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Food webs trace the flow of organic matter and energy among producers and consumers; for pelagic marine food webs, network complexity directly influences the amount and form of carbon exported to the deep ocean via the biological pump. Here we present a synoptic view of mixed layer food web dynamics observed during the late summer 2018 EXport Processes in the Ocean from Remote Sensing (EXPORTS) field campaign in the subarctic Northeast Pacific at the long-running time-series site, Ocean Station Papa. Carbon biomass reservoirs of phytoplankton, microzooplankton, and bacterioplankton, were approximately equal while mesozooplankton biomass was 70% lower. Live organisms composed ∼40% of the total particulate organic carbon within the mixed layer: the remainder was attributed to detritus. Rates of carbon transfer among reservoirs indicated production and assimilation rates were well balanced by losses, leaving little organic carbon available for export. The slight positive net community production rate generated organic carbon that was exported from the system in the form of food web byproducts, such as large fecal pellets generated by mesozooplankton. This characteristically regenerative food web had relatively slow turnover times with small-magnitude transfers of carbon relative to standing stocks that occurred amidst a high background concentration of detrital particles and dissolved organic matter. The concurrent estimation of food web components and rates revealed that separated processes dominated the transfer of carbon within the food web compared to those that contributed to export.Plain Language SummaryThe biological carbon pump drives a downward flux of organic matter from the sunlit surface ocean to the vast ocean interior. Ecological interactions in the surface ocean directly affect the amount and type of carbon that is exported to the deep ocean. In this study, we present a synthesis of the late summer mixed layer food web in the Northeast Pacific that was extensively characterized during the 2018 EXport Processes in the Ocean from Remote Sensing (EXPORTS) field campaign. We found the majority of carbon was recycled within the mixed layer by microbes through multiple transfers between producers and consumers. Larger organisms, mesozooplankton and salps, only consumed a small amount of carbon but through the formation of sinking fecal pellets were the main mechanism of transporting carbon out of the system. The study highlights the need to concurrently study microbial and large organism dynamics to develop a predictive understanding of the fate of organic carbon in the oceans.Key PointsThe microbial loop dominated carbon flow in the late summer mixed layer food web of the North Pacific, most net production was respired leaving little carbon available for export.Active production and consumption of organic carbon occurred amid a high background of detrital particulate organic carbon (58% of total) with slow turnover time, 66 d.Mesozooplankton which had relatively minor carbon consumption rates created the majority of export production due to efficient repackaging of consumed material.

Bacterioplankton play a central role in carbon cycling, yet their relative contributions to carbon production and removal can be difficult to constrain. As part of the Export Processes in the Ocean from RemoTe Sensing (EXPORTS) program, this study identifies potential influences of bacterioplankton community and dissolved organic matter (DOM) composition on carbon cycling at Ocean Station Papa in August 2018. Surface (5–35 m) bacterioplankton production rates and stocks spanned a 2- to 3-fold range over the 3-week cruise and correlated positively with the DOM degradation state, estimated using the mole proportion of total dissolved amino acids. When the DOM was more degraded, 16S rRNA gene amplicon data revealed a less diverse bacterioplankton community with a significant contribution from members of the Flavobacteriaceae family. Over the course of 7–10 d, as the DOM quality improved (became less degraded) and bacterioplankton productivity increased, the responding bacterioplankton community became more diverse, with increased relative contributions from members of the SAR86, SAR11 and AEGEAN-169 clades. The cruise mean for mixed layer, depth-integrated bacterioplankton carbon demand (gross bacterioplankton production) was 5.2 mmol C m−2 d−1, representing 60% of net primary production, where the difference between net primary production and bacterioplankton carbon demand was less than sinking flux at 50 m. The concentrations of dissolved organic carbon (cruise average of 58.5 µM C) did not exhibit a systematic change over the cruise period. Therefore, we hypothesize that carbon supplied from gross carbon production, values that were 2- to 3-fold greater than net primary production, provided the carbon necessary to account for the sinking flux and bacterioplankton carbon demand that were in excess of net primary production. These findings highlight the central contributions of bacterioplankton to carbon cycling at Ocean Station Papa, a site of high carbon recycling.

