Dissolved Organic Carbon Compounds Research Articles

Karenia brevis and Pyrodinium bahamense Utilization of Dissolved Organic Matter in Urban Stormwater Runoff and Rainfall Entering Tampa Bay, Florida

This study investigated how nitrogen and dissolved organic matter (DOM) from stormwater runoff and rainfall support the growth of Karenia brevis and Pyrodinium bahamense. Excitation–emission matrix spectroscopy coupled with parallel factor analysis tracked changes in the optical properties of DOM in each bioassay, revealing greater reactivity of terrestrial humic-like DOM. Significant increases in cell yield and specific growth rates were observed upon additions of runoff for both species, with significant increases in specific growth rates upon the addition of a 2 in simulated rain event for P. bahamense only. By hour 48, 100% of the dissolved organic nitrogen (DON) in each treatment was utilized by P. bahamense, and by hour 72, over 50% of the DON was utilized by K. brevis. The percentage of bioavailable dissolved organic carbon (DOC) was greater for P. bahamense compared to K. brevis, suggesting a greater affinity for DOC compounds by P. bahamense. However, the bioavailability of DOM for each species could be owed to distinct chemical characteristics of labile DOM conveyed from each site. This study demonstrates that stormwater runoff and rainfall are both sources of labile DOM and DON for K. brevis and P. bahamense, which has implications for blooms of these species in Tampa Bay waters.

Effect of marine sediment on the phase partitioning and isotopic content of riverine DOC

AbstractRivers discharge significant quantities of dissolved organic carbon (DOC) to the ocean, yet biomarker and isotope studies suggest that terrigenous DOC makes up only a small amount DOC in the ocean. One of the removal pathways proposed for riverine DOC is sorption to marine sediments. This process is chemically selective, but whether sorption alters the isotopic composition of riverine DOC is unknown. Because there is isotopic variability across different organic compound classes, sorptive removal of DOC could also alter the isotopic composition of DOC. As a first step in addressing this question, we examined phase partitioning and isotopic composition of a riverine DOC standard in the presence of marine sediment particles. In a series of controlled experiments, the standard was mixed with marine sediment in 35‰ NaCl solution, then separated into particulate and dissolved phases for analyses of mass, δ13C, and ∆14C of organic carbon (OC). Across a range of sediment OC to DOC mass ratios (from < 0.1 to ~ 3), we found that: (1) sediment sorbed 0.8 μg OC per mg of sediment; and (2) DOC compounds with higher ∆14C and lower δ13C values relative to the bulk DOC was preferentially removed from solution. In effect, mixing a riverine DOC standard with marine sediment resulted in increased ∆14C and decreased δ13C of the DOC that remained in solution. These results show that sorption of DOC to sediment can alter the isotopic content of riverine DOC.

Investigating Biochar-Derived Dissolved Organic Carbon (DOC) Components Extracted Using a Sequential Extraction Protocol

Biochar-derived dissolved organic carbon (DOC), as the most important component of biochar, can be released on farmland, improving fertility and playing a role in soil amendment and remediation. The complexity of molecular structures and diversity of DOC compounds have influenced these functions to some extent. A sequential extract protocol consisting of water (25 °C), hot water (80 °C), and NaOH solution (0.05 M) was used to fully extract DOC compounds and gain a thorough understanding of the possible DOC components released from biochar. Rape straw (RS), apple tree branches (ATB), and pine sawdust (PS) were pyrolyzed at 300, 500, and 700 °C, respectively, to make nine distinct biochars. A TOC analyser, ultraviolet-visible spectroscopy (UV–vis), and excitation–emission fluorescence (EEM) spectrophotometer were used in conjunction with parallel factor analysis (PARAFAC) to determine the distribution of DOC content, the diversity of aromaticity, molecular weight characteristics and components of biochar-derived DOC. The results show that the relative distribution of water-extractable fractions ranged from 3.21 to 35.57%, with a low-aromaticity and extremely hydrophilic fulvic-acid-like compounds being found in the highest amounts (C2 and C3). The smallest amount of hot water-extractable components was produced from the release of small-molecule aliphatic compounds adsorbed on biochar and susceptible to migration loss once in a soil solution. More than half of the biochar-derived DOC was released in a NaOH solution, which primarily consisted of humic-acid-like compounds (C1), with higher molecular weights, more aromaticity, and lower bioavailability, according to the distribution of DOC in various extractants. In addition, the pyrolysis temperature and biomass type had a significant impact on the DOC properties released by biochar. As a result, the findings of this study showed that using a sequential extract protocol of water, hot water, and NaOH solution in combination with spectroscopic methods could successfully reveal the diversity of biochar-derived components, which could lead to new insights for the accurate assessment of potential environmental impacts and new directions for biochar applications.

