Time-resolved fluorescence lifetimes of Dissolved Organic Matter in surface waters in the Upper Newport Back Bay estuary in California from May 2021 to July 2022

Website: https://www.bco-dmo.org/dataset/964253
Data Type: Other Field Results
Version: 1
Version Date: 2025-06-09

Project
» RUI: Collaborative Research: Cycling of ethanol and acetaldyhyde in coastal waters (Coastal Water Cycling)
ContributorsAffiliationRole
Clark, CatherineWestern Washington University (WWU)Principal Investigator, Contact
de Bruyn, WarrenChapman University (CU)Principal Investigator
Harrison, Aaron W.Austin CollegeScientist
Manickam, DhivyaChapman University (CU)Scientist
Soenen, KarenWoods Hole Oceanographic Institution (WHOI BCO-DMO)BCO-DMO Data Manager

Abstract
Time-resolved fluorescence lifetimes of dissolved organic matter (DOM) and associated water quality parameters were measured in near-shore surface waters over 14 months from May 2020 to July 2021 on 77 samples from sites near the inlet, mid-estuary, and outlet in the Upper Newport Back Bay estuary in Southern California, USA. Time-resolved fluorescence data were measured with a pulsed diode system (Horiba DeltaFlex Lifetime System) and fit to a tri-exponential model with short, intermediate and long lifetime components (t3: < 1 ns; t1: 1 to 5 ns; t2: 2 to 15 ns). These data were collected to characterize estuarine DOM for a research project on the production and degradation of ethanol and acetaldehyde in this estuary, since these can be produced from DOM in sunlight. The database of DOM fluorescence lifetime measurements in the literature is very small, and may be a useful method of characterizing DOM. These data were used to assess correlations between DOM lifetimes and physicochemical parameters like salinity and DOC concentrations and were collected by Dr. Warren De Bruyn of Chapman University.


Coverage

Location: Upper Newport Back Bay near-shore surface waters at inlet, mid-estuary and outlet.
Spatial Extent: N:33.650327 E:-117.8671967 S:33.6181867 W:-117.9051099
Temporal Extent: 2021-05-20 - 2022-07-13

Methods & Sampling

Upper Newport Back Bay near-shore surface waters at inlet, mid-estuary and outlet. Site 1 (33.650327, -117.8671967), located at the San Diego creek inlet; site 2 (33.6302266, -117.8859726), located mid-estuary; and site 3 (33.6181867, -117.9051099), located near the Newport Beach marina and Pacific Ocean outlet. 

Surface water (<5 cm) was sampled in the morning from the shore, stored in amber glass bottles, transported to the laboratory, filtered through 0.2 micron Durapore filters and stored in the fridge.  

Fluorescence lifetimes were measured using a Horiba DeltaFlex Lifetime System. The DeltaFlex system is a modular Time Correlated Single Photon Counting (TCSPC) system consisting of a high repetition rate LED source, a DD-C picosecond diode controller, a PPD picosecond photodetection module with DDS-1 power supply, and a DH-HT high throughput TCSPC controller.  The timing electronics has almost no counting photon loss and 10 ns dead times (Horiba Inc). Measurements were made with three different pulsed LED sources (DeltaDiode DD-260, DD-280, DD-340) with peak wavelengths of 268 nm, 285 nm and 338 nm and average power of 5 µW, 10 µW, and 2 µW, respectively. The bandwidth and maximum repetition rate for all LED sources was ~ ± 10 nm and 20 MHz respectively.  An instrument response function (IRF) was measured using a LUDOX AS-40 inorganic scattering suspension (Sigma Aldrich) solution.  

This is a summary of methods from De Bruyn et al., 2025 (see related publications).


Data Processing Description

There are a number of methods used to obtain lifetime information from time-resolved fluorescence data. The most common approach, and the approach used here, is the discrete component approach (DCA; Kumke et al., 1998a and b). DCA involves fitting the observed decay to an exponential function of the form:

F(t) = A + B1 e-(t/ τ1) + B2 e-(t/ τ2) + B3 e-(t/ τ3) +….                                                           (1)

 Here A is an offset, Bi are the component amplitudes which reflect the initial fluorescence intensity or population of each component, and τi are the lifetimes of each component.  Amplitudes are reported directly as Bi or as relative values i.e. %Bi = Bi/(B1 +B2 +B3…) x 100.  The fractional contributions of each component to total fluorescence (the fraction of fluorescence photons received from a specific decay component) are given by (Kumke et al., 1998a and b; Chen et al., 2020):

f i = Bi τi / (B1 τ1 + B2 τ2 + B3 τ3)                                                                    (2)

The fractional contribution (fi) is directly proportional to the steady-state fluorescence intensity of a given component.

This is a summary of methods from De Bruyn et al., 2025 (see related publications).


BCO-DMO Processing Description

* reorganized daata table to long format
* added sampling site latitude and longitude to data table


Problem Description

The lower limit for lifetime measurements is estimated to be ~ 1/10 of the IRF FWHM (full width half maximum i.e. time width of the response pulse at 50% of the maximum signal; personal communication Horiba Inc). The FWHM of the IRF is primarily controlled by the source pulse width which, while it can be larger, is typically ~750 ps for the DD-260 and DD-340 sources and ~950ps for the DD-280 source. The measured IRF FWHM was ~1 ns consistent with the typical pulse widths of these sources.  We have therefore treated any measured lifetime less than 100 ps with caution.

The number of components is primarily chosen based on a quality of fit assessment i.e., the χ2 should be below some threshold and residuals should be randomly distributed. A threshold of χ2 < 1.2 where the value does not improve significantly by increasing the number of components is relatively common and is recommended by Horiba Inc.