Lignin phenol, pollen, and diatom analyses were performed on dated sediments (13,533–8993 cal yr B.P.) recovered from Fallen Leaf Lake, California. This multiproxy data set constrains the end of the Tioga glaciation in the Lake Tahoe Basin and reconstructs the response of the region’s aquatic and terrestrial ecosystems to climatic changes that accompanied the Younger Dryas, the end of the Pleistocene, and early Holocene warming. From the Pleistocene to the Holocene, lignin concentrations and syringyl/vanillyl (S/V) ratios increased, while cinnamyl/vanillyl (C/V) ratios and the lignin phenol vegetation index (LPVI) decreased, recording the proliferation of woody plant material and, particularly, the expansion of angiosperms as the Tioga glaciation ended and temperatures warmed. This interpretation is constrained by lignin phenol analyses of plant material from Fallen Leaf Lake’s present-day watershed. Complementary palynological analyses show a transition from a gymnosperm-dominated landscape to a more mixed angiosperm-gymnosperm vegetation assemblage that formed as closed canopy forests became more open and grasses and aster colonized meadows. Aquatic flora assemblages, in the form of greater amounts of green algae and greater percentages of diatom phytoplankton, indicate increased levels of lake primary productivity in response to warming. Principal component analysis (PCA) distinctly resolves the Pleistocene from the Holocene diatom flora. The Pleistocene flora is dominated by cyclotelloids and low-mantled Aulacoseira species that are rare in Fallen Leaf Lake today, but common at higher and colder elevations that may resemble the Pleistocene Fallen Leaf Lake. The Holocene diatom flora is dominated by Aulacoseira subarctica.

International audience; The goal of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) field campaign is to develop a predictive understanding of the export, fate, and carbon cycle impacts of global ocean net primary production. To accomplish this goal, observations of export flux pathways, plankton community composition, food web processes, and optical, physical, and biogeochemical (BGC) properties are needed over a range of ecosystem states. Here we introduce the first EXPORTS field deployment to Ocean Station Papa in the Northeast Pacific Ocean during summer of 2018, providing context for other papers in this special collection. The experiment was conducted with two ships: a Process Ship, focused on ecological rates, BGC fluxes, temporal changes in food web, and BGC and optical properties, that followed an instrumented Lagrangian float; and a Survey Ship that sampled BGC and optical properties in spatial patterns around the Process Ship. An array of autonomous underwater assets provided measurements over a range of spatial and temporal scales, and partnering programs and remote sensing observations provided additional observational context. The oceanographic setting was typical of late-summer conditions at Ocean Station Papa: a shallow mixed layer, strong vertical and weak horizontal gradients in hydrographic properties, sluggish sub-inertial currents, elevated macronutrient concentrations and low phytoplankton abundances. Although nutrient concentrations were consistent with previous observations, mixed layer chlorophyll was lower than typically observed, resulting in a deeper euphotic zone. Analyses of surface layer temperature and salinity found three distinct surface water types, allowing for diagnosis of whether observed changes were spatial or temporal. The 2018 EXPORTS field deployment is among the most comprehensive biological pump studies ever conducted. A second deployment to the North Atlantic Ocean occurred in spring 2021, which will be followed by focused work on data synthesis and modeling using the entire EXPORTS data set.

The oceans teem with heterotrophic bacterioplankton that play an appreciable role in the uptake of dissolved organic carbon (DOC) derived from phytoplankton net primary production (NPP). As such, bacterioplankton carbon demand (BCD), or gross heterotrophic production, represents a major carbon pathway that influences the seasonal accumulation of DOC in the surface ocean and, subsequently, the potential vertical or horizontal export of seasonally accumulated DOC. Here, we examine the contributions of bacterioplankton and DOM to ecological and biogeochemical carbon flow pathways, including those of the microbial loop and the biological carbon pump, in the Western North Atlantic Ocean (∼39–54°N along ∼40°W) over a composite annual phytoplankton bloom cycle. Combining field observations with data collected from corresponding DOC remineralization experiments, we estimate the efficiency at which bacterioplankton utilize DOC, demonstrate seasonality in the fraction of NPP that supports BCD, and provide evidence for shifts in the bioavailability and persistence of the seasonally accumulated DOC. Our results indicate that while the portion of DOC flux through bacterioplankton relative to NPP increased as seasons transitioned from high to low productivity, there was a fraction of the DOM production that accumulated and persisted. This persistent DOM is potentially an important pool of organic carbon available for export to the deep ocean via convective mixing, thus representing an important export term of the biological carbon pump.

