Soil phosphorus availability and soybean response to phosphorus starter fertilizer

Phosphorus fixation in tropical soils may decrease under no-till. In this case, P fertilizer could be surface-spread, which would improve farm operations by decreasing the time spend in reloading the planter with fertilizers. In the long term, less soluble P sources could be viable. In this experiment, the effect of surface-broadcast P fertilization with both soluble and reactive phosphates on soil P forms and availability to soybean was studied with or without fertilization with soluble P in the planting furrow in a long-term experiment in which soybean was grown in rotation with Ruzigrass (Brachiaria ruziziensis). No P or 80 kg ha-1 of P2O5 in the form of triple superphosphate or Arad reactive rock phosphate was applied on the surface of a soil with variable P fertilization history. Soil samples were taken to a depth of 60 cm and soil P was fractionated. Soybean was grown with 0, 30, and 60 kg ha-1 of P2O5 in the form of triple phosphate applied in the seed furrow. Both fertilizers applied increased available P in the uppermost soil layers and the moderately labile organic and inorganic forms of P in the soil profile, probably as result of root decay. Soybean responded to phosphates applied on the soil surface or in the seed furrow; however, application of soluble P in the seed furrow should not be discarded. In tropical soils with a history of P fertilization, soluble P sources may be substituted for natural reactive phosphates broadcast on the surface. The planting operation may be facilitated through reduction in the rate of P applied in the planting furrow in relation to the rates currently applied.

Chemical and Biochemical Properties of Oxisols after Sewage Sludge Application for 16 Years

ABSTRACT The large production of sewage sludge (SS), especially in large urban centers, has led to the suggestion of using this waste as fertilizer in agriculture. The economic viability of this action is great and contributes to improve the environment by cycling the nutrients present in this waste, including high contents of organic matter and plant nutrients. This study evaluated the chemical and biochemical properties of Dystrophic and EutroferricLatossolos Vermelhos (Oxisols) under corn and after SS application at different rates for 16 years. The field experiment was carried out in Jaboticabal, São Paulo State, Brazil, using a randomized block design with four treatments and five replications. Treatments consisted of control - T1 (mineral fertilization, without SS application), 5 Mg ha-1 SS - T2, 10 Mg ha-1 SS - T3, and 20 Mg ha-1 SS - T4 (dry weight base). The data were submitted to variance analysis and means were compared by the Duncan test at 5 %. Sewage sludge increased P extracted by resin in both theLatossolos Vermelhos, Dystrophic and Eutroferric, and the organic matter content in the Dystrophic Latossolo Vermelho. The waste at the rate 20 Mg ha-1 on a dry weight basis promoted increases in acid phosphatase activity in Eutroferric Latossolo Vermelho, basal respiration and metabolic quotient in DystrophicLatossolo Vermelho. The rate 20 Mg ha-1 sewage sludge on a dry weight basis did not alter the soil microbial biomass in both the Latossolos Vermelhos; in addition, it improved corn yields without inducing any symptoms of phytotoxicity or nutrient deficiency in the plants.

Biochar effect on the mineralization of soil organic matter

The objective of this work was to verify whether the addition of biochar to the soil affects the degradation of litter and of soil organic matter (SOM). In order to investigate the effect of biochar on the mineralization of barley straw, soil was incubated with 14C-labelled barley straw with or without unlabelled biochar. To investigate the effect of straw on the mineralization of biochar, soil was incubated with 14C-labelled biochar with or without straw. In addition, to investigate the effect of biochar on old SOM, a soil labelled by applying labelled straw 40 years ago was incubated with different levels of biochar. All experiments had a control treatment, without any soil amendment. The effect of biochar on the straw mineralization was small and nonsignificant. Without biochar, 48±0.2% of the straw carbon was mineralized within the 451 days of the experiment. In comparison, 45±1.6% of C was mineralized after biochar addition of 1.5 g kg-1. In the SOM-labelled soil, the organic matter mineralized more slowly with the increasing doses of biochar. Biochar addition at 7.7 g kg-1 reduced SOM mineralization from 6.6 to 6.3%, during the experimental period. The addition of 15.5 g kg-1 of biochar reduced the mineralized SOM to 5.7%. There is no evidence of increased degradation of either litter or SOM due to biochar addition; consequently, there is no evidence of decreased stability of SOM.