This information is from W. J. De Bruyn, D. Manickam, A. Harrison, C. D. Clark. “Time-resolved fluorescence lifetimes of dissolved organic matter (DOM) as a function of environmental parameters in estuarine waters”. Environmental Science and Pollution Research (2025). https://doi.org/10.1007/s11356-024-35777-3

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Related Publications

Chen, Y., Liu, J., Zhang, X., & Blough, N. V. (2020). Time-Resolved Fluorescence Spectra of Untreated and Sodium Borohydride-Reduced Chromophoric Dissolved Organic Matter. Environmental Science & Technology, 54(19), 12109–12118. https://doi.org/10.1021/acs.est.0c03135 https://doi.org/doi:10.1021/acs.est.0c03135
Methods
Kumke, M. U., Abbt-Braun, G., & Frimmel, F. H. (1998). Time-resolved Fluorescence Measurements of Aquatic Natural Organic Matter (NOM). In Acta hydrochimica et hydrobiologica (Vol. 26, Issue 2, pp. 73–81). Wiley. https://doi.org/10.1002/(sici)1521-401x(199803)26:2<73::aid-aheh73>3.0.co;2-c https://doi.org/10.1002/(SICI)1521-401X(199803)26:2<73::AID-AHEH73>3.0.CO;2-C
Methods
de Bruyn, W. J., Manickam, D., Harrison, A. W., & Clark, C. D. (2025). Time-resolved fluorescence measurements of dissolved organic matter (DOM) as a function of environmental parameters in estuarine waters. Environmental Science and Pollution Research, 32(4), 1952–1970. https://doi.org/10.1007/s11356-024-35777-3
Results

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Parameters

ParameterDescriptionUnits
Date

date sample taken

unitless
Site

location sample was taken

unitless
Latitude

Sampling latitude, south is negative

decimal degrees
Longitude

Sampling longitude, west is negative

decimal degrees
Ex

excitation wavelength

nm (nanometers)
Em

emission wavelength

nm (nanometers)
t1

lifetime of component 1

nanosecond (ns)
t2

lifetime of component 2

nanosecond (ns)
t3

lifetime of component 3

nanosecond (ns)
B1

amplitude of component 1; a is negative amplitude

unitless
B2

amplitude of component 2; a is negative amplitude

unitless
B3

amplitude of component 3; a is negative amplitude

unitless
Χ2

chi squared (measure of goodness of fit; <1.2 is well fit)

unitless


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Instruments

Dataset-specific Instrument Name
Horiba DeltaFlex Lifetime System
Generic Instrument Name
Fluorescence Lifetime System
Dataset-specific Description
Fluorescence lifetimes were measured using a Horiba DeltaFlex Lifetime System. 


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Project Information

RUI: Collaborative Research: Cycling of ethanol and acetaldyhyde in coastal waters (Coastal Water Cycling)

Coverage: Upper Newport Back Bay estuary in Orange County, Southern California


NSF Award Abstract

Ethanol is added to gasoline to increase octane levels and lower the concentrations of carbon monoxide and surface ozone in the atmosphere. As a renewable fuel, ethanol may also help decrease our dependence on gasoline. Increased use of ethanol in the United States and globally as a fossil fuel substitute and additive is expected to increase ethanol levels in the atmosphere. Atmospheric ethanol is converted to acetaldehyde which is a hazardous pollutant. To understand the impact of increasing ethanol usage, it is important to understand the cycling of ethanol and acetaldehyde in the environment--how they are produced, consumed, and interconverted. Because these compounds can cross from air into water, this requires understanding what happens to these compounds in both the atmosphere and in seawater and other surface waters. This proposal focuses on improving our understanding of processes that produce and consume ethanol and acetaldehyde in coastal seawater and other coastal surface waters like estuaries and salt marshes. This project will measure the rates of photochemical production of ethanol and acetaldehyde, as well as their chemical and biological degradation rates. The project will also measure the rate and efficiency of the biological production of acetaldehyde from ethanol by microbial organisms in these waters. The scientists have an excellent track record of involving undergraduate students, including underrepresented minorities, in their research and as co-authors on publications, a trend they plan to continue with this project. These students would be trained in analytical chemistry and environmental research and would present their research findings at local and national conferences. Lastly, the PIs also plan outreach activities with high school STEM programs to improve student diversity in environmental research.

The primary sink for ethanol in the troposphere is reaction with OH to produce acetaldehyde. Acetaldehyde levels in the troposphere are also expected to increase with increased use of ethanol. Changes in the atmospheric concentrations of these species are expected to have a significant impact on the oxidative capacity of the troposphere. To understand future impacts, it is important to understand current tropospheric budgets which have significant uncertainties for both species. One of the largest sources of uncertainty is the role of the oceans and surface waters in cycling these species into and out of the troposphere. The current understanding is limited by the very small database of ambient concentration measurements in both air and water and an incomplete insight into the processes that control concentrations in seawater and surface waters; these processes represent a complex interplay between biological and photochemical sources and sinks, and air-water exchange. To improve the current understanding of the cycling of ethanol and acetaldehyde in coastal seawater and surface waters, this project will measure: 1) chemical and biological degradation rates of ethanol and acetaldehyde in coastal waters; 2) the rate and efficiency of the biological production of acetaldehyde from ethanol by microbial organisms; 3) ethanol and acetaldehyde concentrations in air and surface waters; 4) the ethanol and acetaldehyde source strength of estuary and saltmarsh sediments; and 5) ethanol and acetaldehyde photochemical production rates in surface waters.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.



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Funding

Funding SourceAward
NSF Division of Ocean Sciences (NSF OCE)
NSF Division of Ocean Sciences (NSF OCE)

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