Author(s): Morrow, RM; Ohman, MD; Goericke, R; Kelly, TB; Stephens, BM; Stukel, MR | Abstract: Predicting marine carbon sequestration in a changing climate requires mechanistic understanding of the processes controlling sinking particle flux under different climatic conditions. The recent occurrence of a warm anomaly (2014–2015) followed by an El Nino (2015–2016) in the southern sector of the California Current System presented an opportunity to analyze changes in the biological carbon pump in response to altered climate forcing. We compare primary production, mesozooplankton grazing, and carbon export from the euphotic zone during quasi-Lagrangian experiments conducted in contrasting conditions: two cruises during warm years - one during the warm anomaly in 2014 and one toward the end of El Nino 2016 – and three cruises during El Nino-neutral years. Results showed no substantial differences in the relationships between vertical carbon export and its presumed drivers (primary production, mesozooplankton grazing) between warm and neutral years. Mesozooplankton fecal pellet enumeration and phaeopigment measurements both showed that fecal pellets were the dominant contributor to export in productive upwelling regions. In more oligotrophic regions, fluxes were dominated by amorphous marine snow with negligible pigment content. We found no evidence for a significant shift in the relationship between mesozooplankton grazing rate and chlorophyll concentration. However, mass-specific grazing rates were lower at low-to-moderate chlorophyll concentrations during warm years relative to neutral years. We also detected a significant difference in the relationship between phytoplankton primary production and photosynthetically active radiation between years: at similar irradiance and nutrient concentrations, productivity decreased during the warm events. Whether these changes resulted from species composition changes remains to be determined. Overall, our results suggest that the processes driving export remain similar during different climate conditions, but that species compositional changes or other structural changes require further attention.

The bioavailability of organic matter (OM) to marine heterotrophic bacterioplankton is determined by both the chemical composition of OM and the microbial community composition. In the current study, changes in OM bioavailability were identified at Ocean Station Papa as part of the 2018 Export Processes in the Ocean from Remote Sensing (EXPORTS) field study. Removal rates of carbon (C) in controlled experiments were significantly correlated with the initial composition of total hydrolyzable amino acids, and C removal rates were high when the amino acid degradation index suggested a more labile composition. Carbon remineralization rates averaged 0.19 ± 0.08 μmol C L–1 d–1 over 6–10 days while bacterial growth efficiencies averaged 31 ± 7%. Amino acid composition and tandem mass spectrometry analysis of compound classes also revealed transformations to a more degraded OM composition during experiments. There was a log2-fold increase in the relative abundances of 16S rDNA-resolved bacterioplankton taxa in most experiments by members of the Methylophilaceae family (OM43 genus) and KI89A order. Additionally, when OM was more bioavailable, relative abundances increased by at least threefold for the classes Bacteroidetes (Flavobacteriaceae NS2b genus), Alphaproteobacteria (Rhodobacteraceae Sulfitobacter genus), and Gammaproteobacteria (Alteromonadales and Ectothiorhodospiraceae orders). Our data suggest that a diverse group of bacterioplankton was responsible for removing organic carbon and altering the OM composition to a more degraded state. Elevated community diversity, as inferred from the Shannon–Wiener H index, may have contributed to relatively high growth efficiencies by the bacterioplankton. The data presented here shed light on the interconnections between OM bioavailability and key bacterioplankton taxa for the degradation of marine OM.

