Response of wheat to additional nitrogen fertilizer application after pig slurry on over-fertilized soils

Pig slurry is a valuable nutrient resource but constitutes a waste disposal problem in areas of high animal density. In the semiarid area of Pla d’Urgell, in the Ebro Valley, North-East Spain, irrigated crops receive large amounts of nutrients in the form of manure and mineral fertilizers. We studied the effect of pig slurry and additional side-dress mineral fertilizers on irrigated wheat, Triticum aestivum L., on a coarse loam soil, with high soil P and K levels. Yields increased by 62.3% when using pig slurry. The application of ammonium sulfate nitrate sidedress did not significantly increase wheat production. The average apparent recoveries were higher for potassium (88.7%) than for nitrogen (51.3%) and phosphorus (36.3%). Greater amounts of soil NO3-N were measured over the four growing seasons, which was consistent with the amount of N applied. Macronutrient and micronutrient uptake was significant higher for pig slurry treatments, but only small differences were found between the pig slurry and pig slurry plus ammonium sulfate nitrate treatments. The unfertilized treatment showed significantly lower soil P, K, Cu and Zn content than pig slurry treatments; 34%, 21%, 34%, and 26% respectively. These findings could be used to develop a nutrient management plan based on knowledge of soil test results and crop nutrient removal. This could help to improve the use of pig slurry and mineral fertilizers on limited available land areas and prevent the accumulation of potentially toxic elements in soils and the export of nutrients through agricultural drainage.

Effects of inorganic nitrogen (NH4Cl) and biodegradable organic carbon (CH3COONa) additions on a pilot-scale seawater biofilter

Biofilters degrade only a small fraction of the natural organic matter (NOM) contained in seawater which is the leading cause of biofouling in downstream processes. This work studies the effects of chemical additions on NOM biodegradation by biofilters. In this work, biofiltration of seawater with an empty bed contact time (EBCT) of 6 min and a hydraulic loading rate of 10 m h-1 reduces the biological oxygen demand (BOD7) by 8%, the dissolved organic carbon (DOC) by 6% and the UV absorbance at 254 nm (A254) by 7%. Different amounts of ammonium chloride are added to the seawater (up to twice the total dissolved nitrogen in untreated seawater) to study its possible effect on the removal of NOM by a pilot-scale biofilter. Seawater is amended with different amounts of easily biodegradable dissolved organic carbon (BDOC) supplied as sodium acetate (up to twice the DOC) for the same purpose. The results of this work reveal that the ammonium chloride additions do not significantly affect NOM removal and the sodium acetate is completely consumed by the biofiltration process. For both types of chemical additions, the BOD7, DOC and A254 in the outlet stream of the biofilter are similar to the values for the untreated control. These results indicate that this biofilter easily removes the BDOC from the seawater when the EBCT is not above 6 min. Furthermore, nitrogen does not limit the NOM biodegradation in seawater under these experimental conditions.

Removal of organic matter and nutrients from slaughterhouse wastewater by using Eichhornia crassipes and evaluation of the generated biomass composting

The objective of this research was to evaluate the performance of the aquatic macrophyte Eichhornia crassipes applied in situ in a slaughter house treatment system, located in the west of the Paraná state, Brazil, regarding the nutrients removal and organic matter. Moreover, it aimed to obtain data from the production, management and composting practices of the biomass generated in the system. During 11 months of macrophytes development, physic and chemical parameters were monitored and plant density was controlled by periodical removal of excess biomass, which was weekly monitored and it is expressed in kg of aquatic plant per m² covered area. The degradation of the macrophytes removed from the treatment system was evaluated at the pilot scale in eight composting piles of 0.60 m³ that underwent four different treatments and two repetitions: T1 - water hyacinth (Eichhornia crassipes); T2 - water hyacinth and swine excrement (7:1), T3 - water hyacinth, swine excrement and earth (7:1:0,67), and T4 - water hyacinth, swine excrement and cellulosic gut (7:1:0,67), for a period of 90 days. The results indicated maximum removal efficiencies of 77.2% for COD; 77.8% for BOD, 87.9% for total nitrogen, 47.5% for ammonia nitrogen and 38.9% for total phosphorus for a five-day retention time. For biomass stabilization by composting, considering the C:N ratio as an indicator of compost maturity, it was observed that treatment T4 resulted in the shortest stabilization period (60 days). No difference was verified in the biostabilization rates at 5% level by the F test.

