Prostate-specific antigen flare induced by 223RaCl2 in patients with metastatic castration-resistant prostate cancer.

PURPOSE: Prostate-specific antigen (PSA) flare is a well-known phenomenon in patients with prostate cancer, but its impact during radium-223 dichloride (223RaCl2) therapy is still unclear. This radioisotope has shown to improve overall survival in metastatic castration-resistant prostate cancer (mCRPC). We sought to evaluate the impact of PSA flare on survival and its relation with metabolic parameters on 18F-labeled sodium fluoride PET/CT. METHODS: We conducted a retrospective study of 168 patients with mCRPC (median age 69; median PSA 29.7) receiving 223RaCl2. Overall survival (OS) and progression-free survival (PFS), estimated by the Kaplan-Meier method and compared using a log-rank test, were evaluated for patient groups corresponding to different definitions of PSA flare. Metabolic 18F-fluoride PET/CT data were analyzed as well. RESULTS: Immediate PSA decline was observed in 49 patients (29.2%), whereas no PSA response was observed in 59 patients (35.1%). PSA flare (defined as rise after the first cycle followed by decrease below the baseline) was observed in 20 patients (11.9%) and PSA flare followed by a decrease from peak but not below baseline was observed in 40 (23.8%). The first flare subgroup had a median PFS and OS of 20.8 and 23.9 months, respectively. These outcomes were not significantly different from patients with immediate PSA decrease, but were significantly better than in patients with persistent PSA elevation (3.1 months for PFS and 11.5 months for OS, p < 0.001). Moreover, the PSA flare group showed an alkaline phosphatase (ALP) decrease significantly greater than non-responders (p = 0.003). Metabolic 18F-fluoride PET/CT data were available in 35 patients at baseline and during 233RaCl2 therapy. The tumor burden reduction, expressed by ΔTLF10 and ΔFTV10, was more evident within PSA flare group below baseline than non-responders (p = 0.005 and 0.001, respectively). CONCLUSIONS: This report suggests that a flare does not necessarily indicate lack of response to 223RaCl2 therapy.

The effect of feed intake containing whole cottonseed on blood parameters of Nellore bulls / Efeito do consumo de rações contendo caroço de algodão sobre parâmetros sanguíneos de bovinos Nelore

The aim of this study was to evaluate the effect of diets containing whole cottonseed (WC) on blood biochemical parameters of bulls. Thirty bulls with 30±6 months and 382.7±28.4kg were kept in feedlot (85 days) and fed the following WC levels: 0, 2.22, 4.44, 6.66, 8.88 and 11.11%. In comparing biochemical indicators from the beginning to the end of the experiment, the control group (CG) and those fed diets containing 2.22, 8.88 and 11.11% of WC had an increase (P<0.05) in serum Ca concentrations (8.34±0.65−9.56±0.92mEqL-1). In relation to Fe (202.79±69.04−300.04±79.88µg/dL), the CG and those treated with 6.66% WC showed an increase (P<0.05) in serum concentrations. As to the Mg (1.92±0.18−2.40±0.27mEqL-1), groups treated with diet containing 2.22, 4.44 and 6.66% of WC had higher (p<0.05) concentrations at the end of the study. Regarding blood lipids, groups with diets containing 2.22; 4.44; 6.66 and 8.88% of WC increased (p<0.05), respectively, in concentrations of HDL, TG, VLDL and COL. The group that received 11.11% of WC increased (P<0.05) in the concentrations of COL and HDL. It can be concluded that diets containing WC, caused no alterations in the concentrations of blood parameters analyzed in this study, with the exception of Mg.(AU)

