Jutta Niggemann

Global Charcoal Mobilization from Soils via Dissolution and Riverine Transport to the Oceans

Dissolving Charcoal Biomass burning produces 40 to 250 million tons of charcoal per year worldwide. Much of this is preserved in soils and sediments for thousands of years. However, the estimated production rate of charcoal is significantly larger than that of decomposition, and Jaffe et al. (p. 345; see the Perspective by Masiello and Louchouarn) calculate that a large fraction of the charcoal produced by fires is lost from the land through dissolution and transport to the oceans. A larger-than-assumed fraction of charcoal produced by wildfires leaches out of soils and is transported to the oceans. [Also see Perspective by Masiello and Louchouarn] Global biomass burning generates 40 million to 250 million tons of charcoal every year, part of which is preserved for millennia in soils and sediments. We have quantified dissolution products of charcoal in a wide range of rivers worldwide and show that globally, a major portion of the annual charcoal production is lost from soils via dissolution and subsequent transport to the ocean. The global flux of soluble charcoal accounts to 26.5 ± 1.8 million tons per year, which is ~10% of the global riverine flux of dissolved organic carbon (DOC). We suggest that the mobilization of charcoal and DOC out of soils is mechanistically coupled. This study closes a major gap in the global charcoal budget and provides critical information in the context of geoengineering.

Deciphering ocean carbon in a changing world

Dissolved organic matter (DOM) in the oceans is one of the largest pools of reduced carbon on Earth, comparable in size to the atmospheric CO2 reservoir. A vast number of compounds are present in DOM, and they play important roles in all major element cycles, contribute to the storage of atmospheric CO2 in the ocean, support marine ecosystems, and facilitate interactions between organisms. At the heart of the DOM cycle lie molecular-level relationships between the individual compounds in DOM and the members of the ocean microbiome that produce and consume them. In the past, these connections have eluded clear definition because of the sheer numerical complexity of both DOM molecules and microorganisms. Emerging tools in analytical chemistry, microbiology, and informatics are breaking down the barriers to a fuller appreciation of these connections. Here we highlight questions being addressed using recent methodological and technological developments in those fields and consider how these advances are transforming our understanding of some of the most important reactions of the marine carbon cycle.

Inefficient microbial production of refractory dissolved organic matter in the ocean

Dissolved organic matter (DOM) in the oceans constitutes a major carbon pool involved in global biogeochemical cycles. More than 96% of the marine DOM resists microbial degradation for thousands of years. The composition of this refractory DOM (RDOM) exhibits a molecular signature ubiquitously detected in the deep oceans. Surprisingly efficient microbial transformation of labile into stable forms of DOM has been shown previously, implying that microorganisms apparently produce far more RDOM than needed to sustain the global pool. Here we show, by assessing the microbial formation and transformation of DOM in unprecedented molecular detail for 3 years, that most of the microbial DOM is different from RDOM in the ocean. Only <0.4% of the net community production is channelled into a form of DOM that is undistinguishable from oceanic RDOM. Our study provides a molecular background for global models on the production, turnover and accumulation of marine DOM.

Fate of the Amazon River dissolved organic matter in the tropical Atlantic Ocean

Constraining the fate of dissolved organic matter (DOM) delivered by rivers is a key to understand the global carbon cycle, since DOM mineralization directly influences air-sea CO2 exchange and multiple biogeochemical processes. The Amazon River exports large amounts of DOM, and yet the fate of this material in the ocean remains unclear. Here we investigate the molecular composition and transformations of DOM in the Amazon River-ocean continuum using ultrahigh resolution mass spectrometry and geochemical and biological tracers. We show that there is a strong gradient in source and composition of DOM along the continuum, and that dilution of riverine DOM in the ocean is the dominant pattern of variability in the system. Alterations in DOM composition are observed in the plume associated with the addition of new organic compounds by phytoplankton and with bacterial and photochemical transformations. The relative importance of each of these drivers varies spatially and is modulated by seasonal variations in river discharge and ocean circulation. We further show that a large fraction (50–76%) of the Amazon River DOM is surprisingly stable in the coastal ocean. This results in a globally significant river plume with a strong terrigenous signature and in substantial export of terrestrially derived organic carbon from the continental margin, where it can be entrained in the large-scale circulation and potentially contribute to the long-term storage of terrigenous production and to the recalcitrant carbon pool found in the deep ocean.

