Validation of plant dynamic model by online and laboratory measurements – a tool to predict online COD loads out of production of mechanical printing papers

COD discharges out of processes have increased in line with elevating brightness demands for mechanical pulp and papers. The share of lignin-like substances in COD discharges is on average 75%. In this thesis, a plant dynamic model was created and validated as a means to predict COD loading and discharges out of a mill. The assays were carried out in one paper mill integrate producing mechanical printing papers. The objective in the modeling of plant dynamics was to predict day averages of COD load and discharges out of mills. This means that online data, like 1) the level of large storage towers of pulp and white water 2) pulp dosages, 3) production rates and 4) internal white water flows and discharges were used to create transients into the balances of solids and white water, referred to as “plant dynamics”. A conversion coefficient was verified between TOC and COD. The conversion coefficient was used for predicting the flows from TOC to COD to the waste water treatment plant. The COD load was modeled with similar uncertainty as in reference TOC sampling. The water balance of waste water treatment was validated by the reference concentration of COD. The difference of COD predictions against references was within the same deviation of TOC-predictions. The modeled yield losses and retention values of TOC in pulping and bleaching processes and the modeled fixing of colloidal TOC to solids between the pulping plant and the aeration basin in the waste water treatment plant were similar to references presented in literature. The valid water balances of the waste water treatment plant and the reduction model of lignin-like substances produced a valid prediction of COD discharges out of the mill. A 30% increase in the release of lignin-like substances in the form of production problems was observed in pulping and bleaching processes. The same increase was observed in COD discharges out of waste water treatment. In the prediction of annual COD discharge, it was noticed that the reduction of lignin has a wide deviation from year to year and from one mill to another. This made it difficult to compare the parameters of COD discharges validated in plant dynamic simulation with another mill producing mechanical printing papers. However, a trend of moving from unbleached towards high-brightness TMP in COD discharges was valid.

Estudo comparativo da seletividade de um método cinético-catalítico: a determinação de Cr(VI) pela oxidação da o-dianisidina pelo peróxido de hidrogênio

Selectivity studies for the determination of Cr(VI) using the catalytic oxidation of the o-dianisidine by hydrogen peroxide showed two distincts situations. In the first, when interferents were studied by a univariate procedure, Cr(III) and Cu(II) cause serious interferences even at the 2:1 proportion, relative to Cr(VI), while Fe(III) interfered at the 15:1 ratio and EDTA at the 10:1 ratio. On the other hand, when a multivariate investigation was performed, Cr(III) did not present any significant principal effects and its significant interaction effects were negative, in contrast to EDTA, that presented positive interaction effects although, like Cr(III), did not show significant interaction effects. In view of the interferent's action it become necessary to separate Cr(VI) by extraction with methylisobutylketone in a chloridric acid medium before its determination in vegetals and in wastewater from a cellulose industry samples. Using this procedure, the method precision is ±0,5% at the 10 ng/mL Cr(VI) concentration level. The detection and quantification limits, calculated by means of absorbance measurements of ten replicates of blank reagents were 1,1 and 3,2 ng/mL, respectively. The results obtained with real samples showed a relative standard deviation between 1,2% and 3,0% relative to their reference values.

Método potenciométrico para determinação de cobre em cachaça

'Cachaça' is the Brazilian name for the spirit obtained from sugarcane. According to Brazilian regulations, it may be sold raw or with addition of sugar and may contain up to 5 mg/L of copper. Copper in "cachaça" was determined by titration with EDTA, using a homemade copper membrane electrode for end-point detection. It was found a pooled standard deviation of 0,057 mg/L and there was no significant difference between the results obtained by the potentiometric method and by flame atomic absorption spectrometry with standard addition. Among the 21 'cachaça' samples from 16 different brands analyzed, three overpassed the legal copper limit. For its characteristics of accuracy, precision, and speed, the potentiometric method may be employed advantageously in routine analysis, specially when low cost is a major concern.

