Recovery of carboxylic acids from aqueous streams by extraction and back extraction

Separation of carboxylic acids from aqueous streams is an important part of their manufacturing process. The aqueous solutions are usually dilute containing less than 10 % acids. Separation by distillation is difficult as the boiling points of acids are only marginally higher than that of water. Because of this distillation is not only difficult but also expensive due to the evaporation of large amounts of water. Carboxylic acids have traditionally been precipitated as calcium salts. The yields of these processes are usually relatively low and the chemical costs high. Especially the decomposition of calcium salts with sulfuric acid produces large amounts of calcium sulfate sludge. Solvent extraction has been studied as an alternative method for recovery of carboxylic acids. Solvent extraction is based on mixing of two immiscible liquids and the transfer of the wanted components form one liquid to another due to equilibrium difference. In the case of carboxylic acids, the acids are transferred from aqueous phase to organic solvent due to physical and chemical interactions. The acids and the extractant form complexes which are soluble in the organic phase. The extraction efficiency is affected by many factors, for instance initial acid concentration, type and concentration of the extractant, pH, temperature and extraction time. In this paper, the effects of initial acid concentration, type of extractant and temperature on extraction efficiency were studied. As carboxylic acids are usually the products of the processes, they are wanted to be recovered. Hence the acids have to be removed from the organic phase after the extraction. The removal of acids from the organic phase also regenerates the extractant which can be then recycled in the process. The regeneration of the extractant was studied by back-extracting i.e. stripping the acids form the organic solution into diluent sodium hydroxide solution. In the solvent regeneration, the regenerability of different extractants and the effect of initial acid concentration and temperature were studied.

Transfer of passive immunity and serum proteinogram in the first six months of life of Criollo Lageano and black and white holstein calves

The objective of this study was to evaluate and compare the transfer of passive immunity and the proteinogram in Criollo Lageano (CL) and Black and White Holstein (BWH) calves. Two groups were utilized with 13 Criollo Lageano and 10 BWH calves. Blood samples were collected for the measurement of total serum protein, electrophoresis of serum proteins, activity of the gamma glutamyl transferase, and concentration of IgG by the method of the zinc sulfate turbidity in periods between 24 and 36 hours of life, 15, 30, 60, 90, 120, 150 and 180 days. Statistical analysis was performed by ANOVA and Tukey test at 5% significance level, and correlations between variables were calculated. Variations of serum proteins followed a pattern of physiological behavior over the first six months of life and production of immunoglobulins was active earlier in BWH calves and slower in the Criollo Lageano, without causing any impact on their health. Gamma globulin in the first days of life (24-36h) was correlated with IgG (r=0.87 for CL and r=0.89 for BWH), PTS (r=0.91 for CL and r=0.92 for BWH), Glob (r=0.99 for CL and r=0.98 for BWH) and GGT (r=0.14 for CL and r=0.83 for BWH). It was concluded that there was no failure in the transfer of passive immunity in Criollo Lageano calves but this failure occurred in the BWH calves. IgG values estimated by the zinc sulfate turbidity and serum proteins were considered good indicators of the transfer of passive immunity in calves between 24 and 36 hours of life.

Sanitizer residues in the milk of cows which had passed through footbaths

Copper sulfate and sodium hypochlorite are used in footbath solutions for the prevention and treatment of bovine digital diseases; however, data on the residues of such elements in milk are sparse in Brazil. This study evaluated the cost of applying the footbath treatment and the total amount of copper and chlorite residues in the milk of healthy cows after they had passed through these footbath solutions. Two groups of 7 cows each (GI and GII) were studied. In the case of GI, 1% sodium hypochlorite was used and for GII 5% copper sulfate was employed in the footbath. The milk samples were collected before the 7-day footbath treatment period (M0) and 24 h (M1), 48 h (M2), 72 h (M3) and 15 days (M15) after the last footbath. Statistical analysis to compare the different samples within each group was carried out by applying Friedman's test, followed by Dunn's test (p<0.05). It was concluded that the amount of total chlorites and copper in the milk of healthy cattle after routine daily footbaths for a period of 7 days presented some variations. However, the concentrations observed were considered insufficient to represent a risk to human health. The cost of the footbath solutions was found to be reasonable.

