An environmentally friendly flow system for high-sensitivity spectrophotometric determination of free chlorine in natural waters

A green and highly sensitive analytical procedure was developed for the determination of free chlorine in natural waters, based on the reaction with N,N-diethyl-p-phenylenediamine (DPD). The flow system was designed with solenoid micro-pumps in order to improve mixing conditions by pulsed flows and to minimize reagent consumption as well as waste generation. A 100-cm optical path flow cell based on a liquid core waveguide was employed to increase sensitivity. A linear response was observed within the range 10.0 to 100.0 mu g L(-1), with the detection limit, coefficient of variation and sampling rate estimated as 6.8 mu g (99.7% confidence level), 0.9% (n = 20) and 60 determinations per hour, respectively. The consumption of the most toxic reagent (DPD) was reduced 20,000-fold and 30-fold in comparison to the batch method and flow injection with continuous reagent addition, respectively. The results for natural and tap water samples agreed with those obtained by the reference batch spectrophotometric procedure at the 95% confidence level. (C) 2010 Elsevier By. All rights reserved.

Photoelectrocatalytic production of active chlorine on nanocrystalline titanium dioxide thin-film electrodes

The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L-1 of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L-1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.

Preliminary investigations into oxidation of paralytic shellfish poisons (saxitoxins and derivatives) in drinking water by chlorine

The fresh water cyanobacterium Anabaena circinalis produces saxitoxin (STX) and several other toxins with similar basic structural skeleton. Collectively, these toxins are known as Paralytic Shellfish Poisons or PSPs. These toxins are water soluble and can escape into the water body after cell lysis. The presence of these toxins in drinking water is a serious threat to human health. The present work has shown that Paralytic Shellfish Poisons (PSPs) in drinking water can be removed by chlorination at high pH (>9.0), provided a residual of 0.5 mg/L of free chlorine is present after 30 minutes of contact time.

An Environmental Friendly Procedure for Photometric Determination of Hypochlorite in Tap Water Employing a Miniaturized Multicommuted Flow Analysis Setup

A photometric procedure for the determination of ClO(-) in tap water employing a miniaturized multicommuted flow analysis setup and an LED-based photometer is described. The analytical procedure was implemented using leucocrystal violet (LCV; 4,4', 4 ''-methylidynetris (N, N-dimethylaniline), C(25)H(31)N(3)) as a chromogenic reagent. Solenoid micropumps employed for solutions propelling were assembled together with the photometer in order to compose a compact unit of small dimensions. After control variables optimization, the system was applied for the determination of ClO(-) in samples of tap water, and aiming accuracy assessment samples were also analyzed using an independent method. Applying the paired t-test between results obtained using both methods, no significant difference at the 95% confidence level was observed. Other useful features include low reagent consumption, 2.4 mu g of LCV per determination, a linear response ranging from 0.02 up to 2.0 mg L(-1) ClO(-), a relative standard deviation of 1.0% (n = 11) for samples containing 0.2 mg L(-1) ClO(-), a detection limit of 6.0 mu g L(-1) ClO(-), a sampling throughput of 84 determinations per hour, and a waste generation of 432 mu L per determination.

A critical evaluation of a flow-cell based on a liquid core waveguide for chemiluminescence measurements

Liquid-core waveguides (LCWs), devices that constrain the emitted radiation minimizing losses during the transport, are an alternative to maximize the amount of detected radiation in luminescence. In this work, the performance of a LCW flow-cell was critically evaluated for chemiluminescence measurements, by using as model the oxidation of luminol by hydrogen peroxide or hypochlorite. An analytical procedure for hypochlorite determination was also developed, with linear response in the range 0.2-3.8 mg/L (2.7-51 mu mol/L), a detection limit estimated as 8 mu g/L (0.64 mu mol/L) at the 99.7% confidence level and luminol consumption of 50 mu g/determination. The coefficients of variation were 3.3% and 1.6% for 0.4 and 1.9 mg/L CIO(-), respectively, with a sampling rate of 164 determinations/h. The procedure was applied to the analysis of Dakin`s solution samples, yielding results in agreement with those obtained by iodometric titration at the 95% confidence level. Copyright (c) 2008 John Wiley & Sons, Ltd.

