| Contributors | Affiliation | Role |
|---|---|---|
| Raven, Morgan Reed | University of California-Santa Barbara (UCSB) | Principal Investigator |
| Evans, Natalya | University of California-Santa Barbara (UCSB) | Scientist |
| Martinez, Aaron | University of California-Santa Barbara (UCSB) | Scientist |
| Neibauer, Jacquelyn A. | University of Washington (UW) | Scientist |
| Crotteau, Molly | University of California-Santa Barbara (UCSB) | Student |
| Fishburn, Jordan | University of California-Santa Barbara (UCSB) | Student |
| Karagiannis, Marianna | University of California-Santa Barbara (UCSB) | Student |
| Rauch, Shannon | Woods Hole Oceanographic Institution (WHOI BCO-DMO) | BCO-DMO Data Manager |
Nine sediment cores were collected from three different sites in Clayoquot Sound, Vancouver Island, Canada in October 2023. One core was used for porewater sampling; this core was sampled immediately with Rhizon samplers. A second core was extruded under argon for geochemical measurements. (See "Related Datasets" for the sediment geochemical data.) 1 milliliter (mL) of sediment was added to a cryovial and frozen at -20 degrees Celsius (°C) for future DNA extraction. 5 mL of sediment was added to an exetainer containing 5 mL of 1 N NaOH to measure sediment methane concentrations. The remaining sediment from each extruded interval was added immediately to falcon tubes containing 10 mL of 20% zinc acetate to precipitate sulfides and halt microbial activity. A third archive core was immediately frozen at -20°C.
Porewater samples from each core were aliquoted to measure pH and the concentrations of dissolved Fe(II), sulfate, and sulfide. pH was determined using the dye meta-cresol purple via a UV-Vis spectrophotometer (Genesys 150) (Clayton and Byrne 1993). Fe(II) was determined using a ferrozine assay (Jeitner 2014). Sulfate was measured via ion chromatography (Metrohm 930 Compact IC Flex). Sulfide was precipitated as zinc sulfide in the field by adding 4 mL of porewater to 4 mL of sparged 20% zinc acetate solution. To avoid sulfate contamination, porewater zinc sulfide samples were subjected to a strong acid hydrolysis (6 N HCl, 60°C, 2 hours) under N₂ to volatilize zinc sulfides; sulfide was trapped as zinc sulfide in 5% zinc acetate solution, oxidized to sulfate with 30% H₂O₂, and measured via ion chromatography (Metrohm 930 Compact IC Flex).
Samples analyzed in this study were collected within Ahousaht Territory, on the west coast of Vancouver Island, British Columbia. We respectfully acknowledge the Ahousaht Nation and the Maaqutusiis Hahoulthee Stewardship Society for their stewardship of these lands and for the opportunity to conduct research within their territory.
Organic C/N/S concentrations were calculated with a sulfanilamide standard curve (0.5 – 25 micromoles (µmole) N, 1.5 – 75 µmole C, 0.25 – 12 µmole S). Sample δ13C values were calibrated using carbon isotope standards USGS-61 (35.05‰), 62 (-14.79‰), and 63 (1.17‰) run in triplicate and are reported relative to Vienna Pee Dee Belemnite. Sulfate concentrations were calibrated using a sulfate standard curve (0.1 – 100 parts per million (ppm)). Fe(II) concentrations were calibrated using a Fe(II) standard curve (0 – 80 µM).
- Imported original file "20251007_FJ_porewater.csv" into the BCO-DMO system.
- Converted the date field to YYYY-MM-DD format.
- Saved the final file as "992752_v1_porewater_geochemistry.csv".
