Johannes A.C. Barth

Carbon Isotope Fractionation during Aerobic Biodegradation of Trichloroethene by Burkholderia cepacia G4: a Tool To Map Degradation Mechanisms

ABSTRACT The strain Burkholderia cepacia G4 aerobically mineralized trichloroethene (TCE) to CO2 over a time period of ∼20 h. Three biodegradation experiments were conducted with different bacterial optical densities at 540 nm (OD540s) in order to test whether isotope fractionation was consistent. The resulting TCE degradation was 93, 83.8, and 57.2% (i.e., 7.0, 16.2, and 42.8% TCE remaining) at OD540s of 2.0, 1.1, and 0.6, respectively. ODs also correlated linearly with zero-order degradation rates (1.99, 1.11, and 0.64 μmol h−1). While initial nonequilibrium mass losses of TCE produced only minor carbon isotope shifts (expressed in per mille δ13CVPDB), they were 57.2, 39.6, and 17.0‰ between the initial and final TCE levels for the three experiments, in decreasing order of their OD540s. Despite these strong isotope shifts, we found a largely uniform isotope fractionation. The latter is expressed with a Rayleigh enrichment factor, ε, and was −18.2 when all experiments were grouped to a common point of 42.8% TCE remaining. Although, decreases of ε to −20.7 were observed near complete degradation, our enrichment factors were significantly more negative than those reported for anaerobic dehalogenation of TCE. This indicates typical isotope fractionation for specific enzymatic mechanisms that can help to differentiate between degradation pathways.

A review of CO2 and associated carbon dynamics in headwater streams: A global perspective

Terrestrial carbon export via inland aquatic systems is a key process in the global carbon cycle. It includes loss of carbon to the atmosphere via outgassing from rivers, lakes or reservoirs and carbon fixation in the water column as well as in sediments. This review focuses on headwater streams that are important because their stream biogeochemistry directly reflects carbon input from soils and groundwaters that becomes superimposed by additional inputs further downstream. Major drivers of carbon dioxide partial pressures (pCO2) in streams and mechanisms of terrestrial dissolved inorganic, organic and particulate organic carbon (DIC, DOC, and POC) influxes are summarized in this work. Our analysis indicates that the global river average pCO2 of 3,100 ppmV is more often exceeded by contributions from small streams when compared to rivers with larger catchments (>500 km2). Because of their large proportion in global river networks (>96 % of the total number of streams), headwaters contribute large – but still poorly quantified – amounts of CO2 to the atmosphere. Conservative estimates imply that globally 36 % (i.e. 0.93 Pg C yr-1) of total CO2 outgassing from rivers and streams originate from headwaters. We also discuss challenges in determination of CO2 sources, concentrations and fluxes. To overcome uncertainties of CO2 sources and its outgassing from headwater streams on the global scale, new investigations are needed that should include groundwater data. Such studies would also benefit from applications of integral CO2 outgassing isotope approaches and multi-scale geophysical imaging techniques.

Carbon isotope fractionation during reductive dechlorination of TCE in batch experiments with iron samples from reactive barriers

Reductive dechlorination of trichloroethene (TCE) by zero-valent iron produces a systematic enrichment of 13C in the remaining substrate that can be described using a Rayleigh model. In this study, fractionation factors for TCE dechlorination with iron samples from two permeable reactive barriers (PRBs) were established in batch experiments. Samples included original unused iron as well as material from a barrier in Belfast after almost 4 years of operation. Despite the variety of samples, carbon isotope fractionations of TCE were remarkably similar and seemed to be independent of iron origin, reaction rate, and formation of precipitates on the iron surfaces. The average enrichment factor for all experiments was -10.1 per thousand (+/- 0.4 per thousand). These results indicate that the enrichment factor provides a powerful tool to monitor the reaction progress, and thus the performance, of an iron-reactive barrier over time. The strong fractionation observed may also serve as a tool to distinguish between insufficient residence time in the wall and a possible bypassing of the wall by the plume, which should result in an unchanged isotopic signature of the TCE. Although further work is necessary to apply this stable isotope method in the field, it has potential to serve as a unique monitoring tool for PRBs based on zero-valent iron.

Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring

A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of Integrated Ocean Drilling Program (IODP) Expedition 313 (New Jersey Shallow Shelf) were analyzed for chemical composition and stable isotope ratios. The analyses indicate a previously unknown complex geometry of the underlying fresh-water lens with alternating fresh-water–salt-water intervals divided by sharp boundaries in the upper part of the cores. Three fluid sources were identified: (1) meteoric fresh water, (2) marine seawater, and (3) brine. The pore-fluid stable isotope values define a mixing line with end members that have δ18O and δ2H values of –7.0‰ and –41‰ for fresh water, and –0.8‰ and –6‰ for salt water, respectively. This is similar to the modern mean value of New Jersey precipitation and today’s New Jersey shelf water. For fresh water, this either indicates modern meteoric recharge via aquifers that crop out on mainland New Jersey or emplacement at a time with climatic and hydrologic conditions similar to modern. An origin from Pleistocene glacial meltwaters with depleted isotope values is not confirmed by stable isotope data of this study. Salt water also represents modern isotope values suggesting an infiltration along permeable, coarse-grained sandy units. The lower core parts are characterized by mixing with brine fluids that originate from evaporites in the deep underground. Stable carbon isotope analyses of gas and fluids prove the existence of methane formation from degradation of marine organic matter and CO2 reduction in the lower core parts below ∼350 m below seafloor. Methane concentrations above 10000 ppm and δ13Cmethane values of ∼–80‰ were measured. Methane formation is also indicated by authigenic carbonates with low δ13Ccarbonate values. Although not reaching the surface at present conditions, the venting out of variable fluxes of methane from passive continental margins due to sea-level fluctuations is significant for the long-term carbon cycle. Authigenic carbonates indicate the precipitation from pore fluids with marine oxygen stable isotope ratios at low temperatures. The geochemical data and interpretations presented in this study supply the missing link between existing onshore and offshore data and may provide the basis for an integrated approach to construct a geochemical transect across the New Jersey shallow shelf.

Stable carbon isotope analysis of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) in natural waters- results from a worldwide proficiency test

RATIONALE Stable carbon isotope ratios of dissolved inorganic (DIC) and organic carbon (DOC) are of particular interest in aquatic geochemistry. The precision for this type of analysis is typically reported in the range of 0.1‰ to 0.5‰. However, there is no published attempt that compares δ(13)C measurements of DIC and DOC among different laboratories for natural water samples. METHODS Five natural water samples (lake water, seawater, two geothermal waters, and petroleum well water) were analyzed for δ(13)CDIC and δ(13)CDOC values by five laboratories with isotope ratio mass spectrometry (IRMS) in an international proficiency test. RESULTS The reported δ(13)CDIC values for lake water and seawater showed fairly good agreement within a range of about 1‰, whereas geothermal and petroleum waters were characterized by much larger differences (up to 6.6‰ between laboratories). δ(13)CDOC values were only comparable for seawater and showed differences of 10 to 21‰ for other samples. CONCLUSIONS This study indicates that scatter in δ(13)CDIC isotope data can be in the range of several per mil for samples from extreme environments (geothermal waters) and may not yield reliable information with respect to dissolved carbon (petroleum wells). The analyses of lake water and seawater also revealed a larger than expected difference and researchers from various disciplines should be aware of this. Evaluation of analytical procedures of the participating laboratories indicated that the differences cannot be explained by analytical errors or different data normalization procedures and must be related to specific sample characteristics or secondary effects during sample storage and handling. Our results reveal the need for further research on sources of error and on method standardization.

Pleistocene paleo-groundwater as a pristine fresh water resource in southern Germany – evidence from stable and radiogenic isotopes

Shallow groundwater aquifers are often influenced by anthropogenic contaminants or increased nutrient levels. In contrast, deeper aquifers hold potentially pristine paleo-waters that are not influenced by modern recharge. They thus represent important water resources, but their recharge history is often unknown. In this study groundwater from two aquifers in southern Germany were analyzed for their hydrogen and oxygen stable isotope compositions. One sampling campaign targeted the upper aquifer that is actively recharged by modern precipitation, whereas the second campaign sampled the confined, deep Benkersandstein aquifer. The groundwater samples from both aquifers were compared to the local meteoric water line to investigate sources and conditions of groundwater recharge. In addition, the deep groundwater was dated by tritium and radiocarbon analyses. Stable and radiogenic isotope data indicate that the deep-aquifer groundwater was not part of the hydrological water cycle in the recent human history. The results show that the groundwater is older than ~20,000 years and most likely originates from isotopically depleted melt waters of the Pleistocene ice age. Today, the use of this aquifer is strictly regulated to preserve the pristine water. Clear identification of such non-renewable paleo-waters by means of isotope geochemistry will help local water authorities to enact and justify measures for conservation of these valuable resources for future generations in the context of a sustainable water management.

