Salinidade em petróleo bruto: otimização de metodologia e proposta de um novo método para extração de sais em petróleo

The quantity of salts in the crude oils depends on the origin and of the wells production and these salts cause several problems during the transport and the process of refine as corrosions, incrustations and deactivation of the employed catalysts in the refineries. In this study were implemented changes for improvements in the execution of ASTM D 6470 method and has also developed a new methodology of extraction system of salts using process of mechanical agitation without heating. The results of the optimization produce larger efficiency and safety to the process compared to the traditional ASTM method.

A Equação-Mestra: atingindo o equilíbrio

In the last years, a great interest in nonequilibrium systems has been witnessed. Although the Master Equations are one of the most common methods used to describe these systems, the literature about these equations is not straightforward due to the mathematical framework used in their derivations. The goals of this work are to present the physical concepts behind the Master Equations development and to discuss their basic proprieties via a matrix approach. It is also shown how the Master Equations can be used to model typical nonequilibrium processes like multi-wells chemical reactions and radiation absorption processes.

Occurrence of agrochemicals in surface waters of shallow soils and steep slopes cropped to tobacco

Tobacco cultivation in shallow soils and steep landscape under intense use of agrochemicals contributes to environment degradation. In this study, we assessed the concentration of agrochemicals in draw wells used for human consumption and a creek in a small catchment predominantly cropped to tobacco. Chlorpyrifos, flumetralin, and iprodione were determined by gas chromatography with electron capture detection, while imidalcloprid, atrazine, simazine, and clomazone were quantified by high-performance liquid chromatography with UV detection. Considering all sampling sites, all agrochemicals were detected at least once, except for flumetralin. The occurrence of agrochemicals in tobacco crops is a consequence of their fast transfer to surface water.

Métodos para análises de HPA e BTEX em águas subterrâneas de postos de revenda de combustíveis: um estudo de caso em Campo Grande, MS, Brasil

Two methods using headspace solid-phase microextraction and gas chromatography - mass spectrometry were developed for the determination of polycyclic aromatic hydrocarbons (PAH) and BTEX. Best results were obtained using DVB/CAR/PDMS fiber, with 10 min extraction at 25 °C and 0.15 min desorption at 260 °C (BTEX), and PDMS/DVB fiber, with 60 min extraction at 90 °C, 10% NaCl and 5 min desorption at 270 °C (PAH). LOD intervals were 3x10-2 - 5x10-2 µg L-1 (BTEX) and 1.6x10-3 - 1.4 µg L-1 (PAH). The methods were applied to forty-five groundwater samples from monitoring wells of gas stations and only benzene level exceeded the limit established by Brazilian regulations.

PCA: uma ferramenta para identificação de traçadores químicos para água de formação e água de injeção associadas à produção de petróleo

This study describes the use of Principal Component Analysis to evaluate the chemical composition of water produced from eight oil wells in three different production areas. A total of 609 samples of produced water, and a reference sample of seawater, were characterized according to their levels of salinity, calcium, magnesium, strontium, barium and sulphate (mg L-1) contents, and analyzed by using PCA with autoscaled data. The method allowed the identification of variables salinity, calcium and strontium as tracers for formation water, and variables magnesium and sulphate as tracers for seawater.

