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.     

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.     

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.     

Developing spatially stratified N(2)O emission factors for Europe

We investigate the possibility to replace the – so-called – Tier 1 IPCC approach to estimate soil N₂O emissions with stratified emissions factors that take into account both N-input and the spatial variability of the environmental conditions within the countries of the European Union, using the DNDC-Europe model. Spatial variability in model simulations is high and corresponds to the variability reported in literature for field data. Our results indicate that (a) much of the observed variability in N₂O fluxes reflects the response of soils to external conditions, (b) it is likely that national inventories tend to overestimate the uncertainties in their estimated direct N₂O emissions from arable soils; (c) on average over Europe, the fertilizer-induced emissions (FIE) coincide with the IPCC factors, but they display large spatial variations. Therefore, at scales of individual countries or smaller, a stratified approach considering fertilizer type, soil characteristics and climatic parameters is preferable.     

Effect of biochar on nitrous oxide emission and its potential mechanisms

Extensive use of biochar to mitigate nitrous oxide (N₂O) emission is limited by the lack of understanding on the exact mechanisms altering N₂O emission from biochar-amended soil. Biochars produced from rice straw and dairy manure at 350 and 500 °C by oxygen-limited pyrolysis were used to investigate their influence on N₂O emission. A quadratic effect of biochar levels was observed on the N₂O emissions. The potential mechanisms were explored by terminal restriction fragment length polymorphism (T-RFLP) and real-time polymerase chain reaction (qPCR). A lower relative abundance of bacteria, which included ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), was observed at 4% biochar application rate. Reduced copy numbers of the ammonia monooxygenase gene amoA and the nitrite reductase gene nirS coincided with decreased N₂O emissions. Therefore, biochar may potentially alter N₂O emission by affecting ammonia-oxidizing and denitrification bacteria, which is determined by the application rate of biochar in soil.

Implications:Biochar research has received increased interest in recent years because of the potential beneficial effects of biochar on soil properties. Recent research shows that biochar can alter the rates of nitrogen cycling in soil systems by influencing nitrification and denitrification, which are key sources of the greenhouse gas nitrous oxide (N₂O). However, there are still some controversial data. The purpose of this research was to (1) examine how applications of different dose of biochar to soil affect emission of N₂O and (2) improve the understanding of the underlying mechanisms.     

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.     

Fate of citalopram during water treatment with O3, ClO2, UV and Fenton oxidation

In the present study we investigate the fate of citalopram (CIT) at neutral pH using advanced water treatment technologies that include O₃, ClO₂ oxidation, UV irradiation and Fenton oxidation. The ozonation resulted in 80% reduction after 30 min treatment. Oxidation with ClO₂ removed >90% CIT at a dosage of 0.1 mg L⁻¹. During UV irradiation 85% reduction was achieved after 5 min, while Fenton with addition of 14 mg L⁻¹ (Fe²⁺) resulted in 90% reduction of CIT. During these treatment experiments transformation products (TPs) were formed from CIT, where five compounds were identified by using high resolution and tandem mass spectrometry. Among these desmethyl-citalopram and citalopram N-oxide have been previously identified as human metabolites, while three are novel and published here for the first time. The three TPs are a hydroxylated dimethylamino-side chain derivative, a butyrolactone derivative and a defluorinated derivative of CIT.     

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.     

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.     

Treatment of polychlorinated biphenyls in two surface soils using catalyzed H₂O₂ propagations

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H₂O₂ propagations (CHP—modified Fenton’s reagent). The two soils were first evaluated for the potential for in situ treatment based on two criteria: (1) temperature (<40 °C after CHP reagent addition), and (2) hydrogen peroxide longevity (>24 h). In situ CHP remediation was more applicable to the Fletcher soil, while the Merrimack soil was better suited to ex situ treatment based on temperature increases and hydrogen peroxide lifetimes. Using the highest hydrogen peroxide concentrations appropriate for in situ treatment in each soil, PCB destruction was 94% in the Fletcher soil but only 48% in the Merrimack soil. However, 98% PCB destruction was achieved in the Merrimack soil using conditions more applicable to ex situ treatment (higher hydrogen peroxide concentrations with temperatures >40 °C). Analysis of degradation products by gas chromatography/mass spectroscopy showed no detectable chlorinated degradation products, suggesting that the products of PCB oxidation were rapidly dechlorinated and degraded. The results of this research document that the two PCB-contaminated soils studied can be effectively treated using aggressive CHP conditions, and that such a detailed bench study provides important information before implementing field treatment.     

