Controls on 13C and 14C variability in soil CO2

14C dating of groundwater depends on the isotopic composition of both the solid carbonate and the soil CO2 and requires the use of 14C age correction models. To better assess the variability of the 14C activity of soil CO2 (A14Csoil-CO2) and the δ13C of soil CO2 (δ13Csoil-CO2), which are two parameters used in 14C age correction models, we studied the different processes involving carbon isotopes in the soil. The approach used experimental data from two sites in France (Fontainebleau sands and Astian sands) and a steady-state transport model. In most cases, the 14C activity (A14C) of atmospheric CO2 is directly used in the 14C age correction models as the A14Csoil-CO2. However, we demonstrate that since 1950, the evolution of the A14Csoil-CO2 reflects the competition between the fluxes of root-derived CO2 and organic matter-derived CO2. Therefore, the A14Csoil-CO2 must be used to date groundwater that is younger than 60 years old. Moreover, the δ13C of soil CO2 (δ13Csoil-CO2) showed large seasonal variations that must be taken into account in selecting the δ13Csoil-CO2 for 14C age correction models.

Kattilaveden kulkeutuminen höyryyn soodakattilassa

Tämän työn tarkoituksena on selvittää, miten höyryn kosteuden erotus toimii Kemijärven Sellun soodakattilassa. Höyryn kosteuden erotuksen toiminta tarkastetaan määrittämällä höyryn kosteus tulistetussa höyryssä. Höyryyn kulkeutuvan kattilaveden määrä määritettiin käyttäen merkkiaineena natriumia, jota kulkeutuu höyryyn kattilavesipisaroiden sekä ruiskutusveden mukana. Pieniä määriä kulkeutuu myös haihtumalla, mikä on otettu laskuissa huomioon. Kattilaveden ja höyryn natriumpitoisuuksien suhteen perusteella lasketaan kosteusprosentti. Kattilaveden kulkeutuessa höyryyn kulkeutuu veden mukana myös epäpuhtauksia, jotka turbiiniin joutuessaan saattavat aiheuttaa korroosiota sekä kerrostumia turbiinin siivistössä. Kosteuden erotuksen parantamiseksi on esitetty muutosehdotus siten, että nykyinen poimulevyerottimilla toteutettu sekundäärierotus korvattaisiin uudella teräsverkkoerottimella. Tällöin pystyttäisiin poistamaan entistä pienempiä pisaroita ja vähentämään höyryyn kulkeutuvan kattilaveden määrää.

In-line Monitoring of Precipitation Process using Raman Spectroscopy and ATR-FTIR

Polymorfian jatkuva seuranta saostuksessa on hyödyllistä suunnittelun ja kidetuotteen ominaisuuksien sekä kiteytystä seuraavan jatkoprosessoinnin kannalta. Tässä diplomityössä on tutkittu L-glutamiinihapon kahden (- ja ß) polymorfimuodon liukoisuuden riippuvuutta pH:sta ja lämpötilasta.Tulokseksi saatiin, että kummankin polymorfin liukoisuus kasvoi sekä pH:ta ettälämpötilaa kasvatettaessa. ¿¿muodon liukoisuus oli korkeampi kuin ß-muodon liukoisuus valituilla pH-arvoilla eri lämpötiloissa. Lisäksi seurattiin puolipanostoimisen saostuksen aikana 1-litraisella laboratoriokiteyttimellä muodostuvan kiteisen polymorfiseoksen koostumusta hyödyntäen in-line Raman-spektroskopiaa. Myös liuoksen pH-muutosta seurattiin sekä liuoksen koostumusta ATR FTIR-spektroskopian (Attenuated Total Reflection Fourier Transform Infrared Spectrometer) avulla. Tutkittavina muuttujina olivat mm. sekoitusintensiteetti, sekoitintyyppi, reaktanttien (natriumglutamaatti ja rikkihappo) konsentraatiot sekä syötetyn rikkihapon syöttökohta kiteyttimessä. Työhön sisältyi 36 koetta ja osa kokeista toistettiin tulosten oikeellisuuden tarkistamiseksi. Inline-mittaustulosten verifioimiseksi kidenäytteet analysoitiin myös käyttämällä konfokaali Raman-mikroskooppia. Kidemorfologiaa tutkittiin SEM-kuvien (Scanning Eletronic Microscope) avulla. Työ osoitti, että Raman-spektroskopia on joustava ja luotettava menetelmä saostusprosessin jatkuvaan seurantaan L-glutamiinihapolla. Alhaiset lähtöainepitoisuudet tuottivat pääasiassa ¿¿muotoa, kun taas alhainen sekoitusteho edisti ß-muodon muodostumista. Syöttökohta vaikutti merkittävästi polymorfiaan. Kun rikkihapon syöttökohta oli epäideaalisesti sekoitetulla vyöhykkeellä, nousi ylikylläisyystaso korkeaksi ja päätuote oli tällöin ß-muotoa. 6-lapainen vinolapaturbiini (nousukulma 45o) ja 6-lapainen levyturbiini eivät merkittävästi poikenneet toisistaan muodostuvien polymorfien osalta.