Expression of P-glycoprotein, multidrug resistance-associated protein, glutathione-S-transferase pi and p53 in canine transmissible venereal tumor

The overexpression of proteins P-glycoprotein (P-gp), multidrug resistance-associated protein (MRP1), mutant p53, and the enzyme glutathione-S-transferase (GSTpi) are related to resistance to chemotherapy in neoplasms. This study evaluated the expression of these markers by immunohistochemistry in two groups of canine TVT, without history of prior chemotherapy (TVT1, n=9) and in TVTs presented unsatisfactory clinical response to vincristine sulfate (TVT2, n=5). The percentage of specimens positively stained for P-gp, MRP1, GSTpi and p53 were, respectively 88.8%, 0%, 44.5% and 22.2% in TVT1 and 80%, 0%, 80% and 0% in TVT2. In TVT1, one specimen presented positive expression for three markers and four specimens for two markers. In TVT2, three specimens expressed P-gp and GSTpi. In conclusion, the canine TVTs studied expressed the four markers evaluated, but just P-gp and GSTpi were significantly expressed, mainly at cytoplasm and cytoplasm and nuclei, respectively, either before chemotherapy as after vincristine sulfate exposure. Future studies are needed to demonstrate the function of these two markers in conferring multidrug resistance (MDR) or predict the response to chemotherapy in canine TVT.

Metallien eluointi kelatoivasta ioninvaihtimesta

Kelatoivat ioninvaihtimet ovat yleensä makrohuokoisia hartseja, joiden avulla metalleja poistetaan ja otetaan mahdollisesti talteen teollisuuden puhdistettavista jätevirroista. Ne muodostavat metalli-ionien kanssa komplekseja runkomateriaaliin kovalenttisesti liitettyjen aktiivisten funktionaalisten ryhmiensä välityksellä. Ioninvaihtimen selektiivisyys eri metalli-ioneja kohtaan vaihtelee riippuen siihen liitetystä kelatoivasta ryhmästä. Työssä tutkitaan metallien tarttumista kelatoiviin ioninvaihtimiin, sekä niiden eluoitumista adsorbentistaan. Kelatoivat ioninvaihtimet sitovat metalli-ioneja tehokkaasti ligandiensa monihampaisuudesta johtuen. Metallien tarttuminen kelatoivaan ioninvaihtimeen ei kuitenkaan ole yksiselitteistä, vaan siihen vaikuttaa muun muassa pH yhdessä monen muun tekijän kanssa. Ioninvaihtimien selektiivisyyttä tarkastellaan työssä lähinnä kovien ja pehmeiden happojen ja emästen HSAB -teorian näkökulmasta. Regeneroinnilla ioninvaihdin saadaan jälleen alkuperäiseen muotoonsa, minkä jälkeen se voidaan käyttää uudelleen. Yleensä regenerointi suoritetaan kemiallisesti. Tässä työssä ioninvaihtimien regenerointia ja kohdemetallin eluointia tarkastellaan paitsi teoriassa, myös kokeellisessa osuudessa. Kokeellisessa osuudessa tutkitaan kuparin (Cu2+) eluoitumista kelatoivasta Dowex M-4195 kationinvaihtohartsista. Kokeissa hartsi ladattiin kuparilla erillisessä panoksessa kuparin ollessa syöttöliuoksessa kuparisulfaattina. Eluointiliuoksina käytettiin 2 ja 5 molaarista rikkihappoa, sekä 2 molaarista ammoniumhydroksidia. Eluointi suoritettiin panostoimisena kolonniajona ja eluaatista otetut näytteet analysoitiin atomiadsorptiospektrofotometrillä. Analyysitulokset esitetään läpäisykäyrinä, joiden perusteella 2M ammoniumhydroksidi on kolmesta tutkitusta eluentista tehokkain eluoimaan kuparia Dowex M-4195 hartsista.