Addition of nitrogen had no effect on yield and quality of apples in an high density orchard carrying a dwarf rootstock

The effect of N addition on apple yield and quality may vary according to the tree vigor. Apple trees developed over vigorous rootstocks had shown no response to N application in Brazil. In this study it was evaluated the effect of N addition to the soil on yield and quality of ´Royal Gala´ apples grafted on a dwarf rootstock (M.9). The orchard was planted in 1995 (2,857 trees ha-1) on an Oxisol containing 40 g kg-1 of organic matter and pH 6.0. The experiment was carried out from 1998 up to 2005. Treatments consisted of rates of N (0, 50, 100 and 150 kg ha-1 year-1 from 1998 to 2001, and respectively 0, 100, 200 and 300 kg ha-1 afterwards), all broadcasted within the tree row in two equal splits, at bud break and after harvest, as ammonium sulfate. Addition of N to the soil had no effect on fruit yield over the six years regardless of the applied rate. Averaged across treatments and years, fruit yield was 52.3 t ha-1. Nitrogen in the leaves (average of 24 g kg-1) or in the fruits (average of 346 mg kg-1) as well as some attributes related to fruit quality (color, firmness, acidity, soluble solids, physiological disorders) were unaffected by N addition. Some plant parameters related to tree vigor, however, grew higher with the increase on N rate. Thus, it is not necessary to apply N to deep Brazilian soils containing high organic matter in order to assure good fruit quality and yield on high-density orchards carrying dwarf rootstocks probably because the N required for tree growth and fruit production is supplied from soil organic matter decay.

L'oxalate: un déchet organique peu soluble, avec conséquences [Oxalate: a poorly soluble organic waste with consequences].

Oxalate is a highly insoluble metabolic waste excreted by the kidneys. Disturbances of oxalate metabolism are encountered in enteric hyperoxaluria (secondary to malabsorption, gastric bypass or in case of insufficient Oxalobacter colonization), in hereditary hyperoxaluria and in intoxication (ethylene glycol, vitamin C). Hyperoxaluria causes a large spectrum of diseases, from isolated hyperoxaluria to kidney stones and nephrocalcinosis formation, eventually leading to kidney failure and systemic oxalosis with life-threatening deposits in vital organs. New causes of hyperoxaluria are arising recently, in particular after gastric bypass surgery, which requires regular and preemptive monitoring. The treatment of hyperoxaluria involves reduction in oxalate intake and increase in calcium intake. Optimal urine dilution and supplementation with inhibitors of kidney stone formation (citrate) are required. Some conditions may need vitamin B6 supplementation, and the addition of probiotics might be useful in the future. Primary care physicians should identify cases of recurrent calcium oxalate stones and severe hyperoxaluria. Further management of hyperoxaluria requires specialized care.

The influence of substratum type and nutrient supply on biofilm organic matter utilization in streams

We investigated the effect of benthic substratum type (sand and rocks) and nutrient supply (N and P) on biofilm structure and heterotrophic metabolism in a field experiment in a forested Mediterranean stream (Fuirosos). Rock and sand colonization and biofilm formation was intensively studied for 44 d at two stream reaches: control and experimental (continuous addition of phosphate, ammonia, and nitrate). Structural (C, N, and polysaccharide content and bacterial and chlorophyll density) and metabolic biofilm parameters (b-glucosidase, peptidase, and phosphatase enzyme activities) were analyzed throughout the colonization process. The epilithic biofilm (grown on rocks) had a higher peptidase activity at the impacted reach, together with a higher algal and bacterial biomass. The positive relationship between the peptidase activity per cell and the N content of the epilithic biofilm suggested that heterotrophic utilization of proteinaceous compounds from within the biofilm was occurring. In contrast, nutrient addition caused the epipsammic biofilm (grown on sand) to exhibit lower b-glucosidase and phosphatase activities, without a significant increase in bacterial and algal biomass. The differential response to nutrient addition was related to different structural characteristics within each biofilm. The epipsammic biofilm had a constant and high C:N ratio (22.7) throughout the colonization. The epilithic biofilm had a higher C:N ratio at the beginning of the colonization (43.2) and evolved toward a more complex structure (high polysaccharide content and low C:N ratio) during later stages. The epipsammic biofilm was a site for the accumulation and degradation of organic matter: polysaccharides and organic phosphorus compounds had higher degradation activities