Decomposition of peatland DOC affected by root exudates is driven by specific r and K strategic bacterial taxa

In peatlands, decomposition of organic matter is limited by harsh environmental conditions and low decomposability of the plant material. Shifting vegetation composition from Sphagnum towards vascular plants is expected in response to climate change, which will lead to increased root exudate flux to the soil and stimulation of microbial growth and activity. We aimed to evaluate the effect of root exudates on the decomposition of recalcitrant dissolved organic carbon (DOC) and to identify microorganisms involved in this process. The exudation was mimicked by an addition of a mixture of 13C labelled compounds into the recalcitrant DOC in two realistic levels; 2% and 5% of total DOC and peatland porewater with added root exudates was incubated under controlled conditions in the lab. The early stage of incubation was characterized by a relative increase of r-strategic bacteria mainly from Gammaproteobacteria and Bacteriodetes phyla within the microbial community and their preferential use of the added compounds. At the later stage, Alphaproteobacteria and Acidobacteria members were the dominating phyla, which metabolized both the transformed 13C compounds and the recalcitrant DOC. Only higher exudate input (5% of total DOC) stimulated decomposition of recalcitrant DOC compared to non-amended control. The most important taxa with a potential to decompose complex DOC compounds were identified as: Mucilaginibacter (Bacteriodetes), Burkholderia and Pseudomonas (Gammaproteobacteria) among r-strategists and Bryocella and Candidatus Solibacter (Acidobacteria) among K-strategists. We conclude that increased root exudate inputs and their increasing C/N ratio stimulate growth and degradation potential of both r-strategic and K-strategic bacteria, which make the system more dynamic and may accelerate decomposition of peatland recalcitrant DOC.

Sorption and desorption of organic matter in soils as affected by phosphate

The contribution of different adsorption processes to soil organic matter (SOM) stabilization and the consequences of the intensification of land use on the adsorption of SOM are not yet fully understood. Therefore, this study aimed to explore the adsorption of dissolved organic carbon (DOC) in soils as well as desorption of organic carbon (OC) caused by phosphate addition. We conducted desorption and sorption experiments with DOC, phosphate (Na2HPO4), and chloride (KCl) in topsoil and subsoil samples from a Ferralsol, an Andosol, and a Podzol. Furthermore, we quantified the size of DOC by size-exclusion chromatography.We found that phosphate addition caused a strong increase in the DOC concentration in all soils. The DOC concentration was elevated by up to a factor of 4.5 compared to a control (water only) within five minutes after phosphate addition and kept increasing further with time, particularly in the Ferralsol. After 10 days, the DOC concentrations in the P addition treatment were between 5.5 and 18.0 times higher than in the control treatment. In contrast, chloride addition did not lead to increased DOC concentrations compared to the control (water only). Phosphate addition led mostly to desorption of organic matter of medium molecular size (10–100 and 100–1000 kDa) in the Ferralsol and the Andosol and of large molecular size (>1000 kDa) in the Podzol. In contrast, potassium chloride addition shifted the size distribution of DOC in the soil solution towards small compounds (<10 kDa), likely because KCl addition affected the aggregation of DOC compounds, in contrast to Na2HPO4 addition. Furthermore, phosphate addition also decreased subsequent sorption of DOC in the Ferralsol and the Andosol by a factor of up to 2.9 and 2.1, respectively.Our results have far-reaching implications because they show that phosphate addition can lead to desorption, and thus to destabilization of SOM, particularly in Ferralsols, and can also prevent further sorption of organic matter in soils. Our study provides a mechanistic explanation of why phosphate addition can decrease soil organic carbon sequestration and stabilization. This mechanism should be considered in the analysis of land-use and tillage effects on SOM sequestration in the future. Furthermore, our study indicates that also medium and large molecular size organic matter is stabilized through adsorption in soils.

