Els valors límit d'exposició professional i límits biològics per a agents químics en l'àmbit de treball, mesura i control. Evolució de la normativa sobre el plom i la seva incidència sobre els accidents laborals i malalties professionals en la indústria ceràmica

L'objectiu d'aquesta tesi és l'estudi dels valors límit d'exposició professional previstos en la normativa actual com a valors de referència per a l'avaluació i control dels riscos que comporta l'exposició a agents químics presents en el lloc de treball, fonamentalment per inhalació, per protegir la salut dels treballadors. No es pretén realitzar ni un estudi epidemiològic ni un estudi d'higiene, només s'utilitzen els valors d'exposició professional per analitzar el compliment de la normativa sobre la presència de plom en l'ambient de treball, i comprovar si el compliment de la normativa comporta la millora de la salut dels treballadors en funció de la millora de les concentracions de valors ambientals o biològics de l'exposició dels treballadors. La Directiva 98/24/CE deroga les Directives 80/1107/CEE sobre la protecció dels treballadors contra els riscos relacionats amb l'exposició a agents químics, físics i biològics durant el treball, i la Directiva 82/605/CEE, sobre la protecció dels treballadors contra riscos relacionats amb una exposició al plom metàl·lic i als seus compostos iònics durant el treball. S'analitza l'evolució de la normativa sobre la presència d'agents químics en l'ambient de treball, i en concret el plom, i la seva incidència en els accidents laborals i malalties professionals, i el compliment de la normativa al final d'un cicle marcat per l'entrada en vigor de la Directiva 98/24/CE. Per realitzar l'anàlisi anteriorment esmentada s'estudia la indústria ceràmica de les comarques gironines, de la construcció, de l'alimentació i decorativa, a través de les mesures de plom en l'ambient laboral i les mesures de plom en sang dels treballadors d'aquesta indústria des de 1991 a 1996.