Effects of land use conversion and fertilization on CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O fluxes from typical hilly red soil

Land use conversion and fertilization have been widely reported to be important managements affecting the exchanges of greenhouse gases between soil and atmosphere. For comprehensive assessment of methane (CH₄) and nitrous oxide (N₂O) fluxes from hilly red soil induced by land use conversion and fertilization, a 14-month continuous field measurement was conducted on the newly converted citrus orchard plots with fertilization (OF) and without fertilization (ONF) and the conventional paddy plots with fertilization (PF) and without fertilization (PNF). Our results showed that land use conversion from paddy to orchard reduced the CH₄ fluxes at the expense of increasing the N₂O fluxes. Furthermore, fertilization significantly decreased the CH₄ fluxes from paddy soils in the second stage after conversion, but it failed to affect the CH₄ fluxes from orchard soils, whereas fertilizer applied to orchard and paddy increased soil N₂O emissions by 68 and 113.9 %, respectively. Thus, cumulative CH₄ emissions from the OF were 100 % lower, and N₂O emissions were 421 % higher than those from the PF. Although cumulative N₂O emissions were stimulated in the newly converted orchard, the strong reduction of CH₄ led to lower global warming potentials (GWPs) as compared to the paddy. Besides, fertilization in orchard increased GWPs but decreased GWPs of paddy soils. In addition, measurement of soil moisture, temperature, dissolved carbon contents (DOCs), and ammonia (NH₄ ⁺-N) and nitrate (NO₃ ^?-N) contents indicated a significant variation in soil properties and contributed to variations in soil CH₄ and N₂O fluxes. Results of this study suggest that land use conversion from paddy to orchard would benefit for reconciling greenhouse gas mitigation and citrus orchard cultivation would be a better agricultural system in the hilly red soils in terms of greenhouse gas emission. Moreover, selected fertilizer rate applied to paddy would lead to lower GWPs of CH₄ and N₂O. Nevertheless, more field measurements from newly converted orchard are highly needed to gain an insight into national and global accounting of CH₄ and N₂O emissions.     

Satellite derived trends in NO2 over the major global hotspot regions during the past decade and their inter-comparison

We assessed satellite derived tropospheric NO₂ distribution on a global scale and identified the major NO₂ hotspot regions. Combined GOME and SCIAMACHY measurements for the period 1996-2006 have been used to compute the trends over these regions. Our analysis shows that tropospheric NO₂ column amounts have increased over the newly and rapidly developing regions like China (11 ± 2.6%/year), south Asia (1.76 ± 1.1%/year), Middle East (2.3 ± 1%/year) and South Africa (2.4 ± 2.2%/year). Tropospheric NO₂ column amounts show some decrease over the eastern US (−2 ± 1.5%/year) and Europe (0.9 ± 2.1%/year). We found that although tropospheric NO₂ column amounts decreased over the major developed regions in the past decade, the present tropospheric NO₂ column amounts over these regions are still significantly higher than those observed over newly and rapidly developing regions (except China). Tropospheric NO₂ column amounts show some decrease over South America and Central Africa, which are major biomass burning regions in the Southern Hemisphere.     

The growth response of Alternanthera philoxeroides in a simulated post-combustion emission with ultrahigh [CO2] and acidic pollutants

Although post-combustion emissions from power plants are a major source of air pollution, they contain excess CO₂ that could be used to fertilize commercial greenhouses and stimulate plant growth. We addressed the combined effects of ultrahigh [CO₂] and acidic pollutants in flue gas on the growth of Alternanthera philoxeroides. When acidic pollutants were excluded, the biomass yield of A. philoxeroides saturated near 2000 μmol mol⁻¹ [CO₂] with doubled biomass accumulation relative to the ambient control. The growth enhancement was maintained at 5000 μmol mol⁻¹ [CO₂], but declined when [CO₂] rose above 1%, in association with a strong photosynthetic inhibition. Although acidic components (SO₂ and NO₂) significantly offset the CO₂ enhancement, the aboveground yield increased considerably when the concentration of pollutants was moderate (200 times dilution). Our results indicate that using excess CO₂ from the power plant emissions to optimize growth in commercial green house could be viable.     

Mitigating Global Warming Potentials of Methane and Nitrous Oxide Gases from Rice Paddies under different irrigation regimes

A field experiment was conducted in Bangladesh Agricultural University Farm to investigate the mitigating effects of soil amendments such as calcium carbide, calcium silicate, phosphogypsum, and biochar with urea fertilizer on global warming potentials (GWPs) of methane (CH₄) and nitrous oxide (N₂O) gases during rice cultivation under continuous and intermittent irrigations. Among the amendments phosphogypsum and silicate fertilizer, being potential source of electron acceptors, decreased maximum level of seasonal CH₄ flux by 25–27 % and 32–38 % in continuous and intermittent irrigations, respectively. Biochar and calcium carbide amendments, acting as nitrification inhibitors, decreased N₂O emissions by 36–40 % and 26–30 % under continuous and intermittent irrigations, respectively. The total GWP of CH₄ and N₂O gases were decreased by 7–27 % and 6–34 % with calcium carbide, phosphogypsum, and silicate fertilizer amendments under continuous and intermittent irrigations, respectively. However, biochar amendments increased overall GWP of CH₄ and N₂O gases.     

