Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

N2O emissions from municipal solid waste landfills with selected infertile cover soils and leachate subsurface irrigation

This study presents the field investigations into the effects of cover soils and leachate subsurface irrigation on N₂O emissions from municipal solid waste landfills. Landfill Site A and Site B, covered with carefully chosen infertile soils, were selected to monitor their diurnal and seasonal variations of N₂O emissions. The annual average N₂O flux was 469 ± 796 μg N₂O-N m⁻² h⁻¹ in Site B with leachate subsurface irrigation, three times that of Site A without leachate irrigation. When an additional soil containing lower contents of carbon and nitrogen was introduced to cover part of Site B, its N₂O fluxes decreased by 1-2 orders of magnitude compared with the left area of Site B. This suggested that carefully selected cover soils could substantially reduce N₂O emissions even under leachate subsurface irrigation. Statistical analysis proved that the availabilities of soil moisture and mineralized nitrogen were the key parameters controlling landfill N₂O emissions.     

Do lagoons near concentrated animal feeding operations promote nitrous oxide supersaturation?

Animal wastewater lagoons nearby concentrated animal feeding operations (CAFOs) represent the latest tendency in global animal farming, severely impacting the magnitude of greenhouse gas emissions, including nitrous oxide (N₂O). We hypothesized that lagoon wastewater could be supersaturated with N₂O as part of incomplete microbial nitrification/denitrification processes, thereby regulating the N₂O partitioning in the gaseous phase. The objectives of this study were: (i) to investigate the magnitude of dissolved N₂O concentrations in the lagoon; and (ii) to determine the extent to which supersaturation of N₂O occurs in wastewater lagoons. Dissolved N₂O concentrations in the wastewater samples were high, ranging from 0.4 to 40.5 μg N₂O mL⁻¹. Calculated dissolved N₂O concentrations from the experimentally measured partition coefficients were much greater than those typically expected in aquatic systems (<∼0.6 μg N₂O mL⁻¹). Knowledge of the factors controlling the magnitude of N₂O supersaturation could potentially bridge mass balance differences between in situ measurements and global N₂O models.     

Impact of biochar application to a Mediterranean wheat crop on soil microbial activity and greenhouse gas fluxes

Biochar has been recently proposed as a management strategy to improve crop productivity and global warming mitigation. However, the effect of such approach on soil greenhouse gas fluxes is highly uncertain and few data from field experiments are available. In a field trial, cultivated with wheat, biochar was added to the soil (3 or 6 kg m⁻²) in two growing seasons (2008/2009 and 2009/2010) so to monitor the effect of treatments on microbial parameters 3 months and 14 months after char addition. N₂O, CH₄ and CO₂ fluxes were measured in the field during the first year after char addition. Biochar incorporation into the soil increased soil pH (from 5.2 to 6.7) and the rates of net N mineralization, soil microbial respiration and denitrification activity in the first 3 months, but after 14 months treated and control plots did not differ significantly. No changes in total microbial biomass and net nitrification rate were observed. In char treated plots, soil N₂O fluxes were from 26% to 79% lower than N₂O fluxes in control plots, excluding four sampling dates after the last fertilization with urea, when N₂O emissions were higher in char treated plots. However, due to the high spatial variability, the observed differences were rarely significant. No significant differences of CH₄ fluxes and field soil respiration were observed among different treatments, with just few exceptions. Overall the char treatments showed a minimal impact on microbial parameters and GHG fluxes over the first 14 months after biochar incorporation.     

Dissolution of mimetite Pb5(AsO4)3Cl in low-molecular-weight organic acids and EDTA

Due to its relatively low solubility, mimetite Pb₅(AsO₄)₃Cl may control Pb and As(V) solution levels at a low value in contaminated soils. The time-dependent dissolution of mimetite by low-molecular-weight organic acids (LMWOAs) such as acetic, lactic, citric, and ethylene diamine tetra-acetic acid (EDTA) was determined. At pH 3.5, the presence of citric acid or EDTA significantly increases the solubility of mimetite while acetic or lactic acids show little effect. The effect of all organic anions on the dissolution of mimetite increased with the increase in solution pH. The rate of mimetite dissolution depended on the kind and concentration of organic solvents in the sequence r_EDTA > r_lactate > r_acetate > r_citrate. Soluble Pb and As(V) released in LMWOAs and EDTA were higher than the WHO guideline value for these elements in drinking water (10 μg As(V) L⁻¹, 10 μg Pb L⁻¹). This suggests that soil organic acids in rhizosphere can potentially liberate Pb and As(V) from mimetite in contaminated soils.     