Utilizing Colored Dissolved Organic Matter to Derive Dissolved Black Carbon Export by Arctic Rivers

Wildfires have produced black carbon (BC) since land plants emerged. Condensed aromatic compounds, a form of BC, have accumulated to become a major component of the soil carbon pool. Condensed aromatics leach from soils into rivers, where they are termed dissolved black carbon (DBC). The transport of DBC by rivers to the sea is a major term in the global carbon and BC cycles. To estimate Arctic river DBC export, 25 samples collected from the six largest Arctic rivers (Kolyma, Lena, Mackenzie, Ob’, Yenisey and Yukon) were analyzed for dissolved organic carbon (DOC), colored dissolved organic matter (CDOM), and DBC. A simple, linear regression between DOC and DBC indicated that DBC accounted for 8.9 ± 0.3% DOC exported by Arctic rivers. To improve upon this estimate, an optical proxy for DBC was developed based upon the linear correlation between DBC concentrations and CDOM light absorption coefficients at 254 nm (a254). Relatively easy to measure a254 values were determined for 410 Arctic river samples between 2004 and 2010. Each of these a254 values was converted to a DBC concentration based upon the linear correlation, providing an extended record of DBC concentration. The extended DBC record was coupled with daily discharge data from the six rivers to estimate riverine DBC loads using the LOADEST modeling program. The six rivers studied cover 53% of the pan-Arctic watershed and exported 1.5 ± 0.1 million tons of DBC per year. Scaling up to the full area of the pan-Arctic watershed, we estimate that Arctic rivers carry 2.8 ± 0.3 million tons of DBC from land to the Arctic Ocean each year. This equates to ~8% of Arctic river DOC export, slightly less than indicated by the simpler DBC vs DOC correlation-based estimate. Riverine discharge is predicted to increase in a warmer Arctic. DBC export was positively correlated with river runoff, suggesting that the export of soil BC to the Arctic Ocean is likely to increase as the Arctic warms.

Deciphering associations between dissolved organic molecules and bacterial communities in a pelagic marine system.

Dissolved organic matter (DOM) is the main substrate and energy source for heterotrophic bacterioplankton. To understand the interactions between DOM and the bacterial community (BC), it is important to identify the key factors on both sides in detail, chemically distinct moieties in DOM and the various bacterial taxa. Next-generation sequencing facilitates the classification of millions of reads of environmental DNA and RNA amplicons and ultrahigh-resolution mass spectrometry yields up to 10 000 DOM molecular formulae in a marine water sample. Linking this detailed biological and chemical information is a crucial first step toward a mechanistic understanding of the role of microorganisms in the marine carbon cycle. In this study, we interpreted the complex microbiological and molecular information via a novel combination of multivariate statistics. We were able to reveal distinct relationships between the key factors of organic matter cycling along a latitudinal transect across the North Sea. Total BC and DOM composition were mainly driven by mixing of distinct water masses and presumably retain their respective terrigenous imprint on similar timescales on their way through the North Sea. The active microbial community, however, was rather influenced by local events and correlated with specific DOM molecular formulae indicative of compounds that are easily degradable. These trends were most pronounced on the highest resolved level, that is, operationally defined ‘species’, reflecting the functional diversity of microorganisms at high taxonomic resolution.

Molecular Signatures of Biogeochemical Transformations in Dissolved Organic Matter from Ten World Rivers

Rivers carry large amounts of dissolved organic matter (DOM) to the oceans thereby connecting terrestrial and marine element cycles. Photo-degradation in conjunction with microbial turnover is considered a major pathway by which terrigenous DOM is decomposed. To reveal globally relevant patterns behind this process, we performed photo-degradation experiments and year-long bio-assays on DOM from ten of the largest world rivers that collectively account for more than one-third of the fresh water discharge to the global ocean. We furthermore tested the hypothesis that the terrigenous component in deep ocean DOM may be far higher than biomarker studies suggest, because of the selective photochemical destruction of characteristic biomolecules from vascular plants. DOM was molecularly characterized by a combination of non-targeted ultrahigh-resolution mass spectrometry and quantitative molecular tracer analyses. We show that the reactivity of DOM is globally related to broad catchment properties. Basins that are dominated by forest and grassland export more photo-degradable DOM than other rivers. Chromophoric compounds are mainly vascular plant-derived polyphenols, and partially carry a pyrogenic signature from vegetation fires. These forest and grassland dominated rivers lost up to 50% of dissolved organic carbon (DOC) during irradiation, and up to 85% of DOC was lost in total if subsequently bio-incubated for one year. Basins covered by cropland, on the other hand, export DOM with a higher proportion of photo-resistant and bio-available DOM which is enriched in nitrogen. In these rivers, 30% or less of DOC was photodegraded. Consistent with previous studies, we found that riverine DOM resembled marine DOM in its broad molecular composition after extensive degradation, mainly due to almost complete removal of aromatics. More detailed molecular fingerprinting analysis (based on the relative abundance of >4000 DOM molecular formulae), however, revealed clear differences between degraded riverine and deep-sea DOM (molecular Bray-Curtis dissimilarity of ~50%). None of our experimental treatments enhanced the molecular similarity between the rivers and the deep ocean. We conclude that terrigenous DOM retains a specific molecular signature during photo-degradation on much longer time scales than previously assumed and that substantial, thus far unknown, molecular transformations occur prior to downward convection into the deep oceanic basins.

