Growth regime map for liquid-bound granules: further development and experimental validation

An attempt was made to quantify the boundaries and validate the granule growth regime map for liquid-bound granules recently proposed by Iveson and Litster (AlChE J. 44 (1998) 1510). This regime map postulates that the type of granule growth behaviour is a function of only two dimensionless groups: the amount of granule deformation during collision (characterised by a Stokes deformation number, St(def)) and the maximum granule pore saturation, s(max). The results of experiments performed with a range of materials (glass ballotini, iron ore fines, copper chalcopyrite powder and a sodium sulphate and cellulose mixture) using both drum and high shear mixer granulators were examined. The drum granulation results gave good agreement with the proposed regime map. The boundary between crumb and steady growth occurs at St(def) of order 0.1 and the boundary between steady and induction growth occurs at St(def) of order 0.001. The nucleation only boundary occurs at pore saturations that increase from 70% to 80% with decreasing St(def). However, the high shear mixer results all had St(def) numbers which were too large. This is most likely to be because the chopper tip-speed is an over-estimate of the average impact velocity granules experience and possibly also due to the dynamic yield strength of the materials being significantly greater than the yield strengths measured at low strain rates. Hence, the map is only a useful tool for comparing the granulation behaviour of different materials in the same device. Until we have a better understanding of the flow patterns and impact velocities in granulators, it cannot be used to compare different types of equipment. Theoretical considerations also revealed that several of the regime boundaries are also functions of additional parameters not explicitly contained on the map, such as binder viscosity. (C) 2001 Elsevier Science B.V. All rights reserved.

Determination of carbamate and urea pesticide residues in fresh vegetables using microwave-assisted extraction and liquid chromatography

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography– photodiode array (LC–PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250–403 µgkg- 1 in each pesticide. The pesticide residues were extracted using 20mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µgkg- 1 for carbaryl to 12.3 µgkg- 1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds.

Flow injection potentiometric determination of chlorpromazine

New chlorpromazine selective electrodes with a tubular arrangement and no internal reference solution are proposed. Selective membranes are of poly(vinyl chloride) (PVC) with the tetraphenylborate•chlorpromazine (TPB•CPZ) ion-exchanger dissolved in o-nitrophenyl octyl ether (oNPOE). Analytical features of the electrodes were evaluated on a single-channel flow assembly having 500 µl injection volumes and flow-rates of 4.5 ml min−1. For a carrier solution of 3.3×10−3Min sodium sulphate, Nernstian responsewas observed over the concentration range 1.0×10−5 to 1.0×10−2 M. Average slopes were about 59mVdecade−1 and squared correlation coefficients were >0.9984. Slight hiper-Nernstian behaviour was observed in buffer solutions of 4.4 pH; average slopes were of 62.06mVdecade−1. The electrode displayed a good selectivity for CPZ, with respect to, several foreign inorganic and organic species. The selective electrodes were successfully applied to the analysis of pure solutions and pharmaceutical preparations. Proposed method allows the analysis of 84 samples h−1, producing wastewaters of low toxicity. The proposed method offers the advantage of simplicity, accuracy, applicability to coloured and turbid samples, and automation feasibility.

Lime mortars with rice husk ash for ancient masonry

HMC08 - 1st Historical Mortars Conference: Characterization, Diagnosis, Conservation, Repair and Compatibility, LNEC, Lisbon, 24-26 September 2008

Anàlisi dels contaminants orgànics persistents en Citharus linguatula en el litoral català

S’ha estudiat la bioacumulació de contaminants orgànics persistents en el múscul d’una espècie de peix en dos punts del litoral català: al Port de Barcelona i a la costa de Blanes. Citharus linguatula ha estat escollida per les seves característiques d’hàbitats (està més exposada a la contaminació al ser una espècie bentònica). La metodologia emprada consisteix en la homogeneïtzació amb sulfat de sodi i una extracció assistida amb microones amb n-hexà-acetona(1:1 v/v) durant 20 minuts. Els extractes es netegen i es fraccionen amb una columna cromatogràfica d’alúmina que permet la separació dels extractes en dos fraccions: un amb la majoria dels compostos organoclorats (hexaclorbenzè, DDTs, ciclodiens clorats i policlorbifenils) i l’altre amb els isòmers hexaclorciclohexans i els PAHs. Aquestes dos fraccions són posteriorment analitzades en el GC-MS. S’ha pogut corroborar l’elevada presència de PCBs a Barcelona, així com que en aquest punt de mostreig les espècies estan més exposades a la contaminació per organoclorats. S’ha identificat la presència de DDTs en els dos llocs estudiats. Pel que fa als PAHs s’ha pogut observar que a Barcelona també hi ha més presència d’aquests. Cal destacar que la concentració obtinguda dels compostos no es pot donar com a vàlida per l’existència d’indicis d’errors experimentals o d’injecció.

