Lukas Emmenegger

Mechanisms of N2O production in biological wastewater treatment under nitrifying and denitrifying conditions

Nitrous oxide (N2O) is an important greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment, microbial processes such as autotrophic nitrification and heterotrophic denitrification have been identified as major sources; however, the underlying pathways remain unclear. In this study, the mechanisms of N2O production were investigated in a laboratory batch-scale system with activated sludge for treating municipal wastewater. This relatively complex mixed population system is well representative for full-scale activated sludge treatment under nitrifying and denitrifying conditions. Under aerobic conditions, the addition of nitrite resulted in strongly nitrite-dependent N2O production, mainly by nitrifier denitrification of ammonia-oxidizing bacteria (AOB). Furthermore, N2O is produced via hydroxylamine oxidation, as has been shown by the addition of hydroxylamine. In both sets of experiments, N2O production was highest at the beginning of the experiment, then decreased continuously and ceased when the substrate (nitrite, hydroxylamine) had been completely consumed. In ammonia oxidation experiments, N2O peaked at the beginning of the experiment when the nitrite concentration was lowest. This indicates that N2O production via hydroxylamine oxidation is favored at high ammonia and low nitrite concentrations, and in combination with a high metabolic activity of ammonia-oxidizing bacteria (at 2 to 3 mgO2/l); the contribution of nitrifier denitrification by AOB increased at higher nitrite and lower ammonia concentrations towards the end of the experiment. Under anoxic conditions, nitrate reducing experiments confirmed that N2O emission is low under optimal growth conditions for heterotrophic denitrifiers (e.g. no oxygen input and no limitation of readily biodegradable organic carbon). However, N2O and nitric oxide (NO) production rates increased significantly in the presence of nitrite or low dissolved oxygen concentrations.

Determination of biogenic and fossil CO2 emitted by waste incineration based on 14CO2 and mass balances

A field application of the radiocarbon ((14)C) method was developed to determine the ratio of biogenic vs. fossil CO(2) emissions from waste-to-energy plants (WTE). This methodology can be used to assign the Kyoto relevant share of fossil CO(2) emissions, which is highly relevant for emission budgets and emission trading. Furthermore, heat and electricity produced by waste incinerators might be labelled depending on the fossil or biogenic nature of the primary energy source. The method development includes representative on-site CO(2) absorption and subsequent release in the laboratory. Furthermore, a reference value for the (14)C content of pure biogenic waste (f(M,bio)) was determined as 1.130+/-0.038. Gas samples for (14)CO(2) analysis were taken at three WTEs during one month each. Results were compared to an alternative approach based on mass and energy balances. Both methods were in excellent agreement and indicated a fraction of biogenic CO(2) slightly above 50%.

Isotope Signatures of N2O in a Mixed Microbial Population System: Constraints on N2O Producing Pathways in Wastewater Treatment

We present measurements of site preference (SP) and bulk (15)N/(14)N ratios (δ(15)N(bulk)(N2O)) of nitrous oxide (N(2)O) by quantum cascade laser absorption spectroscopy (QCLAS) as a powerful tool to investigate N(2)O production pathways in biological wastewater treatment. QCLAS enables high-precision N(2)O isotopomer analysis in real time. This allowed us to trace short-term fluctuations in SP and δ(15)N(bulk)(N2O) and, hence, microbial transformation pathways during individual batch experiments with activated sludge from a pilot-scale facility treating municipal wastewater. On the basis of previous work with microbial pure cultures, we demonstrate that N(2)O emitted during ammonia (NH(4)(+)) oxidation with a SP of -5.8 to 5.6 ‰ derives mostly from nitrite (NO(2)(-)) reduction (e.g., nitrifier denitrification), with a minor contribution from hydroxylamine (NH(2)OH) oxidation at the beginning of the experiments. SP of N(2)O produced under anoxic conditions was always positive (1.2 to 26.1 ‰), and SP values at the high end of this spectrum (24.9 to 26.1 ‰) are indicative of N(2)O reductase activity. The measured δ(15)N(bulk)(N2O) at the initiation of the NH(4)(+) oxidation experiments ranged between -42.3 and -57.6 ‰ (corresponding to a nitrogen isotope effect Δδ(15)N = δ(15)N(substrate) - δ(15)N(bulk)(N2O) of 43.5 to 58.8 ‰), which is considerably higher than under denitrifying conditions (δ(15)N(bulk)(N2O) 2.4 to -17 ‰; Δδ(15)N = 0.1 to 19.5 ‰). During the course of all NH(4)(+) oxidation and nitrate (NO(3)(-)) reduction experiments, δ(15)N(bulk)(N2O) increased significantly, indicating net (15)N enrichment in the dissolved inorganic nitrogen substrates (NH(4)(+), NO(3)(-)) and transfer into the N(2)O pool. The decrease in δ(15)N(bulk)(N2O) during NO(2)(-) and NH(2)OH oxidation experiments is best explained by inverse fractionation during the oxidation of NO(2)(-) to NO(3)(-).