Dissolved organic matter (DOM) is arguably one of the most complex exometabolomes on earth, and is comprised of thousands of compounds, that together contribute more than 600 × 1015 g carbon. This reservoir is primarily the product of interactions between the upper ocean's microbial food web, yet abiotic processes that occur over millennia have also modified many of its molecules. The compounds within this reservoir play important roles in determining the rate and extent of element exchange between inorganic reservoirs and the marine biosphere, while also mediating microbe-microbe interactions. As such, there has been a widespread effort to characterize DOM using high-resolution analytical methods including nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS). To date, molecular information in DOM has been primarily obtained through calculated molecular formulas from exact mass. This approach has the advantage of being non-targeted, accessing the inherent complexity of DOM. Molecular structures are however still elusive and the most commonly used instruments are costly. More recently, tandem mass spectrometry has been employed to more precisely identify DOM components through comparison to library mass spectra. Here we describe a data acquisition and analysis workflow that expands the repertoire of high-resolution analytical approaches available to access the complexity of DOM molecules that are amenable to electrospray ionization (ESI) MS. We couple liquid chromatographic separation with tandem MS (LC-MS/MS) and a data analysis pipeline, that integrates peak extraction from extracted ion chromatograms (XIC), molecular formula calculation and molecular networking. This provides more precise structural characterization. Although only around 1% of detectable DOM compounds can be annotated through publicly available spectral libraries, community-wide participation in populating and annotating DOM datasets could rapidly increase the annotation rate and should be broadly encouraged. Our analysis also identifies shortcomings of the current data analysis workflow that need to be addressed by the community in the future. This work will lay the foundation for an integrative, non-targeted molecular analysis of DOM which, together with next generation sequencing, meta-proteomics and physical data, will pave the way to a more comprehensive understanding of the role of DOM in structuring marine ecosystems.

Enhanced vertical carbon transport (gravitational sinking and subduction) at mesoscale ocean fronts may explain the demonstrated imbalance of new production and sinking particle export in coastal upwelling ecosystems. Based on flux assessments from 238U:234Th disequilibrium and sediment traps, we found 2 to 3 times higher rates of gravitational particle export near a deep-water front (305 mg C⋅m-2⋅d-1) compared with adjacent water or to mean (nonfrontal) regional conditions. Elevated particle flux at the front was mechanistically linked to Fe-stressed diatoms and high mesozooplankton fecal pellet production. Using a data assimilative regional ocean model fit to measured conditions, we estimate that an additional ∼225 mg C⋅m-2⋅d-1 was exported as subduction of particle-rich water at the front, highlighting a transport mechanism that is not captured by sediment traps and is poorly quantified by most models and in situ measurements. Mesoscale fronts may be responsible for over a quarter of total organic carbon sequestration in the California Current and other coastal upwelling ecosystems.

Carotenoids, a common biochemical class, can be directly linked to long-term carbon storage in the ocean’s water column., The ocean’s biota sequester atmospheric carbon dioxide (CO2) in part by producing dissolved organic matter (DOM) that persists in the ocean for millennia. This long-term accumulation of carbon may be facilitated by abiotic and biotic production of chemical structures that resist degradation, consequently contributing disproportionately to refractory DOM. Compounds that are selectively preserved in seawater were identified in solid-phase extracted DOM (PPL-DOM) using comprehensive gas chromatography (GC) coupled to mass spectrometry (MS). These molecules contained cyclic head groups that were linked to isoprenoid tails, and their overall structures closely resembled carotenoid degradation products (CDP). The origin of these compounds in PPL-DOM was further confirmed with an in vitro β-carotene photooxidation experiment that generated water-soluble CDP with similar structural characteristics. The molecular-level identification linked at least 10% of PPL-DOM carbon, and thus 4% of total DOM carbon, to CDP. Nuclear magnetic resonance spectra of experimental CDP and environmental PPL-DOM overlapped considerably, which indicated that even a greater proportion of PPL-DOM was likely composed of CDP. The CDP-rich DOM fraction was depleted in radiocarbon (14C age > 1500 years), a finding that supports the possible long-term accumulation of CDP in seawater. By linking a specific class of widespread biochemicals to refractory DOM, this work provides a foundation for future studies that aim to examine how persistent DOM forms in the ocean.

The chemical characteristics of bulk (sterile-filtered) and high molecular-weight dissolved organic matter (HMW DOM) were analyzed for freshwater (St. Louis River, Minnesota to Lake Superior) and saline (Elizabeth River, Virginia to Chesapeake Bay) river-to-receiving basin transects. Dissolved organic carbon concentrations and UV–Visible spectroscopy of bulk DOM demonstrated a reduction in organic carbon, colored DOM and aromatic compounds downstream in both transects. The proportion of DOM recoverable via ultrafiltration as HMW material also decreased downstream in both transects, although there was an offset in recoveries between the transects that may be explained by the effects of ionic strength and/or differences in ultrafiltration technique. The analysis of HMW DOM by Fourier transform infrared spectroscopy illustrated similar trends between transects, with a general shift from aromatic/carboxylic compounds nearshore to aliphatic/carbohydrate materials offshore. The parallel changes observed along saline and freshwater transects imply that similar processes play significant roles in the down-gradient alteration of DOM and that ionic strength or pH changes cause second-order effects.