Objetivou-se avaliar o efeito de dietas contendo caroço de algodão (CA) sobre os parâmetros sanguíneos de bovinos. Trinta touros com 30±6 meses e 382,7±28,4kg foram confinados (85 dias) e receberam dietas com as seguintes proporções de CA: 0; 2,22; 4,44; 6,66; 8,88, e 11,11%. Ao se compararem as concentrações dos indicadores bioquímicos do início com as do final do experimento, foi observado que o grupo controle e aqueles com dietas contendo 2,22; 8,88 e 11,11% de CA apresentaram aumento (P<0,05) na concentração sérica de Ca (8,34±0,65−9,56±0,92 mEqL-1). Já em relação ao Fe (202,79±69,04−300,04±79,88µg/dL), observou-se que apenas o grupo controle e aquele tratado com 6,66% apresentaram aumento (P<0,05) em sua concentração. Quanto ao Mg (1,92±0,18−2,40±0,27 mEqL-1), os grupos tratados com 2,22; 4,44 e 6,66% de CA apresentaram maiores concentrações (P<0,05) ao final do estudo. Com relação aos lipídeos sanguíneos, os grupos com dietas contendo 2,22; 4,44; 6,66 e 8,88% de CA tiveram aumento (P<0,05), respectivamente, nas concentrações de HDL, TG, VLDL e COL. O grupo que recebeu 11,11% de CA teve aumento (P<0,05) nas concentrações de COL e HDL. Conclui-se que as dietas contendo CA não causaram alterações (P>0,05) nas concentrações dos parâmetros sanguíneos analisados, com exceção do Mg.(AU)

Mosquitoes (Diptera: Culicidae) from crepuscular period in an Atlantic Forest area in Southern Brazil / Mosquitos (Diptera: Culicidae) do período crepuscular em área de Floresta Atlântica no sul do Brasil

Abstract Crepuscular period is one of the factors that may influence the biting activity of mosquitoes. Many of these insects have a peak activity in this period. The purpose of this study was to investigate the afternoon crepuscular activity of Culicidae in a remaining area of Atlantic Forest in western Santa Catarina, southern Brazil. Moreover, the possible influence of abiotic factors, the abundance and species richness were verified. In order to better analyze the influence of crepuscular period in specific composition and abundance of mosquitoes, the dusk was divided into three periods: pre-sunset, sunset and post-sunset. At the end of the study, nine hundred and eight four specimens distributed in 12 genera and 23 species were collected. Trichoprosopon pallidiventer (Lutz, 1905) (59.76%), Aedes crinifer (Theobald, 1903) (8.13%), Ae. scapularis (Rondani, 1848) (5.89%) were the most abundant species. Spring time presented the greatest abundance and species richness. During the study, among the three periods evaluated, pre-sunset had the greatest abundance and post-sunset the lowest. Pre-sunset and sunset had the greatest similarity between species. Regarding to the abiotic factors evaluated seven and 15 days before sampling, they did not present significant correlation for the three most abundant species. However, temperature had a positive correlation to these species. Moreover, the correlation between collected species and its possible role as vectors of etiological agents of diseases was discussed.

Resumo O período crepuscular é um dos fatores que pode influenciar na atividade hematofágica dos mosquitos. Muitos desses insetos iniciam ou terminam suas atividades nesse período. O objetivo deste trabalho foi estudar os Culicidae que ocorrem no crepúsculo vespertino em uma área de Floresta Atlântica no oeste de Santa Catarina, sul do Brasil. Além disso, foi analisada a possível influência de fatores abióticos, bem como abundância e riqueza de espécies. Para melhor avaliar a influência do período crepuscular na composição das espécies e na abundância destas, o crepúsculo foi dividido em três períodos: pré-crepúsculo, crepúsculo e pós-crepúsculo. Ao final do estudo foram coletados 984 exemplares distribuídos em 12 gêneros e 23 espécies. Trichoprosopon pallidiventer (Lutz, 1905) (59,76%), Aedes crinifer (Theobald, 1903) (8,13%) e Ae. scapularis (Rondani, 1848) (5,89%) foram as espécies mais abundantes. A maior abundância e riqueza de espécies se deram na primavera. Dentre os três períodos estudados, o pré-crepúsculo apresentou a maior abundância de mosquitos, em contrapartida, o pós-crepúsculo apresentou a menor abundância. Os períodos pré-crepuscular e crepuscular apresentaram maior similaridade entre si com relação à composição das espécies. Relacionando os fatores abióticos e as três espécies mais abundantes, não foi observada correlação significativa nos dados avaliados nos sete e 15 dias anteriores às coletas. Entretanto, a temperatura apresentou uma correlação positiva para estas três espécies. A relação entre as espécies coletadas e a potencial transmissão de agentes etiológicos causadores de doenças foi comentada.

Antibacterial activity of oxytetracycline photoproducts in marine aquaculture's water.