Experimental assessment of N2O background fluxes in grassland systems

In the absence of, or between, fertilization events in agricultural systems, soils are generally assumed to emit N2O at a small rate, often described as the ‘background’ flux. In contrast, net uptake of N2O by soil has been observed in many field studies, but has not gained much attention. Observations of net uptake of N2O form a large fraction (about half) of all individual flux measurements in a long-term time series at our temperate fertilized grassland site. Individual uptake fluxes from chamber measurements are often not statistically significant but mean values integrated over longer time periods from days to weeks do show a clear uptake. An analysis of semi-continuous chamber flux data in conjunction with continuous measurements of the N2O concentration in the soil profile and eddy covariance measurements suggests that gross production and gross consumption of N2O are of the same order, and as consequence only a minor fraction of N2O molecules produced in the soil reaches the atmosphere.

Determination of N2O isotopomers with quantum cascade laser based absorption spectroscopy

We present an analytical technique based on direct absorption laser spectroscopy for high precision and simultaneous determination of the mixing ratios of the most abundant nitrous oxide isotopic species: (14)N(15)N(16)O, (15)N(14)N(16)O and (14)N(2) (16)O. A precision of 0.5 ??? was achieved for the site specific isotope ratios of N(2)O at 90 ppm using an averaging time of 300 s.

Impact of Low- and High-Oxidation Diesel Particulate Filters on Genotoxic Exhaust Constituents

Diesel exhaust contains several genotoxic compounds that may or may not penetrate diesel particulate filters (DPFs). Furthermore, the DPF-supported combustion of soot and adsorbed compounds may lead to the formation of additional pollutants. Herein, we compare the impact of 14 different DPFs on emissions of known genotoxic compounds. During a four year period, these DPFs were tested on a heavy duty diesel engine, operated in the ISO 8178/4 C1 cycle. Integral samples, including gas-phase and particle-bound matter were taken. All DPFs were efficient wall-flow filters with solid particulate number filtration efficiencies eta > 98%. On the basis of their CO, NO, and NO(2) emission characteristics, two different filter families were distinguished. DPFs with high oxidation potential (hox, n = 8) converted CO and NO besides hydrocarbons, whereas low oxidation potential DPFs (lox, n = 6) did not support CO and NO oxidation but still converted hydrocarbons. Lox-DPFs reduced NO(2) from 1.0 +/- 0.3 (engine-out) to 0.42 +/- 0.11 g/kWh (eta = 0.59), whereas hox-DPFs induced a NO(2) formation up to 3.3 +/- 0.7 g/kWh (eta = -2.16). Emissions of genotoxic PAHs decreased for both filter families. Conversion efficiencies varied for individual PAHs and were lower for lox- (eta = 0.31-0.87) than for hox-DPFs (eta = 0.75-0.98). Certain nitro-PAHs were formed indicating that nitration is an important step along PAH oxidation. For example, 1-nitronaphthalene emissions increased from 11 to 17 to 21 microg/L without, with lox-, and hox-DPFs respectively, whereas 2-nitronaphthalene emissions decreased from 25 to 19 to 4.7 microg/L. In contrast to our expectations, the nitration potential of lox-DPFs was higher than the one of hox-DPFs, despite the intense NO(2) formation of the latter. The filters converted most genotoxic PAHs and nitro-PAHs and most soot particles, acting as carriers for these compounds. Hox-DPF exhaust remains oxidizing and therefore is expected to support atmospheric oxidation reactions, whereas lox-DPF exhaust is reducing and consuming oxidants such as ozone, when mixed with ambient air.