Modelling, control and supervision for a class of hybrid systems

The aim of this thesis is to narrow the gap between two different control techniques: the continuous control and the discrete event control techniques DES. This gap can be reduced by the study of Hybrid systems, and by interpreting as Hybrid systems the majority of large-scale systems. In particular, when looking deeply into a process, it is often possible to identify interaction between discrete and continuous signals. Hybrid systems are systems that have both continuous, and discrete signals. Continuous signals are generally supposed continuous and differentiable in time, since discrete signals are neither continuous nor differentiable in time due to their abrupt changes in time. Continuous signals often represent the measure of natural physical magnitudes such as temperature, pressure etc. The discrete signals are normally artificial signals, operated by human artefacts as current, voltage, light etc. Typical processes modelled as Hybrid systems are production systems, chemical process, or continuos production when time and continuous measures interacts with the transport, and stock inventory system. Complex systems as manufacturing lines are hybrid in a global sense. They can be decomposed into several subsystems, and their links. Another motivation for the study of Hybrid systems is the tools developed by other research domains. These tools benefit from the use of temporal logic for the analysis of several properties of Hybrid systems model, and use it to design systems and controllers, which satisfies physical or imposed restrictions. This thesis is focused in particular types of systems with discrete and continuous signals in interaction. That can be modelled hard non-linealities, such as hysteresis, jumps in the state, limit cycles, etc. and their possible non-deterministic future behaviour expressed by an interpretable model description. The Hybrid systems treated in this work are systems with several discrete states, always less than thirty states (it can arrive to NP hard problem), and continuous dynamics evolving with expression: with Ki ¡ Rn constant vectors or matrices for X components vector. In several states the continuous evolution can be several of them Ki = 0. In this formulation, the mathematics can express Time invariant linear system. By the use of this expression for a local part, the combination of several local linear models is possible to represent non-linear systems. And with the interaction with discrete events of the system the model can compose non-linear Hybrid systems. Especially multistage processes with high continuous dynamics are well represented by the proposed methodology. Sate vectors with more than two components, as third order models or higher is well approximated by the proposed approximation. Flexible belt transmission, chemical reactions with initial start-up and mobile robots with important friction are several physical systems, which profits from the benefits of proposed methodology (accuracy). The motivation of this thesis is to obtain a solution that can control and drive the Hybrid systems from the origin or starting point to the goal. How to obtain this solution, and which is the best solution in terms of one cost function subject to the physical restrictions and control actions is analysed. Hybrid systems that have several possible states, different ways to drive the system to the goal and different continuous control signals are problems that motivate this research. The requirements of the system on which we work is: a model that can represent the behaviour of the non-linear systems, and that possibilities the prediction of possible future behaviour for the model, in order to apply an supervisor which decides the optimal and secure action to drive the system toward the goal. Specific problems can be determined by the use of this kind of hybrid models are: - The unity of order. - Control the system along a reachable path. - Control the system in a safe path. - Optimise the cost function. - Modularity of control The proposed model solves the specified problems in the switching models problem, the initial condition calculus and the unity of the order models. Continuous and discrete phenomena are represented in Linear hybrid models, defined with defined eighth-tuple parameters to model different types of hybrid phenomena. Applying a transformation over the state vector : for LTI system we obtain from a two-dimensional SS a single parameter, alpha, which still maintains the dynamical information. Combining this parameter with the system output, a complete description of the system is obtained in a form of a graph in polar representation. Using Tagaki-Sugeno type III is a fuzzy model which include linear time invariant LTI models for each local model, the fuzzyfication of different LTI local model gives as a result a non-linear time invariant model. In our case the output and the alpha measure govern the membership function. Hybrid systems control is a huge task, the processes need to be guided from the Starting point to the desired End point, passing a through of different specific states and points in the trajectory. The system can be structured in different levels of abstraction and the control in three layers for the Hybrid systems from planning the process to produce the actions, these are the planning, the process and control layer. In this case the algorithms will be applied to robotics ¡V a domain where improvements are well accepted ¡V it is expected to find a simple repetitive processes for which the extra effort in complexity can be compensated by some cost reductions. It may be also interesting to implement some control optimisation to processes such as fuel injection, DC-DC converters etc. In order to apply the RW theory of discrete event systems on a Hybrid system, we must abstract the continuous signals and to project the events generated for these signals, to obtain new sets of observable and controllable events. Ramadge & Wonham¡¦s theory along with the TCT software give a Controllable Sublanguage of the legal language generated for a Discrete Event System (DES). Continuous abstraction transforms predicates over continuous variables into controllable or uncontrollable events, and modifies the set of uncontrollable, controllable observable and unobservable events. Continuous signals produce into the system virtual events, when this crosses the bound limits. If this event is deterministic, they can be projected. It is necessary to determine the controllability of this event, in order to assign this to the corresponding set, , controllable, uncontrollable, observable and unobservable set of events. Find optimal trajectories in order to minimise some cost function is the goal of the modelling procedure. Mathematical model for the system allows the user to apply mathematical techniques over this expression. These possibilities are, to minimise a specific cost function, to obtain optimal controllers and to approximate a specific trajectory. The combination of the Dynamic Programming with Bellman Principle of optimality, give us the procedure to solve the minimum time trajectory for Hybrid systems. The problem is greater when there exists interaction between adjacent states. In Hybrid systems the problem is to determine the partial set points to be applied at the local models. Optimal controller can be implemented in each local model in order to assure the minimisation of the local costs. The solution of this problem needs to give us the trajectory to follow the system. Trajectory marked by a set of set points to force the system to passing over them. Several ways are possible to drive the system from the Starting point Xi to the End point Xf. Different ways are interesting in: dynamic sense, minimum states, approximation at set points, etc. These ways need to be safe and viable and RchW. And only one of them must to be applied, normally the best, which minimises the proposed cost function. A Reachable Way, this means the controllable way and safe, will be evaluated in order to obtain which one minimises the cost function. Contribution of this work is a complete framework to work with the majority Hybrid systems, the procedures to model, control and supervise are defined and explained and its use is demonstrated. Also explained is the procedure to model the systems to be analysed for automatic verification. Great improvements were obtained by using this methodology in comparison to using other piecewise linear approximations. It is demonstrated in particular cases this methodology can provide best approximation. The most important contribution of this work, is the Alpha approximation for non-linear systems with high dynamics While this kind of process is not typical, but in this case the Alpha approximation is the best linear approximation to use, and give a compact representation.