Denitrification of synthetic concentrated nitrate wastes by aerobic granular sludge under anoxic conditions

The aim of the present work was to determine the denitrification potential of aerobic granular sludge for concentrated nitrate wastes. We cultivated mixed microbial granules in a sequencing batch reactor operated at a superficial air velocity of 0.8 cm s⁻¹. The denitrification experiments were performed under anoxic conditions using serum bottles containing synthetic media with 225-2250 mg L⁻¹ NO₃-N. Time required for complete denitrification varied with the initial nitrate concentration and acetate to nitrate-N mass ratio. Complete denitrification of 2250 mg L⁻¹ NO₃-N under anoxic conditions was accomplished in 120 h. Nitrite accumulation was not significant (<5 mg N L⁻¹) at initial NO₃-N concentrations below 677 mg L⁻¹. However, denitrification of higher concentrations of nitrate (?900 mg N L⁻¹) resulted in buildup of nitrite. Nevertheless, nitrite buildups observed in present study were relatively lower compared to that reported in previous studies using flocculent activated sludge. The experimental results suggest that acetate-fed aerobic granular sludge can be quickly adapted to treat high strength nitrate waste and can thus be used as seed biomass for developing high-rate bioreactors for efficient treatment of concentrated nitrate-bearing wastes.     

Adsorption and breakdown of penicillin antibiotic in the presence of titanium oxide nanoparticles in water

The fate and transport of antibiotics in natural water systems is controlled in part by interactions with nanometer (10⁻⁹ m) metal oxide particles. Experiments were performed by mixing solutions of ampicillin (AMP), a common, penicillin-class human and veterinary antibiotic, with 25 nm-TiO₂ (anatase) nanoparticles at different pH conditions. Both sorption and degradation of AMP were observed in the AMP-nanoparticle solutions. For AMP concentrations from ∼3 μM to 2.9 mM the overall AMP removal from solution can be described by linear isotherms with removal coefficients (K_r) of 3028 (±267) L kg⁻¹ at pH 2, 11,533 (±823) L kg⁻¹ at pH 4, 12,712 (±672) L kg⁻¹ at pH 6, and 1941 (±342) L kg⁻¹ at pH 8. Mass spectral analysis of AMP solutions after removal of the solid nanoparticles yielded ions that indicate the presence of peniclloic acid, penilloic acid and related de-ammoniated by-products as possible compounds resulting from the degradation of AMP at the TiO₂ surface.     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

Salt marsh plants as key mediators on the level of cadmium impact on microbial denitrification

The fate of excess nitrogen in estuaries is determined by the microbial-driven nitrogen cycle, being denitrification a key process since it definitely removes fixed nitrogen as N₂. However, estuaries receive and retain metals, which may negatively affect this process efficiency. In this study, we evaluated the role of salt marsh plants in mediating cadmium (Cd) impact on microbial denitrification process. Juncus maritimus and Phragmites australis from an estuary were collected together with the sediment involving their roots, each placed in vessels and maintained in a greenhouse, exposed to natural light, with tides simulation. Similar non-vegetated sediment vessels were prepared. After 3 weeks of accommodation, nine vessels (three per plant species plus three non-vegetated) were doped with 20 mg/L Cd²⁺ saline solution, nine vessels were doped with 2 mg/L Cd²⁺ saline solution and nine vessels were left undoped. After 10 weeks, vessels were dissembled and denitrification potential was measured in sediment slurries. Results revealed that the addition of Cd did not cause an effect on the denitrification process in non-vegetated sediment but had a clear stimulation in colonized ones (39 % for P. australis and 36 % for J. maritimus). In addition, this increase on denitrification rates was followed by a decrease on N₂O emissions and on N₂O/N₂ ratios in both J. maritimus and P. australis sediments, increasing the efficiency of the N₂O step of denitrification pathway. Therefore, our results suggested that the presence of salt marsh plants functioned as key mediators on the degree of Cd impact on microbial denitrification.     