Yllätys yritysjohdon ennusteissa: Vaikutus osakekurssiin

Tutkielman tavoitteena oli selvittää Suomen osakemarkkinoiden hinnoittamistehokkuutta johdon ennustepoikkeamien tapauksessa. Tarkastelu-ajanjakso on 1.1.2000–31.12.2006. Kiinnostuneita oltiin erityisesti keski-pitkän ja pitkän aikavälin (10 kaupankäyntivuorokautta ja 40 kaupankäyntivuorokautta) epänormaaleista tuotoista. Työn empiriaosuus suoritettiin tapahtumatutkimusmenetelmää hyväksikäyttäen. Empiriaosuudessa laskettiin ennustepoikkeaman aiheuttamat epänormaalit tuotot pienimmän neliösumman regressiota hyväksikäyttäen. Positiivisten poikkeamien aiheuttamat epänormaalit tuotot eivät poikenneet tilastollisesti markkinatuotoista millään tarkasteluvälillä. Negatiivisten epänormaalien tuottojen poikkeamaa havaittiin 10 kaupankäyntivuorokautta ennustepoikkeaman julkaisun jälkeen. Toimialakohtaisessa tarkastelussa parillisten otosten t-testissä havaittiin, että terveydenhuollon, rahoituksen ja informaatioteknologian epänormaalit tuotot poikkesivat markkinatuotoista. Yrityskohtaisia tekijöitä tutkittiin yksinkertaisella t-testillä. Näistä velkaisuusasteella, beetalla, päivätuottojen keskihajonnalla, päivittäisellä liikevaihdolla sekä P/E-luvulla havaittiin voi-tavan ennustaa mahdollisten ennustepoikkeamien esiintymistiheyttä. Sen sijaan markkina-arvolla ja P/B-luvulla ei havaittu yhteyttä ennustepoikkeamien esiintymistiheyteen. Tutkittaessa käyttäytymistieteellisen rahoituksen olettamaa kaupankäyntivolyymin kasvusta ennustepoikkeamaa ympäröivänä aikana ei tilastollista merkittävyyttä löydetty.

Eletrodissolução de ligas de latão empregando sistemas de análise em fluxo para a determinação de cobre, zinco e chumbo por ICP-AES

An on-line electrodissolution procedure implemented in a flow injection system for determination of copper, zinc and lead in brasses alloys by ICP-AES is described. Sample dissolution procedure was carried out by using a PTFE chamber and a DC power supply with constant current. Solid sample was attached to chamber as anode and a gold tubing coupled in the chamber was used as cathode. An electrolytic solution flowing through the gold tubing closed the electric circuit with sample, in order to provide condition for electric dissolution when the DC power supply was switched on. The best results were achieved by using a 1.5 mol l-1 nitric acid solution as electrolyte and a 2.5 A current intensity. The procedure presented a good performance characterized by a relative standard deviation better than < 5% (n=5) and a sample throughput of 180 determinations per hour for Cu, Zn and Pb. Results were in agreement with those obtained by conventional acid dissolution (99% confidence level).

Eletrodissolução anódica em sistema de injeção em fluxo: uma alternativa rápida e eficiente para dissolução de ligas metálicas

Anodic electrodissolution procedure in a flow injection system for determination of constituents in alloys is discussed. This approach implement sample preparation procedure by using a chamber and a DC power supply with constant direct current. Solid sample was attached to chamber as anode. In this review a general overview of these procedure is presented. The procedure presented a good performance characterized by a high sample throughput determinations, good accuracy and relative standard deviation.

Determinação condutométria de carbonato residual do calcário aplicado no solo por análise em fluxo

The objective of this study was to evaluate a flow injection system for determination of residual CO3(2-) in soil amended with lime material. It was used a closed system were the CO2 released from soil sample acidified with 0.5 mol L-1 HCl was capted in a 0.2 mol L-1 NaOH solution. After 16h the capted CO2 was determined by conductivimetry using a flow injection system. The results obtained by the proposed method were significantly correlated with those reported in soil samples used by the International Soil Analytical Exchange Programe. The regression equation was: y = 0.987x -- 0.075 r = 0.996, P > 0.01. For acid soils amended with CaCO3 the method showed a deviation error of 2.7%, detection limit was 0.077 mmol kg-1 of CO3(2-), and a recovery of 99.7% of the total CO3(2-) added in soil sample. The method was easily adapted for routine determination of residual CO3(2-) in soil samples with an analytical frequency of 40 samples per hour.