Puroindoline-b mutations control the lipid binding interactions in mixed puroindoline-a: puroindoline-b systems

The interactions have been investigated of puroindoline-a (Pin-a) and mixed protein systems of Pin-a and wild-type puroindoline-b (Pin-b+) or puroindoline-b mutants (G46S mutation (Pin bH) or W44R mutation (Pin-bS)) with condensed phase monolayers of an anionic phospholipid (L-α-dipalmitoylphosphatidyl-dl-glycerol (DPPG)) at the air/water interface. The interactions of the mixed systems were studied at three different concentration ratios of Pin-a:Pin-b, namely 3:1, 1:1 and 1:3 in order to establish any synergism in relation to lipid binding properties. Surface pressure measurements revealed that Pin-a interaction with DPPG monolayers led to an equilibrium surface pressure increase of 8.7 ± 0.6 mN m-1. This was less than was measured for Pin-a:Pin-b+ (9.6 to 13.4 mN m-1), but was significantly more than was measured for Pin-a:Pin-bH (4.0 to 6.2 mN m-1) or Pin-a:Pin-bS (3.8 to 6.3 mN m-1) over the complete range of concentration ratio. Consequently, surface pressure increases were shown to correlate to endosperm hardness phenotype, with puroindolines present in hard-textured wheat varieties yielding lower equilibrium surface pressure changes. Integrated amide I peak areas from corresponding external reflectance Fourier-transform infrared (ER-FTIR) spectra, used to indicate levels of protein adsorption to the lipid monolayers, showed that differences in adsorbed amount were less significant. The data therefore suggest that Pin-b mutants having single residue substitutions within their tryptophan-rich loop that are expressed in some hard-textured wheat varieties influence the degree of penetration of Pin-a and Pin-b into anionic phospholipid films. These findings highlight the key role of the tryptophan-rich loop in puroindoline-lipid interactions.

Economic analysis of integrated weed management in field bean (Phaseolus vulgaris L.)

Field experiments were conducted in field bean in the north-eastern part of the Republic of Croatia to compare weed control and crop response under different management practices within the critical period of field bean production. The practices consisted in broadcast application of labelled rate of preemergence herbicide (PRE) and postemergence herbicide application: (POST) broadcast, band application over the rows, and band application combined with mechanical cultivation using of different herbicide doses recommended by the manufacturer (2x, 1x, 1/2x, 1/4x, 1/8x). In 1999, weed control with PRE application of pendimethalin was superior to POST bentazone application due to late emergence of weeds and lack of residual herbicide control. In 2000 bentazone combined with cycloxydim controlled weeds in field bean better than PRE herbicide application. Based on the results of this research, single PRE or POST application of herbicide did not control a broad spectrum of weeds and did not provide the commercially acceptable full season control. Reduced rates of herbicide are not advisable tinder high weed pressure.

Response of a weed community to different management practice in field bean

Weed control strategies for field beans were studied in North-eastern Croatia. This study focused on how different weed management practices affect weed community composition. The recommended pre-emergence herbicide application was compared to different treatments of post-emergence herbicide (broadcasted or banded over crop rows) and mechanical weed control in order to explore the response of a weed community to different management practice. Weed density data were used to compare total community densities by weed management strategies and to calculate diversity indices (Shannon's H', Shannon's E and Margalef's D-MG). Data were analyzed using ANOVA and multivariate technique. Weed community structure was generally similar in the post-emergence herbicide treatments, which were dominated by a few species that had high relative abundance values, while most of the species were of lower abundance. Notable fluctuations in weed communities corresponded with variation in weather patterns and management practice.