High-performance liquid chromatography of the renal blood flow marker p-aminohippuric acid (PAH) and its metabolite N-acetyl PAH improves PAH clearance measurements.

PAH (N-(4-aminobenzoyl)glycin) clearance measurements have been used for 50 years in clinical research for the determination of renal plasma flow. The quantitation of PAH in plasma or urine is generally performed by colorimetric method after diazotation reaction but the measurements must be corrected for the unspecific residual response observed in blank plasma. We have developed a HPLC method to specifically determine PAH and its metabolite NAc-PAH using a gradient elution ion-pair reversed-phase chromatography with UV detection at 273 and 265 nm, respectively. The separations were performed at room temperature on a ChromCart (125 mmx4 mm I.D.) Nucleosil 100-5 microm C18AB cartridge column, using a gradient elution of MeOH-buffer pH 3.9 1:99-->15:85 over 15 min. The pH 3.9 buffered aqueous solution consisted in a mixture of 375 ml sodium citrate-citric acid solution (21.01 g citric acid and 8.0 g NaOH per liter), added up with 2.7 ml H3PO4 85%, 1.0 g of sodium heptanesulfonate and completed ad 1000 ml with ultrapure water. The N-acetyltransferase activity does not seem to notably affect PAH clearances, although NAc-PAH represents 10.2+/-2.7% of PAH excreted unchanged in 12 healthy subjects. The performance of the HPLC and the colorimetric method have been compared using urine and plasma samples collected from healthy volunteers. Good correlations (r=0.94 and 0.97, for plasma and urine, respectively) are found between the results obtained with both techniques. However, the colorimetric method gives higher concentrations of PAH in urine and lower concentrations in plasma than those determined by HPLC. Hence, both renal (ClR) and systemic (Cls) clearances are systematically higher (35.1 and 17.8%, respectively) with the colorimetric method. The fraction of PAH excreted by the kidney ClR/ClS calculated from HPLC data (n=143) is, as expected, always <1 (mean=0.73+/-0.11), whereas the colorimetric method gives a mean extraction ratio of 0.87+/-0.13 implying some unphysiological values (>1). In conclusion, HPLC not only enables the simultaneous quantitation of PAH and NAc-PAH, but may also provide more accurate and precise PAH clearance measurements.

A prospective, randomized, and controlled study of fluid management in children with severe head injury: lactated Ringer's solution versus hypertonic saline.