ORGANIC MATTER AND HUMIC FRACTIONS OF A HAPLIC ACRISOL AS AFFECTED BY COMPOSTED PIG SLURRY

The goal of this study was to investigate the effect of composted pig slurry (PS) on the organic matter concentration and distribution of humic acid (HA), fulvic acid (FA) and humin (HU) fractions. The fractions were quantified following the addition of composted PS to the soil, which was produced with no acidification (T2) or with acidification with H3PO4 (T3); and in soil without compost addition (T1). The HA chemical composition was analyzed by FTIR spectroscopy. The addition of the two composts did not change the soil carbon concentration but affected the distribution of the humic fractions. For the three treatments, the carbon concentration of humic substances increased until 52 days following compost addition, with more pronounced increases with the addition of non-acidified PS compost (14.5 g kg-1) and acidified PS compost (15.1 g kg-1). This increase was reflected in both the FA and HA concentrations. The addition of compost with PS acidification resulted in the formation of larger humic micelles (HA) with higher aromatic content and fewer functional groups than the non-acidified PS compost. These findings, together with a lower proportion of carbohydrate-type structures, indicated the presence of more stable humic micelles in the soil treated with acidified PS compost.

Effect of organic amendments on sclerotial germination, mycelial growth, and Sclerotium rolfsii-induced diseases

The addition of organic residues to soil is an option to control some soil-borne diseases. Benzaldehyde and powders of kudzu (Pueraria lobata), velvetbean (Mucuna deeringiana), and pine-bark (Pinus elliottii and P. taeda) added to soil could reduce certain soil-borne diseases. This study evaluated the effects of benzaldehyde and the dried powders of kudzu, velvetbean, and pine-bark as soil amendments on germination and formation of sclerotia, on mycelial growth of Sclerotium rolfsii, on plant survival, and disease incidence. The data showed that high amounts of benzaldehyde (0.4 ml kg-1 of soil) and velvetbean (100 g kg-1) inhibited S. rolfsii mycelial growth and sclerotium germination. However, low amounts of benzaldehyde (0.1 ml kg-1), kudzu (25 g kg-1), and pine-bark (25 g kg-1) stimulated mycelial growth and sclerotium germination. Kudzu (25-100 g kg-1) and velvetbean (25-100 g kg-1) inhibited the formation of sclerotia. Nevertheless, benzaldehyde at 0.2 and 0.4 ml kg-1 stimulated the formation of sclerotia. Kudzu (50 and 100 g kg-1) and pine-bark (50 g kg-1) favored the colonization of sclerotia by Trichoderma sp. The numbers of soybean (Glycine max) plants were higher and diseased plants were lower than the non-amend soil in the following treatments: kudzu (50 and 100 g kg-1), velvetbean (50 and 100 g kg-1), and pine-bark (50 g kg-1). Disease severity on tomato (Lycopersicon esculentum) plants was low in soil treated with kudzu or velvetbean (30 and 35 g kg-1) and pine-bark (35 g kg-1). Dried powders of kudzu, velvetbean, or pine-bark added to soil can reduce disease by reducing pathogen inoculum.