Toxicological aspects of treatment to remove cyanobacterial toxins from drinking water determined using the heterozygous P53 transgenic mouse model

The presence of toxic cyanobacteria in drinking water reservoirs renders the need to develop treatment methods for the 'safe' removal of their associated toxins. Chlorine has been shown to successfully remove a range of cyanotoxins including microcystins, cylindrospermopsin and saxitoxins. Each cyanotoxin requires specific treatment parameters, particularly solution pH and free chlorine residual. However, currently there has not been any investigation into the toxicological effect of solutions treated for the removal of these cyanotoxins by chlorine. Using the P53(def) transgenic mouse model mate and female C57BL/6J hybrid mice were used to investigate potential cancer inducing effects from such oral dosing solutions. Both purified cyanotoxins and toxic cell-free extract cyanobacterial solutions were chlorinated and administered over 90 and 170 days (respectively) in drinking water. No increase in cancer was found in any treatment. The parent cyanotoxins, microcystins, cylindrospermopsin and saxitoxins were readily removed by chlorine. There was no significant increase in the disinfection byproducts trihalomethanes or haloacetic acids, levels found were well below guideline values. Histological examination identified no effect of treatment solutions except male mice treated with chlorinated cylindrospermopsin (as a cell free extract). In this instance 40% of males were found to have fatty vacuolation in their livers, cause unknown. It is recommended that further toxicology be undertaken on chlorinated cyanobacterial solutions, particularly for non-genotoxic carcinogenic compounds, for example the Tg. AC transgenic mouse model. (C) 2003 Elsevier Science Ltd. All rights reserved.

Simulação da qualidade da água em parte de ao Grande Porto

Este trabalho tem como objetivo a modelação hidráulica e de qualidade de água de parte de uma rede de distribuição a alta pressão do grande Porto. Após calibração de um modelo utilizado no software EPANet foi possível simular o decaimento do cloro livre num troço da rede de abastecimento. Foi ainda possível concluir que os valores dos parâmetros característicos do modelo de qualidade são uma constante de decaimento no seio do fluido de 1,78 dia-1 (0,001239 min-1) a cerca de 22 ºC e, no ramal 6244-6245 Ramalde – Cabanas – Pedrouços, uma constante de decaimento na parede da tubagem de forma generalizada de 0,28 m/dia. Não foi possível obter conclusões sobre a adutora 6261 Jovim-Nova Sintra 2, ficando explícita a necessidade de um maior controlo sobre a variável temperatura.

Kationinvaihtohartsien hapetuskestävyys

Hyvin puhdasta vettä vaativissa sovelluksissa käytettävät kationinvaihtohartsit eivät saisi vuotaa puhdistettavaan veteen mitään vieraita aineita. Todellisuudessa hartsit kuitenkin vuotavat hyvin pieniä määriä erilaisia yhdisteitä käytön aikana. Aineet, joita kationinvaihtohartsi päästää veteen, ovat osaksi hartsin polymerointireaktion aikana sen rungon sisään jääneitä yhdisteitä. Nämä voidaan suurimmaksi osaksi poistaa pesemällä hartsia. Osittain niitä syntyy myös hartsin polystyreenidivinyylibentseenirungon (PS-DVB) hapettuessa. Hapettumisen seurauksena syntyneet yhdisteet ovat pääosin orgaanisia sulfonaatteja. Tämä työ koskee ydinvoimalaitoksissa käytettäviä pulverihartseja, joita käytetään primääripiirissä kiertävän lauhdeveden puhdistukseen ja jotka joutuvat siellä alttiiksi hapettumiselle. Yleensä hapettuminen on hidasta ja se johtuu veteen liuenneesta hapesta. Hapettuminen nopeutuu huomattavasti, jos vedessä on läsnä hapettimia tai siirtymämetalli-ioneja. Tällaisia hapettimia ovat esimerkiksi vetyperoksidi, otsoni, vapaa kloori, typpihappo ja kromi. Vetyperoksidin vaikutuksesta hartsin runkoon muodostuu hydroperoksidiryhmä, jonka hajoamisesta alkaa reaktioiden sarja, joka lopulta johtaa hartsin polymeerirungon katkeamiseen. Siirtymämetalli-ionit katalysoivat peroksidien hajoamista. Tavallisimpia hapetusta katalysoivia metalli-ioneja ovat rauta ja kupari, joiden katalyyttinen aktiivisuus on suuri. Tässä työssä pyrittiin selvittämään, onko mahdollista valmistaa hartseja, jotka kestävät hapettumista paremmin kuin nykyisin käytössä olevat hartsit. Sen tutkimiseksi tehtiin kiihdytettyjä hapetuskokeita käyttäen hapettimena vetyperoksidia ilman siirtymämetalli-ioni katalyyttejä. Hapetuskokeet tehtiin kaupallisesti saatavilla hartseilla ja uusilla työtä varten syntetisoiduilla koehartseilla. Hapetuskokeiden etenemistä seurattiin mittaamalla veteen liuenneiden orgaanisten aineiden kokonaismäärää (TOC-analyysi) ja liuoksessa esiintyvien orgaanisten sulfonaattien määrää johtokykymittauksin. Saadut tulokset antoivat viitteitä siitä, että hartsin synteesiolosuhteilla voi olla suurempi vaikutus sen hapetuskestävyyteen kuin synteesissä käytetyillä raaka-aineilla.

