Processes and factors controlling N₂O production in an intensively managed low carbon calcareous soil under sub-humid monsoon conditions

An automated system for continuous measurement of N₂O fluxes on an hourly basis was employed to study N₂O emissions in an intensively managed low carbon calcareous soil under sub-humid temperate monsoon conditions. N₂O emissions occurred mainly within two weeks of application of NH₄⁺-based fertilizer and total N₂O emissions in wheat (average 0.35 or 0.21 kg N ha⁻¹ season⁻¹) and maize (average 1.47 or 0.49 kg N ha⁻¹ season⁻¹) under conventional and optimum N fertilization (300 and 50-122 kg N ha⁻¹, respectively) were lower than previously reported from low frequency measurements. Results from closed static chamber showed that N₂O was produced mainly from nitrification of NH₄⁺-based fertilizer, with little denitrification occurring due to limited readily oxidizable carbon and low soil moisture despite consistently high soil nitrate-N concentrations. Significant reductions in N₂O emissions can be achieved by optimizing fertilizer N rates, using nitrification inhibitors, or changing from NH₄⁺- to NO₃^ˉ-based fertilizers.     

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.     

Effect of land-use change on CH4 and N2O emissions from freshwater marsh in Northeast China

The wetlands play an important role in global carbon and nitrogen storage, and they are also natural sources of greenhouse gases such as methane (CH₄) and nitrous oxide (N₂O). Land-use change is an important factor affecting the exchange of greenhouse gases between wetlands and the atmosphere. However, few studies have investigated the effect of land-use change on CH₄ and N₂O emissions from freshwater marsh in China. Therefore, a field study was carried out over a year to investigate the seasonal changes of the emissions of CH₄ and N₂O at three sites (Deyeuxia angustifolia marsh, dryland and rice field) in the Sanjiang Plain of Northeast China. Marsh was the source of CH₄ showing a distinct temporal variation. Maximum fluxes occurred in June and the highest value was 20.69 ± 2.57 mg CH₄ m^?2 h^?1. The seasonal change of N₂O fluxes from marsh was not obvious, consisted of a series of emission pulses. The marsh acted as a N₂O sink during winter, while became a N₂O source in the growing season. The results showed that gas exchange between soil/snow and the atmosphere in the winter season contributed greatly to the annual budgets. The winter season CH₄ flux was about 3.24% of the annual flux and the winter uptake of N₂O accounted for 13.70% of the growing-season emission. Conversion marsh to dryland resulted in a shift from a strong CH₄ source to a weak sink (from 199.12 ± 39.04 to ?1.37 ± 0.68 kg CH₄ ha^?1 yr^?1), while increased N₂O emissions somewhat (from 4.07 ± 1.72 to 4.90 ± 1.52 kg N₂O ha^?1 yr^?1). Conversion marsh to rice field significantly decreased CH₄ emission from 199.12 ± 39.04 to 94.82 ± 9.86 kg CH₄ ha^?1 yr^?1 and N₂O emission from 4.07 ± 1.72 to 2.09 ± 0.79 kg N₂O ha^?1 yr^?1.     

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.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Effects of nitrogen deposition and soil fertility on cover and physiology of Cladonia foliacea (Huds.) Willd., a lichen of biological soil crusts from Mediterranean Spain

We are fertilizing a thicket with 0, 10, 20 and 50 kg nitrogen (N) ha⁻¹ yr⁻¹ in central Spain. Here we report changes in cover, pigments, pigment ratios and FvFm of the N-tolerant, terricolous, lichen Cladonia foliacea after 1-2 y adding N in order to study its potential as biomarker of atmospheric pollution. Cover tended to increase. Pigments increased with fertilization independently of the dose supplied but only significantly with soil nitrate as covariate. β-carotene/chlorophylls increased with 20-50 kg N ha⁻¹ yr⁻¹ (over the background) and neoxanthin/chlorophylls also increased with N. (Neoxanthin+lutein)/carotene decreased with N when nitrate and pH seasonalities were used as covariates. FvFm showed a critical load above 40 kg N ha⁻¹ yr⁻¹. Water-stress, iron and copper also explained variables of lichen physiology. We conclude that this tolerant lichen could be used as biomarker and that responses to N are complex in heterogeneous Mediterranean-type landscapes.     

