PCDD/F inhibition by prior addition of urea to the solid fuel in laboratory experiments and results statistical evaluation

The objectives of this work were to study the effect of urea addition to the fuel before the combustion on the suppression of PCDD/F emissions, to examine the influence of urea to PCDD/F isomer patterns by employing statistical analysis techniques and to determine the most effective method of urea addition. Urea in the form of powder and as an aqueous solution was mixed with RDF and the fuel mixtures were incinerated in a lab-scale reactor at 1000 degrees C. PCDD/F emitted during combustion experiments were collected in a quartz wool filter downstream the reactor unit. Analysis and quantification of PCDD/F showed that urea significantly affected PCDD/F emissions. Combustion of RDF containing 10% w/w urea resulted in PCDD/F emissions lower than 8 I-TEQ ng/g RDF, while the corresponding average value from single RDF combustion was 17 I-TEQ ng/g RDF. The PCDD/F prevention capacity of urea was independent from the method of urea addition to the fuel, as similar results were obtained after the addition of urea in the solid and in the aqueous phases. Results assessment by statistical methods showed that isomer patterns remained almost stable and were not affected by the method of urea addition.     

Urea as a PCDD/F inhibitor in municipal waste incineration

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at approximately 730 degrees C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Urea as a PCDD/F Inhibitor in Municipal Waste Incineration

ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at ~730 °C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Short-term alleviation of aluminum phytotoxicity by urea application in acid soils from south China

A laboratory experiment was conducted to study effects of urea fertilizer on the chemical composition of soil solutions over time, and to determine Al toxicity as a function of rates of urea application. The experiment revealed that addition of urea fertilizer to soils caused drastic changes in soil pH during the hydrolysis and nitrification stages of urea transformation in the experiment. These pH changes, depending on the N rate of urea application and time courses, had variable effects on soil exchangeable Al, extracted with artificial solutions containing 1 mol l(-1) KCl. The Al mobilization rate could be resolved into two phases: A declining phase for Al was attributed to the urea-induced hydrolysis while a second rising phase was dependent with the nitrification of added N fertilizer. The decreases in exchangeable Al reached the greatest in 4-7 days after fertilization, consistent with soil pH increase. Decreased Al availability had been observed as a consequence of increasing urea addition and soil pH when using Root elongation of maize seedlings as the estimators. Results from the present study demonstrate that urea fertilizer to the surface of soils may lead to a temporary immobilization of Al and, therefore, alleviated Al toxicity to plant seedlings.     

PCDD/F reduction in incinerator flue gas by adding urea to RDF feedstock

The effect of urea on PCDD/F formation in a pilot incinerator was studied by incinerating urea with refuse-derived fuel (RDF) at three concentrations (0.1%, 0.5% and 1.0%, of the fuel feed). A distinct reduction in both PCDD/F and chlorophenol concentrations could be noticed when urea was introduced into the system. Partial-least-square (PLS) analysis of the data showed the importance of certain chlorophenol isomers as PCDD/F precursors, pointing to the possibility that the impact point of the urea inhibitor could be before the precursor molecules, i.e. chlorophenols, have been formed.     

尿素/高锰酸钾湿法烟气脱氮的试验研究

采用高锰酸钾和尿素配制成不同浓度的吸收溶液,在填有金属鲍尔环的管式吸收反应器中,对模拟烟气进行湿法烟气脱氮的研究。试验结果表明,用尿素和高锰酸钾配制成的吸收液进行湿法烟气脱氮,可以高效地脱除模拟烟气中的氮氧化物,高锰酸钾含量的增加可以显著提高脱氮效率,是决定脱氮效率高低的重要因素,在尿素和高锰酸钾含量分别为5%和0.60g/L时可以达到91.5%的平均脱氮效率;尿素含量、吸收液有效柱高和外加的SO2气体均对脱氮效率产生不同程度的影响。     

Influence of exogenous urea on photosynthetic pigments, 14CO2 uptake, and urease activity in Elodea densa—environmental implications

