A routine chemical procedure was developed at the Ede Hertelendi Laboratory of Environmental Studies (HEKAL), in Debrecen which can measure the dissolved organic radiocarbon content of groundwater as well as the inorganic and total fraction. The typical background of this non-purgeable dissolved organic radiocarbon preparation is 0.73 ± 0.14 percent modern carbon (pMC), using a carbon contamination correction on fossil dissolved material (potassium hydrogen phthalate) samples.

Results from earlier laboratory and field experiments were interrogated for the possibilities of sequestration, or long-term accumulation, of carbon from excess greenhouse gases in the atmosphere. In the laboratory study, samples of three (top) soils dominated by kaolinite and illite (together), smectite, and allophane were examined for the adsorption and desorption of dissolved organic carbon (DOC). Adsorption and desorption of DOC were carried out on clay fractions extracted physically and after first native organic matter and then iron oxides were removed chemically. Labeled organic material was added to the soils to assess the priming effect of organic carbon (OC). In the field, changes in OC were measured in sandy soils that had been amended by additions of clay for between 3 and 17 years, both through incorporation of exogenous clay and delving of in situ clay. The laboratory experiments demonstrated that a portion of DOC was held strongly in all soils. The amount of DOC adsorbed depended on clay mineral types, including Fe oxides. Much adsorbed DOC was lost by desorption in water and a substantial amount of native OC was lost on priming with new OC. Addition of clay to soils led to increased OC. Therefore, addition of clay to soil may enhance net sequestration of C. Organic carbon close to mineral surfaces or within microaggregates is held most strongly. Carbon sequestration may occur in subsoils with unsaturated mineral surfaces. However, incorporation of carbon into macroaggregates from enhanced plant growth might be most effective in removing excess carbon from the atmosphere, albeit over the short-term.

This note describes improvements of UV oxidation method that is used to measure carbon isotopes of dissolved organic carbon (DOC) at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS). The procedural blank is reduced to 2.6 ± 0.6 μg C, with Fm of 0.42 ± 0.10 and δ13C of –28.43 ± 1.19‰. The throughput is improved from one sample per day to two samples per day.

We discuss present and developing techniques for studying radiocarbon in marine organic carbon (C). Bulk DOC (dissolved organic C) Δ14C measurements reveal information about the cycling time and sources of DOC in the ocean, yet they are time consuming and need to be streamlined. To further elucidate the cycling of DOC, various fractions have been separated from bulk DOC, through solid phase extraction of DOC, and ultrafiltration of high and low molecular weight DOC. Research using 14C of DOC and particulate organic C separated into organic fractions revealed that the acid insoluble fraction is similar in 14C signature to that of the lipid fraction. Plans for utilizing this methodology are described. Studies using compound specific radiocarbon analyses to study the origin of biomarkers in the marine environment are reviewed and plans for the future are outlined. Development of ramped pyrolysis oxidation methods are discussed and scientific questions addressed. A modified elemental analysis (EA) combustion reactor is described that allows high particulate organic C sample throughput by direct coupling with the MIniCArbonDAtingSystem.

This study describes a procedural blank assessment of the ultraviolet photochemical oxidation (UV oxidation) method that is used to measure carbon isotopes of dissolved organic carbon (DOC) at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS). A retrospective compilation of Fm and δ13C results for secondary standards (OX-II, glycine) between 2009 and 2018 indicated that a revised blank correction was required to bring results in line with accepted values. The application of a best-fit mass-balance correction yielded a procedural blank of 22.0 ± 6.0 µg C with Fm of 0.30 ± 0.20 and δ13C of –32.0 ± 3.0‰ for this period, which was notably higher and more variable than previously reported. Changes to the procedure, specifically elimination of higher organic carbon reagents and improved sample and reactor handling, reduced the blank to 11.0 ± 2.75 µg C, with Fm of 0.14 ± 0.10 and δ13C of –31.0 ± 5.5‰. A thorough determination of the entire sample processing blank is required to ensure accurate isotopic compositions of seawater DOC using the UV oxidation method. Additional efforts are needed to further reduce the procedural blank so that smaller DOC samples can be analyzed, and to increase sample throughput.

We report on an initial long-term study of dissolved inorganic and organic carbon (DIC) from Sabino Creek, located in Sabino Canyon, Pima County, Arizona. The purpose of this study was to monitor changes in dissolved radiocarbon (14C) with time and to understand the processes contributing to these variations. Our results span the period 2009–2016 and show a mixing trend between dissolved inorganic and organic carbon modern end-members with an older component. This study provides preliminary information for more detailed research on recycling of organic components in this stream system.

