Synergies of chemodenitrification and denitrification in a saline inland lake.

The interconnection between biotic and abiotic pathways involving the nitrogen and iron biogeochemical cycles has recently gained interest. While lacustrine ecosystems are considered prone to the biotic nitrate reduction (denitrification), their potential for promoting the abiotic nitrite reduction (chemodenitrification) remains unclear. In the present study, batch incubations were performed to assess the potential for chemodenitrification and denitrification in the saline inland lake Gallocanta. Sulfidic conditions are found in top sediments of the system while below (5-9 cm), it presents low organic carbon and high sulfate and ferrous iron availability. Anoxic incubations of sediment (5-9 cm) and water from the lake with nitrite revealed potential for chemodenitrification, especially when external ferrous iron was added. The obtained isotopic fractionation values for nitrite (ɛ15NNO2) were -6.8 and -12.3 ‰ and therefore, fell in the range of those previously reported for the nitrite reduction. The more pronounced ɛ15NNO2 (-12.3 ‰) measured in the experiment containing additional ferrous iron was attributed to a higher contribution of the chemodenitrification over biotic denitrification. Incubations containing nitrate also confirmed the potential for denitrification under autotrophic conditions (low organic carbon, high ferrous iron). Higher reaction rate constants were found in the experiment containing 100 µM compared to 400 µM nitrate. The obtained ɛ15NNO3 values (-8.5 and -15.1 ‰) during nitrate consumption fell in the range of those expected for the denitrification. A more pronounced ɛ15NNO3 (-15.1 ‰) was determined in the experiment presenting a lower reaction rate constant (400 µM nitrate). Therefore, in Gallocanta lake, nitrite generated during nitrate reduction can be further reduced by both the abiotic and biotic pathways. These findings establish the significance of chemodenitrification in lacustrine systems and support further exploration in aquatic environments with different levels of C, N, S, and Fe. This might be especially useful in predicting nitrous oxide emissions in natural ecosystems.

Upside down sulphate dynamics in a saline inland lake.

The sulphur cycle has a key role on the fate of nutrients through its several interconnected reactions. Although sulphur cycling in aquatic ecosystems has been thoroughly studied since the early 70's, its characterisation in saline endorheic lakes still deserves further exploration. Gallocanta Lake (NE Spain) is an ephemeral saline inland lake whose main sulphate source is found on the lake bed minerals and leads to dissolved sulphate concentrations higher than those of seawater. An integrative study including geochemical and isotopic characterization of surface water, porewater and sediment has been performed to address how sulphur cycling is constrained by the geological background. In freshwater and marine environments, sulphate concentration decreases with depth are commonly associated with bacterial sulphate reduction (BSR). However, in Gallocanta Lake sulphate concentrations in porewater increase from 60 mM at the water-sediment interface to 230 mM at 25 cm depth. This extreme increase could be caused by dissolution of the sulphate rich mineral epsomite (MgSO4·7H2O). Sulphur isotopic data was used to validate this hypothesis and demonstrate the occurrence of BSR near the water-sediment interface. This dynamic prevents methane production and release from the anoxic sediment, which is advantageous in the current context of global warming. These results underline that geological context should be considered in future biogeochemical studies of inland lakes with higher potential availability of electron acceptors in the lake bed compared to the water column.

Characterisation of the natural attenuation of chromium contamination in the presence of nitrate using isotopic methods. A case study from the Matanza-Riachuelo River basin, Argentina.

