Risk management measures for REACH registered intermediate substances in pulp mill

Tämän työn tavoitteena on antaa kuvaus riskinhallintamenetelmistä viidelle välituotekemikaalille, joita käytetään Stora Enson Imatran tehtailla. Välituotekemikaalit ovat mustalipeä, viherlipeä, valkolipeä, natriumbisulfiitti ja natriumsulfiitti. Nämä kemikaalit ovat jo rekisteröityjä ECHA:an ja rekisteröintiin liittyen ECHA:an on toimitettava myös kuvaus riskinhallintamenetelmistä. Työn alussa kuvaillaan työn kannalta olennaiset säädökset ja viranomaiset, jotka valvovat kemikaalien käyttöä ja valmistusta Euroopan Unionin alueella. Tämän jälkeen kerrotaan yleisesti välituotekemikaalien rekisteröintikriteereistä. Työn loppuosa käsittää kuvauksen riskinhallintamenetelmistä jokaiselle kemikaalille. Riskinhallintamenetelmät sisältävät eristyksen teknisin keinoin, menettelytapa- ja valvontatekniikat, johtamistavat ja henkilökunnan koulutuksen ja välituotekemikaalien kuljetuksen. Myös jokaisen kemikaalin ominaisuudet on kuvattu ja lyhyt prosessikuvaus kemikaalien valmistuksesta ja käytöstä on esitetty helpottamaan ymmärtämistä.

Estudo da fotocatálise heterogênea sobre Ti/TiO2 na descoloração de corantes sintéticos

The main goal of this paper was to study the degradation of synthetic dyes using photoelectrocatalytic properties of particulate films of TiO2 supported on plates of titanium and stimulated by UV-Vis radiation. The dyes decolorizations were measured using spectrophotometric methods to verify which the conditions on Ti/TiO2 electrode was the best for the photoelectrodegradation of them. The results showed that decolorization rates were higher than 90% during a period of 270 min. FT-IR spectroscopy showed that intermediate substances were formed after the decolorization and N=N group/aromatic structures were preserved independently of the specific structure of the dyes.

MOLLUSCICIDAL AND LARVICIDAL ACTIVITIES OF Atriplex inflata AERIAL PARTS AGAINST THE MOLLUSK Galba truncatula, INTERMEDIATE HOST OF Fasciola hepatica

Fasciolosis is a widespread parasitosis of farm live-stock in many developing countries. For this reason, it is necessary to search for new substances against parasitic diseases caused by flukes. Indeed, a wide variety of terrestrial plants have been subjected to chemical and pharmacological screening in order to discover their potential for human medicinal use. The molluscicidal and larvicidal activities of Atriplex inflata were tested on Galba truncatula and Fasciola hepatica larval stages infecting this snail in Tunisia. Phytochemical tests were conducted on extracts in order to establish a meaningful relationship with molluscicidal and larvicidal activities. The molluscicidal activity was evaluated by subjecting snails to sample aqueous solutions. Accordingly, hexane, ethyl acetate, methanol and methanol-water (8:2, v-v) were used as extraction solvents. As a result, hexane and ethyl acetate extracts showed potent activity, according to the World Health Organization, giving LC50 = 7.59 mg/L and 6.69 mg/L for hexane extracts of leaves and fruits, respectively. Ethyl acetate extracts gave LC50 = 5.90 mg/L and 7.32 mg/L for leaves and fruits, successively. Molluscicidal activities of powders were less potent on snails, but active according to the World Health Organization. Hexane and ethyl acetate extracts from leaves and fruits gave potent larvicidal activities with a delay rate exceeding 45.50% (45.50- 98.92%). Phytochemical tests showed that these activities may be attributed to the presence of triterpenoids and/or sterols.

The use of total luminescence spectroscopy in the investigation of the effects of different rice management practices on humic substances of a planosol

In the Earth's carbon cycle, C stocks in the soil are higher than in vegetation and atmosphere. Maintaining and conserving organic C concentrations in the soil by specific management practices can improve soil fertility and productivity. The aim of this study was to evaluate the impact of agricultural management techniques and influence of water regime (flooded or drained) on the structure of humic substances by excitation/emission matrix fluorescence. Six samples of a Planosol (Planossolo by the Brazilian System of Soil Classification) were collected from a rice field. Humic substances (HS) were extracted from flooded and drained soil under different agricultural management techniques: conventional tillage, reduced tillage and grassland. Two peaks at a long emission wavelength were observed in the EEM spectra of HA whereas those of the corresponding FA contained a unique fluorophore at an intermediate excitation/emission wavelength pair (EEWP) value. The fluorescence intensity measured by total luminescence (FI TL) of HA was lower than that of the corresponding FA. A comparison of all samples (i.e., the HA values compared to each other) revealed only slight differences in the EEWP position, but the FI TL values were significantly different. In this soil, anoxic conditions and reduced tillage (little plowing) seem to favor a higher degree of humification of the soil organic matter compared with aerated conditions and conventional tillage.