Within the aquatic carbon cycle, dissolved organic carbon (DOC) plays key roles: as a link between terrestrial and aquatic systems, a major food source for biota, a player in photochemical reactions and a sunscreen/competitor for light for aquatic organisms. The molecular-level composition of the dissolved organic matter (DOM) is believed to determine the efficacy of DOM in these roles. While much detailed compositional information is available on selected DOM isolates from both freshwater and marine systems, relatively few studies have presented molecular information for multiple sites within the same system and few of these have focused upon large lakes. Therefore, we present an initial study of surface water DOM characteristics in a temperate large lake (Lake Superior, USA) and selected tributaries. UV–visible spectroscopy, electrospray mass spectrometry and Fourier transform infrared spectroscopy (FTIR) analyses of bulk DOM, along with FTIR and direct temperature-resolved mass spectrometry analyses of C 18 extracts, illustrate a shift from higher molecular weight organic matter enriched in protein and lignin at the tributary sites toward compositionally different material in the open lake. Differences in optical characteristics and DOC concentration between tributary and open lake sites are consistent with possible photodegradation of tributary DOM. Comparison of our FTIR data with those from a previous Chesapeake Bay study indicates that DOM in both the freshwater tributaries and the open lake contain a wider range of aromatic and carbohydrate components than that in the saltwater tributary and bay. This highlights the need for further cross system comparisons of natural organic matter composition.

Transport of pesticide to groundwater is governed in part by sorption of the pesticide to soil particles. Sorption may be dependent on soil moisture conditions, but limited data are available from which to elucidate the effect. Our objective was to determine the effect of soil water content on the sorption coefficient of a hydrophilic pesticide. Sorption of dicamba (3,6-dichloro-2-methoxybenzoic acid) was measured in three soils, each at two initial water contents. At low water contents (approximately 0.05 kg kg⁻¹), sorption coefficients were similar for all three soils, ranging from 0.01 L kg⁻¹ for the loamy sand to 0.07 L kg⁻¹ for the silty clay loam. At higher water contents (0.19-0.24 kg kg⁻¹), the sorption coefficient for the loamy sand was unchanged, for the silt loam it was doubled, and for the silty clay loam it was increased almost sixfold. Multiple regression analysis revealed a strong linear relationship between the sorption coefficient and the product of soil water content and organic C content (r² = 0.86). The number of dicamba sorption sites probably increases with soil organic C content, while the accessibility of these sites appears to increase with soil water content. This may be caused by the decreasing hydrophobicity of soil organic matter with increasing water content. The effects of water content on pesticide sorption require further research and may ultimately have implications for the methods used to determine sorption and for managing pesticide application.

Organic matter (OM) plays a major role in both terrestrial and oceanic biogeochemical cycles. The amount of carbon stored in these systems is far greater than that of carbon dioxide (CO2 ) in the atmosphere, and annual fluxes of CO2 from these pools to the atmosphere exceed those from fossil fuel combustion. Understanding the processes that determine the fate of detrital material is important for predicting the effects that climate change will have on feedbacks to the global carbon cycle. However, Earth System Models (ESMs) typically utilize very simple formulations of processes affecting the mineralization and storage of detrital OM. Recent changes in our view of the nature of this material and the factors controlling its transformation have yet to find their way into models. In this review, we highlight the current understanding of the role and cycling of detrital OM in terrestrial and marine systems and examine how this pool of material is represented in ESMs. We include a discussion of the different mineralization pathways available as organic matter moves from soils, through inland waters to coastal systems and ultimately into open ocean environments. We argue that there is strong commonality between aspects of OM transformation in both terrestrial and marine systems and that our respective scientific communities would benefit from closer collaboration.

When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with 14C-labeled chemical. The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, Kd, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN Kd values were approximately 2-3 times (average Kd = 0.71 L kg-1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (Kd = 0.33 L kg-1), but similar for the two methods in sand (0.12 vs 0.09 L kg-1) soils. Dicamba Kd values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg-1), however, the Kd values were the same for the two methods in the sand (approximately 0.06 L kg-1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.