Microbial Physiology Governs the Oceanic Distribution of Dissolved Organic Carbon in a Scenario of Equal Degradability

Dissolved organic carbon (DOC) forms one of the largest active organic carbon reservoirs on Earth and reaches average radiocarbon ages of several thousand years. Many previous large scale DOC models assume different lability classes (labile to refractory) with prescribed, globally constant decay rates. In contrast, we assume that all DOC compounds are equally degradable by a heterotrophic microbial community. Based on this central assumption, we simulate DOC concentrations using a simple biogeochemical box model. Parameterized correctly, the simple model of neutral DOC uptake produced a recalcitrant carbon pool of 33mmolC/m3, throughout the entire virtual ocean. The spatial distribution of DOC in the model was independent of the distribution of DOC sources from primary production and particle degradation. Instead, DOC concentrations were primarily driven by spatial gradients in microbial physiology, e.g. mortality rate or growth efficiency. Applying such a gradient, we find DOC concentrations of ~70mmolC/m3 at the surface and ~35mmolC/m3 in the deep ocean. Introducing model variations such as seasonally-varying supply rates or temperature-dependent DOC uptake did not significantly alter model results. DOC spatial patterns are thus not necessarily shaped by the co-cycling of separate reactivity fractions, but can also arise from gradients in physiological parameters determining DOC uptake. We conclude that neutral DOC uptake can lead to realistic large-scale patterns of DOC concentration in the ocean.

Long-term stability of marine dissolved organic carbon emerges from a neutral network of compounds and microbes

Dissolved organic carbon (DOC) is the main energy source for marine heterotrophic microorganisms, but a small fraction of DOC resists microbial degradation and accumulates in the ocean. The reason behind this recalcitrance is unknown. We test whether the long-term stability of DOC requires the existence of structurally refractory molecules, using a mechanistic model comprising a diverse network of microbe-substrate interactions. Model experiments reproduce three salient observations, even when all DOC compounds are equally degradable: (i) >15% of an initial DOC pulse resists degradation, but is consumed by microbes if concentrated, (ii) the modelled deep-sea DOC reaches stable concentrations of 30–40 mmolC/m3, and (iii) the mean age of deep-sea DOC is several times the age of deep water with a wide range from <100 to >10,000 years. We conclude that while structurally-recalcitrant molecules exist, they are not required in the model to explain either the amount or longevity of DOC.

Elevated ammonium delays the impairment of the coral-dinoflagellate symbiosis during labile carbon pollution

