Nitrate-consuming processes in a petroleum-contaminated aquifer quantified using push-pull tests combined with 15N isotope and acetylene-inhibition methods

Nitrate consumption in aquifers may result from several biogenic and abiotic processes such as denitrification, assimilatory NO3- reduction, dissimilatory NO3- reduction to ammonium (DNRA), or abiotic NO3- (or NO2-) reduction. The objectives of this study were to investigate the fate of NO3- in a petroleum-contaminated aquifer, and to assess the feasibility of using single-well push-pull tests (PPTs) in combination with 15N isotope and C2H2 inhibition methods for the quantification of processes contributing to NO3- consumption. Three consecutive PPTs were performed in a monitoring well of a heating oil-contaminated aquifer in Erlen, Switzerland. For each test, we injected 500 l of test solution containing 0.5 mM Br- as conservative tracer and either 0.5 mM unlabeled NO3- or approximately 0.3 mM 15N-labeled NO3- as reactant. Test solutions were sparged during preparation and injection with either N2, Ar or 10% C2H2 in Ar. After an initial incubation period of 1.5-3.2 h, we extracted the test solution/groundwater mixtures from the same location and measured concentrations of relevant species including Br-, NO3-, NO2-, N2O, N2, and NH4+. In addition, we determined the 15N contents of N2, N2O, NH4+, and suspended biomass from 15N/14N isotope-ratio measurements. Average total test duration was 50.5 h. First-order rate coefficients (k) were computed from measured NO3- consumption, N2-15N production and N2O-15N production. From measured NO3- consumption we obtained nearly identical estimates of k for all PPTs with small 95% confidence intervals, indicating good reproducibility and accuracy for the tests. Estimates of k from N2-15N production and N2O-15N production indicated that denitrification accounted for only 46-49% of observed NO3- consumption. Production of N2-15N in the presence of C2H2 was observed during one of the tests, which may be an indicator for abiotic NO3- reduction. Moreover, 15N isotope analyses confirmed occurrence of assimilatory NO3- reduction (0.58 at.% 15N in suspended biomass) and to a smaller extent DNRA (up to 4 at.% 15N in NH4+). Our results indicated that the combination of PPTs, 15N-isotope and C2H2 inhibition methods provided improved information on denitrification as well as alternative fates of NO3- in this aquifer.     

Response of Temperature-limited Forests to Recent Moisture Changes Derived from Tree-ring Stable Carbon Isotopes

Russian Journal of Ecology - Recent climatic changes significantly affected forest ecosystems in northern Eurasia. Trees growing in Siberia are very sensitive to climate change due to strong...     

Effects of elevated ozone on leaf delta13C and leaf conductance of plant species grown in semi-natural grassland with or without irrigation

Stable carbon isotope ratios (delta(13)C) and leaf conductance (g(s)) were measured (2002, 2003) in Holcus lanatus L., Plantago lanceolata L. Ranunculus friesianus (Jord.), and Trifolium pratense L. at two levels of ozone (O(3)) with or without irrigation. In non-irrigated control plots, R. friesianus showed the least negative delta(13)C, and the smallest response to the treatments. Irrigation caused more negative delta(13)C, especially in H. lanatus. Irrespective of irrigation, O(3) increased delta(13)C in relationship to a decrease in g(s) in P. lanceolata and T. pratense. The strongest effect of O(3) on delta(13)C occurred in the absence of irrigation, suggesting that under field conditions lack of moisture in the top soil does not always lead to protection from O(3) uptake. It is concluded that in species such as T. pratense plants can maintain stomatal O(3) uptake during dry periods when roots can reach deeper soil layers where water is not limiting.     

Impact of different nitrogen emission sources on tree physiology as assessed by a triple stable isotope approach

The importance that nitrogen (N) deposition has in driving the carbon (C) sequestration of forests has recently been investigated using both experimental and modeling approaches. Whether increased N deposition has positive or negative effects on such ecosystems depends on the status of the N and the duration of the deposition. By combining δ¹³C, δ¹⁸O, δ¹⁵N and dendrochronological approaches, we analyzed the impact of two different sources of NO_x emissions on two tree species, namely: a broadleaved species (Quercus cerris) that was located close to an oil refinery in Southern Italy, and a coniferous species (Picea abies) located close to a freeway in Switzerland. Variations in the c_i/c_a ratio and the distinction between stomatal and photosynthetic responses to NO_x emissions in trees were assessed using a conceptual model, which combines δ¹³C and δ¹⁸O. δ¹⁵N in leaves, needles and tree rings was found to be a bioindicator of N input from anthropogenic emissions, especially at the oil refinery site. We observed that N fertilization had a stimulatory effect on tree growth near the oil refinery, while the opposite effect was found for trees at the freeway site. Changes in the c_i/c_a ratio were mostly related to variations in δ¹³C at the freeway site and, thus, were driven by photosynthesis. At the oil refinery site they were mainly related to stomatal conductance, as assessed using δ¹⁸O. This study demonstrates that a single method approach does not always provide a complete picture of which physiological traits are more affected by N emissions. The triple isotope approach combined with dendrochronological analyses proved to be a very promising tool for monitoring the ecophysiological responses of trees to long-term N deposition.     

Determination of primary and secondary sources of organic acids and carbonaceous aerosols using stable carbon isotopes

Stable carbon isotope ratio (δ¹³C) data can provide important information regarding the sources and the processing of atmospheric organic carbon species. Formic, acetic and oxalic acid were collected from Zurich city in August–September 2002 and March 2003 in the gas and aerosol phase, and the corresponding δ¹³C analysis was performed using a wet oxidation method followed by isotope ratio mass spectrometry. In August, the δ¹³C values of gas phase formic acid showed a significant correlation with ozone (coefficient of determination (r²) = 0.63) due to the kinetic isotope effect (KIE). This indicates the presence of secondary sources (i.e. production of organic acids in the atmosphere) in addition to direct emission. In March, both gaseous formic and acetic acid exhibited similar δ¹³C values and did not show any correlation with ozone, indicating a predominantly primary origin. Even though oxalic acid is mainly produced by secondary processes, the δ¹³C value of particulate oxalic acid was not depleted and did not show any correlation with ozone, which may be due to the enrichment of ¹³C during the gas - aerosol partitioning.The concentrations and δ¹³C values of the different aerosol fractions (water soluble organic carbon, water insoluble organic carbon, carbonate and black carbon) collected during the same period were also determined. Water soluble organic carbon (WSOC) contributed about 60% to the total carbon and was enriched in ¹³C compared to other fractions indicating a possible effect of gas - aerosol partitioning on δ¹³C of carbonaceous aerosols. The carbonate fraction in general was very low (3% of the total carbon).