Poor efficacy of herbicides in biochar-amended soils as affected by their chemistry and mode of action

We evaluated wheat straw biochar produced at 450 °C for its ability to influence bioavailability and persistence of two commonly used herbicides (atrazine and trifluralin) with different modes of action (photosynthesis versus root tip mitosis inhibitors) in two contrasting soils. The biochar was added to soils at 0%, 0.5% and 1.0% (w/w) and the herbicides were applied to those soil-biochar mixes at nil, half, full, two times, and four times, the recommended dosage (H₄). Annual ryegrass (Lolium rigidum) was grown in biochar amended soils for 1 month. Biochar had a positive impact on ryegrass survival rate and above-ground biomass at most of the application rates, and particularly at H₄. Within any given biochar treatment, increasing herbicide application decreased the survival rate and fresh weight of above-ground biomass. Biomass production across the biochar treatment gradient significantly differed (p < 0.01) and was more pronounced in the case of atrazine than trifluralin. For example, the dose-response analysis showed that in the presence of 1% biochar in soil, the value of GR₅₀ (i.e. the dose required to reduce weed biomass by 50%) for atrazine increased by 3.5 times, whereas it increased only by a factor of 1.6 in the case of trifluralin. The combination of the chemical properties and the mode of action governed the extent of biochar-induced reduction in bioavailability of herbicides. The greater biomass of ryegrass in the soil containing the highest biochar (despite having the highest herbicide residues) demonstrates decreased bioavailability of the chemicals caused by the wheat straw biochar. This work clearly demonstrates decreased efficacy of herbicides in biochar amended soils. The role played by herbicide chemistry and mode of action will have major implications in choosing the appropriate application rates for biochar amended soils.     

Potential of BAC combined with UVC/H2O2 for reducing organic matter from highly saline reverse osmosis concentrate produced from municipal wastewater reclamation

The organic matter present in the concentrate streams generated from reverse osmosis (RO) based municipal wastewater reclamation processes poses environmental and health risks on its disposal to the receiving environment (e.g., estuaries, bays). The potential of a biological activated carbon (BAC) process combined with pre-oxidation using a UVC/H₂O₂ advanced oxidation process for treating a high salinity (TDS ∼ 10 000 mg L⁻¹) municipal wastewater RO concentrate (ROC) was evaluated at lab scale during 90 d of operation. The combined treatment reduced the UVA₂₅₄ and colour of the ROC to below those for the influent of the RO process (i.e., biologically treated secondary effluent), and the reductions in DOC and COD were approximately 60% and 50%, respectively. UVC/H₂O₂ was demonstrated to be an effective means of converting the recalcitrant organic compounds in the ROC into biodegradable substances which were readily removed by the BAC process, leading to a synergistic effect of the combined treatment in degrading the organic matter. The tests using various BAC feed concentrations suggested that the biological treatment was robust and consistent for treating the high salinity ROC. Using Microtox analysis no toxicity was detected for the ROC after the combined treatment, and the trihalomethane formation potential was reduced from 3.5 to 2.8 mg L⁻¹.     

Differences in the Spatial Variability Among CO2, CH4, and N2O Gas Fluxes from an Urban Forest Soil in Japan

The spatial variability of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) fluxes from forest soil with high nitrogen (N) deposition was investigated at a rolling hill region in Japan. Gas fluxes were measured on July 25th and December 5th, 2008 at 100 points within a 100 × 100 m grid. Slope direction and position influenced soil characteristics and site-specific emissions were found. The CO₂ flux showed no topological difference in July, but was significantly lower in December for north-slope with coniferous trees. Spatial dependency of CH₄ fluxes was stronger than that of CO₂ or N₂O and showed a significantly higher uptake in hill top, and emissions in the valley indicating strong influence of water status. N₂O fluxes showed no spatial dependency and exhibited high hot spots at different topology in July and December. The high N deposition led to high N₂O fluxes and emphasized the spatial variability.     

Gene expression responses of paper birch (Betula papyrifera) to elevated CO2 and O3 during leaf maturation and senescence

Gene expression responses of paper birch (Betula papyrifera) leaves to elevated concentrations of CO₂ and O₃ were studied with microarray analyses from three time points during the summer of 2004 at Aspen FACE. Microarray data were analyzed with clustering techniques, self-organizing maps, K-means clustering and Sammon's mappings, to detect similar gene expression patterns within sampling times and treatments. Most of the alterations in gene expression were caused by O₃, alone or in combination with CO₂. O₃ induced defensive reactions to oxidative stress and earlier leaf senescence, seen as decreased expression of photosynthesis- and carbon fixation-related genes, and increased expression of senescence-associated genes. The effects of elevated CO₂ reflected surplus of carbon that was directed to synthesis of secondary compounds. The combined CO₂ + O₃ treatment resulted in differential gene expression than with individual gas treatments or in changes similar to O₃ treatment, indicating that CO₂ cannot totally alleviate the harmful effects of O₃.