The groundwater contamination by hexavalent chromium (Cr(VI)) in a site of the Matanza-Riachuelo River basin (MRB), Argentina, has been evaluated by determining the processes that control the natural mobility and attenuation of Cr(VI) in the presence of high nitrate (NO3-) contents. The groundwater Cr(VI) concentrations ranged between 1.9E-5 mM and 0.04 mM, while the NO3- concentrations ranged between 0.5 mM and 3.9 mM. In order to evaluate the natural attenuation of Cr(VI) and NO3- in the MRB groundwater, Cr and N isotopes were measured in these contaminants. In addition, laboratory batch experiments were performed to determine the isotope fractionation (ε) during the reduction of Cr(VI) under denitrifying conditions. While the Cr(VI) reduction rate is not affected by the presence of NO3-, the NO3- attenuation is slower in the presence of Cr(VI). Nevertheless, no significant differences on ε values were observed when testing the absence or presence of each contaminant. The ε53Cr determined in the batch experiments describe a two- stage trend, in which Stage I is characterized by ε53Cr ~-1.8‰ and Stage II by ε53Cr ~-0.9‰. The respective ε15NNO3 obtained is -23.9‰ whereas ε18ONO3 amount to -25.7‰. Using these ε values and a Rayleigh fractionation model we estimate that an average of 60% of the original Cr(VI) is removed from the groundwater of the contaminated site. Moreover, the average degree of NO3- attenuation by denitrification is found to be about 20%. This study provides valuable information about the dynamics of a complex system that can serve as a basis for efficient management of contaminated groundwater in the most populated and industrialized basin of Argentina.

Use of nitrogen and oxygen isotopes of dissolved nitrate to trace field-scale induced denitrification efficiency throughout an in-situ groundwater remediation strategy.

In the framework of the Life+ InSiTrate project, a pilot-plant was established to demonstrate the viability of inducing in-situ heterotrophic denitrification to remediate nitrate (NO3-)-polluted groundwater. Two injection wells supplied acetic acid by pulses to an alluvial aquifer for 22months. The monitoring was performed by regular sampling at three piezometers and two wells located downstream. In the present work, the pilot-plant monitoring samples were used to test the usefulness of the isotopic tools to evaluate the efficiency of the treatment. The laboratory microcosm experiments determined an isotopic fractionation (ε) for N-NO3- of -12.6‰ and for O-NO3- of -13.3‰. These ε15NNO3/N2 and ε18ONO3/N2 values were modelled by using a Rayleigh distillation equation to estimate the percentage of the induced denitrification at the pilot-plant while avoiding a possible interference from dilution due to non-polluted water inputs. In some of the field samples, the induced NO3- reduction was higher than 50% with respect to the background concentration. The field samples showed a reduced slope between δ18O-NO3- and δ15N-NO3- (0.7) compared to the laboratory experiments (1.1). This finding was attributed to the reoxidation of NO2- to NO3- during the treatment. The NO3- isotopic characterization also permitted the recognition of a mixture between the denitrified and partially or non-denitrified groundwater in one of the sampling points. Therefore, the isotopic tools demonstrated usefulness in assessing the implementation of the field-scale induced denitrification strategy.

Evaluating the potential use of a dairy industry residue to induce denitrification in polluted water bodies: A flow-through experiment.

Improving the effectiveness and economics of strategies to remediate groundwater nitrate pollution is a matter of concern. In this context, the addition of whey into aquifers could provide a feasible solution to attenuate nitrate contamination by inducing heterotrophic denitrification, while recycling an industry residue. Before its application, the efficacy of the treatment must be studied at laboratory-scale to optimize the application strategy in order to avoid the generation of harmful intermediate compounds. To do this, a flow-through denitrification experiment using whey as organic C source was performed, and different C/N ratios and injection periodicities were tested. The collected samples were analyzed to determine the chemical and isotopic composition of N and C compounds. The results proved that whey could promote denitrification. Nitrate was completely removed when using either a 3.0 or 2.0 C/N ratio. However, daily injection with C/N ratios from 1.25 to 1.5 seemed advantageous, since this strategy decreased nitrate concentration to values below the threshold for water consumption while avoiding nitrite accumulation and whey release with the outflow. The isotopic results confirmed that nitrate attenuation was due to denitrification and that the production of DIC was related to bacterial whey oxidation. Furthermore, the isotopic data suggested that when denitrification was not complete, the outflow could present a mix of denitrified and nondenitrified water. The calculated isotopic fractionation values (ε15NNO3/N2 and ε18ONO3/N2) might be applied in the future to quantify the efficiency of the bioremediation treatments by whey application at field-scale.