La comorbidité de l'épuisement professionnel et de la consommation de substances psychoactives.

L’objectif principal du présent mémoire réside dans l’exploration des liens concomitants existant entre les trois dimensions de l’épuisement professionnel telles que définies par Maslach (1981) et la consommation de substances psychoactives, plus précisément au niveau de la consommation épisodique excessive et hebdomadaire à risque d’alcool et de la consommation de médicaments psychotropes. À partir d’un échantillon composé de 1809 travailleurs provenant de 83 milieux de travail québécois, des profils-types correspondant à des formes particulières de comorbidité de santé mentale au travail sont identifiés grâce à la méthode d’analyse en classes latentes. Ainsi quatre profils-types sont dégagés: un premier regroupant les individus dits «sains», dont les scores aux différentes dimensions de l’épuisement professionnel sont faibles et dont la consommation de substances psychoactives est modérée; deux autres correspondant à des formes intermédiaires de risques; et un quatrième rassemblant des travailleurs dits «fragiles» dont les scores pour chacune des dimensions de l’épuisement professionnel se situent dans le quintile le plus élevé et dont les probabilités de consommation de substances psychoactives sont grandes. De plus, cette recherche s’est penchée sur l’identification de facteurs de risque et de protection associés à chacun des profils-types. À cet effet, les résultats des analyses corroborent la plupart des associations retrouvées au sein de la littérature quant aux facteurs du travail (composantes des modèles du stress professionnel de Karasek et Theorell (1990) ainsi que de Siegrist (1990)), hors travail (statut matrimonial, obligations parentales, revenu du ménage) et certaines caractéristiques individuelles (âge et genre). De faibles récompenses et un fort degré de surinvestissement de la part de l’individu se révèlent être des facteurs de risque particulièrement significatifs pour les formes intermédiaires et à risque de comorbidité de la santé mentale au travail. Dans une moindre mesure, une faible utilisation des compétences, des demandes psychologiques élevées, un soutien social inadéquat et le jeune âge expliquent une part de la variation observée entre les différents profils-types. Enfin, les résultats soutiennent une conceptualisation tridimensionnelle de l’épuisement professionnel.

Release of intermediate reactive hydrogen peroxide by macrophage cells activated by natural products

By determining the hydrogen peroxide (H2O2) released in cultures of peritoneal macrophage cells from Swiss mice, we evaluated the action of 27 vegetable compounds (pristimerin, tingenone, jatrophone, palustric acid, lupeol, cladrastin, ocoteine, boldine, tomatine, yohimbine, reserpine, escopoletin, esculine, plumericin, diosgenin, deoxyschizandrin, p-arbutin, mangiferin, and others) using a 2 mg/ml solution of each compound (100 mug/well). Macrophages are cells responsible for the development of the immunological response reaction, liberating more than one hundred compounds into the extracellular environment. Among these are the various cytokines and the intermediate compounds of nitrogen (NO) and oxygen (H2O2). This coordinated sequence of biochemical reactions is known as the oxidative burst. When we compared the results with those obtained with zymosan (an important stimulator of H2O2) we observed that the compounds showing the highest activity were substances 2 (tingenone), 16 (reserpine) and 20. Other substances such as compounds 1, 4, 5, 6, 8, 12, 13, 14, 15, 17, 19, 23, 24, 26, and 27 also showed a certain activity, but with less intensity than the aforementioned ones. Compounds 3, 7, 9, 10, 11, 18, 21, 22 and 25 presented no activity. These results suggest that natural products (mainly tingenone and reserpine and others) with different chemical structures are strong immunological modulators. However, further tests are needed to determine the 'oxidative burst' in future studies.