Labile dissolved organic carbon (DOC) is a major pollutant in coastal marine environments affected by anthropogenic impacts, and may significantly contribute to coral bleaching and subsequent mortality on coastal reefs. DOC can cause bleaching indirectly through the rapid proliferation of copiotrophic and pathogenic bacteria. Here we demonstrate that labile DOC compounds can also impair the coral-dinoflagellate symbiosis by directly affecting coral physiology on both the host and algal symbiont level. In a controlled aquarium experiment, we monitored over several weeks key physiological parameters of the tropical coral Stylophora pistillata exposed to ambient and elevated labile DOC levels (0.1 and 1.0 mM) in combination with low and high nitrogen (i.e. ammonium) conditions (0.2 and 4.0 μM). At the symbiont level, DOC exposure under low ammonium availability decreased the photosynthetic efficiency accompanied by ∼75 % Chl a and ∼50 % symbiont cell reduction. The photosynthetic functioning of the symbionts recovered once the DOC enrichment ceased indicating a reversible shift between autotrophic and heterotrophic metabolism. At the host level, the assimilation of exogenous DOC sustained the tissue carbon reserves, but induced a depletion of the nitrogen reserves, indicated by ∼35 % decreased protein levels. This suggests an imbalanced exogenous carbon to nitrogen supply with nitrogen potentially limiting host metabolism on the long-term. We also demonstrate that increased ammonium availability delayed DOC-induced bleaching likely by keeping symbionts in a photosynthetically competent state, which is crucial for symbiosis maintenance and coral survival. Overall, the present study provides further insights into how coastal pollution can de-stabilize the coral-algal symbiosis and cause coral bleaching. Therefore, reducing coastal pollution and sustaining ecological integrity are critical to strengthen the resilience of coral reefs facing climate change.

Microbial uptake kinetics of dissolved organic carbon (DOC) compound groups from river water and sediments

Dissolved organic matter (DOM) represents a key component of carbon (C) cycling in freshwater ecosystems. While the behaviour of bulk dissolved organic carbon (DOC) in aquatic ecosystems is well studied, comparatively little is known about the turnover of specific DOC compounds. The aim of this study was to investigate the persistence of 14C-labelled low molecular weight (LMW) DOC at a wide range of concentrations (0.1 µM to 10 mM), in sediments and waters from oligotrophic and mesotrophic rivers within the same catchment. Overall, rates of DOC loss varied between compound groups (amino acids > sugars = organic acids > phenolics). Sediment-based microbial communities contributed to higher DOC loss from river waters, which was attributed, in part, to its greater microbial biomass. At higher DOC compound concentrations, DOC loss was greater in mesotrophic rivers in comparison to oligotrophic headwaters. A lag-phase in substrate use within sediments provided evidence of microbial growth and adaptation, ascribed here to the lack of inorganic nutrient limitation on microbial C processing in mesotrophic communities. We conclude that the higher microbial biomass and available inorganic nutrients in sediments enables the rapid processing of LMW DOC, particularly during high C enrichment events and in N and P-rich mesotrophic environments.

Optical Properties of Dissolved Organic Matter in Urban Fountains

Optical properties of dissolved organic carbon compounds (DOC) in selected fountains in Olsztyn (Poland) were investigated. The DOC fraction was isolated by using a membrane filter (Sartorius, pore size 0.45 μm). The amount of absorption for the DOC fraction was determined using the UV spectrophotometry method (UV range) at wavelength: 203 nm (A203), 250 nm (A250), 254 nm (A254) and 365 nm (A365). Then the absorption ratios were determined: A250/A365 and A254/A203. The aim of the study was to determine the contribution of macromolecules (hardly biodegradable, having an aromatic character) in the fraction of DOC. The variability of DOC compounds in the water of fountains was investigated depending on the water supply method (also subjected to disinfection) and depending on the period of research (season of the year) or the impact of the environment. It was shown that the average A250/A365 values were three times lower in fountains not subjected to disinfection than in artificial fountains. The A254/A203 parameter was on average several times lower in artificial fountains where the water was chlorinated. The Kruskal-Wallis test confirmed that the differences between the artificial objects and the other two in the average values of A250/A365 and A254/A203 ratios are significant. The values of these quotients indicate that natural and semi-natural fountains are characterized by a high share of aromatic compounds with high molecular weight. For artificial objects, the effect of the study period on differences in average values of A250/A365 and A254/A203 was not confirmed. The U Mann-Whitney test showed that there are differences in the mean values of A254/A203 between the semi-natural and natural fountain, and the changes of A250/A365 in these fountains are related to the date of sampling. After examining the influence of the catchment and anthropogenic pressure, it was found that in the semi-natural fountain, the quality of the DOC fraction changed due to the supply of allochthonous organic matter (leaves, waterfowl and its feeding by resting people). In the case of a fountain on a natural reservoir, the relatively high primary production and allochthonous inflow of DOC had significant influence on the DOC character (leaching from slopes with rainfall, groundbaits using by anglers).