Oxytetracycline (OTC) is one of the most used antibiotics in aquaculture. The main concern related to its use is the bacterial resistance, when ineffective treatments are applied for its removal or inactivation. OTC photo-degradation has been suggested as an efficient complementary process to conventional methods used in intensive fish production (e.g.: ozonation). Despite this, and knowing that the complete mineralization of OTC is difficult, few studies have examined the antibacterial activity of OTC photoproducts. Thus, the main aim of this work is to assess whether the OTC photoproducts retain the antibacterial activity of its parent compound (OTC) after its irradiation, using simulated sunlight. For that, three Gram-negative bacteria (Escherichia coli, Vibrio sp. and Aeromonas sp.) and different synthetic and natural aqueous matrices (phosphate buffered solutions at different salinities, 0 and 21‰, and three different samples from marine aquaculture industries) were tested. The microbiological assays were made using the well-diffusion method before and after OTC has been exposed to sunlight. The results revealed a clear effect of simulated sunlight, resulting on the decrease or elimination of the antibacterial activity for all strains and in all aqueous matrices due to OTC photo-degradation. For E. coli, it was also observed that the antibacterial activity of OTC is lower in the presence of sea-salts, as demonstrated by comparison of halos in aqueous matrices containing or not sea-salts.

Mosquitoes (Diptera: Culicidae) from crepuscular period in an Atlantic Forest area in Southern Brazil.

Crepuscular period is one of the factors that may influence the biting activity of mosquitoes. Many of these insects have a peak activity in this period. The purpose of this study was to investigate the afternoon crepuscular activity of Culicidae in a remaining area of Atlantic Forest in western Santa Catarina, southern Brazil. Moreover, the possible influence of abiotic factors, the abundance and species richness were verified. In order to better analyze the influence of crepuscular period in specific composition and abundance of mosquitoes, the dusk was divided into three periods: pre-sunset, sunset and post-sunset. At the end of the study, nine hundred and eight four specimens distributed in 12 genera and 23 species were collected. Trichoprosopon pallidiventer (Lutz, 1905) (59.76%), Aedes crinifer (Theobald, 1903) (8.13%), Ae. scapularis (Rondani, 1848) (5.89%) were the most abundant species. Spring time presented the greatest abundance and species richness. During the study, among the three periods evaluated, pre-sunset had the greatest abundance and post-sunset the lowest. Pre-sunset and sunset had the greatest similarity between species. Regarding to the abiotic factors evaluated seven and 15 days before sampling, they did not present significant correlation for the three most abundant species. However, temperature had a positive correlation to these species. Moreover, the correlation between collected species and its possible role as vectors of etiological agents of diseases was discussed.

Meat characteristics of cattle fed diets containing whole cottonseed / Características da carne de bovinos alimentados com dietas contendo caroço de algodão

Sensory and instrumental analyses evaluated the meat and fat characteristics of feedlot-finished steers fed a diet containing cottonseed. Global impression, texture, meat color, and fat color were assessed. Thirty Nellore bulls with an average age of 30 ± 6 months and initial body weight of 382.7 ± 28.4kg were kept in feedlot stalls and fed the following cottonseed levels: 0; 2.22 %; 4.44 %; 6.66 %; 8.88 %; 11.11 % of the dietary dry matter. The cottonseed used in this experiment had an average free gossypol content of 4.5g/kg of cottonseed. The overall impression of the samples, assessed by the triangle test for difference, did not differ for more than 62 % of the panelists (P>0.01). The shear strength of roasted meat varied from 6.00 to 6.54kg. According to texture profile analysis (TPA), the hardness, springiness, and chewiness of roast meat ranged from 24.15 to 28.01 N, 0.52 to 0.56, 8.42 to 11.01 N, respectively; of raw meat, 9.51 to 13.86 N, 0.26 to 0.29, and 1.38 to 1.81 N, respectively. The different treatments did not affect meat texture, meat color, or fat color (P>0.05). Meat color, luminosity, and red intensity ranged from 37.71 to 42.85, 20.68 to 25.25, and 6.74 to 8.61, respectively; fat color, luminosity, and yellow intensity ranged from 62.26 to 63.78, 11.13 to 11.62, and 10.53 to 10.86, respectively. Cottonseed intake of up to 1.13kg/animal/day, equivalent to a free gossypol intake of 5.05g/animal/day, in place of soybean meal and ground corn, did not significantly change the global sensory impression, texture, and color of the meat and fat.(AU)

