Pacific Ocean samples were collected from Station ALOHA (22.45°N, 158.00°W) during the Hawaii Ocean Time-series (HOT) 301 cruise aboard the R/V Ka`imikai-O-Kanaloa in April 2018. Atlantic Ocean samples were collected from Hydrostation S (31.67°N, 64.17°W) during the Bermuda Atlantic Time Series (BATS) 358 cruise aboard the R/V Atlantic Explorer in April 2019. River samples were collected from the main stem of the Amazon (Brazil), Congo (Democratic Republic of the Congo), Northern Dvina (Russia), Kolyma (Russia), and Mississippi Rivers (USA) at various time points between 2011 and 2018. Samples were analyzed for dissolved black carbon (DBC), dissolved organic carbon (DOC), and stable carbon isotopes. Data are published in Table 1 and as Supplemental Data in Wagner et al., 2019 (doi: 10.1038/s41467-019-13111-7).

Table of Contents

• Coverage
• Dataset Description
  • Methods & Sampling
  • Data Processing Description
• Data Files
• Related Publications
• Parameters
• Instruments
• Deployments
• Project Information
• Funding

Sample collection: Pacific Ocean samples were collected from Station ALOHA (22.45°N, 158.00°W) during the Hawaii Ocean Time-series (HOT) 301 cruise aboard the R/V Ka`imikai-O-Kanaloa. Samples from surface and mesopelagic depths (5, 110, 765, and 1000 m) were obtained from two casts on April 17, 2018 and the deep water sample (3500 m) was collected on April 18, 2018. Atlantic Ocean samples were collected from Hydrostation S (31.67°N, 64.17°W) during the Bermuda Atlantic Time Series (BATS) 358 cruise aboard the R/V Atlantic Explorer. Water samples were collected along a depth profile (1, 70, 2000, and 3000 m) on April 8, 2019. All seawater samples were collected using Niskin bottles mounted to the CTD rosette. For each sample, ~10 L was passed, by gravity, through a precleaned in-line capsule filter (Whatman Polycap; 0.2 μm) into acid-cleaned Nalgene fluorinated HDPE carboys and pre-combusted glass vials and acidified to pH 2 using HCl prior to solid phase extraction and DOC analysis. River samples were collected from the main stem of the Amazon, Congo, Northern Dvina, Kolyma, and Mississippi Rivers, upstream of the river mouth where marine inputs were not observed (salinity = 0). One surface water sample was collected from the Amazon River near Óbidos (Brazil; April 20, 2018; 1.92°S, 55.53°W). The Congo River was sampled from a site upstream of the cities of Kinshasa–Brazzaville on the main stem (DR Congo; 4.18°S, 15.21°E). Five samples were collected from the Congo River between August 2011 and April 2012 to account for potential hydrologically driven variations in DBC isotopic composition in a low latitude, subtropical river. Four samples were collected from the Northern Dvina River in Arkhangelsk (64.55°N, 40.51°E) between October 2013 and May 2016 to capture isotopic variations in a high latitude river with extremely variable hydrology. One sample was collected from the Kolyma River, upstream of the city of Cherskiy (August 30, 2015; 68.75°N, 161.29°E). One sample was collected from the Belle Chase Ferry Landing on the Mississippi River, just south of New Orleans, LA (USA; February 23, 2016; 29.82°N, 90.00°W). All river samples were collected in situ using an oil-free pump equipped with a pre-cleaned, in-line capsule filter (Whatman Polycap, 0.2 μm) directly into acid-cleaned Nalgene bottles and pre-combusted glass vials. Samples were acidified to pH 2 using HCl prior to solid phase extraction and DOC analysis.