This paper analyzes the effect of exogenous urea in increased concentration gradient (0, 100, 500 and 1,000 mg L^?1) on photosynthetic pigments (measured spectrophotometrically), uptake of ¹⁴CO₂ (using radioisotope), and urease activity (by measuring ammonia with Nessler’s reagent) in leaves of Elodea densa Planch. We have observed that low concentration of urea (100 mg L^?1) stimulates the accumulation of photosynthetic pigments and intensifies photosynthesis in E. densa, whereas high concentration (1,000 mg L^?1) suppresses these processes. Urease activity increased by approximately 2.7 and 8 fold when exogenous urea concentrations were 100 and 500 mg L^?1, respectively. However, exogenous urea in high concentration (1,000 mg L^?1) decreased urease activity by 1.5 fold compared to the control. The necessity of mitigating urea and other nitrogen-containing compounds (NH₃ from urea) in water bodies has been discussed with emphasis on the potential for phytoremediation of urea using common water weed viz. E. densa.     

Optimum conditions for microbial carbonate precipitation

The type of bacteria, bacterial cell concentration, initial urea concentration, reaction temperature, the initial Ca(2+) concentration, ionic strength, and the pH of the media are some factors that control the activity of the urease enzyme, and may have a significant impact on microbial carbonate precipitation (MCP). Factorial experiments were designed based on these factors to determine the optimum conditions that take into consideration economic advantage while at the same time giving quality results. Sporosarcina pasteurii strain ATCC 11859 was used at constant temperature (25°C) and ionic strength with varying amounts of urea, Ca(2+), and bacterial cell concentration. The results indicate that the rate of ureolysis (k(urea)) increases with bacterial cell concentration, and the bacterial cell concentration had a greater influence on k(urea) than initial urea concentration. At 25 mM Ca(2+) concentration, increasing bacterial cell concentration from 10(6) to 10(8)cells mL?1 increased the CaCO(3) precipitated and CO(2) sequestrated by over 30%. However, when the Ca(2+) concentration was increased 10-fold to 250 mM Ca(2+), the amount of CaCO(3) precipitated and CO(2) sequestrated increased by over 100% irrespective of initial urea concentration. Consequently, the optimum conditions for MCP under our experimental conditions were 666 mM urea and 250 mM Ca(2+) at 2.3×10? cells mL?1 bacterial cell concentration. However, a greater CaCO(3) deposition is achievable with higher concentrations of urea, Ca(2+), and bacterial cells so long as the respective quantities are within their economic advantage. X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray analyzes confirmed that the precipitate formed was CaCO(3) and composed of predominantly calcite crystals with little vaterite crystals.     

Effectiveness of urea in enhancing the extractability of 2,4,6-trinitrotoluene from chemically variant soils

One of the major challenges in developing an effective phytoremediation technology for 2,4,6-trinitrotoluene (TNT) contaminated soils is limited plant uptake resulting from low solubility of TNT. The effectiveness of urea as a solubilizing agent in increasing plant uptake of TNT in hydroponic systems has been documented. Our preliminary greenhouse experiments using urea were also very promising, but further characterization of the performance of urea in highly-complex soil-solution was necessary. The present study investigated the natural retention capacity of four chemically variant soils and optimized the factors influencing the effectiveness of urea in enhancing TNT solubility in the soil solutions. Results show that the extent of TNT sorption and desorption varies with the soil properties, and is mainly dependent on soil organic matter (SOM) content. Hysteretic desorption of TNT in all tested soils suggests irreversible sorption of TNT and indicates the need of using an extractant to increase the release of TNT in soil solutions. Urea significantly (p < 0.0001) enhanced TNT extraction from all soils, by increasing its solubility at the solid/liquid interface. Soil organic matter content and urea application rates showed significant effects, whereas pH did not exert any significant effect on urea catalysis of TNT extraction from soil. The optimum urea application rates (125 or 350 mg kg⁻¹) for maximizing TNT extraction were within the limits set by the agronomic fertilizer-N rates used for major agricultural crops. The data obtained from this batch study will facilitate the optimization of a chemically-catalyzed phytoremediation model for cleaning up TNT-contaminated soils.     