Alpine glaciers are valuable archives for the reconstruction of human impact on the environment. Besides dating purposes, measurement of radiocarbon (14C) content provides a powerful tool for long-term source apportionment studies on the carbonaceous aerosols incorporated in ice cores. In this work, we present an extraction system for 14C analyses of dissolved organic carbon (DOC) in ice cores. The setup can process ice samples of up to 350 g mass and offers ultra-clean working conditions for all extraction steps. A photo-oxidation method is applied by means of external UV irradiation of the sample. For an irradiation time of 30 min with catalyzation by addition of Fe2+ and H2O2, we achieve an efficiency of 96 ± 6% on average. Inert gas working conditions and stringent decontamination procedures enable a low overall blank of 1.9 ± 1.6 μg C with a F14C value of 0.68 ± 0.13. This makes it possible to analyze the DOC in ice samples with a carbon content of as low as 25 μg C kg−1 ice. For a first validation, the new method was applied to ice core samples from the Swiss Alps. The average DOC concentration and F14C values for the Fiescherhorn ice core samples show good agreement with previously reported data for the investigated period of 1925–1936 AD.

The first ultraviolet photochemical oxidation (UVox) extraction method for marine dissolved organic carbon (DOC) as CO2 gas was established by Armstrong and co-workers in 1966. Subsequent refinement of the UVox technique has co-evolved with the need for high-precision isotopic (Δ14C, δ13C) analysis and smaller sample size requirements for accelerator mass spectrometry radiocarbon (AMS 14C) measurements. The UVox line at UC Irvine was established in 2004 and the system reaction kinetics and efficiency for isolating seawater DOC rigorously tested for quantitative isolation of ∼1 mg C for AMS 14C measurements. Since then, improvements have been made to sampling, storage, and UVox methods to increase overall efficiency. We discuss our progress, and key UVox system parameters for optimizing precision, accuracy, and efficiency, including (1) ocean to reactor: filtration, storage and preparation of DOC samples, (2) cryogenic trap design, efficiency and quantification of CO2 break through, and (3) use of isotopic standards, blanks and small sample graphitization techniques for the correction of DOC concentrations and Fm values with propagated uncertainties. New DOC UVox systems are in use at many institutions. However, rigorous assessment of quantitative UVox DOC yields and blank contributions, DOC concentrations and carbon isotopic values need to be made. We highlight the need for a community-wide inter-comparison study.

We report marine dissolved organic carbon (DOC) ∆14C from seawater collected from the North central Pacific Ocean (NCP) in 2015. These measurements show DOC ∆14C values averaged –235±5‰ (n=3) in the mixed layer (24–81 m) and –544±5‰ (n=5) in the deep water (1500–5139 m). A comparison of these data with two previously published DOC ∆14C profiles from the NCP in 1985 and 1987 reveals that deep DOC ∆14C values have decreased. We discuss several possible mechanisms that could cause such a shift in DOC ∆14C values, including spatial inhomogeneity and temporal variability due to changes in the dissolution and ∆14C value of surface derived particles in the deep sea. We find that forthcoming profiles of DOC ∆14C results from the NCP will determine the primary mechanisms controlling deep DOC ∆14C distributions, and changes over the past three decades.

The standard procedure for storing/preserving seawater dissolved organic carbon (DOC) samples after field collection is by freezing (–20°C) until future analysis can be made. However, shipping and receiving large numbers of these samples without thawing presents a significant logistical problem and large monetary expense. Access to freezers can also be limited in remote field locations. We therefore test an alternative method of preserving and storing samples for the measurement of DOC concentrations ([DOC]), stable carbon (δ13C), and radiocarbon (as ∆14C) isotopic values via UV photooxidation (UVox). We report a total analytical reproducibility of frozen DOC samples to be [DOC]±1.3 µM, ∆14C±9.4‰, and δ13C±0.1‰, comparable to previously reported results (Druffel et al. 2013). Open Ocean DOC frozen versus acidified duplicates were on average offset by ∆DOC±1.1 µM, ∆∆14C± –1.3‰, and ∆δ13C± –0.1‰. Coastal Ocean frozen vs. acidified sample replicates, collected as part of a long-term (380-day) storage experiment, had larger, albeit consistent offsets of ∆DOC±2.2 µM, ∆∆14C±1.5‰, and ∆δ13C± –0.2‰. A simple isotopic mass balance of changes in [DOC], ∆14C, and δ13C values reveals loss of semi-labile DOC (2.2±0.6 µM, ∆14C=–94±105‰, δ13C=–27±10‰; n=4) and semi-recalcitrant DOC (2.4±0.7 µM, ∆14C=–478±116‰, δ13C=–23.4±3.0‰; n=3) in Coastal and Open Ocean acidified samples, respectively.