Novel laser spectroscopic technique for continuous analysis of N2O isotopomers--application and intercomparison with isotope ratio mass spectrometry.

RATIONALE Nitrous oxide (N(2)O), a highly climate-relevant trace gas, is mainly derived from microbial denitrification and nitrification processes in soils. Apportioning N(2)O to these source processes is a challenging task, but better understanding of the processes is required to improve mitigation strategies. The N(2)O site-specific (15)N signatures from denitrification and nitrification have been shown to be clearly different, making this signature a potential tool for N(2)O source identification. We have applied for the first time quantum cascade laser absorption spectroscopy (QCLAS) for the continuous analysis of the intramolecular (15)N distribution of soil-derived N(2)O and compared this with state-of-the-art isotope ratio mass spectrometry (IRMS). METHODS Soil was amended with nitrate and sucrose and incubated in a laboratory setup. The N(2)O release was quantified by FTIR spectroscopy, while the N(2)O intramolecular (15)N distribution was continuously analyzed by online QCLAS at 1 Hz resolution. The QCLAS results on time-integrating flask samples were compared with those from the IRMS analysis. RESULTS The analytical precision (2σ) of QCLAS was around 0.3‰ for the δ(15)N(bulk) and the (15)N site preference (SP) for 1-min average values. Comparing the two techniques on flask samples, excellent agreement (R(2)= 0.99; offset of 1.2‰) was observed for the δ(15)N(bulk) values while for the SP values the correlation was less good (R(2 )= 0.76; offset of 0.9‰), presumably due to the lower precision of the IRMS SP measurements. CONCLUSIONS These findings validate QCLAS as a viable alternative technique with even higher precision than state-of-the-art IRMS. Thus, laser spectroscopy has the potential to contribute significantly to a better understanding of N turnover in soils, which is crucial for advancing strategies to mitigate emissions of this efficient greenhouse gas.

Compact multipass optical cell for laser spectroscopy

A multipass cell (MPC) design for laser absorption spectroscopy is presented. The development of this new type of optical cell was driven by stringent criteria for compactness, robustness, low volume, and ease of use in optical systems. A single piece of reflective toroidal surface forms a near-concentric cavity with a volume of merely 40 cm(3). Contrary to traditional MPCs, this design allows for flexible path-length adjustments by simply changing the aiming angle of the laser beam at the entrance window. Two effective optical path lengths of 2.2 and 4.1 m were chosen to demonstrate the cells suitability for high-precision isotope ratio measurements of CO(2) at 1% and ambient mixing ratio levels.

Fossil and biogenic CO2 from waste incineration based on a yearlong radiocarbon study

We describe the first long-term implementation of the radiocarbon (¹⁴C) method to study the share of biogenic (%Bio C) and fossil (%Fos C) carbon in combustion CO₂. At five Swiss incinerators, a total of 24 three-week measurement campaigns were performed over 1 year. Temporally averaged bag samples were analyzed for ¹⁴CO₂ by accelerator mass spectrometry. Significant differences between the plants in the share of fossil CO₂ were observed, with annual mean values from 43.4 ± 3.9% to 54.5 ± 3.1%. Variations can be explained by the waste composition of the respective plant. Based on our dataset, an average value of 48 ± 4%Fos C was determined for waste incineration in Switzerland. No clear annual trend in %Fos C was observed for four of the monitored incinerators, while one incinerator showed considerable variations, which are likely due to the separation and temporary storage of bulky goods.

Dual-wavelength quantum cascade laser for trace gas spectroscopy

We demonstrate a sequentially operating dual-wavelength quantum cascade laser with electrically separated laser sections, emitting single-mode at 5.25 and 6.25 μm. Based on a single waveguide ridge, this laser represents a considerable asset to optical sensing and trace gas spectroscopy, as it allows probing multiple gas species with spectrally distant absorption features using conventional optical setups without any beam combining optics. The laser capability was demonstrated in simultaneous NO and NO2 detection, reaching sub-ppb detection limits and selectivity comparable to conventional high-end spectroscopic systems.