Selection of microorganisms producer of lipase for fat removal from biodiesel purification water

The objective this study has been the selection of lipase productor microorganism, for removal of oils and grease, in the pre-treatment of biodiesel wastewater washing. For this, analyses of the physicist-chemistries characteristics had been made with the wastewater of the biodiesel washing, and then it had been isolated and chosen, by means of determinations of the lipase activity. Following, it was made a test of fat biodegradation, in the conditions: pH (5.95), temperature (35 ºC), rotation (180 rpm) and ammonium sulfate as nitrogen source (3 g L-1) and establishing as variable the two microorganism preselected and the time (24; 48; 72; 96 and 120 h). The biodiesel purification wastewater had presented high potential of environmental impact, presenting a concentration of O of 6.76 g L-1. From the six isolated microbiological cultures, two microorganisms (A and B) had been selected, with enzymatic index of 0.56 and 0.57, respectively. The treatment of the wastewater using the isolated microorganism (Klebsiella oxytoca) had 80% of the fatty removal in 48 h.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

Reduction of nitrogen oxide emissions in lime kiln

Different nitrogen oxide removal technologies for rotary lime kiln are studied in this thesis, the main focus being in commercial technologies. Post-combustion methods are investigated in more detail as potential possible NOx removal with combustion methods in rotary lime kiln is more limited or primary methods are already in use. However, secondary methods as NOx scrubber, SNCR or SCR technologies are not listed as the Best Available Technologies defined by European Union. BAT technologies for NOx removal in lime kiln are (1) Optimised combustion and combustion control, (2) Good mixing of fuel and air, (3) Low-NOx burner and (4) Fuel selection/low-N fuel. SNCR method is the most suitable technique for NOx removal in lime kiln when NOx removal from 50 % to 70 % is required in case primary methods are already in use or cannot be applied. In higher removal cases ammonia slip is an issue in SNCR. By using SCR better NOx reduction can be achieved but issues with catalyst materials are expected to arise because of the dust and sulphur dioxide which leads to catalyst poison formation in lower flue gas temperatures. NOx scrubbing has potential when simultaneous NOx and SO2 removal is required. The challenge is that NO cannot be scrubbed directly, but once it is oxidized to NO2 or further scrubbing can be performed as the solubility of NO2 is higher. Commercial installations have not been made regarding SNCR, SCR or NOx scrubbing regarding rotary lime kiln. For SNCR and SCR the closest references come from cement industry.

Polystyrene Anchored Vanillin Schiff Base—Complexation and Ion Removal Studies

A set of six new polystyrene anchored metal complexes have been synthesized by the reaction of the metal salt with the polystyrene anchored Schiff base of vanillin. These complexes were characterized by elemental analyses, Fourier transform infrared spectroscopy, diffuse reflectance studies, thermal studies, and magnetic susceptibility measurements. The elemental analyses suggest a metal : ligand ratio of 1 : 2. The ligand is unidentate and coordinates through the azomethine nitrogen. The Mn(II), Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic while Zn(II) is diamagnetic. The Cu(II) complex is assigned a square planar structure, while Zn(II) is assigned a tetrahedral structure and Mn(II), Fe(III), Co(II), and Ni(II) are all assigned octahedral geometry. The thermal analyses were done on the ligand and its complexes to reveal their stability. Further, the application of the Schiff base as a chelating resin in ion removal studies was investigated. The polystyrene anchored Schiff base gave 96% efficiency in the removal of Ni(II) from a 20-ppm solution in 15 min, without any interference from ions such as Mn(II), Co(II), Fe(III), Cu(II), Zn(II), U(VI), Na , K , NH4 , Ca2 , Cl , Br , NO3 , NO2 ,and CH3CO2 . The major advantage is that the removal is achieved without altering the pH.

