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The Dissolved Carbon Conundrum

An advanced exploration into the nature, sources, sinks, and transformations of dissolved organic carbon (DOC), detailing its critical role in global biogeochemical cycles.

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Overview

Defining Dissolved Organic Carbon (DOC)

Dissolved Organic Carbon (DOC) is operationally defined as the fraction of organic carbon that passes through a filter with a pore size typically ranging from 0.22 to 0.7 micrometers. The carbon retained on the filter is classified as particulate organic carbon (POC). A closely related term, Dissolved Organic Matter (DOM), encompasses the total mass of dissolved organic material, including elements beyond carbon, and is often used interchangeably with DOC, though DOM typically contains roughly twice the mass of DOC.

Global Significance

DOC is a substantial component of both marine and freshwater systems, representing one of the largest cycled reservoirs of organic matter on Earth. It holds an amount of carbon comparable to the atmosphere and constitutes up to 20% of all organic carbon globally. DOC serves as a fundamental nutrient source, supporting microbial growth and playing a pivotal role in the Earth's carbon cycle, particularly through the microbial loop.

Origins of DOC

DOC originates from both within and outside aquatic systems. Autochthonous DOC arises from internal sources like aquatic plants and algae. In contrast, allochthonous DOC originates externally, primarily from soils and terrestrial plants, often entering water bodies via runoff or leaching. The composition and behavior of DOC are influenced by its origin and subsequent environmental processing.

Terrestrial Ecosystems

Soil DOC Dynamics

In terrestrial ecosystems, dissolved organic matter (DOM) is a dynamic pool influencing soil processes. Soil DOM originates from various inputs, including atmospheric deposition, litter decomposition, root exudates, and microbial activity. Its availability and fate are governed by interactions with soil minerals (like clays and oxides) through adsorption/desorption processes, as well as transformations involving mineralization, immobilization, and the composition of soil organic matter itself. Land use and management practices significantly modulate these interactions.

Leaching and Runoff

During organic matter decomposition in soils, a significant portion of carbon is released as CO2. However, leaching processes can transport dissolved organic carbon (DOC) downwards towards the water table, potentially contaminating groundwater with nutrients and pollutants. Surface runoff also carries DOM and associated xenobiotics into rivers and lakes. Soil type and topography influence the extent of these losses.

Soil DOC

Sources and Sinks in Soil

The soil system involves complex inputs and outputs of dissolved organic carbon. Key sources include atmospheric deposition, plant litter, root exudates, and microbial biomass. Processes like adsorption to mineral surfaces, particularly clays and iron/aluminum oxides, influence DOC retention. Conversely, mineralization by microbes, immobilization into microbial biomass, and losses via leaching and runoff represent major sinks. The interplay of these factors is modulated by soil properties, land use, and management strategies.

Groundwater DOC

Transport and Transformation

Dissolved organic carbon (DOC) leaches from vegetation and litter, percolating through the soil profile to reach groundwater. During this subsurface transport, DOC undergoes modification through physicochemical and biological processes, including sorption onto soil minerals, biodegradation, and biosynthesis by soil microbes. Hydrophobic molecules tend to adsorb more strongly to minerals, increasing their retention time, while hydrophilic molecules are more mobile. Bioavailable DOM is actively decomposed, altering its molecular weight and composition, with microbial metabolites potentially entering the groundwater DOC pool.

Freshwater Ecosystems

Carbon Forms and Fluxes

Freshwater systems contain both organic and inorganic carbon, divided into particulate and dissolved phases. DOC typically constitutes about 90% of the total aquatic organic carbon, with concentrations varying widely based on ecosystem characteristics. Inorganic carbon exists in equilibrium between dissolved CO2, bicarbonate, and carbonate ions, influenced by water pH. Carbon enters these systems primarily from terrestrial sources, undergoing transformations like photosynthesis (P) and respiration (R), and is eventually transported to oceans, buried in sediments, or released as CO2. Inland waters represent a significant global carbon sink.