The radiocarbon content of dissolved organic carbon (DOC) in rivers, lakes, and other non-saline waters can provide valuable information on carbon cycling dynamics in the environment. DOC is typically prepared for 14C analysis by accelerator mass spectrometry (AMS) either by ultraviolet (UV) oxidation or by freeze-drying and sealed tube combustion. We present here a new method for the rapid analysis of 14C of DOC using wet chemical oxidation (WCO) and automated headspace sampling of CO2. The approach is an adaption of recently developed methods using aqueous persulfate oxidant to determine the δ13C of DOC in non-saline water samples and the 14C content of volatile organic acids. One advantage of the current method over UV oxidation is higher throughput: 22 samples and 10 processing standards can be prepared in one day and analyzed in a second day, allowing a full suite of 14C processing standards and blanks to be run in conjunction with samples. A second advantage is that there is less potential for cross-contamination between samples.

We studied the relationships between soil nutrient availability and microbial biomass and activity of two contrasting soil conditions in a tropical deciduous forest in western Mexico. Hilltops have higher pH, water, dissolved organic C, and ammonium concentrations than hillslopes. Our main hypothesis was that soil microbial biomass, microbial activity and bacterium species richness would be higher in soils with high availability of nutrients. Fifteen soil cores, 0–5 cm depth, were taken in the dry, early rainy and rainy season, from each of the ten replicate plots in hilltop and hillslope positions located on three contiguous small watersheds. We measured moisture, C, N and P availability, potential C mineralization, net nitrification, microbial biomass and culturable heterotrophic and nitrifying bacteria in composite samples from each plot. Microbial biomass, species richness of culturable heterotrophic bacteria and C mineralization were significantly higher on hilltops than on hillslopes. Net nitrification was, in contrast, significantly higher on hillslopes than on hilltops and counts of culturable nitrifying bacteria were also significantly higher in the rainy-season samples. Hilltops and hillslopes had low similarity in composition of culturable heterotrophic bacterial species, particularly during the rainy season. The results suggested that C and N availability and seasonal changes in soil moisture are important controlling factors for some soil culturable-bacterial species, which may affect both C mineralization and nitrification in these tropical deciduous forest soils.

Concentrations of dissolved monocarbohydrates (MCHO) and polycarbohydrates (PCHO) were analysed in a variety of ice habitats from summer Weddell Sea sea ice (surface ponds, ice cores, gap layers and platelet ice). The dissolved organic carbon (DOC) pool in these habitats was also measured and the contribution of carbohydrate to this pool was assessed. The DOC concentrations within all sea ice habitats were high compared to surface seawater concentrations with values up to 958μMC being measured. Total carbohydrates (TCHO) were highest in the ice cores and platelet ice samples, up to 31% of the DOC pool, a reflection of the high algal biomass in these two habitat classes. TCHO in the other habitats ranged between 10% and 29% of DOC. The ratios of MCHO to PCHO varied considerably between the ice habitats: in surface ponds and ice cores MCHO was 70% of the TCHO pool, whereas in gap layers and platelet ice there were lower PCHO concentrations resulting in MCHO being 88% of TCHO.

Throughfall and soil solution chemistry were studied for 1 y in a tropical montane forest in the Luquillo Mountains of Puerto Rico. Passage of precipitation through the forest canopy resulted in an increase in the concentration and flux of all solutes except H+ and NO3−. Throughfall chemistry showed no strong seasonal patterns, but concentrations of many solutes declined during weeks of high rainfall. Enrichment in throughfall relative to precipitation was similar to values reported recently for several other tropical sites, with the exception of NH4+, which was particularly high at this site. Based on net throughfall deposition of Cl−, dry deposition of marine aerosols appears to be a relatively minor component (c. 15%) of total deposition. In soil solution, no seasonal patterns in concentration were evident and variability was highest for elements with high biological activity (especially N). Concentrations and fluxes of K+ and dissolved organic carbon (DOC) showed the largest declines as throughfall passed through the soil profile; concentrations of most other elements increased or were relatively constant. Declining DOC flux through the soil profile appears to be due to sorption processes similar to those observed in many temperate forests. Concentrations and fluxes of HCO3− and SiO2 increased substantially in soil solution, but never approached those observed in the stream. This suggests that additional weathering must occur as groundwater moves from this ridgetop site to the stream.

A simple procedure is described in order to estimate the biodegradable fraction of dissolved organic carbon (DOC), particulate organic carbon (POC) and total organic carbon (TOC) in water samples. Methodological improvements of the method which includes aerobic incubation in batch and carbon measurements are presented. First applications to natural and waste water samples show the usefulness of the method in the field of water treatment and management of surface water.