Uma abordagem robusta de cálculo aplicada a um sistema potenciométrico de medida de concentrações hidrogeniônicas em soluções aquosas

The data analyzed in this work were generated following the methodology developed by Molina et al.(J. Electroanal. Chem., 1979) for the calibration of a potentiometric system of measurement of hydrogen-ion concentrations resulting from neutralizations, at 25 ºC, of acidic or alkaline solutions at constant ionic strength (0.1 mol.l-1) held with NaClO4. The observed data present a serious deviation in relation to the mathematical model derived from the Nernst equation, for pH values ranging from 3 to 11, where pH=-log[H+]. We show that the minimization of the sum of the absolute values of the residuals gives estimates that are not influenced by outlying values.

Sistema em fluxo para determinação espectrofotométrica de uréia em plasma de sangue animal empregando leguminosa como fonte natural da enzima urease

A spectrophotometric flow injection analysis (FIA) procedure employing natural urease enzyme source for the determination of urea in animal blood plasma was developed. Among leguminous plants used in the Brazilian agriculture, the Cajanus cajan specie was selected as urease source considering its efficiency and availability. A minicolumn was filled with leguminous fragments and coupled to the FIA manifold, where urea was on-line converted to ammonium ions and subsequently it was quantified by spectrophotometry. The system was employed to determine urea in animal plasma samples without any prior treatment. Accuracy was assessed by comparison results with those obtained employing the official procedure and no significant difference at 90 % confidence level was observed. Other profitable features such as an analytical throughput of 30 determinations per hour, a reagent consumption of 19.2 mg sodium salicylate, 0.5 mg sodium hipochloride and a relative standard deviation of 1.4 % (n= 12) were also obtained.

Determinação de baixas concentrações de cobre em águas naturais por espectrofotometria de absorção atômica em chama usando um sistema SIA com uma coluna de poli(etilenimina)

This paper describes a sequential injection analysis (SIA) set-up coupled to a flame atomic absorption spectrometer (FAAS) to accomplish the determination of low concentrations of copper in drinking waters. Copper is first retained under neutral media in an on-line 29x1.6 mm column filled with poly(ethylenimine) immobilised on silica gel. The retained analyte is then eluted by flowing through the column 250 mL of a nitric acid solution. The selection of 3.85 ml of sample enabled to obtain a detection limit of 0.27 mug/L and a sampling rate of about 24 samples/h. There was a good agrement between the results of 12 samples furnished by the proposed procedure and by electrothermal atomic absorption spectrometry. Repeatability assessment gave a relative standard deviation of 1.3 % after ten replicate analysis of a sample containing about 70 mug/L in copper..

Desenvolvimento de um método de MEFS com CG-DIC para determinação de 1,4 dioxana em amostras de cosméticos

A headspace solid-phase microextraction (HS-SPME) for the determination of 1,4 dioxane in cosmetics by gas chromatography is described. A manual SPME holder with 85 µm polyacrylate coating is utilized. The method is determined to have good resolution, satisfactory linerity (correlation coefficient r=0.997 for 0.20-10.00 mg Kg-1 range), a relative standard deviation of 6.3% and a detection limit of 5.00 µg Kg-1. Some cosmectic products were analyzed.

Avaluació dels nivells de nitrats i duresa a l'aigua de consum a quatre zones d'Espanya participants a l'estudi epidemiològic Infància i Medi Ambientl (INMA)