Predator‐induced changes in dissolved organic carbon dynamics

The fate of dissolved organic carbon (DOC) is partly determined by its availability to microbial degradation. Organisms at upper trophic levels could influence the bioavailability of DOC via cascading effects on primary producers and bacteria. Here we experimentally tested whether the presence of fish in aquatic food webs can indirectly affect the composition of the DOC pool. We found that fish had strong positive effects on phytoplankton biomass that affected the dynamics of DOC composition. Specifically, fish increased protein‐like, algae‐derived DOC mid‐experiment, concurrent with the strongest fish‐induced increase in phytoplankton biomass. Fish also increased bacterial abundance, altered the community composition and diversity of bacteria, and temporarily increased DOC compounds with fluorescence properties indicative of microbially‐reprocessed organic matter. Overall, our experiment revealed that fish can positively influence the substrate (algae‐produced DOC) and the key players (bacteria) of the microbial carbon pump. Consequently, fish could contribute to carbon sequestration by stimulating both the production of bioavailable DOC and the microbial degradation of bioavailable to persistent DOC. We propose this as a novel mechanism whereby the loss of predators from global ecosystems could alter carbon cycling.

Variations in dissolved organic carbon concentrations across peatland hillslopes

Peatlands are important terrestrial carbon stores and dissolved organic carbon (DOC) is one of the most important contributors to carbon budgets in peatland systems. Many studies have investigated factors affecting DOC concentration in peatland systems, yet hillslope position has been thus far overlooked as a variable that could influence DOC cycling. This study investigates the importance of hillslope position with regard to DOC cycling. Two upland peat hillslopes were studied in the Peak District, UK, to determine what impact, if any, hillslope position had upon DOC concentration. Hillslope position was found to be a significant factor affecting variation in soil pore water DOC concentration, with bottom-slope positions having significantly lower DOC concentrations than up-slope because of dilution of DOC as water moves down-slope and is flushed out of the system via lateral throughflow. Water table drawdown on steeper mid-slopes increased DOC concentrations through increased DOC production and extended residence times allowing a build-up of humic-rich DOC compounds. Hillslope position did not significantly affect DOC concentrations in surface runoff water because of the dilution of near-surface soil pore water by precipitation inputs, while stream water had similar water chemistry properties to soil pore water under low-flow conditions.

Dissolved Organic Carbon in Groundwater Overlain by Irrigated Sugarcane.

Elevated dissolved organic carbon (DOC) has been detected in groundwater beneath irrigated sugarcane on the Burdekin coastal plain of tropical northeast Australia. The maximum value of 82 mg/L is to our knowledge the highest DOC reported for groundwater beneath irrigated cropping systems. More than half of the groundwater sampled in January 2004 (n = 46) exhibited DOC concentrations greater than 30 mg/L. DOC was progressively lower in October 2004 and January 2005, with a total decrease greater than 90% indicating varying load(s) to the aquifer. It was hypothesized that the elevated DOC found in this groundwater system is sourced at or near the soil surface and supplied to the aquifer via vertical recharge following above average rainfall. Possible sources of DOC include organic-rich sugar mill by-products applied as fertilizer and/or sugarcane sap released during harvest. CFC-12 vertical flow rates supported the hypothesis that elevated DOC (>40 mg/L) in the groundwater results from recharge events in which annual precipitation exceeds 1500 mm/year (average = 960 mm/year). Occurrence of elevated DOC concentrations, absence of electron acceptors (O2 and NO3 (-) ) and both Fe(2+) and Mn(2+) greater than 1 mg/L in shallow groundwater suggest that the DOC compounds are chemically labile. The consequence of high concentrations of labile DOC may be positive (e.g., denitrification) or negative (e.g., enhanced metal mobility and biofouling), and highlights the need to account for a wider range of water quality parameters when considering the impacts of land use on the ecology of receiving waters and/or suitability of groundwater for irrigated agriculture.