Metaanin muodostumisen mallintaminen kaatopaikalla

Methane-rich landfill gas is generated when biodegradable organic wastes disposed of in landfills decompose under anaerobic conditions. Methane is a significant greenhouse gas, and landfills are its major source in Finland. Methane production in landfill depends on many factors such as the composition of waste and landfill conditions, and it can vary a lot temporally and spatially. Methane generation from waste can be estimated with various models. In this thesis three spreadsheet applications, a reaction equation and a triangular model for estimating the gas generation were introduced. The spreadsheet models introduced are IPCC Waste Model (2006), Metaanilaskentamalli by Jouko Petäjä of Finnish Environment Institute and LandGEM (3.02) of U.S. Environmental Protection Agency. All these are based on the first order decay (FOD) method. Gas recovery methods and gas emission measurements were also examined. Vertical wells and horizontal trenches are the most commonly used gas collection systems. Emission measurements chamber method, tracer method, soil core and isotope measurements, micrometeorological mass-balance and eddy covariance methods and gas measuring FID-technology were discussed. Methane production at Ämmässuo landfill of HSY Helsinki Region Environmental Services Authority was estimated with methane generation models and the results were compared with the volumes of collected gas. All spreadsheet models underestimated the methane generation at some point. LandGEM with default parameters and Metaanilaskentamalli with modified parameters corresponded best with the gas recovery numbers. Reason for the differences between evaluated and collected volumes could be e.g. that the parameter values of the degradable organic carbon (DOC) and the fraction of decomposable degradable organic carbon (DOCf) do not represent the real values well enough. Notable uncertainty is associated with the modelling results and model parameters. However, no simple explanation for the discovered differences can be given within this thesis.

Assessment of hydrochemical quality of ground water under some urban areas within sana'a secreteriat

Groundwater from nine wells of three different districts, located at Sana'a secretariat was analyzed for hydrochemical quality assessment. Measurements of water quality parameters including pH, EC, CO3(2-), HCO3-, Cl-, NO3-, SO4(2-), Ca2+, Mg2+, Fe3+, K+, and Na+ were carried out . Classification of the groundwater samples according to Cl, SO4(2-), CO3(2-) and HCO3-, hardness (H), total dissolved solids (TDS), base-exchange, and meteoric genesis was demonstrated. Suitability of ground water samples for irrigation and industrial uses according to sodium adsorption ration (SAR), ratio of dissolved sodium (RDS), residual sodium carbonate (RSC) and saturation index (SI) was also investigated. The results of this study showed that almost all ground water samples were of good quality that makes them suitable for drinking and domestic uses. Results also indicated that even though some of the ground water samples were suitable for irrigation purposes, almost all of them were found not be good for industrial uses. Despite all drawbacks of the sewerage system built around Sana'a secretariat at the beginning of the first decade of the third millennium, the results of this study indicate that there is scope of significant improvement in Sana'a secretariat ground water quality.