L’aigua és un dels components bàsics per a la vida i una font d’exposició a contaminants ubiqua, ja que tota la població en consumeix. L’estudi epidemiològic INMA avaluarà si l’exposició a nitrats durant l’embaràs i a la duresa de l’aigua durant la infància es relaciona amb el baix pes al néixer i l’èczema atòpica, respectivament. Objectiu: Fer una avaluació dels nivells de nitrats i duresa de l’aigua en aigua de consum de la població de l’estudi INMA. Metodologia: l’estudi descriptiu realitzat a quatre de les set cohorts INMA, a Astúries, Guipúscoa, Sabadell i València. S’ha recopilat dades dels nivells de nitrats i duresa a l’aigua de consum dels municipis durant el període d’interès (2003 al 2008 i 2004 al 2012), a través d’ajuntaments i companyies d’aigua. S’ha calculat la mitjana, la desviació estàndard, el màxim i el mínim dels nivells de nitrat i de duresa en total i segons l’àrea geogràfica, l’any i l’estació. A Sabadell s’han fet tres mostrejos d’aigua per analitzar la duresa a diferents punts de la ciutat. Resultats: el nivell promig de nitrats (mg/L NO3-) és de 4,2 a Astúries, 4,0 a Guipúscoa, 9,2 a Sabadell i 15,2 a València. El nivell promig de duresa (mg/L CaCO3) és de 89,1 a Astúries, 132,7 al Guipúscoa, 178,3 a València i 230,9 a Sabadell. En l’anàlisi que es va realitzar a Sabadell, es detecta una duresa lleugerament inferior a la reportada sense variabilitat geogràfica. No s’observa una pauta clara de variabilitat estacional ni de variabilitat temporal tant per nitrats com per duresa. Conclusions: S’ha detectat variabilitat en els nivells de nitrats i duresa de l’aigua a les zones d’estudi. Els nivells de nitrats són moderats i els més alts es troben a zones agrícoles de València. La duresa de l’aigua és força alta degut al domini calcari dels subsòls de les zones d’estudi.

Emprego de reagente em suspensão em sistema de injeção em fluxo: determinação espectrofotométrica de sulfato em águas naturais

This paper presents an automatic procedure employing a reagent in the form of a slurry in a flow-injection system. The feasibility of the proposal is demonstrated by sulphate determination in water using the Barium Chloranilate method, which is based on the precipitation of barium sulphate. The release of a stoichiometric amount of highly colored chloranilic ions is monitored at 528 nm. The reaction is carried out in alcoholic medium in order to reduce the solubility of the reagent. A considerable improvement in the sensitivity is attained by adding ferric ions to the released chloranilic ions. An on-line filtration step to separate the excess reagent from the released chloranilic ions was necessary. In addition, a column containing a cation exchange resin was included in the manifold to remove potentially interfering ions. The proposed procedure is suitable for 30 determinations per hour and the relative standard deviation is less than 2%. The analytical curve is linear between 0.0 and 40 mg L-1 and the determination limit is about 2.0 mg L-1SO4(2-). Accuracy was confirmed by running several samples already analysed by a standard turbidimetric procedure.

Espectrometria de absorção atômica com atomização eletrotérmica em filamento de tungstênio: uma re-visão crítica

In this review it is presented some aspects of electrothermal atomic absorption spectrometry with tungsten coil (ETAW-AAS) since its beginning until the present days as well as the perspectives for this technique. Some aspects concerning its development and theoretical concepts are discussed. The analytical figures of merit such as limit of detection (LD), characteristic mass (m0), relative standard deviation (RSD), accuracy and precision are evaluated, compared and discussed considering published works. It is also evaluated its advantages, applications, limitations and instrumental development. The use of diode laser as radiation source and its perspectives to ETAW are also discussed.

Determinação espectrofotométrica de dipirona em produtos farmacêuticos por injeção em fluxo pela geração de íons triiodeto

A flow injection spectrophotometric procedure was developed for the determination of metamizol in pharmaceutical formulations. The system is based on the reaction between metamizol and triiodide generated in the system by mixing iodate and iodide-starch solutions. The absorbance of triiodide-starch complex giving a steady-state baseline value which was monitored at 580 nm. The inverse peaks caused by metamizol samples were measured and there was a direct relationship between absorbance decreasing and metamizol concentration from 1.4 x 10-4 to 7.0 x 10-4 mol L-1. The RSD was 0.45 % for a metamizol solution 4.2 x 10-4 mol L-1 (n = 10) with a detection limit (three-fold blank standard deviation/slope) of 6.0 x 10-5 mol L-1 The feasibility of the system was demonstrated for the determination of metamizol in commercial samples with sixty results obtained per hour. The results obtained for metamizol in pharmaceutical formulations using the proposed flow procedure and those obtained using an iodimetric procedure are in agreement at the 95% confidence level and within an acceptable range of error.