Morfologian hallinta nikkelin sulfidisaostuksessa

Diplomityön tarkoituksena oli tutkia nikkelin sulfidisaostuksessa syntyvien kiteiden morfologiaa ja siihen vaikuttavia parametreja. Syntyvien kiteiden kasvua ja morfologiaa tutkittiin kiteen muodostumisen ja kasvun teorioiden avulla. Saostuksen olosuhteet, kuten lämpötila, paine ja pH vaikuttavat muodostuvien kiteiden morfologiaan. Muilla parametreilla, kuten liuoksen ylikylläisyydellä, epäpuhtauksilla, lisäaineilla, sekoituksella ja reaktioajalla on myös suuri merkitys. Kokeiden avulla haluttiin liuoskoostumuksen, saostusolosuhteiden ja muiden komponenttien vaikutusta nikkelisulfidikiteiden morfologiaan. Kokeissa käytettiin kahta eri sulfidilähdettä: natriumvetysulfidia ja rikkivetyä. Puolipanoskokeissa nikkelipitoisuus oli 1,5 g/l, paine 101,3 kPa ja sekoitusnopeus 650 rpm. Saostuskokeet tehtiin natriumsulfaatti- 5 g/l ja ammoniumsulfaattiliuoksissa 300 g/l. Saostuskokeissa muuttujia olivat saostimen konsentraatio ja määrä, rauta- ja magne-siumepäpuhtaudet, lämpötila ja lisäaineet. Diplomityön kokeellisessa osassa morfologiaa tutkittiin suoraan valomikroskoopin ja pyyhkäisyelektronimikroskoopin (SEM) avulla. Morfologiaa tutkittiin myös epäsuorasti laskeutumisnopeuden, keskimääräisen partikkelikoon, ja ominaispinta-alamittausten avulla. Saostimen pitoisuuden vaikutukset partikkelimuotoon olivat pieniä, mutta vaikutukset ominaispinta-alaan ja partikkelikokoon olivat suuria. Natriumlauryylisul-faatti ja EDTA ohjasivat partikkelien rakennetta levymäisemmäksi, joka johti hitaaseen laskeutumisnopeuteen. Polyakryylihappo lisäaineena muuttaa partikkelien morfologiaa kuutiomaisemmaksi. Flokkulanttien ja raudan morfologiset vaikutukset olivat pieniä. Partikkelikoko ja omaispinta-ala pienenivät selvästi magnesiumpitoisuuden kasvaessa. Lämpötilan kasvattaminen lisäsi epäsäännöllisten kiteiden määrää ja muodostuneet kiteet olivat enemmän neulamaisia.

Effects of intramammary infection on whey proteinograms of sheep during lactation

The study aimed to identify potential biomarkers of mammary gland infection in Santa Inês sheep. Commercial flocks of sheep provided the same hygiene, sanitary, and nutritional management under semi-intensive production systems were monitored during the lactation stage-and assessed 15, 30, 60, and 90 days after delivery (through the end of lactation and weaning). The California Mastitis Test (CMT) was performed on the mammary glands. Milk was collected for bacterial examination and protein analysis. Bacterial culture and biochemical characterization of the samples were performed. Forty-two milk samples from healthy glands (negative CMT and bacterial testing) and 43 milk samples from infected glands (positive CMT and bacterial testing) taken at the predefined time points were assessed. A rennin solution was used to obtain the whey. The proteins analysis was performed using sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), which allowed for the quantification of nine whey proteins produced in healthy glands: serum albumin, lactoferrin, IgA, IgG heavy-chain (IgG HC), IgG light-chain (IgG LC), total IgG (IgG HC + IgG LC), α-lactalbumin, β-lactoglobulin, protein with MW 15.000 Da, protein with MW 29.000 Da and eleven whey proteins secreted by infected glands, including haptoglobin and α-1-acid glycoprotein. A comparison of whey proteins between healthy and infected glands showed increases (P<0.05) in the secreted and total contents of all proteins, except for IgG LC and α-lactoalbumin. The most significant changes were observed in α-1-acid glycoprotein, lactoferrin and haptoglobin, which showed three-, five-, and seven-fold increases in secretion, respectively. This study showed that haptoglobin, α-1-acid glycoprotein, lactoferrin, albumin, and the IgA and IgG immunoglobulins may serve as potential biomarkers for mammary gland infection in sheep.

Potential utilization ways of recovered chemical products from digestate

The study evaluates the potential application of chemical substances, obtained from biogas plants` by-products. Through the anaerobic digestion process with biogas the large amount of digestate is produced. This digestate mainly consists on the organic matter with the high concentration of nutrients such as nitrogen and phosphorus. During ammonia stripping and phosphorus precipitation the products- ammonia water, ammonium sulfate, ammonium nitrate, ferrous phosphate, aluminum phosphate, calcium phosphate and struvite can be recovered. These chemicals have potential application in different industrial sectors. According to Finnish market and chemicals properties, the most perspective industrial applications were determined. Based on the data, obtained through the literature review and market study, the ammonia water was recognized as a most perspective recovered substances. According to interview provided among Finnish companies, ammonia water is used for flue gas treatment in SNCR technology. This application has a large scale in the framework of Finnish industrial sectors. As well nitrogen with phosphorous can be used as a source of nutrients in the biological wastewater treatment plants of paper mills.