Mikkelin Pursialan pohjavesialueen haitta-aineet

Mikkelin talousvedestä kahden kolmasosan tullessa Pursialan pohjavesialueelta on alueen suojeleminen tärkeää. Pohjaveden laatua uhkaavat etenkin alueella sattuneet pohjavedenpilaantumistapaukset. Merkittävimmät pohjaveden pilaantumistapaukset ovat VAPO Oy:n sahan aiheuttama pohjaveden pilaantuminen kloorifenoleilla (CP) ja VR:n ratapölkkykyllästämön aiheuttama pohjaveden pilaantuminen kreosoottiöljyllä sekä Rinnekadun Nesteen aiheuttama pohjaveden pilaantuminen MTBE:llä. Alueella on tehty tutkimuksia ja kunnostuksia pilaantumiin liittyen, mutta näiden tuloksia ei ole aikaisemmin koottu yhteen. Tämän työn tavoitteena oli koota tulokset samaan aineistoon. Työssä keskityttiin kloorifenolien leviämisen tarkasteluun sen Pursialan pohjavedenottamolle muodostaman suurimman uhan vuoksi. Kallioperätietojen, maanpintatietojen ja näytetietojen pohjalta laadittiin myös pienoismalli CP-pilaantuman leviämisen kokonaiskuvan hahmottamiseksi. Työn tavoitteena oli lisäksi tehdä riskitarkastelua CP-pilaantumaan liittyen ja etsiä keinoja hallita havaittuja riskejä. Riskinhallintaan liittyen työssä tutkittiin kloorifenoleilla pilaantuneen alueen maaperä- ja kalliotietoja sekä pohjaveden laatutietoja. Pursialan pohjavedessä on runsaasti rautaa ja mangaania sekä aggressiivista hiilihappoa. Pohjaveden pH on alueella noin 6,5, lämpötila noin 7,5 ºC ja happipitoisuus noin 0,7 mg/l. Pursialan kaupunginalueen kallioperässä on havaittavissa VAPO Oy:n sahalta vedenottamolle etenevä kalliopainanne, jota pitkin CP etenee. Alueen kallioperä on kiillegneissiä, jossa on pohjois–etelä-suuntaista rakoilua. Maaperätuloksien perusteella on havaittavissa vettä hyvin johtavien maakerrosten jatkuminen koko vedenottamon ja sahan välisen matkan, mikä tarkoittaa, että CP-pitoisella pohjavedellä voi olla aiemmin oletettua nopeampikin yhteys sahalta vedenottamolle. Suurin CP-pitoisuus noin 100 000 µg/l on mitattu KY-5-altaan kohdalle asennetun M14-pohjavesiputken pohjasta. Talousvesiasetuksen raja-arvo CP:lle on 10 µg/l. Sahan ja vedenottamon puolivälissä on havaittu yli 10 000 µg/l meneviä CP-pitoisuuksia. Suurin vedenottamon kaivoista (kaivo 10) mitattu pitoisuus on 149 µg/l. Jakotukilta raakavedestä otetuissa näytteissä tai talousvedessä ei ole kuitenkaan havaittu talousvesiasetuksen ylittäviä CP-pitoisuuksia. Pienoismallin perusteella CP sijaitsee sahan alueella lähellä kallionpintaa ja hajaantuu koko pohjavesipatjaan vedenottamolle päin mentäessä. CP-mittaustuloksissa on havaittavissa pulssimaisuutta. Tämä johtuu todennäköisesti Saimaan pinnan vaihtelun seurauksena muuttuvasta rantaimeytyneen pohjaveden määrästä. Saimaan pinnan nousu näyttäisi tuloksien perusteella nostavan CP-pitoisuuksia saha-alueella ja laskevan lähellä vedenottamoa. Pohjaveden pintatietojen perusteella tehdyn tarkastelun mukaan pohjavesi voi kulkeutua sahalta vedenottamolle parhaimmillaan noin vuodessa. Työssä arvioitiin KY-5–liuoksen vuosittaiseksi käyttömääräksi noin 648–970 m3. Allassakkaa arvioitiin syntyneen yhteensä noin 10–31 m3. Pohjaveteen arvioitiin joutuneen toiminnan aikana yhteensä noin 3 000–4 000 kg CP:tä. Kloorifenolit esiintyvät pohjavedessä lähes täysin kloorifenolaatteina. Kloorifenolien hajoaminen ja muuntuminen pohjavedessä on epätodennäköistä. Käsitteellisen mallin mukaan kloorifenolipilaantuman suurimmat riskit aiheutuvat kloorifenolien mahdollisuudesta pilata Pursialan vedenottamon talousvesi. Tällä hetkellä riskejä hallitaan kloorifenolien leviämisen tarkkailulla, sahan ja vedenottamon puolivälissä sijaitsevalla koepumppauksella sekä varautumalla aktiivihiilijauheen syöttöön talousvesiprosessiin. Koepumppauksen avulla on saatu ylös tällä hetkellä noin 69 kg kloorifenoleita. Tutkimuksen perusteella suositeltavimmat riskinhallintatoimet tulevaisuudessa ovat sahalla sijaitseva kunnostuspumppaus, sahan ja vedenottamon väliin sijoittuva suojapumppaus- ja vesiverhoyhdistelmä sekä sahan rannan kautta tapahtuvan rantaimeytymisen estäminen.

Estimation of alluvial recharge in the semiarid

In areas where there is irrigated agriculture, the recuperation of water reserves in alluvial aquifers may occur preferentially due to precipitation. Recharging can be evaluated from variation information of water depth measured in piezometers or observation wells. Thus, the aim of this research is to study the recharge in the alluvial aquifer formed by the Mimoso temporary stream in the semiarid region of Pernambuco (PE), Brazil, using the method of the fluctuation of the water level. This system is typical on the Brazilian Northeast semiarid region, using groundwater for domestic supply and for irrigation on small scale agriculture. Monthly potentiometric levels and rainfall data were used. The selected period for the study, from January 2002 to October 2009, involved extreme events of flooding and droughts as well as regular years, providing a better understanding of the behavior of the alluvial recharge. It was found that the system responds significantly to precipitation events. It was also observed that even with different soil textures in the study area, recharge factors were not significantly different. The study provided a better understanding of the behavior of aquifer recharge and its relationship with the soil and the rainfall events in the region.