分段进水SBR短程生物脱氮过程中N2O产生及控制

利用SBR,控制曝气量为60 L/h,利用在线pH曲线控制曝气时间,成功实现了短程生物脱氮过程,并考察了不同进水方式下SBR运行性能及N2O产量。结果表明,分段进水能够有效降低短程生物脱氮过程中外加碳源投加量。在原水进水碳氮比较低时,采用递增进水量的进水方式,能够有效降低生物脱氮过程中NO-2积累量,从而降低系统N2O产量。1次进水、2次等量进水和2次递增进水方式下,生物脱氮过程中N2O产量分别为11.1、8.86和5.04 mg/L。硝化过程中NO-2-N的积累是导致系统N2O产生的主要原因。部分氨氧化菌(AOB)在限氧条件下以NH+4-N作为电子供体,NO-2-N作为电子受体进行反硝化,最终产物是N2O。     

Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H₂O and CO₂. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 10⁶ ± 3.9 × 10⁵ M⁻¹ s⁻¹ (pre-exponential factor) and E_a = 77 ± 8 kJ mol⁻¹ (activation energy).     

Polarity effect of pulsed corona discharge for the oxidation of gaseous elemental mercury

The effect of polarity on the oxidation of Hg⁰ was examined in the presence of O₂ via a pulsed corona discharge (PCD). The experimental result showed no difference in the energy yield of Hg⁰ oxidation at both positive and negative PCDs (∼8 μg Hg W h⁻¹ at following conditions: total flow rate = 2 L min⁻¹ (Hg⁰ = 50 μg N m⁻³, O₂ = 10%, and N₂ balance), temperature = 150 °C, and specific energy density = 5-15 W h N m⁻³). This suggests that the positive PCD process used to control gaseous air pollutants may play an essential key role in Hg⁰ oxidation because it consumes enough energy (∼15 W h N m⁻³) but an electrical precipitator could not because it consumes less energy (∼0.3 W h N m⁻³) to oxidize Hg⁰.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Assessment of denitrification process in lower Ishikari river system,Japan

Sediment denitrification rate and its role in removal of dissolved nitrate load in lower Ishikari river system were examined. Denitrification rate were measured using acetylene inhibition technique on the sediment samples collected during August 2009–July 2010. The denitrification rate varied from 0.001 to 1.9 μg N g⁻¹ DM h⁻¹ with an average value of 0.21 μg N g⁻¹ DM h⁻¹ in lower Ishikari river system. Denitrification rate showed positive correlation with dissolved nitrate concentration in the river basin, indicating overlying water column supplied nitrate for the sediment denitrification processes. Nutrient enrichment experiments result showed that denitrification rate increased significantly with addition of nitrate in case of samples collected from Barato Lake however no such increase was observed in the samples collected from Ishikari river main channel and its major tributaries indicating that factors other than substrate concentration such as population of denitrifier and hydrological properties of stream channel including channel depth and flow velocity may affects the denitrification rate in lower Ishikari river system. Denitrification rate showed no significant increase with the addition of labile carbon (glucose), indicating that sediment samples had sufficient organic matter to sustain denitrification activity. The result of nutrient spiraling model indicates that in- stream denitrification process removes on an average 5% d⁻¹ of dissolve nitrate load in Ishikari river. This study was carried out to fill the gap present in the availability of riverine denitrification rate measurement and its role in nitrogen budget from Japanese rivers characterize by small river length and high flow rate.     

Factors affecting the growth rates of ammonium and nitrite oxidizing bacteria

The maximum specific growth rates of both ammonium oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) were investigated under varying aerobic solids retention time (SRT_a) and in the presence/absence of anoxic (alternating) conditions. Two bench SBRs, reactor R1 and R2, were run in parallel for 150 d. Reactor R1 was operated in aerobic conditions while R2 operated in alternating anoxic/aerobic conditions. The feed (synthetic wastewater), temperature, hydraulic retention time and mixing were identical in both reactors. The SRT_a in both reactors was, sequentially, set at four values: 5, 4, 3 and 2 d.Kinetic tests with the biomasses from both reactors were carried out to estimate the maximum specific growth rates (μ_max) at each tested SRT_a and decay rates, in both aerobic and anoxic conditions. The kinetic parameters of nitrifier were estimated through the calibration of a two step nitrification-denitrification activated sludge model.The results point to a slightly higher μ_max,AOB and μ_max,NOB in alternating conditions, while both μ_max,AOB and μ_max,NOB were shown not to vary in the tested range of SRT_a (from 2 to 5 d) at 20 °C. They were relatively high when compared to literature data: 1.05 d⁻¹ < μ_max,AOB < 1.4 d⁻¹ and 0.91 d⁻¹ < μ_max,NOB < 1.31 d⁻¹. The decay coefficients of both AOB and NOB were much higher in aerobic (from 0.22 d⁻¹ to 0.28 d⁻¹) than in anoxic (0.04 d⁻¹ to 0.16 d⁻¹) conditions both in R1 and R2, which explained the higher nitrification rates observed in the alternating reactor.     