OBJECTIVES: Resuscitation in severe head injury may be detrimental when given with hypotonic fluids. We evaluated the effects of lactated Ringer's solution (sodium 131 mmol/L, 277 mOsm/L) compared with hypertonic saline (sodium 268 mmol/L, 598 mOsm/L) in severely head-injured children over the first 3 days after injury. DESIGN: An open, randomized, and prospective study. SETTING: A 16-bed pediatric intensive care unit (ICU) (level III) at a university children's hospital. PATIENTS: A total of 35 consecutive children with head injury. INTERVENTIONS: Thirty-two children with Glasgow Coma Scores of <8 were randomly assigned to receive either lactated Ringer's solution (group 1) or hypertonic saline (group 2). Routine care was standardized, and included the following: head positioning at 30 degrees; normothermia (96.8 degrees to 98.6 degrees F [36 degrees to 37 degrees C]); analgesia and sedation with morphine (10 to 30 microg/kg/hr), midazolam (0.2 to 0.3 mg/kg/hr), and phenobarbital; volume-controlled ventilation (PaCO2 of 26.3 to 30 torr [3.5 to 4 kPa]); and optimal oxygenation (PaO2 of 90 to 105 torr [12 to 14 kPa], oxygen saturation of >92%, and hematocrit of >0.30). MEASUREMENTS AND MAIN RESULTS: Mean arterial pressure and intracranial pressure (ICP) were monitored continuously and documented hourly and at every intervention. The means of every 4-hr period were calculated and serum sodium concentrations were measured at the same time. An ICP of 15 mm Hg was treated with a predefined sequence of interventions, and complications were documented. There was no difference with respect to age, male/female ratio, or initial Glasgow Coma Score. In both groups, there was an inverse correlation between serum sodium concentration and ICP (group 1: r = -.13, r2 = .02, p < .03; group 2: r = -.29, r2 = .08, p < .001) that disappeared in group 1 and increased in group 2 (group 1: r = -.08, r2 = .01, NS; group 2: r = -.35, r2 =.12, p < .001). Correlation between serum sodium concentration and cerebral perfusion pressure (CPP) became significant in group 2 after 8 hrs of treatment (r = .2, r2 = .04, p = .002). Over time, ICP and CPP did not significantly differ between the groups. However, to keep ICP at <15 mm Hg, group 2 patients required significantly fewer interventions (p < .02). Group 1 patients received less sodium (8.0 +/- 4.5 vs. 11.5 +/- 5.0 mmol/kg/day, p = .05) and more fluid on day 1 (2850 +/- 1480 vs. 2180 +/- 770 mL/m2, p = .05). They also had a higher frequency of acute respiratory distress syndrome (four vs. 0 patients, p = .1) and more than two complications (six vs. 1 patient, p = .09). Group 2 patients had significantly shorter ICU stay times (11.6 +/- 6.1 vs. 8.0 +/- 2.4 days; p = .04) and shorter mechanical ventilation times (9.5 +/- 6.0 vs. 6.9 +/- 2.2 days; p = .1). The survival rate and duration of hospital stay were similar in both groups. CONCLUSIONS: Treatment of severe head injury with hypertonic saline is superior to that treatment with lactated Ringer's solution. An increase in serum sodium concentrations significantly correlates with lower ICP and higher CPP. Children treated with hypertonic saline require fewer interventions, have fewer complications, and stay a shorter time in the ICU.

Micromorphological characterization and lithification of microbial mats from the Ebro Delta (Spain)

The structural organization of microbial mats from the Ebro Delta (Spain) and their accretion and partial lithification processes were explored using scanning electron microscopy in back-scattered electron mode and low-temperature scanning electron microscopy. Two differentiated zones were distinguished in a transverse section of a fragment taken from the mat at a depth of 2.5 mm. The first consisted of an upper layer in which the dominant microorganisms, Microcoleus spp., actively grew in an embedded slack matrix of exopolysaccharides. Microcoleus filaments were oriented parallel to the surface and to each other, with filaments below arranged perpendicularly to one another but without crossing. Most of the minerals present were allochthonous grains of calcium phosphate biocorroded by cyanobacteria. The second zone was below a depth of 1 mm and made up of accretion layers with large deposits of calcium carbonate and smaller amounts of calcium phosphate of biological origin. The predominance of a particular type of mineral precipitation with a characteristic external shape and/or texture within a zone, e.g., sponge-like deposits of calcium phosphate, appears to depend on the taxa of the prevailing microorganisms