Maailmanhistoria - yksityistetty!

Nimekkeen selitys: Historioitsija René Groussettin ja kirjailijoiden H. G. Wellsin ja Octavio Pazin käsitykset maailmanhistoriasta.

Herbicide detection in groundwater in Córrego Rico-SP watershed

Due to the large amount of pesticides applied in agriculture, mainly herbicides, there is a growing concern about a possible environmental contamination with these products, including water bodies. Given the above, the aim of the present work was to detect and quantify herbicides through multiresidue analysis in water samples collected in semi-artesian wells and springs in a rural area of the city of Jaboticabal (SP). Samples were collected from 32 wells and 13 water springs, in three different seasons: October 2010, February 2011 and May 2011. Additionally, samples at a residence in the urban area were also collected. Analysis using high performance liquid chromatography coupled to mass spectrometry was performed and herbicides ametryn, amicarbazone, clomazone, diclosulan, diuron, hexazinone, imazapic, imazapyr, isoxaflutole, S-metolachlor, sulfentrazone, sulfometuron-methyl, and tebuthiuron were evaluated. In semi-artesian wells, an incresed quantity of herbicides was found in comparison with the water springs. Among the tested herbicides, hexazinone, imazapyr and sulfentrazone were detected in measurable amounts in accordance with the analytical method applied, while clomazone was the most common herbicide being detected in more than 60% of the samples. Ametryn, diuron and amicarbazone herbicides were also detected. Diclosulan, imazapic, isoxaflutole, S-metolachlor, sulfometuron-methyl, and tebuthiuron were not detected in any sample. Inappropriate use of these products without prior knowledge of the behavior of the soil can lead to groundwaters and water springs contamination, thus an ongoing monitoring of this resource becomes very important.

Havumetsälintuja Pohjois-Amerikasta

Kirjallisuusarvostelu

Kaatopaikkakaasujen käsittelyn kehittäminen Korvenmäen kaatopaikalla

Työssä tutkittiin Salossa sijaitsevan Korvenmäen kaatopaikan kaasunkeräysjärjestelmää. Tavoitteena oli selvittää kaatopaikkakaasun talteenoton merkittävimmät haasteet, löytää ratkaisuja ongelmiin ja hajuhaittojen vähentämiseen sekä arvioida keräysjärjestelmän parannusten ja kaatopaikalle tulevan pintarakenteen vaikutus talteenottoon ja hajuhaittoihin. Korvenmäen kaatopaikalla on käytössä vaakakeräysjärjestelmä, jonka merkittävimpiä ongelmia ovat olleet kaatopaikkakaasun matala talteenottoaste, happipitoisuuden nousu, järjestelmän hankala säädettävyys sekä kaatopaikalla ja ympäristössä havaitut hajuhaitat. Muodostuvan ja karkaavan kaatopaikkakaasun määrää arvioitiin Jouko Petäjän metaanilaskentamallin avulla. Tulosten perusteella kaasua muodostuu runsaasti, mutta suurin osa siitä pääsee karkaamaan ympäristöön, sillä arvioitu kaatopaikkakaasun talteenottoaste on tällä hetkellä vain 11 %. Kaasujen käsittelykäytäntöjä suomalaisilla kaatopaikoilla selvitettiin kyselytutkimuksella. Tutkimuksen mukaan kaasunkeräyksen ongelmat ja hajuhaitat ovat yleisiä, mutta erilaisilla toimenpiteillä niitä voidaan huomattavasti vähentää. Korvenmäelle suositeltavia kehitystoimia ovat kaasulinjoihin yhdistettyjen suotoveden keräys- ja tarkkailukaivojen tiivistäminen, vanhojen vaakalinjojen kunnon tarkistus ja korjaus sekä pystykaivojen asentaminen kaasunkeräyksen tehostamiseksi. Pintarakenne tulee valmistuttuaan vähentämään karkaavan kaasun ja kaasulinjoihin imeytyvän ilman määrää. Hajuhaittojen hallinnassa tärkeintä on toimiva kaasunkeräys, mutta lisäksi suositellaan rikkivetyä hapettavien päivittäispeittomateriaalien levittämistä kaatopaikan pinnalle. Kehitystoimenpiteiden myötä kaatopaikkakaasun talteenottoaste tulee paranemaan ja hajuhaitat vähenevät. Kerättävän kaasumäärän kasvaessa mikroturbiinilaitoksen kapasiteettia voidaan lisätä, jotta kaasu saadaan mahdollisimman tehokkaasti hyödynnettyä energiana.