Geochemical and geothermal study of springs in the Ossola-Simplon Region

Geological, hydrogeological and geochemical surveys were carried out in the Piedilago area (Ossola-Simplon region) in order to investigate the geothermal resources present in this area. Following these surface exploration efforts an exploratory geothermal well of 248 m was drilled in 1991. It discharges a thermal water with temperatures up to 43 degrees C and calcium (sodium) sulphate composition with a TDS close to 1350 mg/l. Chemical geothermometers suggest a reservoir temperature close to 45 degrees C indicating that the well virtually produces the pure uncooled thermal water. The Piedilago ex-ample is here considered as the departure point to establish both general criteria for further geothermal investigations in young mountains chains and taking into consideration all the available data on geology and fluid geochemistry of thermal systems in the Ossola-Simplon region, to constrain a geothermal model for the Lower Pennine Zone.

The thermal circuits of the Argentera Massif (western Alps, Italy): An example of low-enthalpy geothermal resources controlled by Neogene alpine tectonics

This work presents geochemistry and structural geology data concerning the low enthalpy geothermal circuits of the Argentera crystalline Massif in northwestern Italian Alps. I n this area some thermal springs (50-60 degreesC), located in the small Bagni di Vinadio village, discharge mixtures made up of a Na-Cl end-member and a Na-SO4 component. The latter is also discharged by the thermal springs of Terme di Valdieri located some kilometres apart within the same tectonic complex. Both end-members share the same meteoric origin and the same reservoir temperature, which is close to 150 degreesC. Explanations are thus required to understand how they reach the surface and how waters of the same origin and circulating in similar rocks can attain such different compositions. Sodium-sulphate waters discharged at both sites, likely represent the common interaction product of meteoric waters with the widespread granitic-migmatitic rocks of the Argentera Massif, whereas Na-CI waters originate through leaching of mineralised cataclastic rocks, which are rich in phyllosilicatic minerals and fluid inclusions, both acting as Cl- sources. Due to the relatively low inferred geothermal gradient of the region, -25C/km, meteoric waters have to descend to depths of 5.5-6 km to attain temperatures of similar to 150 degreesC. These relevant depths can be reached by descending meteoric waters, due to the recent extensional stress field, which allows the development of geothermal circulations at greater depths than in other sectors of the Alps by favouring a greater fractures aperture. The ascent of the thermal waters rakes place along brittle shear zones. In both sites, the thermal waters emerge at the bottoms of the valleys, close to either the lateral termination of a brittle shear zone at Terme di Valdieri, or a step-over between two en-echelon brittle shear zones at Bagni di Vinadio. These observations attest to a strong control operated on the location of outlet regions by both brittle tectonics and the minima in hydraulic potential inside the fractured massif.

Determination of herbicides residues in soil by small scale extraction

Herbicides such as trifluralin, simazine, atrazine, metribuzin and metolachlor are used in Brazilian agriculture. The efficiency of a small scale method for determination of these herbicides and two degradation products (deisopropylatrazine and deethylatrazine) in soil samples was evaluated. The compounds were extracted from soil samples (5 g) with 20 ml of ethyl acetate in a mechanical shaker for 50 min. Following the extraction, the supernatant was dried through anhydrous sodium sulphate, concentrated and analysed by high resolution gas chromatography (HRGC) with thermionic specific detection (TSD). Mean recoveries obtained from soil samples fortified at three different levels ranged from 81 to 115% with relative standard deviation (RSD) values varying from 1.2 to 12.7%. The method detection limits ranged from 0.01 to 0.06 mg kg-1. The methodology was applied using soil samples from farms located near the town of Araraquara, in the State of São Paulo, Brazil.