A novel molecular approach for tracing terrigenous dissolved organic matter into the deep ocean

Marine dissolved organic matter (DOM) contains one of the largest exchangeable organic carbon pools on Earth. Riverine input represents an important source of DOM to the oceans, yet much remains to be learned about the fate of the DOM linking terrestrial to oceanic carbon cycles through rivers at the global scale. Here we use ultrahigh-resolution mass spectrometry to identify 184 molecular formulae that are indicators of riverine inputs (referred to as t-Peaks) and to track their distribution in the deep North Atlantic and North Pacific Oceans. The t-Peaks were found to be enriched in the Amazon River, to be highly correlated with known tracers of terrigenous input, and to be observed in all samples from four different rivers characterized by vastly different landscapes and vegetation coverage spanning equatorial (Amazon and Congo), subtropical (Altamaha), and Arctic (Kolyma) regions. Their distribution reveals that terrigenous organic matter is injected into the deep ocean by the global meridional overturning circulation, indicating that a fraction of the terrigenous DOM introduced by rivers contributes to the DOM pool observed in the deep ocean and to the storage of terrigenous organic carbon. This novel molecular approach can be used to further constrain the transfer of DOM from land to sea, especially considering that Fourier transform ion cyclotron resonance mass spectrometer analysis is becoming increasingly frequent in studies characterizing the molecular composition of DOM in lakes, rivers, and the ocean.

Dissolved Black Carbon in the Headwaters-to-Ocean Continuum of Paraíba Do Sul River, Brazil

Rivers annually carry 25-28 Tg carbon in the form of pyrogenic dissolved organic matter (dissolved black carbon, DBC) into the ocean, which is equivalent to about 10% of the entire riverine land-ocean flux of dissolved organic carbon (DOC). The objective of this study was to identify the main processes behind the release and turnover of DBC on a riverine catchment scale. As a model system, we chose the headwater-to-ocean continuum of Paraiba do Sul River (Brazil), the only river system with long-term DBC flux data available. The catchment was originally covered by Atlantic rain forest (mainly C3 plants) which was almost completely destroyed over the past centuries by slash-and-burn. As a result, large amounts of wood-derived charcoal reside in the soils. Today, fire-managed pasture and sugar cane (both dominated by C4 plants) cover most of the catchment area. Water samples were collected along the river, at the main tributaries, and also along the salinity gradient in the estuary and up to 35 km offshore during three different seasons. DBC was determined on a molecular level as benzenepolycarboxylic acids (BPCAs). Stable carbon isotopes (δ13C) were determined in solid phase extractable DOC (SPE-DOC) to distinguish C4 and C3 sources. Our results clearly show a relationship between hydrology and DBC concentrations in the river, with highest DBC concentrations and fluxes in the wet season (flux of 770 moles .sec 1 in 2013 and 59 moles .sec 1 in 2014) and lowest in the dry season (flux of 27 moles .sec 1). This relationship indicates that DBC is mainly mobilized from the upper soil horizons during heavy rainfalls. The relationship between DBC concentrations and δ13C-SPE-DOC indicated that most of DBC in the river system originated from C3 plants, i.e. from the historic burning event of the Atlantic rain forest. A conservative mixing model could largely reproduce the observed DBC fluxes within the catchment and the land to ocean continuum. Comparably slight deviations from conservative mixing were accompanied by changes in the molecular composition of DBC (i.e. the ratio of benzenepenta- to benzenehexacarboxylic acid) that are indicative for photodegradation of DBC.

Environmental Drivers of Dissolved Organic Matter Molecular Composition in the Delaware Estuary

Estuaries as connectors of freshwater and marine aquatic systems are hotspots of biogeochemical element cycling. In one of the best studied temperate estuaries, the Delaware Estuary (USA), we investigated the variability of dissolved organic matter (DOM) over five sampling cruises along the salinity gradient in August and November of 3 consecutive years. Dissolved organic carbon (DOC) concentrations were more variable in the upper reaches of the estuary (245±49 µmol L-1) than at the mouth of the estuary (129±14 µmol L-1). Bulk DOC decreased conservatively along the transect in November but was non-conservative with increased DOC concentrations mid-estuary in August. Detailed analysis of the solid-phase extractable DOM pool via ultrahigh resolution mass spectrometry (Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) revealed compositional differences at the molecular level that were not reflected in changes in concentration. Besides the mixing of terrestrial and marine endmember signatures, river discharge levels and biological activity were found to impact DOM molecular composition. DOM composition changed less between August and November than along the salinity gradient. Relative contributions of presumed photolabile DOM compounds did not reveal non-conservative behavior indicative of photochemical processing; suggesting that on the timescales of estuarine mixing photochemical removal of molecules plays a minor role in the turbid Delaware Bay. Overall, a large portion of molecular formulae overlapped between sampling campaigns and persisted during estuarine passage. Extending the analysis to the structural level via the fragmentation of molecular masses in the FT-ICR-MS cell, we found that the relative abundance of isomers along the salinity gradient did not change, indicating a high structural similarity of aquatic DOM independent of the origin. These results point towards a recalcitrant character of the DOM supplied by the Delaware River. We demonstrate that in addition to bulk DOC quantification, detailed information on molecular composition is essential for constraining sources of DOM and to identify the processes that impact estuarine DOM, thereby controlling amount and composition of DOM eventually discharged to the ocean through estuaries.