In situ enzyme immunoassay for titration of a Brazilian hepatitis A virus strain (HAF-203)

Hepatitis A virus (HAV) replicates relatively slowly in cell culture without a cytopathic effect, a fact that limits the use of tissue culture assays. The radioimmunofocus assay is the standard method for HAV titration, although it is labor intensive and requires the use of radioisotopes. A simple, rapid and objective infectivity assay based on an in situ enzyme immunoassay (EIA) is described here for a Brazilian cell culture-adapted HAV strain (HAF-203). The assay uses a peroxidase-labeled polyclonal antibody to fixed monolayers as an indicator of infection. EIA may be completed within 7 days using serial 5-fold dilutions of the virus, yielding a titer of 5.024 log 50% tissue culture infective dose (TCID50)/ml for HAF-203. This technique had a detection limit of 1.1 log TCID50/ml and the specificity was demonstrated by detecting no reaction on the columns of uninfected wells. The reproducibility (with intra- and inter-assay coefficients of variation ranging from 1.9 to 3.8% and from 3.5 to 9.9%, respectively) and quantitation of the assay were demonstrated by close agreement in virus infectivity titers among different assays of the same amount of virus and between assays of different amounts of virus. Furthermore, this assay does not require the use of radiolabeled antibodies. We describe here an efficient EIA that is highly reproducible and that could be used to monitor HAV growth in cell culture and to determine the quantity of HAV antigen needed for diagnostic assays. This is the first report of the infectious titer of the Brazilian cell culture-adapted HAV strain (HAF-203).

Analysis of five streptokinase formulations using the euglobulin lysis test and the plasminogen activation assay

Streptokinase, a 47-kDa protein isolated and secreted by most group A, C and G ß-hemolytic streptococci, interacts with and activates human protein plasminogen to form an active complex capable of converting other plasminogen molecules to plasmin. Our objective was to compare five streptokinase formulations commercially available in Brazil in terms of their activity in the in vitro tests of euglobulin clot formation and of the hydrolysis of the plasmin-specific substrate S-2251™. Euglobulin lysis time was determined using a 96-well microtiter plate. Initially, human thrombin (10 IU/ml) and streptokinase were placed in individual wells, clot formation was initiated by the addition of plasma euglobulin, and turbidity was measured at 340 nm every 30 s. In the second assay, plasminogen activation was measured using the plasmin-specific substrate S-2251™. Streptase™ was used as the reference formulation because it presented the strongest fibrinolytic activity in the euglobulin lysis test. The Unitinase™ and Solustrep™ formulations were the weakest, showing about 50% activity compared to the reference formulation. All streptokinases tested activated plasminogen but significant differences were observed. In terms of total S-2251™ activity per vial, Streptase™ (75.7 ± 5.0 units) and Streptonase™ (94.7 ± 4.6 units) had the highest activity, while Unitinase™ (31.0 ± 2.4 units) and Strek™ (32.9 ± 3.3 units) had the weakest activity. Solustrep™ (53.3 ± 2.7 units) presented intermediate activity. The variations among the different formulations for both euglobulin lysis test and chromogenic substrate hydrolysis correlated with the SDS-PAGE densitometric results for the amount of 47-kDa protein. These data show that the commercially available clinical streptokinase formulations vary significantly in their in vitro activity. Whether these differences have clinical implications needs to be investigated.