尿素/三乙醇胺吸收烟气NO_x的实验研究

以尿素作为吸收液,与NOx反应生成N2和CO2,脱除烟气中的氮氧化物。以一套双级串连的填料塔为主体反应器,分别对气速、液气比、反应物浓度、添加剂浓度和反应温度等参数对尿素溶液吸收NOx反应的影响进行了实验研究,获得了优化实验工况,研究结果显示,在气速为0.1 m/s、液气比为16 L/m3、三乙醇胺为0.01%（质量比）、尿素浓度为13%（质量比）工况下,反应温度为30~70℃,脱硝总效率可达50%以上,且随着NOx体积分数增加而提高。     

Control of ammonia and urea emissions from urea manufacturing facilities of Petrochemical Industries Company (PIC), Kuwait

Petrochemical Industries Company (PIC) in Kuwait has mitigated the pollution problem of ammonia and urea dust by replacing the melting and prilling units of finished-product urea prills with an environmentally friendly granulation process. PIC has financed a research project conducted by the Coastal and Air Pollution Program’s research staff at the Kuwait Institute for Scientific Research to assess the impact of pollution control strategies implemented to maintain a healthy productive environment in and around the manufacturing premises. The project was completed in three phases: the first phase included the pollution monitoring of the melting and prilling units in full operation, the second phase covered the complete shutdown period where production was halted completely and granulation units were installed, and the last phase encompassed the current modified status with granulation units in full operation. There was substantial decrease in ammonia emissions, about 72%, and a 52.7% decrease in urea emissions with the present upgrading of old melting and prilling units to a state-of-the-art technology “granulation process” for a final finished product. The other pollutants, sulfur dioxide (SO₂), nitrogen oxides (NO_x), and volatile organic compounds (VOCs), have not shown any significant change, as the present modification has not affected the sources of these pollutants.

Implications: Petrochemical Industries Company (PIC) in Kuwait has ammonia urea industries, and there were complaints about ammonia and urea dust pollution. PIC has resolved this problem by replacing “melting and prilling unit” of final product urea prills by more environmentally friendly “granulation unit.” Environmental Pollution and Climate Program has been assigned the duty of assessing the outcome of this change and how that influenced ammonia and urea dust emissions from the urea manufacturing plant.     

Mitigating nitrous oxide and methane emissions from soil in rice-wheat system of the Indo-Gangetic plain with nitrification and urease inhibitors

Mitigation of methane (CH4) and nitrous oxide (N2O) emissions from soil is important to reduce the global warming. Efficacy of five nitrification inhibitors, i.e. neem (Azadirachta melia) cake, thiosulphate, coated calcium carbide, neem oil coated urea and dicyandiamide (DCD) and one urease inhibitor, hydroquinone, in mitigating N2O and CH4 emissions from fertilized soil was tested in rice-wheat system in the Indo-Gangetic plains. The closed chamber technique was used for the collection of gas samples, which were analyzed using gas chromatography. Reduction in N2O emission on the application of nitrification/urease inhibitors along with urea ranged from 5% with hydroquinone to 31% with thiosulphate in rice and 7% with hydroquinone to 29% with DCD in wheat crop. The inhibitors also influenced the emission of CH4. While application of neem coated urea, coated calcium carbide, neem oil and DCD reduced the emission of CH4; hydroquinone and thiosulphate increased the emission when compared to urea alone. However, the global warming potential was lower with the inhibitors (except hydroquinone) as compared to urea alone, suggesting that these substances could be used for mitigating greenhouse gas emission from the rice-wheat systems.     

Chemically catalyzed uptake of 2,4,6-trinitrotoluene by Vetiveria zizanioides

The efficiency of vetiver grass (Vetiveria zizanioides) in removing 2,4,6-trinitrotoluene (TNT) from aqueous media was explored in the presence of a common agrochemical, urea, used as a chaotropic agent. Chaotropic agents disrupt water structure, increasing solubilization of hydrophobic compounds (TNT), thus, enhancing plant TNT uptake. The primary objectives of this study were to: (i) characterize TNT absorption by vetiver in hydroponic media, and (ii) determine the effect of urea on chemically catalyzing TNT uptake by vetiver grass in hydroponic media. Results showed that vetiver exhibited a high TNT uptake capacity (1.026 mgg(-1)), but kinetics were slow. Uptake was considerably enhanced in the presence of urea, which significantly (p<0.001) increased the 2nd-order reaction rate constant over that of the untreated (no urea) control. Three major TNT metabolites were detected in the roots, but not in the shoot, namely 1,3,5-trinitrobenzene, 4-amino 2,6-dinitrotoluene, and 2-amino 4,6-dinitrotoluene, indicating TNT degradation by vetiver grass.     