| Parameter | Description | Units |
| site | Site number (51.5, 47, or 48) where sediment core was taken | unitless |
| latitude | Latitude of sampling location | decimal degrees |
| longitude | Longitude of sampling location | decimal degrees |
| date | Date sample was collected | unitless |
| core | The sediment cores were labeled porewater, highres, and archive | unitless |
| depth | Sampling depth relative to sediment-water interface | centimeters |
| H2S | Concentration of porewater sulfide | millimolar |
| H2S_e | Error associated with H2S | millimolar |
| SO4 | Concentration of porewater sulfate | millimolar |
| SO4_e | Error associated with SO4 | millimolar |
| Fe | Concentration of dissolved Fe(II) in sediment porewater | micromolar |
| Fe_e | Error associated with Fe | micromolar |
| pH | pH of sediment porewater | micromolar |
| Dataset-specific Instrument Name | Metrosep A Supp 5 100/4.0 column and Metrohm 930 Compact IC Flex |
| Generic Instrument Name | Ion Chromatograph |
| Dataset-specific Description | Used to measure concentrations of sulfate, sulfide, AVS, and CRS. |
| Generic Instrument Description | Ion chromatography is a form of liquid chromatography that measures concentrations of ionic species by separating them based on their interaction with a resin. Ionic species separate differently depending on species type and size. Ion chromatographs are able to measure concentrations of major anions, such as fluoride, chloride, nitrate, nitrite, and sulfate, as well as major cations such as lithium, sodium, ammonium, potassium, calcium, and magnesium in the parts-per-billion (ppb) range. (from http://serc.carleton.edu/microbelife/research_methods/biogeochemical/ic....) |
| Dataset-specific Instrument Name | Mulitcorer |
| Generic Instrument Name | Multi Corer |
| Dataset-specific Description | Used to collect sediment cores. |
| Generic Instrument Description | The Multi Corer is a benthic coring device used to collect multiple, simultaneous, undisturbed sediment/water samples from the seafloor. Multiple coring tubes with varying sampling capacity depending on tube dimensions are mounted in a frame designed to sample the deep ocean seafloor. For more information, see Barnett et al. (1984) in Oceanologica Acta, 7, pp. 399-408. |
| Dataset-specific Instrument Name | Genesys 150 UV-Vis Spectrophotometer |
| Generic Instrument Name | Spectrophotometer |
| Dataset-specific Description | Used to measure Fe(II) and pH. |
| Generic Instrument Description | An instrument used to measure the relative absorption of electromagnetic radiation of different wavelengths in the near infra-red, visible and ultraviolet wavebands by samples. |
| Website | |
| Platform | R/V Rachel Carson (UW) |
| Start Date | 2023-10-02 |
| End Date | 2023-10-08 |
| Description | See more information from R2R: https://www.rvdata.us/search/cruise/RC0107 |
NSF Award Abstract:
CAREER: Particle-Hosted Sulfur Cycling and Organic Matter Burial in Oxygen Deficient Zones
Areas of the ocean without dissolved oxygen are called anoxic zones. These environments are increasing due to human activities and climate change. Large amounts of organic carbon are buried in sediments below anoxic zones. However, we do not fully understand why organic carbon is preserved in these zones. This project seeks to understand a newly discovered process that may contribute to carbon preservation in anoxic zones. The process is called organic matter sulfurization. Through this process, organic matter is transformed and effectively ?pickled? by reacting with sulfide. Rapid sulfurization reactions were identified for the first time in sinking marine particles and may have larger effect on carbon burial in sediments than previously thought. This project will be the first to provide measurements of the scale and significance of rapid organic matter sulfurization in modern anoxic zones. This project includes field and laboratory studies. The research will involve a team of students, including a graduate student and six undergraduates, who will be supported through a peer mentorship program. Undergraduate researchers will be recruited from the inaugural class of a newly developed Practical Research Skills course (Earth 101A) at the University of California Santa Barbara. It seeks to help undergraduates develop critical thinking and observational skills that have broad applicability. This project will launch a self-sustaining and vigorous research program in marine biogeochemistry, heavily invested in undergraduate research education, with impacts that will outlast its five-year duration.
The overarching research goal of this project is to assess the contribution of sulfurization reactions to organic carbon preservation in anoxic environments. After constructing and testing a set of customized particle traps, an expedition will be conducted to the marine anoxic zone off the coast of Mexico. Sinking particles, suspended materials, and surface sediments will be collected at three sites on the Mexican shelf and slope, that have generally high local productivity and gradients in bottom-water oxygen concentration. In the field, the rates and isotopic fractionation of microbial sulfate reduction and organic sulfur formation will be measured with stable and radioactive isotope tracers. Subsequently, organic sulfur sources from both natural samples and laboratory experiments will be characterized using mass spectrometry, X-ray absorption spectroscopy, and other geochemical techniques. Together, the results of this work will identify the timing and location of organic matter sulfurization in this environment, which have substantial implications for both modeling marine carbon fluxes and interpreting the geologic record. This study will provide the first quantitative estimates of the scale of organic matter sulfurization in anoxic marine zones, its contribution to sedimentary carbon burial, and its sensitivities to environmental change. Simultaneously, this project will improve the Earth Science undergraduate curriculum at the University of California Santa Barbara through the development of a clear, supportive, and accessible mechanism for including students in research.
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.
| Funding Source | Award |
|---|---|
| NSF Division of Ocean Sciences (NSF OCE) |