Quantification of biodegradation rate of hydrocarbons in a contaminated aquifer by CO2 δ13C monitoring at ground surface.

Ground surface analysis of CO2 emissions with δ13C determination is experimentally demonstrated to be a potential methodology to monitor, on line, the dynamics of petroleum-hydrocarbon biodegradation in soil aquifers, thanks to the improvement of the Isotopic Ratio Infra Red Spectroscopy technique. Biodegradation rate of remaining hydrocarbon substrates in groundwater can be quantified using basic application of the Rayleigh equations, by δ13CCO2 analysis released at ground surface above the pollution plume instead of usual approaches based on groundwater hydrocarbons δ13C analysis, when physical and chemical properties for the contaminated site meet appropriate conditions. The validation approach for that gasoline contaminated specific site is discussed and verified by comparison of first order attenuation rate constant determined from δ13CCO2 analysis emitted at ground surface and from δ13CTOLUENE analysis in ground water. A kinetic fractionation factor α of 0.9979 (or ε value of -2.1 ± 0.5‰) is estimated for the biodegradation of the most reactive hydrocarbon substrates (TEX). The treatment of this Rayleigh equations by linear regression of δ13CCO2 values along the predominant direction of groundwater flow leads to the following results and conclusions for that site: (i) first order biodegradation rate constants (and annual variation) are maximum after the activation of a Permeable Reactive Barrier (PRB) in May 2014: 0.92(+0.29-0.17) year-1, and during July and October: 0.46(+0.14-0.09) year-1 and minimum in mid-winter in February 2015: 0.17(+0.05-0.03) year-1, given by the estimation range for ε. These results are in the lower range with reported in literature for similar contaminated sites (1.6-18 year-1) considering natural attenuation under sulfate reducing conditions and (ii) the seasonal variation of the first order biodegradation rate constant is mainly correlated with the seasonal variation of the CO2 flux, where maximum values are in summers and minimum values in winters. Both seasonal variations are mainly due to the annual cycle of the natural biodegradation activity at the scale of the pollution plume, rather than the activation of the PRB. This work demonstrates that δ13CCO2 analysis released at ground surface from biodegradation of groundwater hydrocarbons could provide, under characterized and appropriate conditions, a non-intrusive (without soil samplings), fast, and low-cost online method to monitor and therefore to optimize soil remediation processes in real time. (Monitored Natural Attenuation or Enhanced Bioremediation).

The distribution of dissimilatory nitrate reduction to ammonium bacteria in multistage constructed wetland of Jining, Shandong, China.

Dissimilatory nitrate reduction to ammonium (DNRA) is an important process of nitrate reduction in the environment. The distribution of DNRA bacteria and the relationships with environmental factors in multistage constructed wetland were investigated in this study. The quantitative real-time polymerase chain reaction analysis showed that the abundance of DNRA bacteria at all sites ranged from 2.10 × 1010 to 1.10 × 1011 copies/g of dry sediments. The Anaeromyxobacter (belong to Deltaproteobacteria) was the most abundant DNRA bacteria at all sites. The Geobater known as DNRA bacteria was also identified in this study. The abundances of DNRA bacteria, denitrifying bacteria, and anammox bacteria were conspicuously negatively correlated with Eh and positively correlated with the NO3--N removal efficency by statistical analysis.

Response of C and N cycles to N fertilization in Sphagnum and Molinia-dominated peat mesocosms.

Plant communities play an important role in the C-sink function of peatlands. However, global change and local perturbations are expected to modify peatland plant communities, leading to a shift from Sphagnum mosses to vascular plants. Most studies have focused on the direct effects of modification in plant communities or of global change (such as climate warming, N fertilization) in peatlands without considering interactions between these disturbances that may alter peatlands' C function. We set up a mesocosm experiment to investigate how Greenhouse Gas (CO2, CH4, N2O) fluxes, and dissolved organic carbon (DOC) and total dissolved N (TN) contents are affected by a shift from Sphagnum mosses to Molinia caerulea dominated peatlands combined with N fertilization. Increasing N deposition did not alter the C fluxes (CO2 exchanges, CH4 emissions) or DOC content. The lack of N effect on the C cycle seems due to the capacity of Sphagnum to efficiently immobilize N. Nevertheless, N supply increased the N2O emissions, which were also controlled by the plant communities with the presence of Molinia caerulea reducing N2O emissions in the Sphagnum mesocosms. Our study highlights the role of the vegetation composition on the C and N fluxes in peatlands and their responses to the N deposition. Future research should now consider the climate change in interaction to plants community modifications due to their controls of peatland sensitivity to environmental conditions.

A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: Field implementation at a hydrocarbon contaminated site under bio-remediation.

Real-time methods to monitor stable isotope ratios of CO2 are needed to identify biogeochemical origins of CO2 emissions from the soil-air interface. An isotope ratio infra-red spectrometer (IRIS) has been developed to measure CO2 mixing ratio with δ(13)C isotopic signature, in addition to mixing ratios of other greenhouse gases (CH4, N2O). The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ(13)C of CO2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ(13)C of the CO2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO2 emissions have been measured with an isotopic signature δ(13)C suggesting that CO2 comes from petroleum hydrocarbon biodegradation. This first field implementation shows that rapid and accurate measurement of isotopic signature of CO2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO2 efflux and is promising as a monitoring tool for aerobic bio-treatment.

Effects of pH on nitrogen transformations in media-based aquaponics.

To investigate the effects of pH on performance and nitrogen transformations in aquaponics, media-based aquaponics operated at pH 6.0, 7.5 and 9.0 were systematically examined and compared in this study. Results showed that nitrogen utilization efficiency (NUE) reached its maximum of 50.9% at pH 6.0, followed by 47.3% at pH 7.5 and 44.7% at pH 9.0. Concentrations of nitrogen compounds (i.e., TAN, NO2(-)-N and NO3(-)-N) in three pH systems were all under tolerable levels. pH had significant effect on N2O emission and N2O conversion ratio decreased from 2.0% to 0.6% when pH increased from 6.0 to 9.0, mainly because acid environment would inhibit denitrifiers and lead to higher N2O emission. 75.2-78.5% of N2O emission from aquaponics was attributed to denitrification. In general, aquaponics was suggested to maintain pH at 6.0 for high NUE, and further investigations on N2O mitigation strategy are needed.