The effect of diet manipulation on nitrous oxide and methane emissions from manure application to incubated grassland soils

Changes to agricultural management, particularly of the nitrogen (N) input to farms, have great potential for mitigating emissions of N containing gases, especially the greenhouse gas nitrous oxide (N₂O). Manipulating diets fed to livestock is a potential method for controlling N excretion and emissions of greenhouse gases (GHG's) to the atmosphere. We selected three slurries derived from sheep that had been fed, either ensiled ryegrass (Lolium hybridicum), lucerne (Medicago sativa) or kale (Brassica oleracea) and applied them to a grassland soil from the UK in a laboratory experiment using a special He/O₂ atmosphere incubation facility. The resulting fluxes of N₂O, CH₄ and N₂ were measured, with the largest total N fluxes generated by the ryegrass slurry treatment (14.23 ryegrass, 10.84 lucerne, 13.88 kale and 4.40 kg N ha⁻¹ from the control). Methane was emitted only from the ryegrass slurry treatment. The isotopomer signatures for N₂O in the control and lucerne slurry treatments indicated that denitrification was the main process responsible for N₂O emissions.     

Impact of carbon source on nitrous oxide emission from anoxic/oxic biological nitrogen removal process and identification of its emission sources

Wastewater treatment is an important source of nitrous oxide (N₂O), which is a strong greenhouse gas and dominate ozone-depleting substance. The purpose of this study was to evaluate the effect of carbon source on N₂O emission from anoxic/oxic biological nitrogen removal process. The mechanisms of N₂O emission were also studied. Long-term experiments were operated to evaluate the effect of three different carbon sources (i.e., glucose, sodium acetate, and soluble starch) on N₂O emission characteristics. And batch experiments, in the presence or absence of specific inhibitors, were carried out to identify the sources of N₂O emission. The ammonia-oxidizing bacteria (AOB) and denitrifiers community compositions under different circumstances were also analyzed based on which the underlying mechanisms of N₂O emission were elucidated. The conversion ratios of N₂O in reactors with glucose, sodium acetate, and soluble starch were 5.3 %, 8.8 %, and 2.8 %, respectively. The primary process responsible for N₂O emission was nitrifier denitrification by Nitrosomonas-like AOB, while denitrification by heterotrophic denitrifiers acted as the sink. Reactor with sodium acetate showed the highest N₂O emission, together with the highest nitrogen and phosphate removal ratios. Carbon source has a significant impact on N₂O emission quantity and relatively minor effect on its production mechanism.     

Zerovalent iron encapsulated chitosan nanospheres - a novel adsorbent for the removal of total inorganic arsenic from aqueous systems

Evaluation of Chitosan zerovalent Iron Nanoparticle (CIN) towards arsenic removal is presented. Addition of chitosan enhances the stability of Fe(0) nano particle. Prepared adsorbent was characterized by FT-IR, SEM EDX, BET and XRD. It was found that, with an initial dose rate of 0.5 g L⁻¹, concentrations of As (III) and As (V) were reduced from 2 mg L⁻¹ to <5 μg L⁻¹ in less than 180 min and the adsorbent was found to be applicable in wide range of pH. Langmuir monolayer adsorption capacity was found to be 94 ± 1.5 mg g⁻¹ and 119 ± 2.6 mg g⁻¹ at pH 7 for As (III) and As (V) respectively. Major anions including sulfate, phosphate and silicate did not cause significant interference in the adsorption behavior of both arsenite and arsenate. The adsorbent was successfully recycled five times and applied to the removal of total inorganic arsenic from real life groundwater samples.