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  • Updated temperature correction for computing seawater nitrate with in situ ultraviolet spectrophotometer and submersible ultraviolet nitrate analyzer nitrate sensors
Title: Updated temperature correction for computing seawater nitrate with in situ ultraviolet spectrophotometer and submersible ultraviolet nitrate analyzer nitrate sensors
Abstract Sensors that use ultraviolet (UV) light absorption to measure nitrate in seawater at in situ temperatures require a correction to the calibration coefficients if the calibration and sample temperatures are not identical. This is mostly due to the bromide molecule, which absorbs more UV light as temperature increases. The current correction applied to in situ ultraviolet spectrophotometer (ISUS) and submersible ultraviolet nitrate analyzer (SUNA) nitrate sensors generally follows Sakamoto et al. (2009, Limnol. Oceanogr. Methods 7, 132–143). For waters warmer than the calibration temperature, this correction model can lead to a 1–2 μmol kg−1positive bias in nitrate concentration. Here we present an updated correction model, which reduces this small but noticeable bias by at least 50%. This improved model is based on additional laboratory data and describes the temperature correction as an exponential function of wavelength and temperature difference from the calibration temperature. It is a better fit to the experimental data than the current model and the improvement is validated using two populations of nitrate profiles from Biogeochemical Argo floats navigating through tropical waters. One population is from floats equipped with ISUS sensors while the other arises from floats with SUNA sensors on board. Although this model can be applied to both ISUS and SUNA nitrate sensors, it should not be used for OPUS UV nitrate sensors at this time. This new approach is similar to that used for OPUS sensors (Nehir et al., 2021, Front. Mar. Sci. 8, 663800) with differing model coefficients. This difference suggests that there is an instrumental component to the temperature correction or that there are slight differences in experimental methodologies.  more » « less
Award ID(s):
1946578 1936222 2110258
PAR ID:
10469412
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Limnology and Oceanography: Methods
Volume:
21
Issue:
10
ISSN:
1541-5856
Format(s):
Medium: X Size: p. 581-593
Size(s):
p. 581-593
Sponsoring Org:
National Science Foundation
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Scientfically uninteresting. ## ***STOX Oxygen Profiles.zip*** Contains high precision oxygen profiles taken on the two Sally Ride cruises using STOX oxygen sensors. The data is provided as .txt and .mat formats along with miscellaneous data from the CTD. Oxygen measurements from the floats were referenced to STOX oxygen profiles taken from the ship on the two cruises because these provide much more stable and high precision measurements. STOX sensors are described in detail in Revsbech, N. P.; Larsen, L. H.; Gundersen, J.; Dalsgaard, T.; Ulloa, O. and Thamdrup, B. ( 2009) Determination of ultra‐low oxygen concentrations in oxygen minimum zones by the STOX sensor. Limnology and Oceanography: Methods, 7, pp.371-381. DOI:10.4319/lom.2009.7.371. And from their manufacturer [https://unisense.com/products/stox-microsensor/](https://unisense.com/products/stox-microsensor/) STOX data was collected on two cruises of the research vessel, Sally Ride, SR 2114 and SR2011. Data from each CTD cast with a STOX profile is in a separate folder in this archive. In each, the raw data is in a ****.txt*** file and the converted Matlab data is in a ****.mat*** file. MATLAB scripts to read the ****.mat*** file are included in each folder. Data names and units are: Ship Cruise Station Cast Year Month Day Hour Minute * Depth [m] * Latitude [deg]  * Longitude [deg] * Density [sigma-theta,kg/m^3]  * Temperature [ºC]  * Salinity * Beam Attenuation [1/m] * Fluorescence [mg Chla/m3]  * PAR [umol/m2/s] * Oxygen_SBE [µmol/kg]) * Oxygen_STOX [µmol/kg] * STOX_SD [µmol/kg] * STOX_n [µmol/kg] * NO3-Suna [uM] ## **Optode Calibration.zip**  Contains all of the calibration data used to calibrate the optodes including the anoxic laboratory points, the manufacturers' calibration points, and the coefficients of the calibration model for each optode.  **Seabird 63 Optodes** Anoxic calibration data and model fit are in ***AnoxicCalibration/SBE63/2020/*** and ***/2021/***. The 2020 data was used in the final calibration. * Files are *******Tau0model.mat*** where **** is the optode serial number * Variable ***meta*** explains each variable, repeated here. Calibration model is '1./Taup.*exp(-(Etau+Etau2.*(K-283.15).^2)/R/K )*(1+Drift *(days since start) )' Variables are * Taup: 'Phase [uS]' * Etau: 'Energy is Etau+Etau2*(T-10C) [J/mol] * Drift: 'Drift coefficient in the model [1/days] * Ttau: 'Time scale of drift [days] * Drift_uSday: 'Model Drift uS/day' * Dcal: 'Robust Drift. The drift line is Dcal(2)+ Dcal(1)*(Yearday of 2021) in uMol. Drift is Dcal(1) [uMol/day] * Drms: 'RMS drift fit error [uS] * Derr: 'Uncertainty in Dcal; Drift uncertainty is Derr(1) [uMol/day]'  Calibration points from the anoxic tank are in structure ***RawS.