Shelf life of minimally processed carrot and green pepper

The postharvest losses of horticultural products justify the use of preservation techniques. The processing not only adds value to the products, but also makes the products more convenient to the consumers. The objective of this research was to define the methodologies for the minimal processing of carrot and green pepper as to the type and intensity of the adoption of conservation techniques, and to monitor the products after processing through microbiological, physicochemical and nutritional analysis. The vegetables were washed and they were immersed in cold (7ºC) water with 100 mg L-1 free chlorine for sanitation, followed by centrifugation for 5 min. The product was put into BOPP/LDPE (biaxially orientated polypropylene/low-density polyethylene) plastic bags, which were sealed under atmospheric air, vacuum and modified atmosphere (2% O2, 10% CO2, 88% N2) and stored at 1ºC±1ºC. The approximate composition of the vegetables stayed stable during the storage period, in the three tested treatments. The contents of vitamin C for the samples of minimally processed carrot and green pepper did not present differences among treatments. The contents of beta-carotene decreased slightly during the storage period for the minimally processed carrot and green pepper. After processing, carrot and green pepper had psychrotrophic counts of 10²-10(5) and 10³-10(6) CFU g-1, respectively. Anaerobic mesophiles and total coliforms were found in green peppers, representing 1.6x10³ - 7.4x10(5) and <10.g-1 - 7.4x10(5), respectively. Total and fecal coliforms, anaerobic mesophiles and Salmonella were not found in carrots. Salmonella was not found in green pepper.

Avaliação da influência do nacl em pastas de cimento portland para cimentação de poços de petróleo em zonas evaporíticas

One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate

Formas de preparo de figo-da-índia minimamente processado

The objective of this study was to evaluate the influence of methods of preparation in postharvest conservation of minimally processed products of cactus pear fruits. Ripe cactus pear fruits orange-fleshed, from a commercial orchard in the region of Valinhos, SP, Brazil, were used. After selection, the fruits were washed and the surface sanitized with a solution of dichloro s. triazinatriona sodium dihydrate (Sumaveg (R)) 200 mg 100g(-1) of free chlorine for 5 minutes. Fruits were then stored at 12 degrees C for 12 hours before processing. The first process was the removal of the shell and ends. Then, the fruits were cut longitudinally into two halves, peeled and sliced in 2 cm thick cross-sections. The whole fruit, halves and slices were packaged in polyethylene terephthalate containers (Neoforma (R) N-94). These units were stored at 3 degrees C for 16 days and analyses were performed every 4 days. The weight loss, the content of soluble solids (SS), the titratable acidity (TA), the ratio (SS / TA) and the ascorbic acid content were evaluated and the sensory analysis of products was performed. Whole fruits were preferred concerning the purchase intent and showed better results regarding the content of soluble solids, titratable acidity, soluble solids / titratable acidity and ascorbic acid content. The highest weight loss was observed in slices.