Molluscicidal activity of some marine substances against the snail Biomphalaria glabrata (Mollusca, Planorbidae)

Freshwater snails of the genus Biomphalaria play a major role as intermediate hosts of Schistosoma mansoni, the etiologic agent of schistosomiasis. While Biomphalaria spp. control by molluscicides is one of the main strategies to reduce the snail population in infected areas, there are few effective molluscicides commercially available. Natural products may be considered as potentially useful and safe molluscicides. We have evaluated the molluscicidal activity of 12 extracts from ten marine organisms on adult and embryonic stages of Biomphalaria glabrata. Only extracts of the red algae Liagora farinosa and of the sponge Amphimedon viridis presented molluscicidal activity. Lethal concentration (LC)(50) values obtained were 120 mu g/mL for L. farinosa CH2Cl2 extract (apolar fraction) and 20 mu g/mL for A. viridis extract and halitoxin. The polar alga fraction and halitoxin had no effect on B. glabrata embryos. The algae apolar fraction was active on B. glabrata in all embryonic development stages, with LC50 values for blastulae at 42 mu g/mL, gastrulae at 124 mu g/mL, trochophore at 180 mu g/mL, and veliger at 222 mu g/mL. This is the first report of extracts from marine organisms which presented molluscicidal activity.

New routes to enantioenriched substances through small organic molecules

In this thesis we will disclose the results obtained from the diastereoisomeric salt formation (n salt, p salt and p1,n1 salt) between non-racemic trans-chrysanthemic acid (trans-ChA) and pure enantiomers of threo-2-dimethylamino-1-phenyl-1,3-propanediol (DMPP). The occurrence of p1,n1 salt formation can have profound effects on enantiomer separation of scalemic (non-racemic) mixtures. This phenomenon when accompanied by substrate self-association impedes the complete recovery of the major enantiomer through formation of an inescapable racemate cage. A synthetic sequence for the asymmetric synthesis of bicyclo[3.2.0]heptanones and bicyclo[3.2.0]hept-3-en-6-ones through a cycloaddition strategy is reported. The fundamental step is a [2+2]-cycloaddition of an enantiopure amide derived from the reaction between a set of acids and an oxazolidinone as the chiral auxiliary. The inter- and intramolecular cycloaddition of in situ-generated keteniminium salts gives bicycles with a good enantioselection. A key intermediate of Iloprost, a chemically stable and biologically active mimic of prostacyclin PGI2 is synthesized following a ‘green approach’. An example of simple optical resolution of this racemic intermediate involving the diastereoisomeric salt formation is described.

Übergangsmetallvermittelte [2+2+2]-Zyklotrimerisierungsreaktionen zum Aufbau anellierter Phthalide : Intermediate zur Synthese von Anguzyklinonen

Anguzykline sind eine große Gruppe von Naturstoffen. Ihnen ist gemein, dass sie eine Benz[a]anthracen-Struktur besitzen oder dass sie in der Biosynthese aus einer Verbindung mit einem solchem Grundgerüst hervorgegangen sind. Viele Vertreter der Anguzykline sind bioaktive Substanzen mit insbesondere antibiotischer Wirkung. In dieser Arbeit wurde eine flexible, modulare Synthese für Anguzykline erarbeitet. Eine Schlüsselreaktion stellte die intramolekulare [2+2+2]-Zykloaddition aus Triinen zu Phthaliden dar. Die in dieser Umwandlung eingesetzten Triine enthalten eine Diin- und eine Monoinkomponente, die über eine Esterbindung miteinander verknüpft sind. Die intramolekulare [2+2+2]-Zyklotrimerisierung wurde an zwei verschiedenen Strukturen der Triinsysteme untersucht: Zum einen Triine, in denen Nona-2,8-diinsäuren mit 1-Aryl-propargylalkoholen verknüpft waren und zum anderen Substrate, in denen die Propargylsäureester von 1-Aryl-nona-2,8-diin-1-olen gebildet wurden. Für die Umsetzung wurden zwei verschiedene Katalysatoren verwendet. Neben dem Wilkinsonkatalysator wurde der Rutheniumkatalysator [Cp*RuCl(cod)] eingesetzt. Beide Katalysatoren sind für die Reaktion geeignet und ergänzen sich hinsichtlich der verschiedenen Triinsysteme. Die Phthalide dienten als Intermediate für den Aufbau eines Tetrahydrobenz[a]anthrachinon-Grundgerüst. Zum Aufbau dieser Struktur wurde eine Synthesesequenz zur Gerüstumlagerung vorgestellt und die Synthesemethode auf verschiedene Vertreter der Anguzyklin-Familie angewendet. Besonderes Augenmerk wurde auf die Synthese des Urdamycinon B gelegt, in dem das Grundgerüst C-glykosidisch mit einem Olivosesubstituenten verknüpft ist.