Crystallization of selected anions and cations from mine waters

The aim of this Master’s thesis was to review some methods that are already being utilized in a field of mine water purification and to find and study possible new methods and chemicals for mine water purification by precipitation. The target was also to list the optimal process conditions for these precipitating chemicals. Separation methods were reviewed for several anions and cations, but being a real topical issue, sulphate removal was selected to be in the main focus. Sulphate salts e.g. Na2SO4 are relatively soluble in water, which makes the separation processes difficult. Eutectic freeze crystallization was studied more closely in laboratory tests for sodium sulphate removal. Gravimetric solubility tests were made for three cases of mixed electrolyte solutions: Na2SO4 – NaOH, BaSO4 – NaOH and Na3PO4 – NaOH. The aim of these experiments was to study the effect of NaOH addition on solubility of the studied salt. These phenomena were however noticed to be difficult to see in the used laboratory tests. Thus mathematical modelling was utilized to contribute the laboratory experiments and to bring additional information of the influence of NaOH presence on solubility of selected electrolytes, Na2SO4 and Na3PO4. The results from mathematical modelling of activity coefficients suggest Na2SO4 and Na3PO4 to be precipitated rather with presence and with higher concentrations of NaOH, since the raise of NaOH concentration decreases the solubility of these electrolytes in water.

Episodes of water deprivation enhance daily hypertonic NaCl intake in rats

Water and 1.8% NaCl intake was recorded daily in adult male rats (N = 6) submitted to four water deprivations plus four sodium appetite tests, each at the end of each 7-day interval, or in controls (non-deprived, N = 6). Water deprivation was achieved by removing water and 1.8% NaCl for 24 h. Water was then offered for 2 h. At the end of this period, 1.8% NaCl was also offered in addition to water (sodium appetite test). Average daily 1.8% NaCl intake was enhanced from 5.2 ± 1.0 to 15.7 ± 2.5 ml from the first to the fifth week in the experimental group and was unchanged in the control group. Daily water intake was not altered in either group. Thus, repeated episodes of water deprivation enhance daily NaCl intake.

Potentiation of carbon tetrachloride hepatotoxicity by pentosan polysulfate in rats

Few data are available in the literature regarding the effect of pentosan polysulfate (PPS) on normal and fibrotic rat livers. In addition, the combination of PPS and carbon tetrachloride (CCl4) has not been studied so far. The objective of this study was to assess the effect of PPS on rat livers treated or not with CCl4 for the induction of liver fibrosis. The study consisted of four stages: 1) hepatic fibrosis induction with CCl4 (N = 36 rats); 2) evaluation of the effect of PPS on CCl4-induced hepatic fibrosis (N = 36 rats); 3) evaluation of the effect of higher doses of PPS in combination with CCl4 (N = 50 rats); 4) evaluation of the presence of an enzymatic inductor effect by PPS (N = 18 rats) using the sodium pentobarbital test which indirectly evaluates hepatic microsomal enzyme activity in vivo. Adult (60 to 70 days) male Wistar rats weighing 180 to 220 g were used. All animals receiving 0.5 ml 8% CCl4 (N = 36) developed hepatic fibrosis, and after 8 weeks they also developed cirrhosis. No delay or prevention of hepatic fibrosis was observed with the administration of 5 mg/kg PPS (N = 8) and 1 mg/kg PPS (N = 8) 1 h after the administration of CCl4, but the increased hepatotoxicity resulting from the combination of the two substances caused massive hepatic necrosis in most rats (N = 45). PPS (40 mg/kg) alone caused hepatic congestion only after 8 weeks, but massive hepatic necrosis was again observed in association with 0.5 ml CCl4 after 1 to 4 weeks of treatment. Unexpectedly, sleeping time increased with time of PPS administration (1, 2, or 3 weeks). This suggests that PPS does not function as an activator of the hepatic microsomal enzymatic system. Further studies are necessary in order to clarify the unexpected increase in hepatotoxicity caused by the combination of CCl4 and high doses of PPS, which results in massive hepatic necrosis.