Complexation and ion removal studies of a polystyrene anchored Schiff base

This paper reports the synthesis of a series of six new polystyrene anchored metal complexes of Co(II), Fe(III), Ni(II), Cu(II), Zn(II), and dioxouanium(VI) using the polystyrene anchored Schiff base of 2-nitrobenzaldehyde and the corresponding metal salts. The metal salts used were anhydrous FeCl3, CoCl2 Æ 6H2O, Ni(CH3COO)2 Æ 4H2O, Cu(CH3- COO)2 Æ H2O, Zn(CH3COO)2 Æ 2H2O, and UO2(CH3COO) Æ 2H2O. Physico chemical characterizations have been made from diffuse reflectance and vibrational spectra, elemental analysis, magnetic measurements, and TG studies. The elemental analysis suggest a 1:2 metal:ligand ratio when the complexation has carried out at 70 C for about 12 h reflux. The ligand is monodentate and coordinates through the azomethine nitrogen. The Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic whereas Zn(II) and U(VI) are diamagnetic. Zn(II) is assigned a tetrahedral structure, Cu(II) and Co(II) are assigned a square planar structure and Fe(III), Ni(II), and U(VI) are all assigned an octahedral structure. The polystyrene anchored ligand has been developed as an excellent reagent for the removal of Cu(II). Optimum conditions have been developed for the removal of metal ion from solutions by studying the effect of change of concentration of metal ion, ligand, effect of pH, time of reflux, and interference effect of other ions. It was found that within a span of 20 min it is possible to remove 90% of the metal ion from a 30 ppm metal ion solution in the pH range 4–5.5.

Biological nutrient removal in SBR technology: from floccular to granular sludge

Biological nutrient removal has been studied and applied for decades in order to remove nitrogen and phosphorus from wastewater. However, more anthropogenic uses and the continued demand for water have forced the facilities to operate at their maximum capacity. Therefore, the goal of this thesis is to obtain more compact systems for nutrient removal from domestic wastewater. In this sense, optimization and long-term stabilization of high volume exchange ratios reactors, treating higher volumes of wastewater, have been investigated. With the same target, aerobic granular sludge was proposed as a reliable alternative to reduce space and increase loading rates in treatment plants. However, the low organic loading rate from low-strength influents (less than 1 Kg COD•m-3d-1) results in slower granular formation and a longer time to reach a steady state. Because of that, different methodologies and operational conditions were investigated in order to enhance granulation and nutrient removal from domestic wastewater.

Splanchnic metabolism of nitrogenous compounds and urinary nitrogen excretion in steers fed alfalfa under conditions of increased absorption of ammonia and L-arginine supply across the portal-drained viscera

Effects of increased ammonia and/or arginine absorption across the portal-drained viscera (PDV) on net splanchnic (PDV and liver) metabolism of nitrogenous compounds and urinary N excretion were investigated in six cathetenzed Hereford x Angus steers (501 +/- 1 kg BW) fed a 75% alfalfa:25% (as-fed basis) corn-soybean meal diet (0.523 MJ of ME/[kg BW0.15.d]) every 2 h without (27.0 g of N/kg of dietary DM) and with 20 g of urea/kg of dietary DM (35.7 g of N/kg of dietary DM) in a split-plot design. Net splanchnic flux measurements were obtained immediately before beginning and ending a 72-h mesenteric vein infusion of L-arginine (15 mmol/h). For 3 d before and during arginine infusion, daily urine voided was measured and analyzed for N composition. Feeding urea increased PDV absorption (P < 0.01) and hepatic removal (P < 0.01) of ammonia N, accounting for 80% of increased hepatic urea N output (P < 0.01). Numerical increases in net hepatic removal of AA N could account for the remaining portion of increased hepatic urea N output. Arginine infusion increased hepatic arginine removal (P < 0.01) and hepatic urea N output (P < 0.03) and switched hepatic ornithine flux from net uptake to net output (P < 0.01), but numerical changes in net hepatic removal of ammonia and AA N could not account fully for the increase in hepatic urea N output. Increases in urine N excretion equaled quantities of N fed as urea or infused as arginine. Estimated salivary urea N excretion was not changed by either treatment. Urea cycle regulation occurs via a complex interaction of mechanisms and requires N sources other than ammonia, but the effect of increased ammonia absorption on hepatic catabolism of individual AA in the present study was not significant.

Influence of earthworm Eisenia fetida on removal efficiency of N and P in vertical flow constructed wetland.