Avaliou-se, por meio de análise sensorial e instrumental, o efeito da adição de caroço de algodão à dieta de bovinos confinados sobre as características da carne e da gordura. Foram avaliadas a impressão global, a textura, a cor da carne e a cor da gordura. Trinta touros da raça Nelore, com médias de idade e peso vivo inicial de 30 ± 6 meses e 382,7 ± 28,4kg, foram confinados e receberam dietas com os seguintes teores de caroço de algodão: 0; 2,22%; 4,44%; 6,66%; 8,88%; 11,11% na matéria seca da dieta. O caroço de algodão utilizado neste experimento apresentou conteúdo médio de 4,5g de gossipol livre/kg de caroço de algodão. A impressão global da carne, avaliada por meio de teste triangular de diferença, mostrou que mais de 62% dos provadores não perceberam diferença significativa (P>0,01) entre as amostras. A textura da carne assada avaliada por meio do teste de força de cisalhamento variou de 6,00 a 6,54kg. Na análise do perfil de textura (TPA) da carne assada, a dureza, a elasticidade e a mastigabilidade variaram, respectivamente, de 24,15 a 28,01N, de 0,52 a 0,56N e de 8,42 a 11,01N. Na TPA da carne crua, variaram, respectivamente, de 9,51 a 13,86N, de 0,26 a 0,29N e de 1,38 a 1,81N. Na avaliação da cor da carne, a luminosidade, a intensidade de vermelho e a intensidade de amarelo da cor da carne variaram, respectivamente, de 37,71 a 42,85, de 20,68 a 25,25 e de 6,74 a 8,61. E para a cor da gordura, variaram, respectivamente, de 62,26 a 63,78, de 11,13 a 11,62 e de 10,53 a 10,86. A textura, a cor da carne e a cor da gordura não apresentaram diferenças significativas (P>0,05) entre os diferentes tratamentos. O consumo de caroço de algodão em até 1,13kg/animal/dia, que resultou no consumo de 5,05g de gossipol livre/animal/dia, em substituição ao farelo de soja e ao grão de milho triturado, não causou alterações significativas nas características da carne quanto à impressão sensorial global, à textura, à cor da carne e à cor da gordura.(AU)

Use of sunlight to degrade oxytetracycline in marine aquaculture's waters.

Oxytracycline (OTC) is a broad spectrum antibiotic authorized for use in European aquaculture. Its photo-degradation has been widely studied in synthetic aqueous solutions, sometimes resorting to expensive methods and without proven effectiveness in natural waters. Thus, this work studied the possibility to apply the solar photo-degradation for removal of OTC from marine aquaculture's waters. For that, water samples were collected at different locals of the water treatment circuit, from two different aquaculture companies. Water samples were firstly characterized regarding to pH, salinity, total suspended solids (TSS), organic carbon and UV-Vis spectroscopic characteristics. Then, the samples were spiked with OTC and irradiated using simulated sunlight in order to evaluate the matrix effects on OTC photo-degradation. From kinetic results, the apparent quantum yields and the outdoor half-life times, at 40°N for midsummer and midwinter days were estimated by the first time for these conditions. For a midsummer day, at sea level, the outdoor half-life time predicted for OTC in these aquaculture's waters ranged between 21 and 25 min. Additionally, the pH and salinity effects on the OTC photo-degradation were evaluated and it has been shown that high pH values and the presence of sea salt increase the OTC photo-degradation rate in aquaculture's waters, compared to results in deionised water. The results are very promising to apply this low-cost methodology using the natural sunlight in aquaculture's waters to remove OTC.

Parâmetros genéticos para características produtivas e biométricas em abelha Melipona quadrifasciata anthidioides LEPELETIER / Genetic parameters for production and biometrics traits in honey bee Melipona quadrifasciata anthidioides LEPELETIER