Catalytic hydrolysis of urea from wastewater using different aluminas by a fixed bed reactor

In order to find an effective method for treating urea wastewater, the experiments on the hydrolysis of urea in wastewater were conducted in a fixed bed reactor with different aluminas (α-Al₂O₃, γ-Al₂O₃, and η-Al₂O₃) as catalysts respectively in contrast with inert ceramic particle. The results indicate that the three alumina catalysts show obvious catalytic activity for urea hydrolysis at 125 °C. The order of activity is η-Al₂O₃?>?γ-Al₂O₃?>?α-Al₂O₃, and the activity difference increases with increasing temperature. According to the characterization results, surface acidity has little impact on the activity of catalyst. However, it was found that surface basicity of alumina catalyst plays an important role in catalytic hydrolysis of urea, and the activity of catalyst may be also influenced by the basic strength. With η-Al₂O₃ as catalyst, the urea concentration in wastewater is reduced to 4.96 mg/L at a temperature of 165 °C. Moreover, the η-Al₂O₃ shows a good stability for urea hydrolysis. The hydrolysis of urea over η-Al₂O₃ catalyst can evidently reduce the reaction temperature and is promising to replace industrial thermal hydrolysis process.     

The fate of nitrogen in a moderately alkaline and calcareous soil amended with biosolids and urea

The determination of nitrogen (N) based loading rates for land application of biosolids is challenging and site specific. Over loading may contribute to environmental, agricultural, or human health problems. The objective of this study was to monitor N mineralization and losses in a moderately alkaline and calcareous desert soil amended with either anaerobically digested (AN) or lime-stabilized (LS) biosolids, and irrigated with and without urea enriched water. For Experiment 1, N inputs, leaching and residuals in soil were evaluated in an open soil column system. For Experiment 2, ammonia (NH₃) emissions were evaluated in a closed soil column system. In Experiment 1, AN and LS biosolids increased soil ON (organic N) by three and two fold, respectively. Respective net N mineralization of ON from biosolids alone was 90% and 62% without urea, and 71% and 77%, respectively with added urea. Nitrogen leaching losses and residuals in amended soil did not account for all N inputs into the soil/biosolids system. In Experiment 2, NH₃ emissions were not significantly different among treated soils with or without added urea, except LS amended soil receiving urea. Ammonia losses did not account for unaccounted N in Experiment 1. We concluded that deep placement and rapid mineralization of AN biosolids promoted anaerobic soil conditions and denitrification, in addition to the high denitrification potential of desert soil. LS biosolids showed greater potential than AN biosolids for safe and beneficial land application to desert soils regardless of biosolids placement and the inclusion of N rich irrigation water.     

Suppression of nitrification and N2O emission by karanjin--a nitrification inhibitor prepared from karanja (Pongamia glabra Vent.)

A laboratory incubation study was undertaken to study nitirification and N2O emission in an alluvial, sandy loam soil (typic ustochrept), fertilized with urea and urea combined with different levels of two nitrification inhibitors viz. karanjin and dicyandiamide (DCD). Karanjin [a furanoflavonoid, obtained from karanja (Pongamia glabra Vent.) seeds] and DCD were incorporated at the rate of 5%, 10%, 15%, 20% and 25% of applied urea-N (100 mg kg(-1) soil), to the soil (100 g) adjusted to field capacity moisture content. Mean N2O flux was appreciably reduced on addition of the inhibitors with urea. Amounts of nitrified N (i.e. (NO3- + NO2-)-N) in total inorganic N (i.e. (NO3 + NO2- + NH4+)-N) in soil were found to be much lower on the addition of karanjin with urea (2-8%) as compared to urea plus DCD (14-66%) during incubation, indicating that karanjin was much more potent nitrification inhibitor than DCD. Nitrification inhibition was appreciable on the application of different levels of karanjin (62-75%) and DCD (9-42%). Cumulative N2O-N loss was found to be in the range of 0.5-80% of the nitrified N at different stages of incubation. Application of karanjin resulted in higher mitigation of total N2O-N emission (92-96%) when compared with DCD (60-71%).     