Combining competition from Lolium perenne and an insect-fungus combination to control Rumex obtusifolius seedlings

Although adult Rumex obtusifolius are problematic weeds, their seedlings are poor competitors against Lolium perenne, particularly in established swards. We investigated the possibility of using this weakness to augment control of R. obtusifolius seedlings with combinations of Gastrophysa viridula (Coleoptera: Chrysomelidae) and the rust fungus Uromyces rumicis. Rumex obtusifolius seedlings were grown in competition with L. perenne sown at different rates and times after R. obtusifolius: they competed successfully with L. perenne when sown 21 days before the grass. Sowing both species at the same time resulted in a dominant grass sward, with R. obtusifolius becoming dominant when sown 42 days prior to L. perenne. Grass sowing rate had no effect on R. obtusifolius growth or biomass. A second experiment investigated how competition from L. perenne sown 21 days after R. obtusifolius combined with damage from G. viridula and/or U. rumicis (applied at either the 3-4- or 10-13-leaf stage, or at both stages) affected the growth and final biomass of R. obtusifolius. Beetle grazing at the latter leaf stage was the only treatment that reduced R. obtusifolius biomass, although rust infection at the earlier application led to an increase in shoot and root weight. The results are discussed in terms of the potential for use of these agents in the field.

Studies on weed infestation and tea growth under various weed management methods in a young Tea (Camellia sinensis [L.] kuntze) plantation

A field experiment was conducted in the low country of Sri Lanka, during the period 1994–1995 to investigate the severity of weed infestation and tea growth in relation to weed management methods in newly established tea (Camellia sinensis[L.] Kuntze). Manual weeding (hand and slash weeding) at various intervals was compared with various herbicides, with or without mulching. Weed control with herbicides was superior to that of hand weeding at 6-week intervals or more. Weed control with oxyfluorfen at 0.29 kg ai ha−1 + paraquat at 0.17 kg ai ha−1 or glyphosate at 0.99 kg ai ha−1 + kaolin at 3.42 kg ha−1 were superior. Plots unweeded for 12 weeks or more produced significantly greater (P < 0.05) weed biomass than plots unweeded for 6 weeks. Although the least weed dry weight (P < 0.05) and the greatest number of weed species were recorded with hand weeding at 2 week intervals, there was no particular benefit on tea growth when compared with hand weeding at 6 and 12 week intervals. Inter row mulching in chemically treated plots was more favorable for tea growth than no mulching, while living weed cover in unmulched slash weeded plots suppressed tea growth. A combination of mulching and herbicides, particularly oxyfluorfen and paraquat, followed by hand weeding at least every 6–8 weeks was considered the most appropriate weed management system for young tea.

Chemical, physical and electrical properties of aged dodecylbenzene: thermal ageing of mixed isomers in air

A commercial dodecylbenzene (DDB) cable oil was aged at temperatures between 90 and 135 degrees C in air and was analyzed using various analytical techniques including optical and infra-red spectroscopy and dielectric analysis. On ageing, the oil darkened, significant oxidation features were found by infra-red spectroscopy and the acid number, water content and dielectric loss all increased. Ageing in the presence of paper or aluminum did not affect the ageing process, whereas ageing was significantly modified by the presence of copper. An absorption at 680 nm ("red absorbers") was detected by ultra-violet/visible spectroscopy followed by the production of an opaque precipitate. A reaction between copper and the acid generated on ageing is thought to produce copper carboxylates, and X-ray fluorescence confirmed that copper was indeed present in both the aged oil and the precipitate. Significantly, once red absorbers were detected, the dielectric loss increased to catastrophically high values and, therefore, the appearance of these compounds may serve as a useful diagnostic indicator. The development of acidity on ageing appears to be key in initiating the destructive copper conversion reaction and hence the control of oil acidity may be key to prolonging the life of DDB cable oils.