Pós-colheita de mangas 'Tommy Atkins' recobertas com quitosana

O objetivo deste trabalho foi avaliar a influência de cobertura de quitosana na pós-colheita de mangas 'Tommy Atkins', colhidas de vez e armazenadas a 23 ºC (65% UR). As mangas foram adquiridas na CEAGESP de Ribeirão Preto-SP, e transportadas ao Laboratório de Tecnologia de Produtos Agrícolas da UNESP de Jaboticabal. Após a seleção, os frutos foram higienizados em solução de dicloro s. triazinatriona sódica di-hidratada (Sumaveg®) a 200 mg 100g-1 de cloro livre por 10 minutos, secadas, imersas nas soluções a 0%; 1,0%; 1,5% e 2,0% de quitosana por 1 minuto, secadas sob ventilação, acondicionadas em bandejas e armazenadas a 23±2 °C e 65±5% UR, por 9 dias. Foram utilizados três repetições com dois frutos cada. Avaliaram-se, a cada três dias, a perda de massa fresca, a cor, a firmeza, os teores de ácido ascórbico, de sólidos solúveis, de acidez titulável e sólidos solúveis / acidez titulável. O recobrimento com quitosana retarda o amadurecimento de mangas 'Tommy Atkins' de vez, durante nove dias de armazenamento a 23 ºC, sendo que a concentração de 1,5% propicia melhor manutenção da cor da polpa, dos teores de sólidos solúveis, de acidez titulável, de ácido ascórbico, dos valores de SS/AT e de firmeza.

Microbiological Evaluation of Chicken Carcasses in an Immersion Chilling System with Water Renewal at 8 and 16 Hours

Since 2004, Brazil has been the leading exporter of chicken. Because of the importance of this sector in the Brazilian economy, food safety must be ensured by control and monitoring of the production stages susceptible to contamination, such as the chilling process. The goal of this study was to evaluate changes in microbial levels on chicken carcasses and in chilling water after immersion in a chilling system for 8 and 16 h during commercial processing. An objective of the study was to encourage discussion regarding the Brazilian Ministry of Agriculture Livestock and Food Supply regulation that requires chicken processors to completely empty, clean, and disinfect each tank of the chilling system after every 8-h shift. Before and after immersion carcasses were collected and analyzed for mesophilic bacteria, Enterobacteriaceae, conforms, and Escherichia coli. Samples of water from the chilling system were also analyzed for residual free chlorine. The results do not support required emptying of the chiller tank after 8 h; these tanks could be emptied after 16 h. The results for all carcasses tested at the 8- and 16-h time points indicated no significant differences in the microbiological indicators evaluated. These data provide both technical and scientific support for discussing changes in federal law regarding the management of immersion chilling water systems used as part of the poultry processing line.

Microbiological and physicochemical treatments applied to metallurgic industry aiming water reuse

Estudou-se o reuso de água de um sistema composto por estação de tratamento de esgoto (ETE) com aeração prolongada e lodo ativado, e em uma estação compacta de tratamento de água (ECTA) de uma indústria metalúrgica. Os processos para obtenção da água de reuso foram: microbiológico e físico-químico. O esgoto doméstico foi bombeado para a ETE, onde houve formação de flocos biológicos e água clarificada. Avaliou-se a eficiência do processo microbiológico da ETE mediante a remoção de demanda bioquímica de oxigênio (DBO), demanda química de oxigênio (DQO) e sólidos sedimentáveis (SS). A eficiência do processo físico-químico de clarificação e desinfecção foi avaliada mediante análises de pH, turbidez, cor, contagem de bactérias heterotróficas aeróbias, cloro livre, dureza, alcalinidade, cloretos, sulfatos, sólidos totais dissolvidos (STD). Na água de reuso além desses parâmetros avaliou-se a toxicidade aguda ao microcrustáceo Daphnia similis.

Comportamento cinético do cloro livre em meio aquoso e formação de subprodutos da desinfecção

One indirect approach to predict the disinfection by-product (DBP) formation potential for a given water source is by evaluation of the kinetic behavior of free chlorine in the liquid phase and chlorine demand determination for different operation conditions of the chlorination process. The objective of this work was to evaluate the kinetic behavior of free chlorine in water or a number of different raw water sources, as well as to investigate the impact of the coagulation process on chlorine demand reduction and DBP formation. It was observed that the higher the total organic carbon (TOC) removal efficiency through coagulation, the lower the liquid phase chlorine demand. Regarding trihalomethane (THM) formation, a ratio of 28 ug/L formed per mg/L of applied chlorine was observed for the waters employed in the experimental investigation.