Characterization of dissolved organic matter in decomposing Norway spruce and silver birch litter

Dissolved organic matter (DOM) plays an important role in transport, storage and cycling of carbon (C) and nitrogen (N) in forest soils where litter is one of the main sources. The aim was to study the amount and characteristics of DOM leached from freshly fallen litters of silver birch (Betula pendula Roth.), Norway spruce (Picea abies (L.) Karst.) and their mixture during decomposition. DOM was collected after irrigation on eight occasions during 252 days incubation in the laboratory at about 18°C, including one freeze‐thaw cycle. During the incubation about 33–35% of C from birch and spruce litter and 40% of C from their mixture was lost. The total cumulative flux of dissolved organic carbon (DOC) from the mixture of litters was approximately 40% larger than that from single litters. The flux of DOC, DON, phenolic compounds and proteins followed a two‐stage pattern during decomposition. In the first stage the initially large fluxes decreased gradually. In the second stage, after freezing and thawing, the fluxes tended to increase again. Mixing birch and spruce litters and a freeze‐thaw cycle seems to increase the decomposition of litter and result in the increased flux of DOC, DON and phenolic compounds. The flux of hemicelluloses and the degradability of DOM were large at the first leaching occasion and decreased during the incubation. Birch had a 40% larger total flux of easily degradable DOM than spruce, supporting the previous consistent signs of greater microbial biomass and activities related to C and N cycling in soil under birch than under spruce. It is known that recalcitrant DOM might be stabilized whereas labile DOM may promote microbial activity and nutrient cycling. We conclude that the storage and cycling of C and N is affected by both tree species and degradation stage of litter in forest soils.

The Microbial Carbon Pump: from Genes to Ecosystems

The majority of marine dissolved organic carbon (DOC) is resistant to biological degradation and thus can remain in the water column for thousands of years, constituting carbon sequestration in the ocean. To date the origin of such recalcitrant DOC (RDOC) is unclear. A recently proposed conceptual framework, the microbial carbon pump (MCP), emphasizes the microbial transformation of organic carbon from labile to recalcitrant states. The MCP is concerned with both microbial uptakes and outputs of DOC compounds, covering a wide range from gene to ecosystem levels. In this minireview, the ATP binding cassette (ABC) transporter is used as an example for the microbial processing of DOC at the genetic level. The compositions of the ABC transporter genes of the two major marine bacterial clades Roseobacter and SAR11 demonstrate that they have distinct patterns in DOC utilization: Roseobacter strains have the advantage of taking up carbohydrate DOC, while SAR11 bacteria prefer nitrogen-containing DOC. At the ecosystem level, bacterially derived RDOC based on d-amino acid biomarkers is reported to be responsible for about a quarter of the total marine RDOC pool. Under future global warming scenarios, partitioning of primary production into DOC could be enhanced, and thus the MCP could play an even more important role in carbon sequestration by the ocean. Joint efforts to study the MCP from multiple disciplines are required to obtain a better understanding of ocean carbon cycle and its coupling with global change.

Photodegradation kinetics of p- tert-octylphenol, 4- tert-octylphenoxy-acetic acid and ibuprofen under simulated solar conditions in surface water