Biokaasulaitoksen rejektivesien vaikutus jätevedenpuhdistamon toimintaan ja rejektivesien esikäsittelyn tarpeellisuus

Diplomityön tavoitteena oli tutkia biokaasulaitoksen rejektivesien ominaisuuksiin vaikuttavia tekijöitä ja rejektiveden esikäsittelyn tarpeellisuutta. Lisäksi tavoitteena oli tarkastella Kouvolaan suunnitteilla olevan Kymen Bioenergia Oy:n biokaasulaitoksen rejektivesien vaikutusta Kouvolan Veden Mäkikylän jätevedenpuhdistamolla. Biokaasulaitoksen rejektivedet ovat yhdyskuntajätevesiin verrattuna selvästi konsentroituneempia. Jätevedenpuhdistamoilla erityisesti rejektiveden korkea typpipitoisuus aiheuttaa lisäkuormitusta. Suomessa toiminnassa oleville biokaasulaitoksille tehdyn kyselytutkimuksen tulosten perusteella rejektiveden typpipitoisuuteen vaikuttaa syötteen typpipitoisuus sekä mädätysjäännöksen kuivauksen tehokkuus. Rejektiveden kiintoainepitoisuudella on puolestaan vaikutusta biologiseen hapenkulutukseen ja välillisesti myös rejektiveden kemialliseen hapenkulutukseen. Rejektivesien jätevedenpuhdistamoilla aiheuttamaa kuormitusta on mahdollista vähentää esikäsittelemällä rejektivedet joko biologisella tai fysikaalis-kemiallisella puhdistusmenetelmällä. Kyselytutkimus kuitenkin osoitti, että rejektivesien esikäsittelyssä ei aina päästä puhdistustavoitteeseen. Jätevedenkäsittelyn sijaan rejektivesiä on mahdollista käyttää lannoitteena, mikäli biokaasulaitoksen syöte ei sisällä jätevedenpuhdistamon lietteitä. Myös Kouvolan Veden Mäkikylän puhdistamolla biokaasulaitoksen rejektivedet tulevat lisäämään merkittävästi tulovirtaaman typpikuormaa. Typpikuorman lisäys edellyttää ilmastusaltaassa ilmastuksen tehostamista sekä kalkin syöttömäärän lisäämistä, jotta jäteveden happipitoisuus ja pH pysyvät typenpoistoreaktioille suotuisina. Lisäksi tulovirtaamasta puolet tullaan ohjaamaan esiselkeyttimen ohi, jotta ilmastusaltaassa on orgaanista ainetta typenpoistoon riittävästi. Mäkikylän puhdistamon typenpoistokapasiteettia on mahdollista kasvattaa lisähiilen syötöllä. Mikäli biokaasulaitoksen kapasiteettilisäyksen jälkeen rejektivesien typpikuoma ylittää lisähiilellä saavutetun lisäkapasiteetin, on rejektivedet esikäsiteltävä.

Adsorptive removal of harmful organic compound from aqueous solutions

Adsorption is one of the most commonly used methods in water treatment processes. It is attractive due to it easy operation and the availability of a wide variety of commercial adsorbents. This doctoral thesis focuses on investigating and explaining the influence of external phase conditions (temperature, pH, ionic strength, acidity, presence of cosolutes) on adsorption phenomena. In order to cover a wide range of factors and phenomena, case studies were chosen from various fields where adsorption is applied. These include the adsorptive removal of surface active agents (used in cleaning chemicals, for example) from aqueous effluents, the removal of hormones (estradiol) from drinking water, and the adsorption of antibiotics onto silica. The latter can beused to predict the diffusion of antibiotics in the aquatic system if they are released into the environment. Also the adsorption of living cells on functionalized polymers to purify infected water streams was studied. In addition to these examples, the adsorptive separation of harmful compounds from internal water streams within a chemical process was investigated. The model system was removal of fermentation inhibitors from lignocelluloses hydrolyzates. The detoxification of the fermentation broth is an important step in the manufacture of bioethanol from wood, but has not been studied previously in connection with concentrated acid hydrolyzates. New knowledge on adsorption phenomena was generated for all of the applications investigated. In most cases, the results could be explained by combining classical theories for individual phenomena. As an example, it was demonstrated how liquid phase aggregation could explain abnormal-looking adsorption equilibrium data. In addition to the fundamental phenomena, also process performance was of interest. This aspect is often neglected in adsorption studies. It was demonstrated that adsorbents should not be selected for a target application based on their adsorption properties only, but regeneration of the spent adsorbent must be considered. It was found that using a suitable amount of organic co-solvent in the regeneration can significantly improve the productivity of the process.