Os objetivos deste trabalho foram estimar componentes de variância genética aditiva, fenotípica e residual e a herdabilidade para características relacionadas com a produção de mel e com a estrutura do ninho de abelhas Melipona quadrifasciata anthidioides. Sessenta colônias de diferentes regiões da Bahia foram transladadas para caixas padronizadas modelo INPA e divididas, originando as gerações parentais G1 e G2. Foram medidas as características: estimativa da produção de mel; número, largura, volume e altura dos potes de mel; número, altura e diâmetro dos potes de pólen; peso; número, largura e diâmetro dos discos de cria e estimativa da população da colônia. As medidas foram corrigidas para o efeito fixo de mês de mensuração. Os componentes de variância e herdabilidade foram estimados por meio do método de semelhança entre parentes, utilizando-se abordagem Bayesiana. As médias e os desvios padrão variaram de 2,01±0,70cm para diâmetro de potes de pólen a 2.333,0±384,1kg para o peso das caixas. Houve indicação de convergência para todas as cadeias obtidas. As estimativas de variância genética aditiva variaram de 0,02cm para as características largura dos potes de mel a 38.587,72kg para o peso. Para as estimativas de variâncias fenotípicas, os valores variaram de 0,05 para a altura dos potes de pólen a 95.136,43kg para o peso; e para as variâncias residuais, os valores encontrados variaram de 0,02 para a variável largura dos potes de mel a 56.548,71kg para o peso. As estimativas de herdabilidade variaram de 0,35 a 0,53. Os resultados demonstraram que as características avaliadas possuem variação genética aditiva que garante boa resposta à seleção.

The aim of this study was to estimate components of genetic variance, phenotypic and residual and heritability for traits related to the production of honey and the nest structure of bee Melipona quadrifasciata anthidioides. Sixty colonies from different regions of Bahia were transferred to standard INPA model boxes and divided, creating the parental generations G1 and G2. The following characteristics were measured: estimated production of honey, number, width, height and volume of the honey pots, number, height and diameter of pollen storage pots, weight, number, length and diameter of the brood combs and estimate the population of the colony. The measurements were corrected for the fixed effects of month of measurement. The variance components and heritability were estimated by the method of similarity between relatives using the Bayesian approach. The mean and standard deviations ranged from 2.01±0.70cm diameter pots for pollen to 2333.0±384.1kg to the weight of the boxes. There was indication of convergence for all the chains obtained. Estimates of the additive genetic variance ranged from 0.02cm to the width characteristics of honey pots to 38587.72kg for weight. For the estimates of phenotypic variance the values ranged from 0.05 for the height of the pollen pots to 95136.43kg for weight; and the residual variance the values varied from 0.02 for the variable width of the honey pots to 56548.71kg for weight. The results showed that the characteristics assessed have additive genetic variation that ensures good response to selection.

Extracorporeal photopheresis combined with pentostatin in the conditioning regimen for canine hematopoietic cell transplantation does not prevent GVHD.

Extracorporeal photopheresis (ECP) and the purine analog pentostatin exert potent immunomodulatory effects. We evaluated the use of these treatment modalities to prevent GVHD in a canine model of unrelated dog leukocyte Ag-mismatched hematopoietic cell transplantation, after conditioning with 920 cGy TBI. We have shown previously in this model that 36/40 dogs given MTX alone as postgrafting immunosuppression engrafted and that 25 of 40 dogs had severe GVHD and median survival of 21 days. In the current study, nine dogs received conditioning with 920 cGy TBI and postgrafting MTX either with ECP on days -2 to -1 alone (n=5) or ECP on days -6 and -5 combined with two doses of pentostatin (days -4 to -3) (n=4). Seven of nine dogs achieved engraftment. Six dogs developed severe acute GVHD (four in the group with ECP alone and two with pentostatin and ECP). We failed to demonstrate a positive impact of ECP and pentostatin for the prevention of GVHD compared with historical control dogs.

Photochemical and microbial alterations of DOM spectroscopic properties in the estuarine system Ria de Aveiro.

The influence of photochemical transformations of chromophoric dissolved organic matter (CDOM) on microbial communities was evaluated in the estuarine system Ria de Aveiro. Two sites, representative of the marine and brackish water zones of the estuary, were surveyed regularly in order to determine seasonal and vertical profiles of variation of CDOM properties. Optical parameters of CDOM indicative of aromaticity and molecular weight were used to establish CDOM sources, and microbial abundance and activity was characterized. Additionally, microcosm experiments were performed in order to simulate photochemical reactions of CDOM and to evaluate microbial responses to light-induced changes in CDOM composition. The CDOM of the two estuarine zones showed different spectral characteristics, with significantly higher values of the specific ultra-violet absorbance at 254 nm (SUVA254) (5.5 times) and of the absorption coefficient at 350 nm (a350) (12 times) and lower SR (S275-295/S350-400) ratio at brackish water compared with the marine zone, reflecting the different amounts and prevailing sources of organic matter, as well as distinct riverine and oceanic influences. At the marine zone, the abundance of bacteria and the activity of Leu-AMPase correlated with a350 and a254, suggesting a microbial contribution to the HMW CDOM pool. The irradiation of DOM resulted in a decrease of the values of a254 and a350 and an increase of the slope S275-295 and of the ratios E2 : E3 (a250/a365) and SR, which in turn increase its bioavailability. However, the extent of photoinduced transformations and microbial responses was dependent on the initial optical characteristics of CDOM. In Ria de Aveiro both photochemical and microbial processes yielded optical changes in CDOM and the overall results of these combined processes determine the fate of CDOM in the estuarine system and have an influence on local productivity and in adjacent coastal areas.