*** Variable ***meta*** explains each variable, repeated here. * K: 'Temperature [Kelvin]' * O2phase: 'O2 phase tau [uS]' * R: 'Gas constant [J/K/mol] * dyd: 'Time since start of record [days]' * TIME: 'Time [matlab datetime] * Omodel: 'Tau computed from model with drift [uS] * OmodelND: 'Tau computed from model with drift removed [uS] **Full Calibration/** contains the oxic calibration points and calibration coefficients Calibration points from Seabird supplied with optode are in **SBE63/*FactoryCalibration/ ****_dd_mmm_yyyy.mat ***where **** is the optode serial number. The calibration date follows. Variables are * Caltime - Calibration time [matlab datum] * ID - Serial number * O2in_mll - Oxygen in tank from winklers [ml/L] * O2out_mll - Oxygen computed from Seabird calibration [ml/L] * S - Salinity [psu] * T - Temperature [deg C] * resid_mll - model residual [ml/L] * tau_us - optode phase lag [microseconds] The oxic part of the optode model calibration coefficients are in ***SBE63/Calfiles/*** Calibration model, coefficients, and check values are in ***Calfiles/_oxic_model.mat*** where **** is the optode SN Data is in structure ***Kfile*** ***Kfile.meta*** explains the variables, repeated here. Model is pO2=eta/K(T) * (1 + a(T)*eta^2.3)^q(T) ; eta= tau0(T)/tau-1.  Note that tau0(T) is computed from *******_Tau0model.mat*** coefficients above. Variables are * Check: 'Test values of T, Tau, and pO2 from SBE cal' * Lk: 'K(T)=polyval(Lk, T) - Matlab call to compute K from Lk polynomial coefficients and T [deg C] * La: 'a(T)=polyval(La,T)' * Lq: 'q(T)=polyval(Lq,T)' **Aanderaa 4330 Optodes** **Anoxic calibration** data and model fit is in ***AnoxicCalibration/AA/*** \**                  **File names and formats are the same as for SBE63 optodes **Full Calibration/AA** **/Factory Calibrations** contains the calibration information supplied with the optodes Files are *******_dd-mmm-yyyy.mat*** with the same format as for the SBE63 The relevant variables are: * Caltime - Calibration time [matlab datenum] * ID - Serial number of optode * O2in_uMol - Calibration bath oxygen [uMol/L] * S - Salinity [psu] * T - Temperature from optode [deg C] * tau_deg - optode output phase [degrees] * meta - Misc information **/Calfiles/********_M0_oxic_model.mat** contain oxic part of the optode model calibration coefficients The format is the same as for SBE63, but there is an extra variable * eta_off: Add this to eta to account for drift since calibration [uS] ## **Calibrated Oxygen.zip** contains both uncalibrated and calibrated optode data for both the ODZ and Argo floats. A README file and Matlab processing programs are included. /***SBE63/xo110**-***.mat*** contain the calibrated data for **ODZ float xo110** Format and data is identical to that in the ***optode*** structure in ***ODZ_Level2_Mat,*** but with 2 extra variables * pO2 – partial pressure of oxygen [mbar] in uncalibrated data * Cal – a structure containing calibrated data -- FINAL DATA IS HERE * pO2: partial pressure of oxygen [mbar] in calibrated data  * Tau0m: Calibration model of anoxic phase [microsecond]. Includes offset. * Tau: Measured phase [microsecond] * Tauoff: offset in Tau from in situ calibration [uS] * eta: (Tau0m+Tauoff)/Tau-1 * O2uM: oxygen concentration [micromoles/kg] * O2umol: same Note that optode(1) is the water oxygen. Optode(2) is a reference optode, which is not of scientific interest.  **/SBE63/Reprocess_SBE63.m** is a MATLAB script showing how to combine calibration data and float data to make calibrated data for SBE63 optodes **/AA/Mat/*FloatID*/*FloatID_profilenum*.mat** contains Argo float data from float FloatID, profile number profilenum. Variables are Data from Argos float archive * mtime, time - time in datetime and datenum formats * lat, lon - GPS position latitude degrees and longitude degrees * P, T, S - CTD pressure [dbar], temperature [deg C], salinity [psu] * Optode - Optode serial number * O2T - Optode temperature [deg C] * O2phase - Optode phase [degrees] * O2umol - Optode oxygen [micromole/kg] Added variables * Kfile - Structure as in Optode Calibration files. Kfile.meta also has metadata * Cal - Structure containing calibrated optode data on the same timebase * Tau - measured phase [degrees] * Tau0m - Model anoxic phase [degrees] * Tauoff - Offset from laboratory calibration [degrees]. Includes offset & drift. * Drift - Drift [degrees/year] * mtime0 - base time for drift [matlab datenum format] * eta - Tau0m/Tau-1 * pO2 - Calibrated Oxygen partial pressure [mbar] * O2umol - Calibrated Oxygen concentration [micromole/kg] * meta - similar list to this one. * SN - same as Optode * Float - FloatID **/AA/Mat/*FloatID*/*FloatID_profilenum*.xls** contains the calibrated data in Excel format ***/AA/Reprocess_3_AA.m*** is a MATLAB script showing how to combine calibration data and float data to make calibrated data for AA optodes ## ***ODZ Raw\.zip*** contains the raw data from 9 custom-built ODZ floats. Level_1 in NASAspeak. They can be read by ***MRVFloatDecode_2023.m*** included in ***ODZ Level 2 files*** ## Code/Software Processing and reading scripts in Matlab (24.1.0.2628055 (R2024a) Update 4) are provided. 
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