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures Biocatalysis opens the door to green and sustainable processes in synthetic chemistry allowing the preparation of single enantiomers, since the enzymes are chiral and accordingly able to catalyze chemical reactions under mild conditions. Immobilization of enzymes enhances process robustness, often stabilizes and activates the enzyme, and enables reuse of the same enzyme preparation in multiple cycles. Although hundreds of variations of immobilization methods exist, there is no universal method to yield the highly active, selective and stable enzyme catalysts. Therefore, new methods need to be developed to obtain suitable catalysts for different substrates and reaction environments. Lipases are the most widely used enzymes in synthetic organic chemistry. The literature part together with the experimental part of this thesis discusses of the effects of immobilization methods mostly used to enhance lipase activity, stability and enantioselectivity. Moreover, the use of lipases in the kinetic resolution of secondary alcohols in organic solvents and in ionic liquids is discussed. The experimental work consists of the studies of immobilization of Burkholderia cepacia lipase (lipase PS) using three different methods: encapsulation in sol-gels, cross-linked enzyme aggregates (CLEAs) and supported ionic liquids enzyme catalysts (SILEs). In addition, adsorption of lipase PS on celite was studied to compare the results obtained with sol-gels, CLEAs and SILEs. The effects of immobilization on enzyme activity, enantioselectivity and hydrolysis side reactions were studied in kinetic resolution of three secondary alcohols in organic solvents, in ionic liquids (ILs), and in their mixtures. Lipase PS sol-gels were shown to be active and stable catalysts in organic solvents and solvent:IL mixtures. CLEAs and SILEs were highly active and enantioselective in organic solvents. Sol-gels and SILEs were reusable in several cycles. Hydrolysis side reaction was suppressed in the presence of sol-gels and CLEAs.

Technology for sugarcane agroindustry waste reuse as granulated organomineral fertilizer

Aiming to evaluate the use of sugarcane industry waste such as byproducts from vinasse concentration process, it was assessed the organomineral fertilizer BIOFOM (concentrated vinasse, filter cake, boiler ash, soot from chimneys and supplemented with mineral fertilizers). The study included characterization and agronomic potential analysis of a test plant (corn), by noting the differences between mineral fertilizers and BIOFOM fertilization until 45 days after sowing. The technology traditionally used to produce BIOFOM was based on vinasse evaporation with high heat transfer coefficients. It was observed that the technology, which can be formulated according to the needs of any crop, could be used in many cases as mineral fertilizer. Therefore, the use of this organomineral fertilizer reduces waste generation of sugarcane industry.

Studies on chemoenzymatic synthesis: Lipase-catalyzed acylation in multistep organic synthesis

In this thesis, biocatalysis is defined as the science of using enzymes as catalysts in organic synthesis. Environmental aspects and the continuously expanding repertoire of available enzymes have firmly established biocatalysis as a prominent means of chemo-, regio- and stereoselective synthesis. Yet, no single methodology can solve all the challenges faced by a synthetic chemist. Therefore, the knowledge and the skills to combine different synthetic methods are relevant. Lipases are highly useful enzymes in organic synthesis. In this thesis, an effort is being made to form a coherent picture of when and how can lipases be incorporated into nonenzymatic synthesis. This is attempted both in the literature review and in the discussion of the results presented in the original publications contained in the thesis. In addition to lipases, oxynitrilases were also used in the work. The experimental part of the thesis comprises of the results reported in four peer-reviewed publications and one manuscript. Selected amines, amino acids and sugar-derived cyanohydrins or their acylated derivatives were each prepared in enantio- or diastereomerically enriched form. Where applicable, attempts were made to combine the enzymatic reactions to other synthetic steps either by the application of completely separate sequential reactions with isolated intermediates (kinetic and functional kinetic resolution of amines), simultaneously occurring reactions without intermediate isolation (dynamic kinetic resolution of amino acid esters) or sequential reactions but without isolating the intermediates (hydrocyanation of sugar aldehydes with subsequent diastereoresolution). In all cases, lipase-catalyzed acylation was the key step by which stereoselectivity was achieved. Lipase from Burkholderia cepacia was a highly selective enzyme with each substrate category, but careful selection of the acyl donor and the solvent was important as well.