This study investigates biomass, density, photosynthetic activity, and accumulation of nitrogen (N) and phosphorus (P) in three wetland plants (Canna indica, Typha augustifolia, and Phragmites austrail) in response to the introduction of the earthworm Eisenia fetida into a constructed wetland. The removal efficiency of N and P in constructed wetlands were also investigated. Results showed that the photosynthetic rate (P n), transpiration rate (T r), and stomatal conductance (S cond) of C. indica and P. austrail were (p < 0.05) significantly higher when earthworms were present. The addition of E. fetida increased the N uptake value by above-ground of C. indica, T. augustifolia, and P. australis by 185, 216, and 108 %, respectively; and its P uptake value increased by 300, 355, and 211 %, respectively. Earthworms could enhance photosynthetic activity, density, and biomass of wetland plants in constructed wetland, resulting in the higher N and P uptake. The addition of E. fetida into constructed wetland increased the removal efficiency of TN and TP by 10 and 7 %, respectively. The addition of earthworms into vertical flow constructed wetland increased the removal efficiency of TN and TP, which was related to higher photosynthetic activity and N and P uptake. The addition of earthworms into vertical flow constructed wetland and plant harvests could be the significantly sustainable N and P removal strategy

Spatio-temporal variations of ozone and nitrogen dioxide concentrations under urban trees and in a nearby open area

The evergreen Quercus ilex L. is one of the most common trees in Italian urban environments and is considered effective in the uptake of particulate and gaseous atmospheric pollutants. However, the few available estimates on O3 and NO2 removal by urban Q. ilex originate from model-based studies (which indicate NO2/O3 removal capacity of Q. ilex) and not from direct measurements of air pollutant concentrations. Thus, in the urban area of Siena (central Italy) we began long-term monitoring of O3/NO2 concentrations using passive samplers at a distance of 1, 5, 10 m from a busy road, under the canopies of Q. ilex and in a nearby open-field. Measurements performed in the period June 2011-October 2013 showed always a greater decrease of NO2 concentrations under the Q. ilex canopy than in the open-field transect. Conversely, a decrease of average O3 concentrations under the tree canopy was found only in autumn after the typical Mediterranean post-summer rainfalls. Our results indicate that interactions between O3/NO2 concentrations and trees in Mediterranean urban ecosystems are affected by temporal variations in climatic conditions. We argue therefore that the direct measurement of atmospheric pollutant concentrations should be chosen to describe local changes of aerial pollution.

An evaluation into the potential of biological processing for the removal of metals from sewage sludges

The use of sewage sludge in agricultural land as a means of sludge disposal and recycling has been shown to be economical and suitable because of the presence of nutrients such as nitrogen and phosphorus. However, municipal sludges often contain high quantities of toxic metals and other compounds that must be removed for its safe use in agricultural soils. The biological leaching of metals from sewage sludges has been shown to be a promising technique for metal detoxifying in such complex matrix. The process efficiency is dependent on several physico-chemical parameters, such as total solids concentration, metal forms, pH-ORP, and temperature. Scale-up of the process has not yet been defined and is still pursuing the correct operational design. Current research involving the bioleaching of metals from sewage sludge and its application to land, which affects soil physical properties, are presented and discussed.

Nitrate Removal on a Cu/Cu2O Photocathode under UV Irradiation and Bias Potential

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The reactive surface of Castor leaf [Ricinus communis L.] powder as a green adsorbent for the removal of heavy metals from natural river water

In this study, a green adsorbent was successfully applied to remove toxic metals from aqueous solutions. Dried minced castor leaves were fractionated into 63-μm particles to perform characterization and extraction experiments. Absorption bands in FTIR (Fourier Transform Infrared Spectroscopy) spectra at 1544, 1232 and 1350 cm-1 were assigned to nitrogen-containing groups. Elemental analysis showed high nitrogen and sulfur content: 5.76 and 1.93%, respectively. The adsorption kinetics for Cd(II) and Pb(II) followed a pseudo-second-order model, and no difference between the experimental and calculated Nf values (0.094 and 0.05 mmol g-1 for Cd(II) and Pb(II), respectively) was observed. The Ns values calculated using the modified Langmuir equation, 0.340 and 0.327 mmol g-1 for Cd(II) and Pb(II), respectively, were superior to the results obtained for several materials in the literature. The method proposed in this study was applied to pre-concentrate (45-fold enrichment factor) and used to measure Cd(II) and Pb(II) in freshwater samples from the Paraná River. The method was validated through a comparative analysis with a standard reference material (1643e). © 2013 Elsevier B.V. © 2013 Elsevier B.V. All rights reserved.