BDE-209: kinetic studies and effect of humic substances on photodegradation in water.

BDE-209 is a brominated flame retardant and a priority contaminant, which has been found in several environmental matrices, namely, in water. To date, there are no quantum yield data for BDE-209 photodegradation by sunlight in water, to allow predicting half-life times in aquatic systems. In this work, the kinetics of BDE-209 photodegradation in water was studied and the influence of different fractions of aquatic humic substances (HS) was evaluated. Aqueous solutions of BDE-209 exposed for different periods of time to simulated sunlight were analyzed by HPLC-UV after being concentrated using dispersive liquid-liquid microextraction (DLLME) or solid-phase extraction (SPE). The photodegradation of BDE-209 in aqueous solution followed pseudo-first-order kinetics. The average quantum yield obtained of 0.010 ± 0.001 (about 20-fold lower than the quantum yield determined in ethanol) allow to predict an outdoor half-life time of 3.5 h. The photodegradation percentage of BDE-209 was not significantly affected by the XAD-4 fraction of HS, but it decreased substantially in the presence of humic and fulvic acids. Light screening by the humic substances could not explain this delay, which is probably the result of the association of the compound with the hydrophobic sites of the humic material.

Kinetics of the PO4-P adsorption onto soils and sediments from the Mondego estuary (Portugal).

In order to assess the status of a North Atlantic Ocean Ecoregion (Mondego system, Portugal) after the implementation of a management programme, a study on PO4-P sorption was carried out. Considering that sorption velocity markedly determines the systems promptness to phosphorus external loading, the kinetics of the sorption of PO4-P onto estuarine sediments and the upstream agricultural soils was studied. The pseudo-second order kinetic equation gave an appropriate description of PO4-P sorption onto these soils and sediments, allowing for a quantitative comparison. For soils, the kinetic constants (k2*, µg(-1) g h(-1)) ranged between 0.007 and 0.017 µg(-1) g h(-1) while, in the case of sediments these ranged between 0.008 and 0.012 µg(-1) g h(-1). Results showed that the reduction of water residence time after the management action was relevant for the system status, affecting its reaction capacity to phosphorus loading.

Photodegradation of the fungicide thiram in aqueous solutions. Kinetic studies and identification of the photodegradation products by HPLC-MS/MS.

In this study, the relevance of photodegradation processes on the persistence of the fungicide thiram in waters was investigated. The photodegradation of thiram in Milli-Q water and in aqueous solutions of humic and fulvic acids, as well as the photodegradation in spiked river water were studied. Both pure thiram and one of its commercial formulations were used to prepare the solutions which were irradiated in a solar light simulator. In general, thiram photodegradation follows pseudo-first order kinetics. The half-life time of thiram 2mgL(-1) in Milli-Q water was 28min. However, the degradation rate of thiram was significantly increased (p=0.02) by the inert components of the thiram commercial formulation as well as by commercial humic acids and by fulvic acids isolated from river water (p<0.004). Thus, the half-life time of thiram decreased to 24min in the presence of the inert formulation components, while, in the presence of both humic and fulvic acids (10mgL(-1)) it decreased to 22min. Furthermore, thiram photodegradation in natural river water showed that there is a significant enhancement of the degradation rate constant of thiram relatively to Milli-Q water, corresponding to a decrease of about 38% in its half-life time. This increase of the degradation rate in river water seems to be higher than that observed in the presence of FA, suggesting that beyond organic matter, other natural river components can increase the thiram photodegradation rate. These results allow us to conclude that photodegradation by solar radiation can be an important degradation pathway of thiram in natural waters. HPLC-MS/MS allowed to identify, for the first time, three products of the photodegradation of thiram in aqueous solution. Three compounds were identified and their structure was corroborated by the MS(n) spectra fragmentation profile. Pathways for the formation of the products from thiram photodegradation are proposed and discussed.