Chemical, physical, and sensory properties of dairy products enriched with conjugated linoleic acid

Recent studies have illustrated the effects of cis-9, trans-11 conjugated linoleic acid (CLA) on human health. Ruminant-derived meat, milk and dairy products are the predominant sources of cis-9, trans-11 CLA in the human diet. This study evaluated the processing properties, texture, storage characteristics, and organoleptic properties of UHT milk, Caerphilly cheese, and butter produced from a milk enriched to a level of cis-9, trans-11 CLA that has been shown to have biological effects in humans. Forty-nine early-lactation Holstein-British Friesian cows were fed total mixed rations containing 0 (control) or 45 g/kg ( on dry matter basis) of a mixture (1:2 wt/wt) of fish oil and sunflower oil during two consecutive 7-d periods to produce a control and CLA-enhanced milk, respectively. Milk produced from cows fed the control and fish and sunflower oil diets contained 0.54 and 4.68 g of total CLA/100 g of fatty acids, respectively. Enrichment of CLA in raw milk from the fish and sunflower oil diet was also accompanied by substantial increases in trans C18:1 levels, lowered C18: 0, cis-C18:1, and total saturated fatty acid concentrations, and small increases in n-3 polyunsaturated fatty acid content. The CLA-enriched milk was used for the manufacture of UHT milk, butter, and cheese. Both the CLA-enhanced butter and cheese were less firm than control products. Although the sensory profiles of the CLA-enriched milk, butter, and cheese differed from those of the control products with respect to some attributes, the overall impression and flavor did not differ. In conclusion, it is feasible to produce CLA-enriched dairy products with acceptable storage and sensory characteristics.

Using an additive to control the electrospinning of fibres of poly(epsilon-caprolactone)

Electrospinning is a route to polymer fibres with diameters considerably smaller than available from most fibre-producing techniques. We explore the use of a low molecular weight compound as an effective control additive during the electrospinning of poly(epsilon-caprolactone). This approach extends the control variables for the electrospinning of nanoscale fibres from the more usual ones such as the polymer molecular weight, solvent and concentration. We show that through the use of dual solvent systems, we can alter the impact of the additive on the electrospinning process so that finer as well as thicker fibres can be prepared under otherwise identical conditions. As well as the size of the fibres and the number of beads, the use of the additive allows us to alter the level of crystallinity as well as the level of preferred orientation of the poly(epsilon-caprolactone) crystals. This approach, involving the use of a dual solvent and a low molar mass compound, offers considerable potential for application to other polymer systems. (C) 2010 Society of Chemical Industry

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Enhancing model predictive control using dynamic data reconciliation

The use of data reconciliation techniques can considerably reduce the inaccuracy of process data due to measurement errors. This in turn results in improved control system performance and process knowledge. Dynamic data reconciliation techniques are applied to a model-based predictive control scheme. It is shown through simulations on a chemical reactor system that the overall performance of the model-based predictive controller is enhanced considerably when data reconciliation is applied. The dynamic data reconciliation techniques used include a combined strategy for the simultaneous identification of outliers and systematic bias.

Novel developments in process optimisation using predictive control

In industrial practice, constrained steady state optimisation and predictive control are separate, albeit closely related functions within the control hierarchy. This paper presents a method which integrates predictive control with on-line optimisation with economic objectives. A receding horizon optimal control problem is formulated using linear state space models. This optimal control problem is very similar to the one presented in many predictive control formulations, but the main difference is that it includes in its formulation a general steady state objective depending on the magnitudes of manipulated and measured output variables. This steady state objective may include the standard quadratic regulatory objective, together with economic objectives which are often linear. Assuming that the system settles to a steady state operating point under receding horizon control, conditions are given for the satisfaction of the necessary optimality conditions of the steady-state optimisation problem. The method is based on adaptive linear state space models, which are obtained by using on-line identification techniques. The use of model adaptation is justified from a theoretical standpoint and its beneficial effects are shown in simulations. The method is tested with simulations of an industrial distillation column and a system of chemical reactors.

Hierarchical control and optimisation of the Tennessee Eastman process

Based on integrated system optimisation and parameter estimation a method is described for on-line steady state optimisation which compensates for model-plant mismatch and solves a non-linear optimisation problem by iterating on a linear - quadratic representation. The method requires real process derivatives which are estimated using a dynamic identification technique. The utility of the method is demonstrated using a simulation of the Tennessee Eastman benchmark chemical process.