Analytical methods for analyzing organic peroxides

Työn tarkoituksena oli kehittää analyyttinen erotusmenetelmä eräässä valmistusprosessissa käytettävän hapettavan aineen ja liuottimen välillä syntyvien reaktiotuotteiden tutkimiseen ja analysoimiseen. Lisäksi tarkoituksena oli tutkia prosessiolosuhteiden turvallisuutta. Kirjallisuusosassa käsitellään erilaisia orgaanisia peroksideja, niiden käyttötarkoituksia ja niiden käyttöön liittyviä huomioitavia asioita. Lisäksi tarkastellaan yleisimpiä analyysimenetelmiä, joita on käytetty erilaisten peroksidien analysoinnissa. Näitä analyysimenetelmiä on useimmiten käytetty nestemäisten näytteiden tutkimuksissa. Harvemmin on analysoitu kaasu- ja kiintoainenäytteitä. Kokeellisessa osassa kehitettiin kirjallisuuden perusteella peroksidiyhdisteille identifiointimenetelmä ja tutkittiin prosessin näytteet. Analyysimenetelmiksi valittiin iodometrinen titraus ja HPLC-UV-MS-menetelmä. Lisäksi käytettiin peroksidimittaukseen soveltuvia testiliuskoja. Tutkimus osoitti, että iodometrisen titrauksen ja testiliuskojen perusteella näytteissä oli vähäisiä määriä peroksideja viikon jälkeen peroksidilisäyksestä. HPLC-UV-MS-analyysien perusteella näytteiden analysointia häiritsi selluloosa, jota löytyi jokaisesta näytteestä.

Ultrasonic and Electrokinetic Remediation of Low Permeability Soil Contaminated with Persistent Organic Pollutants

Electrokinetics has emerged as a potential technique for in situ soil remediation and especially unique because of the ability to work in low permeability soil. In electrokinetic remediation, non-polar contaminants like most organic compounds are transported primarily by electroosmosis, thus the process is effective only if the contaminants are soluble in pore fluid. Therefore, enhancement is needed to improve mobility of these hydrophobic compounds, which tend to adsorb strongly to the soil. On the other hand, as a novel and rapidly growing science, the applications of ultrasound in environmental technology hold a promising future. Compared to conventional methods, ultrasonication can bring several benefits such as environmental friendliness (no toxic chemical are used or produced), low cost, and compact instrumentation. It also can be applied onsite. Ultrasonic energy applied into contaminated soils can increase desorption and mobilization of contaminants and porosity and permeability of soil through developing of cavitation. The research investigated the coupling effect of the combination of these two techniques, electrokinetics and ultrasonication, in persistent organic pollutant removal from contaminated low permeability clayey soil (with kaolin as a model medium). The preliminary study checked feasibility of ultrasonic treatment of kaolin highly contaminated by persistent organic pollutants (POPs). The laboratory experiments were conducted in various conditions (moisture, frequency, power, duration time, initial concentration) to examine the effects of these parameters on the treatment process. Experimental results showed that ultrasonication has a potential to remove POPs, although the removal efficiencies were not high with short duration time. The study also suggested intermittent ultrasonication over longer time as an effective means to increase the removal efficiencies. Then, experiments were conducted to compare the performances among electrokinetic process alone and electrokinetic processes combined with surfactant addition and mainly with ultrasonication, in designed cylinders (with filtercloth separating central part and electrolyte parts) and in open pans. Combined electrokinetic and ultrasonic treatment did prove positive coupling effect compared to each single process alone, though the level of enhancement is not very significant. The assistance of ultrasound in electrokinetic remediation can help reduce POPs from clayey soil by improving the mobility of hydrophobic organic compounds and degrading these contaminants through pyrolysis and oxidation. Ultrasonication also sustains higher current and increases electroosmotic flow. Initial contaminant concentration is an essential input parameter that can affect the removal effectiveness.