Nitrogen doses and weed control via intercropping with gliricidia for corn production

Many studies have demonstrated the beneficial influence of nitrogen doses on corn dry grain yield and green ear yield. Due to a growing concern with environmental degradation, many agricultural practices, adopted in the past, are being reexamined. With regard to weed control, strategies that employ mechanical control, including intercrops, are being the object of renewed interest. The purpose of this study was to evaluate the effects of the application of nitrogen doses (0, 40, 80, and 120 kg N ha-1; as ammonium sulfate) and weed control on the growth, green ear yield, and grain yield of the AG 1051 corn cultivar. A randomized block experimental design with split-plots and nine replications was adopted. In addition to nitrogen rates, the AG 1051 cultivar was submitted to the following treatments, applied to subplots: no weeding, two hoeings (at 20 and 40 days after sowing), and intercropping with gliricídia (Gliricidia sepium). Gliricidia was sowed at corn planting, between the corn rows, using two seedlings per pit, in pits spaced 0.30 m apart. Gliricidia did not provide weed control, and gave plant growth, green ear yield and grain yield values similar to the no weeding treatment. However, regarding the number of mature ears got, intercropping with gliricidia did not differ from the two-hoeing treatment. Weed control did not have an effect on plant height and number of marketable, husked green ears, with the application of 120 kg N ha-1; indicating that nitrogen improved the corn's competitive ability. The two-hoeing treatment provided the best means for total green ears weight, number of marketable husked ears, both unhusked and husked marketable ear weight, grain yield and its components than the other treatments. Nitrogen application increased corn growth, green ear yield, and grain yield, as well as weed green biomass, but reduced the stand and growth of gliricidia.

Respuestas morfológicas y anatómicas de Tessaria absinthioides (Hook. et Arn.) DC. a la salinidad

T. absinthioides, Inuleae, Compositae, is a weedy species that is spreading in the irrigation area of the Colorado River, Argentina. This species can be found in normal and saline soils. Morphological and anatomical variables were measured with two salts, sodium chloride and sodium sulfate, with three levels of osmotic potential -0.4, -0.8 and -1.5 MPa, in hydroponic culture, using Hoagland solution as the cultivation media. The total diameter of the roots of plants growing in Na2SO4 and NaCl increased when the osmotic potential was -0.4 MPa. In plants growing in NaCl this may have resulted from the increase in the size of the cortical cells and in plants growing in Na2SO4, the diameter increased may be due to an increase in the cambial activity. The number and length of shoot internodes decreased with increasing salinity, even though this was not statistically significant. In comparison to the control, the total diameter of the shoot increased at -0.4 MPa and decreased with the reduction of the osmotic potential. In comparison to the control, the length of the leaves decreased at -0.4 MPa and the leaves width increased at the same concentration. The palisade parenchyma appeared less developed in saline conditions. In comparison to the control, the number of hairs increased at -0.4 MPa. T. absinthioides acts as a semihalophytic species, according to the salt ranks it tolerates. The mechanisms of adaptation to saline conditions are succulence in root and stunted growth if the salt in the media is NaCl, and the production of haloxeromorphic characters if the salt in the media is Na2 SO4

Purification and characterisation of a lectin from the red marine alga Pterocladiella capillacea (S.G. Gmel.) Santel. & Hommers.

A lectin present in the marine red alga Pterocladiella capillacea was purified and characterised by extraction of soluble proteins (crude extract) in 20 mM Tris-HCl buffer, pH 7.5. Among the analysed erythrocytes (human blood group A, B and O and the animals ox, goat, chicken and rabbit) the lectin agglutinated specifically rabbit erythrocytes. The hemagglutinating activity assay showed that the lectin was not dependent on divalent cations and was shown to be inhibited by the glycoproteins avidin and mucin. The purification procedure was conduced by precipitation of the crude extract with 80% saturation ammonium sulfate (F0/80) followed by affinity chromatography on guar-gum column. The lectin of P. capillacea was purified 14.5 fold and had a recovery of 27.4% of the original total specific activity present in the crude extract. The absence of carbohydrate suggested that the lectin is not a glycoprotein. The molecular mass of P. capillacea lectin, determined by gel filtration, was 5.8 kDa. SDS-PAGE in the presence of ß-mercaptoethanol gave one band, indicating that the native lectin is a monomeric protein. The activation energy of denaturation process (D G') was calculated to be 106.87 kJ . mol-1 at 70 ºC.