Direct and indirect (sensitized) photolysis of p- tert-octylphenol (OP), 4-octylphenoxy-acetic acid (OP1EC), and ibuprofen (IBU) were investigated in laboratory water and surface water under simulated and natural sunlight conditions. Photodegradation obeyed apparent-first order kinetics with rates increasing in the presence of NO 2 - , NO 3 - , and humic acid (HAC). The bimolecular rate constants, k″, were determined for the reactions of OP and OP1EC with hydroxyl radical ( OH) using photolyzed hydrogen peroxide (H 2O 2) as the hydroxyl radical ( OH) and IBU as the reference compound. The k″ values for OP and OP1EC were (average and standard deviation) (10.9 ± 0.5) × 10 9 M −1 s −1 and (8.6 ± 0.5) × 10 9 M −1 s −1, respectively. Direct photolysis of OP is small with a quantum yield of 0.015 in the range of 285–295 nm. Based on laboratory and average solar intensity data, the estimated half-life of OP in different Singapore surface waters was estimated to range from 0.6 to 2.5 d. The steady state hydroxyl radical concentration ([ OH] ss) was estimated using a kinetic model that considered dissolved organic carbon compounds (DOC), nitrate, and nitrite as OH sources, and DOC, CO 3 2 - and HCO 3 - as scavengers. In surface waters containing DOC 2.3–6.5 mg L −1, nitrate 0–3.2 mg L −1, and nitrite 0–2.5 mg L −1, the calculated [ OH] ss ranged from 5.2 × 10 −15 to 9.6 × 10 −15 M. Half-lives calculations based on this model underestimated the measured half-life by a factor of approximately 4.2 to 1.1. DOC was predicted to be the most important sensitizer except in a sample that contained relatively high nitrate and nitrite. In the presence of NO 3 - , photoreactions produced nitrated OP and IBU. A mechanism for OP photolysis in the presence of nitrate is proposed.

Bioattenuation in Groundwater Impacted by Landfill Leachate Traced with δ13C

The impact on groundwater imparted by the infiltration of high dissolved organic carbon (DOC) leachate from capped, unlined landfills can be attenuated by biogeochemical reactions beyond the waste source, although such reactive loss in the aquifer is difficult to distinguish from conservative advective dispersion. Compound-specific measurement of δ(13)C in carbon species, including CH(4), dissolved inorganic carbon (DIC), and the major DOC compounds (acetate, humic acid, and fulvic acid) provides a constraint in this assessment that can assist in exercises of modeling and prediction of leachate transport. The Trail Road municipal landfill near Ottawa, Ontario, Canada, hosts an unlined sector which produces a highly enriched leachate (DOC >4500 mg/L) that provides a good site to examine reactive attenuation within the receptor aquifer. Acetate, a sentinel component of leachate DOC (~1000 mg C/L), is absent in impacted groundwater. Mass balance calculations together with reaction modeling suggest continued acetate fermentation with calcite control on DIC and δ(13)C(DIC) evolution. In groundwater within 50 m of the landfill, methane concentrations are elevated (~10 mg/L), consistent with acetate fermentation, whereas δ(13)C(CH4) measurements in deeper groundwater range down to -51‰ compared with -60‰ in the landfill demonstrating oxidative loss. DOC in the deep aquifer is remarkably depleted to values less than -40‰ suggesting methanotrophic bacteria selectively consume isotopically light CH(4) to fix carbon. Continued reaction of leachate DOC in groundwater is demonstrated by evolution away from conservative mixing lines on diagrams of δ(13)C vs. concentrations of DIC and DOC.

Physical heterogeneity increases biofilm resource use and its molecular diversity in stream mesocosms.