Nitrogen Oxides Reduction Possibilities at Pulp Mill and Power Plant

Tutkimuksen tarkoituksena oli selvittää typenoksidien vähennysmahdollisuudet Stora Enson Varkauden tehtaiden sellutehtaalla ja voimalaitoksella. Tutkimuksessa käsiteltiin tehdasalueen suurimpia typenoksidien päästölähteitä: soodakattilaa, meesauunia, kuorikattilaa, öljykattilaa ja muovi-alumiinijakeen kaasutuslaitosta. Tutkimuksessa selvitettiin typenoksidipäästöjen syntymekanismit ja erilaisiin polttotekniikoihin soveltuvat typenoksidien vähennystekniikat. Varkauden tehtaiden typenoksidien vuosipäästö vuonna 2001 oli 836 tonnia. Kansallinen lainsäädäntö, kansainväliset sopimukset sekä paras käytettävissä oleva tekniikka (BAT) huomioiden selvitettiin kuhunkin kohteeseen parhaiten soveltuvat ratkaisut. Tutkimuksen perusteella laadittiin toimenpideohjelma, joka määrittelee suositeltavan toteutusjärjestyksen typenoksidien vähennystoimenpiteille. Toimenpideohjelman tärkeimpinä kriteereinä pidettiin vuonna 2004 tulevan uuden ympäristöluvan arvioituja luparajoja sekä toimenpiteiden kustannustehokkuutta. Toteutusjärjestyksessä ensimmäiseksi valittiin koeajojakson järjestäminen ajon optimoimiseksi kiertopetikattilalla ja toiseksi meesauunin ajon optimointi jatkuvatoimisen NOx-analysaattorin avulla. Seuraaviksi toimenpiteiksi ehdotettiin vertikaali-ilmajärjestelmän käyttöönottoa soodakattilalla sekä SNCR-järjestelmän asennusta kuorikattilalle. Saavutettava NOx-vähennys tulisi olemaan 10 – 45 % ja hinta 30 – 3573 EUR vähennettyä NOx-tonnia kohti. Tutkimuksen osana Ilmatieteen laitoksella teetetyn typenoksidien leviämisselvityksen mukaan Stora Enson tehtaiden NOx-päästöjen vaikutus Varkauden ilmanlaatuun on hyvin pieni. Suurin osa NOx-päästöistä aiheutuu liikenteestä.

Associations of Urinary Uromodulin with Clinical Characteristics and Markers of Tubular Function in the General Population.

BACKGROUND AND OBJECTIVES: Allelic variants in UMOD, the gene coding for uromodulin, are associated with rare tubulointerstitial kidney disorders and risk of CKD and hypertension in the general population. The factors associated with uromodulin excretion in the normal population remain largely unknown, and were therefore explored in this study. DESIGN, SETTING, PARTICIPANTS, & MEASUREMENTS: Urinary uromodulin excretion was measured using a validated ELISA in two population-based cohorts that included more than 6500 individuals. The Swiss Kidney Project on Genes in Hypertension study (SKIPOGH) included 817 adults (mean age±SD, 45±17 years) who underwent renal ultrasonography and performed a 24-hour urine collection. The Cohorte Lausannoise study included 5706 adults (mean age, 53±11 years) with fresh spot morning urine samples. We calculated eGFRs using the CKD-Epidemiology Collaboration formula and by 24-hour creatinine clearance. RESULTS: In both studies, positive associations were found between uromodulin and urinary sodium, chloride, and potassium excretion and osmolality. In SKIPOGH, 24-hour uromodulin excretion (median, 41 [interquartile range, 29-57] mg/24 h) was positively associated with kidney length and volume and with creatinine excretion and urine volume. It was negatively associated with age and diabetes. Both spot uromodulin concentration and 24-hour uromodulin excretion were linearly and positively associated (multivariate analyses) with eGFR<90 ml/min per 1.73 m(2). CONCLUSION: Age, creatinine excretion, diabetes, and urinary volume are independent clinical correlates of urinary uromodulin excretion. The associations of uromodulin excretion with markers of tubular functions and kidney dimensions suggest that it may reflect tubule activity in the general population.

