Occupational exposure to volatile organic compounds in the Portuguese printing industry

In the printing industry, volatile organic compounds main sources are the uses of organic solvents, fountain solutions and cleaning agents. Nowadays, one circumstance which might confuse the exposure reality is that the majority of solvents which are often used have a faint odour. Therefore, the conditions at offset printing in regard to solvent exposure may seem acceptable to workers. Fortunately, general ventilation and local exhaust systems have also become more common, and new printing machines, often with automatic cleaning, have entered the market. The health effects of volatile organic solvents are dependent on the chemicals involved but, normally, are associated with affecting the nervous system, the liver and also the kidneys. The purpose of this study was to document the conditions regarding exposure to volatile organic compounds in an offset printing unit and to permit identify task with higher exposure and with priority for preventive measures application. Exposure assessment was done before and after installation of general ventilation and local exhaust equipments and during printing and cleaning procedure.

Ventilation influence in occupational exposure to fungi and volatile organic compounds: poultry case

Introduction - In poultry houses, large-scale production has led to increased bird densities within buildings. Such high densities of animals kept within confined spaces are a source of human health problems related to occupational organic dust exposure. This organic dust is composed of both non-viable particles and viable particulate matter (also called bioaerosols). Bioaerosols are comprised by airborne bacteria, fungi, viruses and their by-products, endotoxins and mycotoxins. Exposure to fungi in broiler houses may vary depending upon the applied ventilation system. Ventilation can be an important resource in order to reduce air contamination in these type of settings. Nevertheless, some concerns regarding costs, sensitivity of the animal species to temperature differences, and also the type of building used define which type of ventilation is used. Aim of the study - A descriptive study was developed in one poultry unit aiming to assess occupational fungal and volatile organic compounds (VOCs) exposure.

Estudo técnico/económico da instalação de uma central de cogeração numa serração de madeira

O pinheiro tem um papel importante na ecologia e economia nacional. O Pinheiro sofre de uma praga severa, denominada por doença da murchidão dos pinheiros, causada pelo nemátodo da madeira do pinheiro (NMP). Apresenta-se como um verme microscópico, invertebrado, medindo menos de 1,5 mm de comprimento. O contágio entre árvores deve-se a vectores biologicamente conhecidos por longicórneo e capricórnio do pinheiro. Os produtores de madeira de pinho são desta forma obrigados a efectuar tratamentos térmicos (HT), de eliminação do NMP e dos seus vectores para que a exportação da madeira serrada cumpra com a norma NP 4487. De modo a manter a competitividade internacional das empresas nacionais, o impacto dos custos do HT deve ser minimizado. O objectivo desta dissertação é efectuar o estudo técnico-económico da implementação de um sistema de cogeração capaz produzir calor para efectuar o tratamento ao NMP e simultaneamente energia eléctrica para vender à rede pública. As receitas da venda de energia eléctrica poderão contribuir para a minimização dos custos do HT. Tendo em conta que os resíduos das serrações de madeira podem ser usados como combustível consideraram-se para avaliação duas tecnologias de cogeração, um sistema de turbina a vapor clássico (ciclo Rankine) e um sistema Organic Rankine Cycle (ORC), permitindo ambas a queima dos resíduos das serrações de madeira. No que diz respeito à avaliação económica, foi desenvolvido um simulador de tecnologia/modalidade de remuneração que efectua cálculos consoante as necessidades térmicas de cada produtor, a potência eléctrica a instalar e indicadores económicos, VAL, TIR e PAYBACK da instalação do sistema de cogeração. O simulador desenvolvido aplica a nova legislação que enquadra o sistema jurídico e remuneratório da cogeração (DL 23/2010), na qual se consideram duas modalidades, geral e especial. A metodologia desenvolvida foi aplicada num caso real de uma serração de madeira e os principais resultados mostram que as soluções apresentadas, turbina a vapor e sistema ORC, não apresentam viabilidade económica. Através da análise de sensibilidade, conclui-se que um dos factores que mais influência a viabilidade económica do projecto é o tempo de funcionamento reduzido. Sendo uma das soluções apresentada a criação de uma central de cogeração para vários produtores de madeira. Uma possível solução para o problema do reduzido tempo de utilização seria o fornecimento do serviço de tratamentos térmicos a outros produtores de paletes de madeira que não possuem estufa própria.