Sulfated bromophenols from Osmundaria obtusiloba (C. Agardh) R. E. Norris (Rhodophyta, Ceramiales)

Two new sulfated oligobromophenols from the marine red algae Osmundaria obtusiloba, 4-(1'-potassium sulfate, 2,3-dibromo, 1',4,5-trihydroxybenzyl) - 4''-(1'''-potassium sulfate, 2'',3''-dibromo, 1''',4'',5''-trihydroxybenzyl) sulfate and 1'-(2, 3-dibromo, 4-potassium sulfate, 1', 4, 5-trihydroxybenzyl) - 4''-(1''' potassium sulfate, 2'', 3''-dibromo, 1''', 4'', 5'' trihydroxybenzyl) sulfate, are herein reported. Besides them it was obtained 2, 2', 3, 3'-tetrabromo-4, 4', 5, 5'-tetrahydroxydiphenylmethane, 2, 3-dibromo-p-hydroxybenzyl methyl ether (methyl lanosol), dipotassium 2,3-dibromo-5-hydroxybenzyl 1',4-disulfate, 24-methylenecolest-5-en-3-beta-ol and alpha-D-mannopyranosyl-(1->2')-glycerate (digeneaside). The structures were determined by analysis of the spectroscopic data (IR, NMR and MS) and comparison with the literature. The 13CNMR data for dipotassium 2,3-dibromo-5hydroxybenzyl-1',4-disulfate are described here for the first time. The present study also suggests a mild method to isolate and to purify sulfated compounds.

Copper accumulation in Xanthomonas campestris pv. vesicatoria

A strain of Xanthomonas campestris pv. vesicatoria showing resistance to 1.2 mM cupric sulfate was analyzed by atomic absorption spectroscopy and ESI (electron spectrophotometry imaging). Accumulation of copper was detected in the periphery of the cell membrane region, suggesting that the mechanism of copper resistance is similar to that previously described for Pseudomonas species. The ESI technique was used to detect copper in the membrane region. Copper-resistance in X. campestris pv. vesicatoria 484 is inducible and occurs by accumulation of the metal and not by efflux mechanism as has been suggested. The growth curve also showed that this system is inducible.

Correlation between high molecular weight gluten subunits composition and bread-making quality in Brazilian wheat

Bread-making quality is one of the most important targets in the genetic improvement of wheat. Although extensive analyses of quality traits such as farinography, sodium dodecyl sulfate (SDS) sedimentation, alveography, and baking are made in breeding programs, these analyses require high amounts of seeds which are obtained only in late generations. In this experiment the statistical correlations between the high molecular weight subunit of glutenin and bread-making quality measured by alveograph, farinograph and SDS sedimentation were evaluated. Seventeen wheat genotypes were grown under the same conditions, each producing about 1 kg of seeds for the evaluations. The high molecular weight (HMW) glutenin subunits were analyzed by SDS-PAGE. Statistical correlations were highly significant between HMW glutenin subunits and alveograph and SDS sedimentation. These results indicate the possibility of manipulating major genes for wheat seed quality by coupling traditional breeding with non-destructive single seed analysis. Only half seed is necessary to perform the SDS-PAGE analysis. Therefore, the other half seed can be planted to generate the progeny. Seed yield and SDS sedimentation were statistically correlated, indicating the possibility of simultaneous selection for both traits

Purification of bovine pancreatic glucagon as a by-product of insulin production

A process for purifying bovine pancreatic glucagon as a by-product of insulin production is described. The glucagon-containing supernatant from the alkaline crystallization of insulin was precipitated using ammonium sulfate and isoelectric precipitation. The isoelectric precipitate containing glucagon was then purified by ion-exchange chromatography on Q-Sepharose FF, gel filtration on Sephadex G-25 and ion-exchange chromatography on S-Sepharose FF. A pilot scale test was performed with a recovery of 87.6% and a purification factor of 8.78 for the first chromatographic step, a recovery of 75.1% and a purification factor of 3.90 for the second, and a recovery of 76.2% and a purification factor of 2.36 for the last one. The overall yield was 50%, a purification factor of 80.8 was obtained and the fraction containing active glucagon (suitable for pharmaceutical preparations) was 84% pure as analyzed by HPLC