Ex vivo antimicrobial efficacy of the EndoVac system plus photodynamic therapy associated with calcium hydroxide against intracanal Enterococcus faecalis.

AIM: To evaluate the ex vivo efficacy of the EndoVac system and photodynamic treatment (PDT) as adjuncts to chemomechanical debridement associated with calcium hydroxide (CaOH2 ) in reducing the levels of intracanal Enterococcus faecalis. METHODOLOGY: One hundred and twenty-five sterile premolar teeth were conventionally accessed, prepared and then contaminated with E. faecalis (ATCC 29212) for 30 days. Teeth were randomly divided into 4 groups: Control (chemomechanical debridement with conventional irrigation); Endovac (chemomechanical debridement with EndoVac system); PDT (chemomechanical debridement with conventional irrigation and PDT) and Endovac+PDT (chemomechanical debridement with EndoVac and PDT). The irrigants used in all groups were 5.25% sodium hypochlorite and 17% EDTA. After treatment, an intracanal dressing (CaOH2 ) was applied in all canals for 7 days. Samples were obtained before (T1) and after the therapeutic procedures (T2) and, after intracanal medication (T3), plated onto BHI media and incubated (37 °C, 48 h) to determine the colony-forming units (CFU mL(-1) ). RESULTS: The overall mean cell counts (CFU mL(-1) ) of E. faecalis were high at the initial contamination (T1). A significant reduction (P < 0.05) of E. faecalis mean counts was observed in all groups from baseline (T1) to both post-therapy samplings (T2 and T3); no differences amongst the groups were detected. No significant change in bacterial counts from T2 to T3 was detected. CONCLUSION: The adjunctive use of the EndoVac system and the photodynamic treatment, in combination or not, was as effective as the conventional chemomechanical debridement associated with CaOH2 on reducing the counts of intracanal E. faecalis.

Effect of long term organic amendments on adsorption-desorption of thiram onto a luvisol soil derived from loess.

The objective of this work was to assess the influence of soil organic amendments on the sorption properties of the fungicide thiram. The organic amendments studied were organic household compost (COM), sewage sludge from municipal water treatment facilities (SLU) and farmyard manure (FYM), which were compared to mineral fertilizer application (MIN). Sorption-desorption experiments were performed using the batch method and the results indicated that the adsorption isotherms were non-linear and were found to conform to the Brunauer-Emmett-Teller (BET) model, suggesting multilayer adsorption and adsorbate-adsorbate interactions after the saturation of the surface layer. In general, distribution coefficient values, K(D), are dependent on, but not proportional to, the initial concentration of thiram. For a fixed thiram initial concentration, a significant correlation (r(2)>0.851; p<0.001) between K(D) values and the soil organic carbon content (OC) was observed. The highest value of K(D) was observed for the soil amended with compost, which is the one with the highest organic carbon content. K(D) values were divided by the soil organic carbon contents in order to obtain organic carbon partition coefficients K(OC). Comparing K(OC) means from 3 (initial concentrations) x 4 (soil organic matter compositions) x 3 (replicates) factorial ANOVA allow us to conclude that there is a significant but not proportional influence of the initial concentration of thiram on those values, but changes in the soil organic matter composition, associated to different soil amendments, have no significant influence on adsorption of thiram. To evaluate the reversibility of thiram adsorption, two consecutive desorption cycles were performed with CaCl(2) 0.01 mol L(-1). The desorption K(D) values were consistently higher (approximately twice) than those for adsorption at the same equilibrium concentrations for all soil samples supporting the existence of hysteresis in the adsorption-desorption behavior of thiram. Despite the fact that the adsorption K(D) values were proportionally increased with increasing total organic carbon content, this was not the case for the desorption K(D) values.

Adsorption-desorption behavior of thiram onto humic acid.

