Natural Abundance Radiocarbon Research Articles

An isotopic (Δ<sup>14</sup>C, δ<sup>13</sup>C, and δ<sup>15</sup>N) investigation of the composition of particulate organic matter and zooplankton food sources in Lake Superior and across a size-gradient of aquatic systems

Abstract. Food webs in aquatic systems can be supported both by carbon from recent local primary productivity and by carbon subsidies, such as material from terrestrial ecosystems, or past in situ primary productivity. The importance of these subsidies to respiration and biomass production remains a topic of debate. While some studies have reported that terrigenous organic carbon supports disproportionately high zooplankton production, others have suggested that phytoplankton preferentially support zooplankton production in aquatic ecosystems. Here we apply natural abundance radiocarbon (Δ14C) and stable isotope (δ13C, δ15N) analyses to show that zooplankton in Lake Superior selectively incorporate recently fixed, locally produced (autochthonous) organic carbon even though other carbon sources are readily available. Estimates from Bayesian isotopic modeling based on Δ14C and δ13C values show that the average lake-wide median contributions of recent in-lake primary production and terrestrial, sedimentary, and bacterial organic carbon to the bulk POM in Lake Superior were 58%, 5%, 33%, and 3%, respectively. However, isotopic modeling estimates also show that recent in situ production contributed a disproportionately large amount (median, 91%) of the carbon in mesozooplankton biomass in Lake Superior. Although terrigenous organic carbon and old organic carbon from resuspended sediments were significant portions (median, 38%) of the available basal food resources, these contributed only a small amount to mesozooplankton biomass. Comparison of zooplankton food sources based on their radiocarbon composition showed that terrigenous organic carbon was relatively more important in rivers and small lakes, and the proportion of terrestrially derived material used by zooplankton correlated with the hydrologic residence time and the ratio of basin area to water surface area.

A two-dimensional, heart-cutting preparative gas chromatograph facilitates highly resolved single-compound isolations with utility towards compound-specific natural abundance radiocarbon (14C) analyses

Motivated by the need to develop clean, high purity preparative enrichments of individual compounds for micro-scale compound-specific natural abundance isotope and radiocarbon ((14)C) analyses, we describe a new, two-dimensional, heart-cutting, low-bleed, three-oven, single GC preparative system, demonstrate its resolving capabilities as applied to a typically complex environmental sample matrix, and investigate the robustness with which it preserves the authigenic (13)C/(12)C and (14)C/(12)C ratios of individual compounds it targets for preparative enrichment. The system is comprised of a programmable temperature vaporizing (PTV) inlet, a single GC oven, two modular, door-mounted, resistively heated low thermal mass (LTM) columns, a preparative fraction collector (PFC), and a Deans pneumatic switching device which facilitates heart-cutting between the system's 1° and 2° chromatographic dimensions. Further, the system's inlet and trapping parameters are optimized for the efficient preparative enrichment of the methyl ether and ester derivatives of the lignin phenol compound class. The lignin phenols include such compounds as the vanillyl and syringyl aldehydes, ethanones, and acids and are unrivaled biomarkers of terrestrial organic matter, some of which are also important components of fragrances and flavors. Using this suite of compounds, the suitability of this augmented preparative capillary GC (PCGC) system was investigated for micro-scale compound-specific (CS) stable isotope and natural abundance radiocarbon analyses (RA). Analysis of a >300 injection enrichment scheme reveals the instrument to fractionate (13)C in predictable ways and to preserve the authigenic Δ(14)C of compounds it targets for preparative enrichment to within 6.7±5.0‰, demonstrating the promising new utility of such systems towards micro-scale CSRA investigations for which clean and high resolution separation techniques are prerequisite.

Natural abundance radiocarbon in soil microbial biomass: Results from a glacial foreland

We present a method for determining the natural abundance radiocarbon ( 14C) content of soil microbial biomass (SMB) based on existing fumigation–extraction procedures. We applied the technique to soils from the foreland of the Ödenwinkelkees glacier in the Austrian Alps, which has a well-characterised chronosequence of soils at different stages of development. Across the chronosequence, SMB contained post-bomb levels of 14C, suggesting it was substantially composed of carbon that had been fixed since the 1960s. Comparison of our results with previous findings from the same site showed that at most stages in the sequence the SMB had a similar 14C content to the bulk soil organic matter (SOM). However, soil respired CO 2 was 14C-depleted relative to SMB, indicating that at least a component of the microbial community was mineralising some older carbon. In the most recently exposed soils, SMB was 14C-enriched compared to both soil respiration and SOM, suggesting that a small component of the microbial biomass that utilises older carbon contributes disproportionately more to the CO 2 efflux. Although other interpretations are possible, this explanation is consistent with the notion that early on in the succession a large proportion of the microbial biomass is dormant.