Nitrous oxide emission from an agricultural field: Comparison between measurements by flux chamber and micrometerological techniques

The soil in a drained fjord area, reclaimed for arable farming, produced N₂O mainly at 75–105 cm depth, just above the ground water level. Surface emissions of N₂O were measured from discrete small areas by closed and open-flow chamber methods, using gas chromatographic analysis and over larger areas by integrative methods: flux gradient (analysis by FTIR), conditional sampling (analysis by TDLAS), and eddy covariance (analysis by TDLAS). The mean emission of N₂O as determined by chamber procedures during a 9-day campaign was 162–202 μg N₂ONm⁻²h⁻¹ from a wheat stubble and 328–467 μg N₂ONm⁻² h⁻¹ from a carrot field. The integrative approaches gave N₂O emissions of 149–495 μg N₂ONm⁻² h⁻¹, i.e. a range similar to those determined with the chamber methods. Wind direction affected the comparison of chamber and integrative methods because of patchiness of the N₂O emission over the area. When a uniform area with a single type of vegetation had a dominant effect on the N₂O gradient at the sampling mast, the temporal variation in N₂O emission determined by the flux gradient/FTIR method and chamber methods was very similar, with differences of only 18% or less in mean N₂O emission, well below the variation encountered with the chamber methods themselves. A detailed comparison of FTIR gradient and chamber data taking into account the precise emission footprint showed good agreement. It is concluded that there was no bias between the different approaches used to measure the N₂O emission and that the precision of the measurements was determined by the spatial variability of the N₂O emission at the site and the variability inherent in the individual techniques. These results confirm that measurements of N₂O emissions from different ecosystems obtained by the different methods can be meaningfully compared.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Effect of topography on nitrous oxide emissions from winter wheat fields in Central France

We assessed nitrous oxide (N₂O) emissions at shoulder and foot-slope positions along three sloping sites (1.6–2.1%) to identify the factors controlling the spatial variations in emissions. The three sites received same amounts of total nitrogen (N) input at 170 kg N ha⁻¹. Results showed that landscape positions had a significant, but not consistent effect on N₂O fluxes with larger emission in the foot-slope at only one of the three sites. The effect of soil inorganic N (NH₄⁺ + NO₃⁻) contents on N₂O fluxes (r² = 0.55, p < 0.001) was influenced by water-filled pore space (WFPS). Soil N₂O fluxes were related to inorganic N at WFPS > 60% (r² = 0.81, p < 0.001), and NH₄⁺ contents at WFPS < 60% (r² = 0.40, p < 0.01), respectively. Differences in WFPS between shoulder and foot-slope correlated linearly with differences in N₂O fluxes (r² = 0.45, p < 0.001). We conclude that spatial variations in N₂O emission were regulated by the influence of hydrological processes on soil aeration intensity.     

Polybrominated diphenyl ethers occurrence in major inflowing rivers of Lake Chaohu (China): Characteristics,potential sources and inputs to lake

Eight commonly occurring polybrominated diphenyl ethers (PBDEs), including BDE 28, 47, 99, 100, 153, 154, 183, 207, and 209, were investigated in water samples from seven major inflowing rivers of Lake Chaohu to determine the distribution characteristics, potential sources and inputs to the lake. The sum of 8 BDE congeners (Σ₈PBDEs) had a concentration varied from 0.31 to 84 ng L⁻¹, with those of BDE 209, BDE 47, BDE 99, and BDE 153 being 0.31–83, <0.012–0.36, <0.012–1.3, and <0.012–0.77 ng L⁻¹, respectively. These levels were in the high range of the global PBDEs concentrations in the water environments. The highest concentrations of Σ₈PBDEs were detected in the western rivers, of which the main pollution sources were strongly related to human activities in urban centers, such as automobile-derived wastes. A sewage treatment plant was likely an important source of the lower brominated BDEs input to one western river. The correlation analyses (all p < 0.05) between PBDEs and DOC, TN, TP, and EC, suggested that the distributions and sources of PBDEs in rivers might also be related with the soil erosion by heave floods. Σ₈PBDEs input to Lake Chaohu from the rivers outlets was estimated at 344 kg yr⁻¹ during the flood season. BDE 209 was the dominant contributor with an input of 340 kg yr⁻¹, followed by BDE 99 (1.3 kg yr⁻¹), BDE 47 (0.83 kg yr⁻¹) and BDE 153 (0.60 kg yr⁻¹).     

Effects of calcium peroxide on arsenic uptake by celery (Apium graveolens L.) grown in arsenic contaminated soil

The ability of calcium peroxide (CaO₂) to immobilize As of contaminated soil was studied using pot and field experiments. In pot experiment, CaO₂ applied at 2.5 and 5 g kg⁻¹ significantly increased celery shoot weight and decreased shoot As accumulation, which was ascribed to the formation of stable crystalline Fe and Al oxides bound As and the reduction of labile As fractions in the soil. The labile As fractions were pH dependent and it followed a “V” shaped profile with the change of pH. In field experiment, the dose of CaO₂ application at 750 kg ha⁻¹ was optimal and at which the celery was found to produce the highest biomass (63.4 Mg ha⁻¹) and lowest As concentration (0.43 mg kg⁻¹). CaO₂ probably has a promising potential as soil amendment to treat As contaminated soils.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Estimates of synthetic fertilizer N-induced direct nitrous oxide emission from Chinese croplands during 1980-2000