The 2014 water release into the arid Colorado River delta and associated water losses by evaporation

For the first time in history, water was intentionally released for environmental purposes into the final, otherwise dry, 160-km stretch of the Colorado River basin, south of the Mexican border. Between March and May 2014 three pulses of water with a total volume of 132×10(6) m(3) were released to assess the restoration potential of endemic flora along its course and to reach its estuary. The latter had not received a sustained input of fresh water and nutrients from its main fluvial source for over 50 years because of numerous upstream dam constructions. During this pulse flow large amounts of water were lost and negligible amounts reached the ocean. While some of these water losses can be attributed to plant uptake and infiltration, we were able to quantify evaporation losses between 16.1 to 17.3% of the original water mass % within the first 80 km after the Morels Dam with water stable isotope data. Our results showed no evidence for freshwater reaching the upper Colorado River estuary and it is assumed that the pulse flow had only negligible influences on the coastal ecosystem. Future water releases that aim on ecological restoration need to become more frequent and should have larger volumes if more significant effects are to be established on the area.

Turnover and release of P-, N-, Si-nutrients in the Mexicali Valley (Mexico): interactions between the lower Colorado River and adjacent ground- and surface water systems.

A study on dissolved nitrate, ammonium, phosphate and silicate concentrations was carried out in various water compartments (rivers, drains, channels, springs, wetland, groundwater, tidal floodplains and ocean water) in the Mexicali Valley and the Colorado River delta between 2012 and 2013, to assess modern potential nutrient sources into the marine system after river damming. While nitrate and silicate appear to have a significant input into the coastal ocean, phosphate is rapidly transformed into a particulate phase. Nitrate is, in general, rapidly bio-consumed in the surface waters rich in micro algae, but its excess (up to 2.02 mg L(-1) of N from NO3 in winter) in the Santa Clara Wetland represents a potential average annual source to the coast of 59.4×10(3)kg N-NO3. Despite such localized inputs, continuous regional groundwater flow does not appear to be a source of nitrate to the estuary and coastal ocean. Silicate is associated with groundwaters that are also geothermally influenced. A silicate receiving agricultural drain adjacent to the tidal floodplain had maximum silicate concentrations of 16.1 mg L(-1) Si-SiO2. Seepage of drain water and/or mixing with seawater during high spring tides represents a potential source of dissolved silicate and nitrate into the Gulf of California.

Quantification of long-term wastewater fluxes at the surface water/groundwater-interface: An integrative model perspective using stable isotopes and acesulfame

The suitability of acesulfame to trace wastewater-related surface water fluxes from streams into the hyporheic and riparian zones over long-term periods was investigated. The transport behavior of acesulfame was compared with the transport of water stable isotopes (δ(18)O or δ(2)H). A calibrated model based on a joint inversion of temperature, acesulfame, and piezometric pressure heads was employed in a model validation using data sets of acesulfame and water stable isotopes collected over 5months in a stream and groundwater. The spatial distribution of fresh water within the groundwater resulting from surface water infiltration was estimated by computing groundwater ages and compared with the predicted acesulfame plume obtained after 153day simulation time. Both, surface water ratios calculated with a mixing equation from water stable isotopes and simulated acesulfame mass fluxes, were investigated for their ability to estimate the contribution of wastewater-related surface water inflow within groundwater. The results of this study point to limitations for the application of acesulfame to trace surface water-groundwater interactions properly. Acesulfame completely missed the wastewater-related surface water volumes that still remained in the hyporheic zone under stream-gaining conditions. In contrast, under stream-losing conditions, which developed after periods of stagnating hydraulic exchange, acesulfame based predictions lead to an overestimation of the surface water volume of up to 25% in the riparian zone. If slow seepage velocities prevail a proportion of acesulfame might be stored in smaller pores, while when released under fast flowing water conditions it will travel further downstream with the groundwater flow direction. Therefore, under such conditions acesulfame can be a less-ideal tracer in the hyporheic and riparian zones and additional monitoring with other environmental tracers such as water stable isotopes is highly recommended.