Dissolved organic carbon analysis and solid phase extraction: Filtered and acidified samples were analyzed for DOC, measured as non-purgable organic carbon using a Shimadzu TOC-L CPH analyzer equipped with an ASI-L autosampler. Sample DOC was quantified using a calibration curve made with a potassium hydrogen phthalate stock solution. Measurement accuracy and reproducibility was assessed by analyzing deep seawater and low carbon water reference materials obtained from the Consensus Reference Material (CRM) project (https://hansell-lab.rsmas.miami.edu/consensus-reference-material/index.html). Analyses of CRM were within 5% of reported values. DOC was isolated from samples via solid phase extraction (SPE; Varian Bond Elut PPL cartridges, 1 g, 6 mL; Dittmar et al., 2008) prior to DBC analysis. Briefly, SPE cartridges were conditioned with methanol, ultrapure water, and acidified water. Filtered and acidified samples were passed through the SPE cartridges by gravity. Isolated DOC was then eluted from the SPE cartridges with methanol and stored at −20 °C until DBC analysis.

Dissolved black carbon quantification: Sample DBC was quantified using the BPCA method, which chemically degrades condensed aromatic compounds into benzenehexacarboxylic acid (B6CA) and benzenepentacarboxylic acid (B5CA) molecular markers. BPCAs were oxidized and quantified following previously described methods (Wagner et al., 2017; Barton and Wagner, 2022). Briefly, aliquots of SPE-DOC (~0.5 mg-C equivalents) were transferred to 2 mL glass ampules and dried under a stream of argon until complete evaporation of methanol. Concentrated HNO3 (0.5 mL) was added to each ampule, then ampules were flame-sealed and heated to 160 °C for 6 h. After oxidation, ampules were opened and HNO3 was dried at 60 °C under a stream of argon. The BPCA-containing residue was re-dissolved in dilute H3PO4 for subsequent analysis by high performance liquid chromatography (HPLC). Quantification of BPCAs was performed using a Dionex Ultimate 3000 HPLC system equipped with an autosampler, pump, and diode array detector. B6CA and B5CA were separated on an Agilent Poroshell 120 phenyl-hexyl column (4.6 × 150 mm, 2.7 μm) using an aqueous gradient of H3PO4 (0.6 M; pH 1) and sodium phosphate (20 mM; pH 6) buffers. BPCAs were quantified using calibration curves for commercially available B6CA and B5CA using a 5mM BPCA-C stock solution. River samples were oxidized and analyzed in duplicate. Ocean samples were oxidized and analyzed in triplicate. The average coefficients of variation for replicate measurements of B6CA and B5CA were <5%. Sample DBC concentrations were calculated using the established power relationship between DBC (μM-C) and the sum of B6CA and B5CA (nM-BPCA) (Stubbins et al., 2015).

Stable carbon isotopic analyses: Riverine and oceanic SPE-DOC methanol extracts were transferred to smooth-walled tin capsules (~0.25 mg-C per capsule) and methanol evaporated to dryness in an oven set to 60 °C. Sample-containing tin capsules were folded and combusted using a Thermo Scientific Flash EA Isolink CNSOH interfaced with a Thermo Scientific Delta V Plus IRMS. The δ13C composition of each sample was calibrated against an internal lab organic matter reference material (chitin from shrimp shells), which was previously calibrated against NIST glutamic acid (RM 8573) and sucrose (RM 8542) primary isotope reference standards. The 13C content is expressed in δ13C per mil (‰) notation relative to Vienna Pee Dee Belemnite (VPDB). River samples were measured in duplicate and ocean samples were measured in triplicate. The standard deviation of replicate EA-IRMS measurements was <0.1‰. Compound-specific stable carbon isotopic values for individual BPCAs were measured using a Dionex Ultimate 3000 HPLC connected to a Delta V IRMS via an LC Isolink interface following methods detailed previously (Wagner et al., 2017). Online oxidation quantitatively converts baseline-separated BPCAs to CO2. BPCA-derived CO2 is then extracted from the mobile phase and dried prior to detection by IRMS. The δ13C values for B5CA and B6CA standards were measured by EA-IRMS following the same procedure described above to calculate and correct for offsets in HPLCIRMS δ13C measurements (Wagner et al., 2017). River samples were analyzed in duplicate and ocean samples were analyzed in triplicate. Standard deviations applied to corrected sample δ13C values were propagated to account for errors associated with replicate EA-IRMS standard BPCA measurements, HPLC-IRMS standard BPCA measurements, and HPLC-IRMS sample BPCA measurements. The 13C content is expressed in δ13C per mil (‰) notation relative to Vienna Pee Dee Belemnite (VPDB). The error associated with corrected δ13C values was typically <0.5‰.