脲硫酸分解磷矿过程氟逸出规律的研究

对脲硫酸分解磷矿过程中酸解剂配比(即尿素加入量)、反应温度、磷矿粉细度、搅拌强度等对磷矿转化率和气相氟逸出率的影响进行了．探讨。实验结果表明．酸解剂配比是影响氟逸出率的最主要因素，由于尿素的加入．可使氟逸出率降低75％以上。     

Evaluation of nitrification inhibitor 3,4-dimethyl pyrazole phosphate on nitrogen leaching in undisturbed soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors (NI) as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, the efficacy of the new NI, 3,4-dimethyl pyrazole phosphate (DMPP), was tested under simulated high-risk leaching situations in two types of undisturbed soil columns. The results showed that the accumulative leaching losses of soil nitrate under treatment of urea with 1.0% DMPP, from columns of silt loam soil and heavy clay soil, were 66.8% and 69.5% lower than those soil columns tested with regular urea application within the 60 days observation, respectively. However, the losses of ammonium leaching were reversely increased 9.7% and 6.7% under the former treatment than the latter one. Application of regular urea with 1.0% DMPP addition can reduce about 59.3%-63.1% of total losses of inorganic nitrogen via leaching. The application of DMPP to urea had stimulated the inhibition effects of DMPP on the ammonium nitrification process in the soil up to 60 days. It is proposed that the DMPP could be used as an effective NI to control inorganic N leaching losses, minimizing the risk of nitrate pollution in shallow groundwater.     

The impact of airport de-icing on a river: the case of the Ouseburn, Newcastle upon Tyne

The damaging effects of airport de-icers to adjacent waterways have been suggested by a number of studies, but none have been able to demonstrate these effects in a field situation. The Ouseburn is a part-urban and partrural catchment of varied land-use and includes a tributary which drains the Newcastle International Airport. The tributary contributes only 3-5% of the river's average flow, yet it had a disproportionately adverse impact upon the river. This paper demonstrates how this was linked to the airport's winter application of urea salt de-icers. An integrated approach involving hydrological, chemical, bacteriological and macroinvertebrate sampling was used. During cold weather, higher levels of ammonia were recorded in the tributary and downstream, and concentrations peaked during runoff events. It is suggested that hydrolysis, facilitated by urea digesting bacteria, and surface runoff is the mechanism by which ammonia enters the stream. The airport tributary had a less diverse macroinvertebrate fauna than expected and had larger numbers of bacteria which were able to utilise urea. In-situ bioassay experiments found large deaths of Gammarus pulex (L.) and low biotic indices at a site downstream of the airport tributary confluence. Together with elevated ammonia levels this suggested that urea application adversely impacted on the main stream's water quality and ecology. The airport authorities have responded by changing to a less toxic de-icer.     

Contributions to ecological chemistry CXII balance of conversion of buturon‐14C in wheat under outdoor conditions 1

Abstract

The urea herbicide buturon (N‐[p‐chlorophenyl] ‐N’ ‐methyl‐N’ ‐isobutinyl‐urea), ¹⁴C‐labeled, was sprayed on winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Upon harvest (three months after application), a total of 49. 2% of the applied radiocarbon was recovered: 2.0% in the plants, 46.9% in the soil, and 0.3% in the leaching water (depth > 50 cm); less than 0.1% was in the grains (0.464 ppm). Only about half of the radioactivity present in plants could be recovered under mild extraction conditions; about half of this was unchanged buturon. In straw and husk extracts, the following metabolites were identified by gaschromatography/mass spectrometry: N‐(p‐chlorophenyl)‐N‐methyl‐O‐methyl‐carbamate (metabolite I), N‐phenyl‐N’ ‐formyl‐urea (metabolite II), two unstable metabolites giving (p‐chlorophenyl)‐isocyanate upon purification (metabolites III and IV), N‐(p‐chlorophenyl)‐N’ ‐methyl‐N’ ‐isobutenylol‐urea (metabolite V), p‐chloroformanilide (metabolite VI) and biologically bound p‐chloroaniline (metabolite VII). In the root and basal stem extract, the following metabolites were identified by gas chromatography/mass spectrometry: N‐(p‐chlorophenyl)‐O‐methyl‐carbamate (metabolite VIII) and N‐(p‐chlorophenyl)‐N’ ‐methyl‐urea (metabolite IX).