Assessing Microbial Uptake of Petroleum Hydrocarbons in Groundwater Systems Using Natural Abundance Radiocarbon

Carbon sources utilized by the active microbial communities in shallow groundwater systems underlying three petroleum service stations were characterized using natural abundance radiocarbon ((14)C). Total organic carbon (TOC) Delta(14)C values ranged from -314 to -972 per thousand and petroleum-extracted residues (EXT-RES) ranged from -293 to -971 per thousand. Phospholipid fatty acids (PLFAs)-biomarkers for active microbial populations-ranged from -405 to -885 per thousand and a comparison of these values with potential carbon sources pointed to significant microbial assimilation of (14)C-free fossil carbon. The most (14)C-depleted PLFAs were found in the samples with the highest concentrations of total petroleum hydrocarbons (TPHs). A radiocarbon mass balance indicated up to 43% of the carbon in microbial PLFAs was derived from TPHs, providing direct evidence for biodegradation at two of three sites. At lower levels of TPHs Delta(14)C values of PLFAs were generally similar to or more enriched than all other carbon in the system indicating microbial utilization of a more (14)C-enriched carbon source and no resolvable evidence for microbial incorporation of petroleum-derived carbon. Results from this study suggest that it is possible to delineate petroleum biodegradation in groundwater systems using these techniques even in complex situations where there exists a wide range in the ages of natural organic matter (i.e., EXT-RES).

Determination of Microbial Carbon Sources and Cycling during Remediation of Petroleum Hydrocarbon Impacted Soil Using Natural Abundance 14C Analysis of PLFA

In a petroleum impacted land-farm soil in Sarnia, Ontario, compound-specific natural abundance radiocarbon analysis identified biodegradation by the soil microbial community as a major pathway for hydrocarbon removal in a novel remediation system. During remediation of contaminated soils by a plant growth promoting rhizobacteria enhanced phytoremediation system (PEPS), the measured Delta(14)C of phospholipid fatty acid (PLFA) biomarkers ranged from -793 per thousand to -897 per thousand, directly demonstrating microbial uptake and utilization of petroleum hydrocarbons (Delta(14)C(PHC) = -1000 per thousand). Isotopic mass balance indicated that more than 80% of microbial PLFA carbon was derived from petroleum hydrocarbons (PHC) and a maximum of 20% was obtained from metabolism of more modern carbon sources. These PLFA from the contaminated soils were the most (14)C-depleted biomarkers ever measured for an in situ environmental system, and this study demonstrated that the microbial community in this soil was subsisting primarily on petroleum hydrocarbons. In contrast, the microbial community in a nearby uncontaminated control soil maintained a more modern Delta(14)C signature than total organic carbon (Delta(14)C(PLFA) = +36 per thousand to -147 per thousand, Delta(14)C(TOC) = -148 per thousand), indicating preferential consumption of the most modern plant-derived fraction of soil organic carbon. Measurements of delta(13)C and Delta(14)C of soil CO(2) additionally demonstrated that mineralization of PHC contributed to soil CO(2) at the contaminated site. The CO(2) in the uncontaminated control soil exhibited substantially more modern Delta(14)C values, and lower soil CO(2) concentrations than the contaminated soils, suggesting increased rates of soil respiration in the contaminated soils. In combination, these results demonstrated that biodegradation in the soil microbial community was a primary pathway of petroleum hydrocarbon removal in the PEPS system. This study highlights the power of natural abundance radiocarbon for determining microbial carbon sources and identifying biodegradation pathways in complex remediation systems.

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

Abstract. Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from −138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution, which was constrained to 71–87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an fbiomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.

Evidence of old carbon used to grow new fine roots in a tropical forest

In this study, we explore how a hurricane disturbance influenced carbon allocation for the production of new fine roots. Before and after a hurricane, we measured the age of carbon (time since fixation from the atmosphere) in fine root structural tissues using natural abundance radiocarbon (14C) measured by accelerator mass spectrometry. Roots were sampled from five seasonally dry tropical forests ranging in age from 6 yr to a mature forest. Structural carbon in combined live + dead roots picked from soil cores sampled 1 month before the hurricane had mean ages ranging from 4 to 11 yr, whereas live roots alone had ages of 1-2 yr. Structural carbon in new live fine roots produced over a period lasting from 3 wk before the hurricane to 2 months after the event had mean ages of between 2 and 10 yr. Contrary to expectations, our results showed that plants allocate long-lived storage carbon pools to the production of new fine roots after canopy defoliation and root mortality. The age of the carbon allocated for new roots increased with forest age and forest above-ground biomass, suggesting an adaptation of plants to survive and recover from severe disturbances.