The adsorption/desorption behavior of pure thiram (Thi-P) and formulated thiram (Thi-F) onto commercial humic acids (HA) was studied using a batch equilibration procedure. Results of adsorption kinetic experiments showed that thiram adsorption is a fast process since 85% of the equilibrium concentration is reached within two hours. Experimental K(D) values between 0.110 to 0.210 L g(-1) were obtained for the adsorption of both Thi-P and Thi-F onto HA, suggesting that thiram is strongly sorbed by humic acids. In general, for both Thi-P and Thi-F, the lower the initial thiram concentration, the stronger is its adsorption (higher K(D) and percentage adsorption values). The adsorption isotherms were found to match the BET model. The results show that thiram adsorption onto condensed humic acids cannot be explained only in terms of specific interactions, such as those identified in studies of adsorption of thiram with humic acids in solution. The comparison of sorption and desorption results allowed the observation of hysteresis phenomena. Desorption K(D) values were consistently higher than those for adsorption at the same equilibrium concentration. Hysteresis was lower for the formulated thiram suggesting that adsorption is more reversible in the presence of the formulation components turning the pesticide more susceptible to be leached.

Influence of fulvic acids and copper ions on thiram determination in water.

The literature concerning the application of solid-phase extraction (SPE) to the concentration of thiram (bis(dimethyldithiocarbamoyl) disulfide) from natural waters is scarce, the available results being contradictory or with no analytical significance. To clarify these contradictory results, a C18-SPE procedure combined with HPLC-UV was applied to thiram analysis in river water, and the influence of several factors on recoveries was studied. This procedure gave thiram recoveries of about 100% when applied to thiram standard solutions. However, when the same procedure was applied to river water samples spiked with thiram, the recoveries depended on the equilibration time after spiking. The influence of river fulvic acids (FAs) and Cu(II) on thiram recoveries from standard solutions was studied as a possible interference for such a result. In the presence of FA, thiram recoveries were always higher than 85%. In the presence of Cu(II), thiram recoveries decreased significantly, due to complexation, but the addition of an excess of EDTA before C18-SPE eliminated that interference, and thiram was completely recovered. However, in river water samples the addition of EDTA had to be done before thiram spiking to obtain a recovery >90%. Thiram standard solutions containing both river FA and Cu(II) showed a behavior similar to the one observed in river water samples. On the basis of these results, the catalytic effect of Cu(II) on the degradation of thiram by FA, with formation of a Cu(II)-dimethyldithiocarbamate complex, was hypothesized.

A solid-phase extraction procedure for the clean-up of thiram from aqueous solutions containing high concentrations of humic substances.

A simple solid-phase extraction (SPE) procedure with an octadecyl bonded phase silica (C(18)) was developed for clean-up of the fungicide thiram from aqueous solutions containing high concentrations of humic substances, for future studies of thiram adsorption onto solid humic substances or soils. Suspensions of humic acids and soil, in aqueous 0.01M CaCl(2) solution, were prepared and used as samples. These extracts were spiked with thiram and immediately applied to a C(18)-SPE cartridge. Thiram was eluted with chloroform and its concentration measured by spectrophotometry at 283nm. Non-spiked aqueous extracts (blanks) and a control sample of thiram in 0.01M CaCl(2) aqueous solution were also prepared and submitted to the same SPE procedure. The results show that humic substances are extensively retained by the C(18) cartridge but are not eluted with CHCl(3). Recoveries of 100-104% were obtained for thiram in the presence of humic substances. The SPE procedure described in this work is an efficient clean-up step to remove the interference of humic substances absorbance and to be coupled to any spectrophotometric or HPLC-UV method, usually used for thiram analysis in food extracts.

Fluorescence and DOC contents of estuarine pore waters from colonized and non-colonized sediments: effects of sampling preservation.

The influence of the colonization of salt marsh sediments with Halimione portulacoides was evaluated by analysing the fluorescent dissolved organic matter (FDOM) in sediment pore waters from a salt marsh at different depths. Cores of sediments at colonized and non-colonized sites were collected from a coastal lagoon (Ria de Aveiro, Portugal). The DOC content of extracted pore waters was determined and characterized by synchronous molecular fluorescence (Deltalambda=60nm) and UV-visible spectroscopies. The common practice of freezing sediment cores for further and later chemical investigation was shown not to be an appropriate methodology of sample preservation. On the contrary, freezing of extracted and filtered pore water seemed not to affect either the DOC content or the fluorescence properties of pore waters. Two types of fluorescent substances were found in the pore waters spectra; one corresponding to humic-like substances and another one resembling proteins. However, major differences were found in the spectra of pore waters depending on both depth and the presence/absence of vegetation colonization.