Data Processing:
All data obtained from instrumentation was processed using Microsoft Excel (version 2016 or 2019) following the methodologies described earlier.

BCO-DMO Processing:
- renamed fields to comply with BCO-DMO naming conventions;
- converted dates to YYYY-MM-DD format;
- replaced "N.D." with "nd" (no data);
- removed directionals from Latitude and Longitude columns; converted S and West to negative values.

Coverage: Global rivers (Amazon, Congo, Mississippi, St. Lawrence, Yukon), Atlantic Ocean (BATS), Pacific Ocean (HOT)

NSF Award Abstract:
The char and soot remaining after fire is broadly referred to as black carbon. When char interacts with water, some of it dissolves and is carried away by rivers to the ocean. This soluble component of char is termed "dissolved black carbon" (DBC). Recent research has revealed DBC to be a major component of the carbon cycle. Most notably, DBC is now known to make up 10% of all dissolved organic carbon that rivers carry to the sea. Once in the ocean, DBC remains there for thousands of years, storing carbon that would otherwise be in the atmosphere as carbon dioxide. As carbon dioxide contributes to the greenhouse effect, with higher carbon dioxide in the atmosphere leading to warmer global temperatures, it is important to understand where DBC in the ocean came from and how long it will stay locked away in the deep ocean. In this funded work, we set out to determine the source of the DBC in the ocean. Based upon our previous work that shows rivers export massive amounts of DBC to the coast, it has been suggested that rivers are the main source of DBC to the open ocean. However, in looking more closely at the DBC in rivers and the oceans, we found them to differ in one critical way: they have different isotopic signatures. This precludes them from having the same source, indicating that the DBC in the oceans is not from rivers. Our preliminary work only looked at a small river in Georgia, USA, and in the coastal waters offshore. In this funded project, we will take a global look at the isotopic signatures of DBC collected from large rivers such as the Amazon, Mississippi, and Yukon, and from the middle of the Atlantic and Pacific Oceans. If we find there is no overlap in the isotopes of the DBC from these major global rivers and ocean waters, we can conclude that rivers are not the main source of oceanic DBC and will need to search for new explanations of how molecules produced by fire end up in the deep ocean.

The project will enhance the career and continue the training of a first-time investigator and train undergraduate students in real world research through the Northeastern University Cooperative Program. In addition, our findings be adapted to produce learning materials for high school students in collaboration with the Science Journal for Kids.

Previous efforts to track DBC sources in natural waters have come with major limitations, preventing definitive connections to be made between oceanic DBC and its pyrogenic source. Photodegradation, a significant removal process for DBC in surface waters, drastically alters the molecular composition of DBC and erases any potential link between DBC chemical composition and its source. Bulk stable carbon isotopic measurements cannot unambiguously identify sources of DOC subcomponents, such as DBC. As such, this project aims to constrain the oceanic source of DBC by measuring compound-specific stable carbon isotopes of molecular markers (benzenepolycarboxylic acids, or BPCAs), derived exclusively from DBC. Our preliminary data show BPCA-specific isotopic values to have a sufficiently wide dynamic range between riverine and oceanic samples to test our hypotheses. In the current proposal, we aim to 1) isotopically characterize the largest quantified flux of DBC to the ocean (global rivers), 2) assess in situ oceanic variation in DBC stable carbon isotopic signatures, and 3) investigate the potential BPCA-specific fractionation effects of DBC photodegradation. In establishing a robust tracer for DBC source, we will be able to accurately constrain sources of oceanic DBC and further investigate the biogeochemical cycling of DBC across the terrestrial-marine continuum. The results of our research will also assist in answering larger research questions, specifically those regarding the fate of terrigenous DOM in the ocean, which have plagued biogeochemists for decades.

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.