Source Apportionment of Atmospheric PAHs in the Western Balkans by Natural Abundance Radiocarbon Analysis

Progress in source apportionment of priority combustion-derived atmospheric pollutants can be made by an inverse approach to inventory emissions, namely, receptor-based compound class-specific radiocarbon analysis (CCSRA) of target pollutants. In the present study, CCSRA of the combustion-derived polycyclic aromatic hydrocarbons (PAHs) present in the atmosphere of the countries of the former republic of Yugoslavia was performed. The carbon stable isotope composition (delta13C) of PAHs varied between -27.68 and -27.19 per thousand, whereas delta14C values ranged from -568 per thousand for PAHs sampled in Kosovo to -288 per thousand for PAHs sampled in the Sarajevo area. The application of an isotopic mass balance model to these delta14C data revealed a significant contribution (35-65%) from the combustion of non-fossil material to the atmospheric PAH pollution, even in urban and industrialized areas. Furthermore, consistency was observed between the isotopic composition of PAHs obtained by high-volume sampling and those collected by passive sampling. This encourages the use of passive samplers for CCSRA applications. This marks the first time that a CCSRA investigation could be executed on a geographically wide scale, providing a quantitative field-based source apportionment, which points out that also non-fossil combustion processes should be targeted for remedial action.

Natural-abundance radiocarbon as a tracer of assimilation of petroleum carbon by bacteria in salt marsh sediments

The natural abundance of radiocarbon ( 14C) provides unique insight into the source and cycling of sedimentary organic matter. Radiocarbon analysis of bacterial phospholipid lipid fatty acids (PLFAs) in salt-marsh sediments of southeast Georgia (USA)—one heavily contaminated by petroleum residues—was used to assess the fate of petroleum-derived carbon in sediments and incorporation of fossil carbon into microbial biomass. PLFAs that are common components of eubacterial cell membranes (e.g., branched C 15 and C 17, 10-methyl-C 16) were depleted in 14C in the contaminated sediment (mean Δ 14C value of +25 ± 19‰ for bacterial PLFAs) relative to PLFAs in uncontaminated “control” sediment (Δ 14C = +101 ± 12‰). We suggest that the 14C-depletion in bacterial PLFAs at the contaminated site results from microbial metabolism of petroleum and subsequent incorporation of petroleum-derived carbon into bacterial membrane lipids. A mass balance calculation indicates that 6–10% of the carbon in bacterial PLFAs at the oiled site could derive from petroleum residues. These results demonstrate that even weathered petroleum may contain components of sufficient lability to be a carbon source for biomass production by marsh sediment microorganisms. Furthermore, a small but significant fraction of fossil carbon is assimilated even in the presence of a much larger pool of presumably more-labile and faster-cycling carbon substrates.

Two Abundant Bioaccumulated Halogenated Compounds Are Natural Products

Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have been found bioaccumulated in the tissues of a variety of aquatic animals and at concentrations comparable to those of anthropogenic halogenated organic compounds, including polychlorinated biphenyls (PCBs). The origin of the MeO-PBDEs has been uncertain; circumstantial evidence supports a natural and/or an industrial source. By analyzing the natural abundance radiocarbon content of two MeO-PBDEs isolated from a True's beaked whale (Mesoplodon mirus), we show that these compounds were naturally produced.

Gas Chromatographic Isolation of Individual Compounds from Complex Matrices for Radiocarbon Dating

This paper describes the application of a novel, practical approach for isolation of individual compounds from complex organic matrices for natural abundance radiocarbon measurement. This is achieved through the use of automated preparative capillary gas chromatography (PCGC) to separate and recover sufficient quantities of individual target compounds for (14)C analysis by accelerator mass spectrometry (AMS). We developed and tested this approach using a suite of samples (plant lipids, petroleums) whose ages spanned the (14)C time scale and which contained a variety of compound types (fatty acids, sterols, hydrocarbons). Comparison of individual compound and bulk radiocarbon signatures for the isotopically homogeneous samples studied revealed that Δ(14)C values generally agreed well (±10%). Background contamination was assessed at each stage of the isolation procedure, and incomplete solvent removal prior to combustion was the only significant source of additional carbon. Isotope fractionation was addressed through compound-specific stable carbon isotopic analyses. Fractionation of isotopes during isolation of individual compounds was minimal (<5‰ for δ(13)C), provided the entire peak was collected during PCGC. Trapping of partially coeluting peaks did cause errors, and these results highlight the importance of conducting stable carbon isotopic measurements of each trapped compound in concert with AMS for reliable radiocarbon measurements. The addition of carbon accompanying derivatization of functionalized compounds (e.g., fatty acids and sterols) prior to chromatographic separation represents a further source of potential error. This contribution can be removed using a simple isotopic mass balance approach. Based on these preliminary results, the PCGC-based approach holds promise for accurately determining (14)C ages on compounds specific to a given source within complex, heterogeneous samples.