A study on mitigating the effect of sulphates in lime stabilised Cochin marine clays

Soft clays known for their high compressibility, low stiffness and low shear strength are always associated with large settlement. In place soil treatment using calcium-based stabilizers like lime and cement is a feasible solution to readdress strength deficiencies and problematic shrink/swell behaviour of unstable subgrade soils. Out of these, lime has been proved unambiguously as the most effective and economical stabilising agent for marine clays. Lime stabilisation creates long-term chemical changes in unstable clay soils to create strong, but flexible, permanent structural layers in foundations and other pavement systems. Even though calcium-based stabilizers can improve engineering properties of soft clays, problems can arise when they are used in soils rich in sulphates. It is possible for marine clays to be enriched with sulphates, either by nature or due to the discharge of nearby industrial wastes containing sulphates. The presence of sulphates is reported to adversely affect the cation exchange and pozzolanic reactions of cement and lime treated soil systems. The anions of sulphates may combine with the available calcium and alumina, and form insoluble ettringite in the soil system. Literature on sulphate attack in lime treated marine clays reports that formation of ettringite in lime-sodium sulphate-clay system is capable of adversely affecting the engineering behavior of marine clays. Only very few studies have been conducted on soft marine clays found along the coastal belt of Kerala and that too, is limited to Cochin marine clays. The studies conducted also have the limitation that the strength behaviour of lime stabilised clay was investigated only for one year. Practically no data pertaining to long term adverse effects likely to be brought about by sulphates on the strength and compressibility characteristics of Cochin marine clays is available. The overriding goal of this investigation was thus to examine the effectiveness of lime stabilisation in Cochin marine clays under varying sulphate contents. The study aims to reveal the changes brought about by varying sulphate contents on both physical and engineering properties of these clays stabilised by lime and the results for various curing periods up to two years is presented in this thesis. Quite often the load causing an unacceptable settlement may be less than the load required to cause shear failure and therefore attempt has been made in this research to highlight sulphate induced changes in both the compressibility and strength characteristics of lime treated Cochin marine clays. The study also aimed at comparing the available IS methods for sulphate quantification and has attempted to determine the threshold level of sulphate likely make these clays vulnerable by lime stabilisation. Clays used in this study were obtained from two different sites in Kochi and contained sulphate in two different concentrations viz., 0.5% and 0.1%. Two different lime percentages were tried out, 3% and 6%. Sulphate content was varied from 1% to 4% by addition of reagent grade sodium sulphate. The long term influence of naturally present sulphate is also investigated. X-ray diffraction studies and SEM studies have been undertaken to understand how the soil-lime reactions are affected in the presence of sodium sulphate. Natural sulphate content of 0.1% did not seem to have influenced normal soil lime reactions but 0.5% sulphate could induce significant changes adversely in both compressibility and strength behaviour of lime treated clays after long duration. Compressibility is seen to increase drastically with increasing sulphate content suggesting formation of ettringite on curing for longer periods. Increase in compression index and decrease in bond strength with curing period underlined the adverse effects induced in lime treated marine clays by the presence of sulphates. Presence of sulphate in concentrations ranging from 0.5 % to 4% is capable of adversely affecting the strength of lime treated marine clays. Considerable decrease is observed with increasing concentrations of sulphate. Ettringite formation due to domination of sodium ions in the system was confirmed in mineralogical studies made. Barium chloride and barium hydroxide is capable of bringing about beneficial changes both in compressibility and strength characteristics of lime treated Cochin marine clays in the presence of varying concentrations of sulphate and is strongly influenced by curing time. Clay containing sodium sulphate has increased strength values when either of barium compounds was used with lime ascompared with specimens treated with lime only. Barium hydroxide is observed to remarkably increase the strength as compared to barium chloride,when used in conjunction with lime to counteract the effect of sulphate.

Episodes of water deprivation enhance daily hypertonic NaCl intake in rats

Water and 1.8% NaCl intake was recorded daily in adult male rats (N = 6) submitted to four water deprivations plus four sodium appetite tests, each at the end of each 7-day interval, or in controls (non-deprived, N = 6). Water deprivation was achieved by removing water and 1.8% NaCl for 24 h. Water was then offered for 2 h. At the end of this period, 1.8% NaCl was also offered in addition to water (sodium appetite test). Average daily 1.8% NaCl intake was enhanced from 5.2 ± 1.0 to 15.7 ± 2.5 ml from the first to the fifth week in the experimental group and was unchanged in the control group. Daily water intake was not altered in either group. Thus, repeated episodes of water deprivation enhance daily NaCl intake.

Damage to the central amygdala produces differential encephalic c-fos expression in the water deprivation-partial rehydration protocol

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

A thin layer electrochemical cell for disinfection of water contaminated with Staphylococcus aureus

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