Newly detected ozone-depleting substances in the atmosphere

Ozone-depleting substances emitted through human activitiescause large-scale damage to the stratospheric ozone layer, and influence global climate. Consequently, the production of many of these substances has been phased out; prominent examples are the chlorofluorocarbons (CFCs), and their intermediate replacements, the hydrochlorofluorocarbons (HCFCs). So far, seven types of CFC and six types of HCFC have been shown to contribute to stratospheric ozone destruction 1,2. Here, we report the detection and quantification of a further three CFCs and one HCFC. We analysed the composition of unpolluted air samples collected in Tasmania between 1978 and 2012, and extracted from deep firn snow in Greenland in 2008, using gas chromatography with mass spectrometric detection. Using the firn data, we show that all four compounds started to emerge in the atmosphere in the 1960s. Two of the compounds continue to accumulate in the atmosphere. We estimate that, before 2012, emissions of all four compounds combined amounted to more than 74,000 tonnes. This is small compared with peak emissions of other CFCs in the 1980s of more than one million tonnes each year 2. However, the reported emissions are clearly contrary to the intentions behind the Montreal Protocol, and raise questions about the sources of these gases.

Substances hazardous to health:the nature of the expertise associated with competent risk assessment

This research investigated expertise in hazardous substance risk assessment (HSRA). Competent pro-active risk assessment is needed to prevent occupational ill-health caused by hazardous substance exposure occurring in the future. In recent years there has been a strong demand for HSRA expertise and a shortage of expert practitioners. The discipline of Occupational Hygiene was identified as the key repository of knowledge and skills for HSRA and one objective of this research was to develop a method to elicit this expertise from experienced occupational hygienists. In the study of generic expertise, many methods of knowledge elicitation (KE) have been investigated, since this has been relevant to the development of 'expert systems' (thinking computers). Here, knowledge needed to be elicited from human experts, and this stage was often a bottleneck in system development, since experts could not explain the basis of their expertise. At an intermediate stage, information collected was used to structure a basic model of hazardous substance risk assessment activity (HSRA Model B) and this formed the basis of tape transcript analysis in the main study with derivation of a 'classification' and a 'performance matrix'. The study aimed to elicit the expertise of occupational hygienists and compare their performance with other health and safety professionals (occupational health physicians, occupational health nurses, health and safety practitioners and trainee health and safety inspectors), as evaluated using the matrix. As a group, the hygienists performed best in the exercise, and this group were particularly good at process elicitation and at recommending specific control measures, although the other groups also performed well in selected aspects of the matrix and the work provided useful findings and insights. From the research, two models of HSRA have been derived, an HSRA aid, together with a novel videotape KE technique and interesting research findings. The implications of this are discussed with respect to future training of HS professionals and wider application of the videotape KE method.

Chitosan Nanoparticles Loaded The Herbicide Paraquat: The Influence Of The Aquatic Humic Substances On The Colloidal Stability And Toxicity.

Polymeric nanoparticles have been developed for several applications, among them as carrier system of pesticides. However, few studies have investigated the fate of these materials in the environment in relation to colloidal stability and toxicity. In nature, humic substances are the main agents responsible for complexation with metals and organic compounds, as well as responsible for the dynamics of these nanoparticles in aquatic and terrestrial environments. In this context, the evaluation of the influence of aquatic humic substances (AHS) on the colloidal stability and toxicity of polymeric nanoparticles of chitosan/tripolyphosphate with or without paraquat was performed. In this study, the nanoparticles were prepared by the ionic gelation method and characterized by size distribution measurements (DLS and NTA), zeta potential, infrared and fluorescence spectroscopy. Allium cepa genotoxicity studies and ecotoxicity assays with the alga Pseudokirchneriella subcapitata were used to investigate the effect of aquatic humic substances (AHS) on the toxicity of this delivery system. No changes were observed in the physical-chemical stability of the nanoparticles due to the presence of AHS using DLS and NTA techniques. However some evidence of interaction between the nanoparticles and AHS was observed by infrared and fluorescence spectroscopies. The ecotoxicity and genotoxicity assays showed that humic substances can decrease the toxic effects of nanoparticles containing paraquat. These results are interesting because they are important for understanding the interaction of these nanostructured carrier systems with species present in aquatic ecosystems such as humic substances, and in this way, opening new perspectives for studies on the dynamics of these carrier systems in the ecosystem.