There is increasing concern that agricultural intensification in China has greatly increased N₂O emissions due to rapidly increased fertilizer use. By linking a spatial database of precipitation, synthetic fertilizer N input, cropping rotation and area via GIS, a precipitation-rectified emission factor of N₂O for upland croplands and water regime-specific emission factors for irrigated rice paddies were adopted to estimate annual synthetic fertilizer N-induced direct N₂O emissions (FIE-N₂O) from Chinese croplands during 1980-2000. Annual FIE-N₂O was estimated to be 115.7 Gg N₂O-N year⁻¹ in the 1980s and 210.5 Gg N₂O-N year⁻¹ in the 1990s, with an annual increasing rate of 9.14 Gg N₂O-N year⁻¹ over the period 1980-2000. Upland croplands contributed most to the national total of FIE-N₂O, accounting for 79% in 1980 and 92% in 2000. Approximately 65% of the FIE-N₂O emitted in eastern and southern central China.     

Perfluorinated compounds in Haihe River and Dagu Drainage Canal in Tianjin, China

In this study, nine perfluorinated compounds (PFCs) were investigated in water and sediment of Haihe River (HR) and Dagu Drainage Canal (DDC), Tianjin, China. The total PFCs in water samples from DDC (40-174 ng L⁻¹) was much greater than those from HR (12-74 ng L⁻¹). PFC contamination was severe at lower reaches of HR due to industry activities, while high PFCs were found in the middle of DDC due to the effluents from wastewater treatment plants. Perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the predominant PFCs in aqueous phase. The total PFCs in sediments from DDC (1.6-7.7 ng g⁻¹ dry weight) were lower as compared to HR (7.1-16 ng g⁻¹), maybe due to the dredging of sediment in DDC conducted recently. PFOS was the major PFC in HR sediments followed by PFOA; while PFHxA was the major PFC in DDC sediments. Organic carbon calibrated sediment-water distribution coefficients (K_OC) were calculated for HR. The Log K_OC ranged from 3.3 to 4.4 for C7-C11 perfluorinated carboxylic acids, increasing by 0.1-0.6 log units with each additional CF₂ moiety. The log K_OC for 8:2 fluorotelomer unsaturated acid was reported for the first time with a mean value of 4.0. The log Koc of PFOS was higher than perfluoronanoic acid by 0.8 log units.     

Long-term effects of clear-cutting and selective cutting on soil methane fluxes in a temperate spruce forest in southern Germany

Based on multi-year measurements of CH₄ exchange in sub-daily resolution we show that clear-cutting of a forest in Southern Germany increased soil temperature and moisture and decreased CH₄ uptake. CH₄ uptake in the first year after clear-cutting (−4.5 ± 0.2 μg C m⁻² h⁻¹) was three times lower than during the pre-harvest period (−14.2 ± 1.3 μg C m⁻² h⁻¹). In contrast, selective cutting did not significantly reduce CH₄ uptake. Annual mean uptake rates were −1.18 kg C ha⁻¹ yr⁻¹ (spruce control), −1.16 kg C ha⁻¹ yr⁻¹ (selective cut site) and −0.44 kg C ha⁻¹ yr⁻¹ (clear-cut site), respectively. Substantial seasonal and inter-annual variations in CH₄ fluxes were observed as a result of significant variability of weather conditions, demonstrating the need for long-term measurements. Our findings imply that a stepwise selective cutting instead of clear-cutting may contribute to mitigating global warming by maintaining a high CH₄ uptake capacity of the soil.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Agricultural ammonia emissions inventory and spatial distribution in the North China Plain

An agricultural ammonia (NH₃) emission inventory in the North China Plain (NCP) on a prefecture level for the year 2004, and a 5 × 5 km² resolution spatial distribution map, has been calculated for the first time. The census database from China's statistics datasets, and emission factors re-calculated by the RAINS model supported total emissions of 3071 kt NH₃-N yr⁻¹ for the NCP, accounting for 27% of the total emissions in China. NH₃ emission from mineral fertilizer application contributed 1620 kt NH₃-N yr⁻¹, 54% of the total emission, while livestock emissions accounted for the remaining 46% of the total emissions, including 7%, 27%, 7% and 5% from cattle, pigs, sheep and goats, and poultry, respectively. A high-resolution spatial NH₃ emissions map was developed based on 1 × 1 km land use database and aggregated to a 5 × 5 km grid resolution. The highest emission density value was 198 kg N ha⁻¹ yr⁻¹.