Marine Ecosystems

Oceanic DOC Pool

The oceanic DOC pool is vast and intricately linked to global carbon cycling. It originates from both autochthonous sources (e.g., phytoplankton, zooplankton grazing) and allochthonous inputs (terrestrial runoff, groundwater, atmospheric deposition). DOC fuels marine food webs and is a major player in the microbial loop. Its distribution is influenced by primary production, grazing, particle dissolution, and exchange with sediments and hydrothermal vents. The composition of DOC ranges from readily degradable (labile) to highly persistent (recalcitrant) forms.

Labile vs. Recalcitrant DOC

DOC is often categorized by its reactivity. Labile DOC is rapidly consumed by microbes, while recalcitrant DOC resists degradation for millennia. This recalcitrant fraction accumulates in the ocean, with average radiocarbon ages ranging from thousands of years. The apparent recalcitrance is an emergent property influenced by molecular composition, size, environmental conditions (temperature, nutrients, light), microbial community structure, and interactions with particles and minerals.

Sources of DOC

Terrestrial and Aquatic Inputs

DOC enters marine systems from diverse origins. Terrestrial sources include soil-derived humic substances leached by rainfall and runoff, as well as atmospheric deposition. Within marine environments, primary producers like phytoplankton and macroalgae release DOC during growth and physiological stress. Zooplankton contribute DOC through sloppy feeding and excretion. Bacteria and viruses also produce DOC via cell lysis and the release of extracellular compounds. Benthic fluxes and hydrothermal vents represent additional, albeit less quantified, sources.

Phytoplankton and Zooplankton Contributions

Phytoplankton release significant amounts of DOC, estimated between 5-30% of their primary production, particularly under high light and low nutrient conditions. Zooplankton also contribute substantially through sloppy feeding and excretion, providing a high-quality substrate for microbial communities, especially when food concentrations are high and large zooplankton species dominate.

Sinks of DOC

Removal Mechanisms

Several processes remove DOC from the ocean water column. These include thermal degradation in hydrothermal systems, abiotic flocculation and sorption onto particles (especially during mixing of fresh and marine waters), and abiotic degradation via photochemical reactions initiated by sunlight. Biotic degradation by heterotrophic marine prokaryotes is considered a major sink, transforming labile DOC into biomass or respiring it as CO2. Photodegradation can also transform recalcitrant DOC into more labile forms, enhancing microbial utilization.

Photochemical and Microbial Degradation

Photodegradation, particularly involving UV radiation, transforms CDOM (colored DOC) into smaller, less colored molecules or inorganic carbon and nutrients. While this often increases DOC bioavailability, it can also lead to the formation of more complex, recalcitrant compounds. Microbial degradation by prokaryotes is crucial for consuming labile DOC. The interplay between these processes, influenced by factors like water mixing, particle interactions, and microbial community composition, dictates the fate of DOC in the ocean.

DOM Isolation and Analysis

Analytical Challenges

Analyzing DOM in natural waters presents challenges due to its low concentrations and the presence of interfering inorganic salts. Techniques like ultrafiltration, reverse osmosis, and solid-phase extraction are employed to concentrate and isolate DOM samples prior to analysis using methods such as NMR or Mass Spectrometry. Solid-phase extraction is often favored for its cost-effectiveness and simplicity.

DOC Pool Characterization

The DOC pool exhibits a spectrum of reactivity, from labile to recalcitrant forms, characterized by varying turnover times. Labile DOC (DOCL) turns over in hours to days, while recalcitrant DOC (DOCR) can persist for thousands of years. This classification is crucial for understanding carbon cycling and storage. The composition and reactivity of DOC are influenced by molecular size, structure, environmental conditions, and microbial processing.

DOC Pool Spectrum from Labile to Recalcitrant
DOC Fraction Acronym Turnover Time Approximate Amount (Tg C)
Labile DOCL Hours to days < 200
Semi-labile DOCSL Weeks to months ~600
Semi-recalcitrant DOCSR Decades ~1400
Recalcitrant DOCR Thousands of years ~63000
Highly Resistant Tens of thousands of years

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A full list of references for this article are available at the Dissolved organic carbon Wikipedia page

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