In vitro effect of low intensity laser on the cytotoxicity produced by substances released by bleaching gel

This in vitro study aimed to analyze the effect of different parameters of phototherapy with low intensity laser on the viability of human dental pulp fibroblasts under the effect of substances released by bleaching gel. Cells were seeded into 96 wells plates (1 x 10³ cells/well) and placed in contact with culture medium conditioned by a 35 % hydrogen peroxide bleaching gel for 40 minutes, simulating the clinical condition of the in-office bleaching treatment. Cells cultured in ideal growth conditions served as positive control group (PC), and the cells grown in conditioned medium and non-irradiated served as negative control group (NC). Cells grown in conditioned medium were submitted to a single irradiation with a diode laser (40 mW, 0.04 cm²) emitting at visible red (660 nm; RL) or near infrared (780 nm; NIR) using punctual technique, in contact mode and energy densities of 4, 6 or 10 J/cm². The cell viability was analyzed through the MTT reduction assay immediately and 24 hours after the irradiation. The data was compared by ANOVA followed by the Tukey's test (p < 0.05). The cell viability increased significantly in 24 hours within each group. The PC presented cell viability significantly higher than NC in both experimental times. Only the NIR/10 J/cm² group presented cell viability similar to that of PC in 24 hours. The phototherapy with low intensity laser in defined parameters is able to compensate the cytotoxic effects of substances released by 35 % hydrogen peroxide bleaching gel.

Effect of nitric oxide inhibitor and donor substances on the infammatory process caused by endodontic irrigants

Nitric oxide (NO) has been considered a key molecule in infammation. OBJECTIVE: The aim of this study was to evaluate the effect of treatment with L-NAME and sodium nitroprussiate, substances that inhibit and release NO, respectively, on tissue tolerance to endodontic irrigants. MATERIAL AND METHODS: The vital dye exudation method was used in a rat subcutaneous tissue model. Injections of 2% Evans blue were administered intravenously into the dorsal penial vein of 14 male rats (200-300 g). The NO inhibitor and donor substances were injected into the subcutaneous tissue in the dorsal region, forming two groups of animals: G1 was inoculated with L-NAME and G2 with sodium nitroprussiate. Both groups received injections of the test endodontic irrigants: acetic acid, 15% citric acid, 17% EDTA-T and saline (control). After 30 min, analysis of the extravasated dye was performed by light absorption spectrophotometry (620 nm). RESULTS: There was statistically signifcant difference (p<0.05) between groups 1 and 2 for all irrigants. L-NAME produced a less intense infammatory reaction and nitroprussiate intensifed this process. CONCLUSIONS: Independently of the administration of NO inhibitors and donors, EDTA-T produced the highest irritating potential in vital tissue among the tested irrigating solutions.

Unsuccessful attacks dominate a drone-preying wasp's hunting performance near stingless bee nests

Bee males (drones) of stingless bees tend to congregate near entrances of conspecific nests, where they wait for virgin queens that initiate their nuptial flight. We observed that the Neotropical solitary wasp Trachypus boharti (Hymenoptera, Cabronidae) specifically preys on males of the stingless bee Scaptotrigona postica (Hymenoptera, Apidae); these wasps captured up to 50 males per day near the entrance of a single hive. Over 90% of the wasp attacks were unsuccessful; such erroneous attacks often involved conspecific wasps and worker bees. After the capture of non-male prey, wasps almost immediately released these individuals unharmed and continued hunting. A simple behavioral experiment showed that at short distances wasps were not specifically attracted to S. postica males nor were they repelled by workers of the same species. Likely, short-range prey detection near the bees' nest is achieved mainly by vision whereas close-range prey recognition is based principally on chemical and/or mechanical cues. We argue that the dependence on the wasp's visual perception during attack and the crowded and dynamic hunting conditions caused wasps to make many preying attempts that failed. Two wasp-density-related factors, wasp-prey distance and wasp-wasp encounters, may account for the fact that the highest male capture and unsuccessful wasp bee encounter rates occurred at intermediate wasp numbers.