThh:mm 1 second NA missing value year fraction of year (Eastern standard time, EST) nominalYear 0.000001 real NA missing value jd.1970 day of year since 1970 (R notation), EST nominalDay 0.000001 real NA missing value doy day of year nominalDay 0.0001 real NA missing value doy.2011 fraction of day of year in 2011, EST nominalDay 0.00000001 real NA missing value ocs.flux flux of carbonyl sulfide (OCS, unit: pmol m-2 s-1) picomolePerMeterSquaredPerSecond 0.000000001 real NA missing value eddy.flux.flag valid data flag 0 OCS flux not calculated by eddy covariance 1 OCS flux calculated by eddy covariance NA missing value grad.flux.flag valid data flag 0 OCS flux not calculated by the gradient flux method 1 OCS flux calculated by the gradient flux method NA missing value ocs.mr mixing ratio of carbonyl sulfide (OCS; unit: pmol mol-1) dimensionless 0.0000001 real NA missing value grad.flux.dz distance between sampling points in gradient method meter 0.1 real NA missing value 20402 hf214-02-ocs-flux-2012-2013.csv carbonyl sulfide flux in 2012-2013 using the 2nd-generation OCS spectrometer hf214-02-ocs-flux-2012-2013.csv 1108245 2fb69590c1dcdee133e78e4329ad0bdf 1 \r\n column , https://harvardforest.fas.harvard.edu/data/p21/hf214/hf214-02-ocs-flux-2012-2013.csv datetime date and time stamp, mean value for the eddy flux integration period YYYY-MM-DDThh:mm:ss 1 second NA missing value igor.time redundant date and time stamp, used by the Igor programming language (seconds since the start of January 1, 1904) second 1 real NA missing value eddy.flux.co2 CO2 eddy flux past the sensor at 29m (umol/m2/s), corrected for high frequency signal attenuation by comparison of the CO2 and temperature cospectra micromolePerMeterSquaredPerSecond 0.0000001 real NA missing value eddy.flux.ocs OCS eddy flux past the sensor at 29m (pmol/m2/s), corrected for high frequency signal attenuation by comparison of the CO2 (not OCS) and temperature cospectra picomolePerMeterSquaredPerSecond 0.000001 real NA missing value stor.flux.co2 CO2 storage flux, i.e. the increase in CO2 storage below 29m micromolePerMeterSquaredPerSecond 0.00000001 real NA missing value stor.flux.ocs OCS storage flux, i.e. the increase in OCS storage below 29m picomolePerMeterSquaredPerSecond 0.0000001 real NA missing value heat.flux sensible heat flux past the sensor at 29m wattPerMeterSquared 7 real NA missing value airt air temperature celsius 0.0000001 real NA missing value airp air pressure millibar 0.00001 real NA missing value rh relative humidity dimensionless 0.00000001 real NA missing value dry.air concentration of dry air molePerCubicMeter 0.000001 real NA missing value par photosynthetically active radiation micromolePerMeterSquaredPerSecond 0.000001 real NA missing value wind.speed mean wind speed metersPerSecond 0.00000001 real NA missing value wind.dir mean wind speed (degrees from north) degree 0.0000001 real NA missing value ustar friction velocity metersPerSecond 0.000000001 real NA missing value co2 mean CO2 molar mixing ratio to dry air (parts per million) dimensionless 0.00001 real NA missing value ocs mean OCS molar mixing ratio to dry air (parts per trillion) dimensionless 0.00001 real NA missing value bad.zero instrument zero reading flag 1 instrument zero reading was in error 0 instrument zero reading was ok NA missing value bad.data instrument data flag 1 instrument data were completely bad 0 instrument data were ok (aside from possible error in the zero level) NA missing value ocs.corr instrument spectral background correction flag 1 instrument spectral background was successfully corrected in post-processing 0 instrument spectral background was not successfully corrected in post-processing NA missing value 5827 hf214-03-ocs-profiles-2012-2013.csv ocs profiles in 2012-2013 hf214-03-ocs-profiles-2012-2013.csv 1390965 50cbc8ab66a3e6883f7238fc08621803 1 \r\n column , https://harvardforest.fas.harvard.edu/data/p21/hf214/hf214-03-ocs-profiles-2012-2013.csv datetime date and time stamp, mean value for the first inlet, i.e. the inlet closest to the ground; add 1 min for each subsequent inlet, i.e. add 3 min to obtain the mean time for the inlet at 12.5m YYYY-MM-DDThh:mm:ss 1 second NA missing value igor.time redundant date and time stamp, used by the Igor programming language (seconds since the start of January 1, 1904) second 1 real NA missing value num.inlets number of sampling inlets active number 1 natural NA missing value co2.0.2m CO2 molar mixing ratio to dry air measured at 0.2m (parts per million) dimensionless 0.00001 real NA missing value co2.1.0m CO2 molar mixing ratio to dry air measured at 1.0m (parts per million) dimensionless 0.00001 real NA missing value co2.7.5m CO2 molar mixing ratio to dry air measured at 7.5m (parts per million) dimensionless 0.00001 real NA missing value co2.12.5m CO2 molar mixing ratio to dry air measured at 12.5m (parts per million) dimensionless 0.00001 real NA missing value co2.18.3m CO2 molar mixing ratio to dry air measured at 18.3m (parts per million) dimensionless 0.00001 real NA missing value co2.24.1m CO2 molar mixing ratio to dry air measured at 24.1m (parts per million) dimensionless 0.00001 real NA missing value co2.29.0m CO2 molar mixing ratio to dry air measured at 29.0m (parts per million) dimensionless 0.00001 real NA missing value ocs.0.2m OCS molar mixing ratio to dry air measured at 0.2m (parts per trillion) dimensionless 0.00001 real NA missing value ocs.1.0m OCS molar mixing ratio to dry air measured at 1.0m (parts per trillion) dimensionless 0.00001 real NA missing value ocs.7.5m OCS molar mixing ratio to dry air measured at 7.5m (parts per trillion) dimensionless 0.00001 real NA missing value ocs.12.5m OCS molar mixing ratio to dry air measured at 12.5m (parts per trillion) dimensionless 0.00001 real NA missing value ocs.18.3m OCS molar mixing ratio to dry air measured at 18.3m (parts per trillion) dimensionless 0.00001 real NA missing value ocs.24.1m OCS molar mixing ratio to dry air measured at 24.1m (parts per trillion) dimensionless 0.00001 real NA missing value ocs.29.0m OCS molar mixing ratio to dry air measured at 29.0m (parts per trillion) dimensionless 0.00001 real NA missing value bad.zero instrument zero reading flag 1 instrument zero reading was in error 0 instrument zero reading was ok NA missing value bad.data instrument data flag 1 instrument data were completely bad 0 instrument data were ok (aside from possible error in the zero level) NA missing value ocs.corr instrument spectral background correction flag 1 instrument spectral background was successfully corrected in post-processing 0 instrument spectral background was not successfully corrected in post-processing NA missing value 8163 atmosphere long-term measurement https://harvardforest.fas.harvard.edu/exist/apps/datasets/showData.html?id=hf004 https://harvardforest.fas.harvard.edu/exist/apps/datasets/showData.html?id=hf209 picomolePerMeterSquaredPerSecond