BackgroundEvidence increasingly shows that stream ecosystems greatly contribute to global carbon fluxes. This involves a tight coupling between biofilms, the dominant form of microbial life in streams, and dissolved organic carbon (DOC), a very significant pool of organic carbon on Earth. Yet, the interactions between microbial biodiversity and the molecular diversity of resource use are poorly understood.Methodology/Principal FindingsUsing six 40-m-long streamside flumes, we created a gradient of streambed landscapes with increasing spatial flow heterogeneity to assess how physical heterogeneity, inherent to streams, affects biofilm diversity and DOC use. We determined bacterial biodiversity in all six landscapes using 16S-rRNA fingerprinting and measured carbon uptake from glucose and DOC experimentally injected to all six flumes. The diversity of DOC molecules removed from the water was determined from ultrahigh-resolution Fourier Transform Ion Cyclotron Resonance mass spectrometry (FTICR-MS). Bacterial beta diversity, glucose and DOC uptake, and the molecular diversity of DOC use all increased with increasing flow heterogeneity. Causal modeling and path analyses of the experimental data revealed that the uptake of glucose was largely driven by physical processes related to flow heterogeneity, whereas biodiversity effects, such as complementarity, most likely contributed to the enhanced uptake of putatively recalcitrant DOC compounds in the streambeds with higher flow heterogeneity.Conclusions/SignificanceOur results suggest biophysical mechanisms, including hydrodynamics and microbial complementarity effects, through which physical heterogeneity induces changes of resource use and carbon fluxes in streams. These findings highlight the importance of fine-scale streambed heterogeneity for microbial biodiversity and ecosystem functioning in streams, where homogenization and loss of habitats increasingly reduce biodiversity.

Analysis of rainwater dissolved organic carbon compounds using fluorescence spectrophotometry

Global rainwater dissolved organic carbon (DOC) flux was recently estimated as 430 × 10 12 g C yr −1, yet little is known about the wide range of chemical compounds present, their sources, temporal patterns of variation, and the subsequent impact on climate and the environment. Precipitation events were sampled in Birmingham, UK between April 2005 and May 2007. Rainwater DOC compounds were analysed using fluorescence spectrophotometry. Three fluorophores were identified: HUmic-LIke Substances (HULIS), TYrosine-LIke Substances (TYLIS) and TRYptophan-LIke Substances (TRYLIS). Peak fluorescence intensities and locations for each substance were examined, and their variations with various meteorological parameters were investigated. The mean HULIS fluorescence intensity from all events was 209 a.u. (with sample fluorescence ranging from 37 a.u. to 995 a.u); mean fluorescence intensity was 469 a.u. (214–988 a.u) and 265 a.u. (50–876 a.u.) for TYLIS and TRYLIS, respectively. Results indicate that highest HULIS fluorescence intensities are experienced during convective events and events of continental origin, suggesting terrestrial/anthropogenic sources. Under well-mixed conditions, HULIS fluorescence intensity decreases, whereas during low wind speed, stagnation of the atmosphere results in higher fluorescence intensities, attributed to a build up of localised sources, particularly anthropogenic. TYLIS and TRYLIS did not show any significant trends for the meteorological variables. Fluorescence spectrophotometry is a fast, non-invasive technique which is demonstrated to be a powerful means of fingerprinting rainfall DOC compounds in real time for small sample volumes.

Allochthonous DOC in floodplain rivers: identifying sources using solid phase microextraction with gas chromatography

Models of carbon transport are an important mechanism for conceptualizing and assessing the significance of matter and energy sources in streams. The development of a fingerprinting technique that identifies the origins of dissolved organic carbon (DOC) would be invaluable for the development of more sophisticated carbon budget models and improving our understanding of energy flow in river systems. This study explores the potential for solid phase microextraction – gas chromatography (SPMEGC) as a technique for fingerprinting DOC leached from allochthonous source materials (e.g., red gum leaves, willow leaves, couch grass, alluvial soil) collected from a floodplain river in NSW, Australia. The SPME-GC technique is a portable, solventless extraction technique that can detect semi-volatile and volatile organic compounds (SV and VOC) including terpenes, fatty acids, fatty acid esters, ketones, alcohols, and aldehydes, and, importantly, has detection limits approaching parts-per-trillion. The semi-volatile and volatile organic compounds found in DOC leachate solutions produced complex chromatograms, consisting of over 100 individual DOC compounds from each allochthonous source. Hierarchical cluster analysis based on peak presence-absence revealed that each of the source materials produce different chemical profiles. The results indicate that the SPMEGC technique in conjunction with multivariate analyses has considerable potential for identifying source specific chemotaxonomic markers in DOC from riverine habitats. These markers may then be used to test and validate existing models of river function by identifying the origins of DOC contributing to instream metabolism.