Simulação do processo Solvay no laboratório didático

The Solvay Process is an important route for the industrial preparation of sodium carbonate from brine and CO2. However, experiments illustrating such process are performed only in a few chemistry courses, mainly because of the difficulties to precipitate out the intermediate product NaHCO3 within the 3 or 4 hours generally available for laboratory classes. In this article we describe a method that properly simulates the Solvay process using glass apparatus that can be found in any chemistry laboratory. The good yields and purity attainable, associated with the short time (~3 hours) required to get the sodium bicarbonate, account for the suitability of our method for chemistry or chemical engineering undergraduate students laboratory classes.

Metil coenzima M redutase (MCR) e o fator 430 (F430)

This review presents studies on methyl coenzyme M reductase, the biological system Factor 430 (F430) and the use of nickel(II) complexes as structural and functional models. The ability of F430 and nickel(II) macrocycle complexes to mediate the reductive dehalogenation of cyclohexyl halogens and the CH3-S bond cleavage of methyl CoM (by sodium borohydride and some intermediate species) proposed for the catalytic cycle of the biological system F430 was reviewed. The importance of the structure of the nickel complexes and the condition of the catalytic reduction reaction are also discussed.

Extração líquido-líquido de urânio(VI) do colofanito de itataia (Santa Quitéria, Ceará) por extratantes orgânicos em presença de ácido fosfórico

This work describes the liquid-liquid extraction of uranium after digestion of colofanite (a fluoroapatite) from Itataia with sulfuric acid. The experiments were run at room temperature in one stage. Among the solutions tested the highest distribution coefficient (D > 60) was found for 40%vol. DEHPA (di(2-ethyl-hexyl)phosphoric acid) + 20% vol. TOPO (trioctylphosphine oxide) in kerosene. Thorium in the raffinate was quantitatively extracted by TOPO (0.1% vol.) in cyclohexane. Uranium stripping and separation from iron was possible using 1.5 mol L-1 ammonium or sodium carbonate (room temperature, one stage). However, pH control is essential for a good separation.

Reaction mixtures formed by nitrite and selected sulfa-drugs showed mutagenicity in acidic medium

Nitrite, which is present in preserved meat and can be produced in the oral cavity by reduction of nitrate taken from vegetables, could react in stomach with nitrosatable drugs, giving genotoxic-carcinogenic N-nitroso compounds (NOC). The mutagenicity of reaction mixtures formed by sodium nitrite and selected sulfa-drugs (sulfathiazole, HST; phtalylsulfathiazole, PhST; complex Co(II)-sulfathiazole, Co(II)-ST) in acidic medium was evaluated using the Salmonella typhimurium reverse mutation assay (Ames test), with TA98 and TA 100 strains. The reactions were carried out at room temperature, with a mole ratio [nitrite]/[sulfa-drug] > 1. The three reaction mixtures showed mutagenic effects in the considered range.

Preparação e utilização de uma argila esmectítica organofílica como adsorvente de fenol

The main goal of this research was the preparation and use of a organophilic smectitic clay able to promoting the adsorption of phenol. In this work was used a natural clay called Chocolate, from Campina Grande - PB (Brazil). The natural clay was treated with a solution of sodium carbonate. After this the sodium clay was treated with quaternary ammonium salt. The adsorptive study was conducted by different values of pH and temperature. The results showed a better performance in adsorptive at pH 7 and temperature 30 ºC, with removal of more than 80% of phenol.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

Resorcinol-formaldehyde (RF) organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C) molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.