Extraction of hemoglobin with calixarenes and biocatalysis in organic media of the complex with pseudoactivity of peroxidase

The present work involves the use of p-tert-butylcalix[4,6,8]arene carboxylic acid derivatives ((t)Butyl[4,6,8]CH2COOH) for selective extraction of hemoglobin. All three calixarenes extracted hemoglobin into the organic phase, exhibiting extraction parameters higher than 0.90. Evaluation of the solvent accessible positively charged amino acid side chains of hemoglobin (PDB entry 1XZ2) revealed that there are 8 arginine, 44 lysine and 30 histidine residues on the protein surface which may be involved in the interactions with the calixarene molecules. The hemoglobin-(t)Butyl[6]CH2COOH complex had pseudoperoxidase activity which catalysed the oxidation of syringaldazine in the presence of hydrogen peroxide in organic medium containing chloroform. The effect of pH, protein and substrate concentrations on biocatalysis was investigated using the hemoglobin-(t)Butyl[6]CH2COOH complex. This complex exhibited the highest specific activity of 9.92 x 10(-2) U mg protein(-1) at an initial pH of 7.5 in organic medium. Apparent kinetic parameters (V'(max), K'(m), k'(cat) and k'(cat)/K'(m)) for the pseudoperoxidase activity were determined in organic media for different pH values from a Michaelis-Menten plot. Furthermore, the stability of the protein-calixarene complex was investigated for different initial pH values and half-life (t(1/2)) values were obtained in the range of 1.96 and 2.64 days. Hemoglobin-calixarene complex present in organic medium was recovered in fresh aqueous solutions at alkaline pH, with a recovery of pseudoperoxidase activity of over 100%. These results strongly suggest that the use of calixarene derivatives is an alternative technique for protein extraction and solubilisation in organic media for biocatalysis.

Fungal and microbial volatile organic compounds exposure assessment in a waste sorting plant

In the management of solid waste, pollutants over a wide range are released with different routes of exposure for workers. The potential for synergism among the pollutants raises concerns about potential adverse health effects, and there are still many uncertainties involved in exposure assessment. In this study, conventional (culture-based) and molecular real-time polymerase chain reaction (RTPCR) methodologies were used to assess fungal air contamination in a waste-sorting plant which focused on the presence of three potential pathogenic/toxigenic fungal species: Aspergillus flavus, A. fumigatus, and Stachybotrys chartarum. In addition, microbial volatile organic compounds (MVOC) were measured by photoionization detection. For all analysis, samplings were performed at five different workstations inside the facilities and also outdoors as a reference. Penicillium sp. were the most common species found at all plant locations. Pathogenic/toxigenic species (A. fumigatus and S. chartarum) were detected at two different workstations by RTPCR but not by culture-based techniques. MVOC concentration indoors ranged between 0 and 8.9 ppm (average 5.3 ± 3.16 ppm). Our results illustrated the advantage of combining both conventional and molecular methodologies in fungal exposure assessment. Together with MVOC analyses in indoor air, data obtained allow for a more precise evaluation of potential health risks associated with bioaerosol exposure. Consequently, with this knowledge, strategies may be developed for effective protection of the workers.

Exposure to microbial volatile organic compounds in a waste-handling unit

The production of MVOC by fungi has been taken into account especially from the viewpoint of indoor pollution with microorganisms but the relevance of fungal metabolites in working environments has not been sufficiently studied. The purpose of this study was to assess exposure to MVOCs in a waste-handling unit. It was used Multirae equipment (RAE Systems) to measured MVOCs concentration with a 10.6 eV lamps. The measurements were done near workers nose and during the normal activities. All measurements were done continuously and had the duration of 5 minutes at least. It was consider the higher value obtained in each measurement. In addition, for knowing fungi contamination, five air samples of 50 litres were collected through impaction method at 140 L/minute, at one meter tall, on to malt extract agar with the antibiotic chloramphenicol (MEA). MVOCs results range between 4.7 ppm and 8.9 ppm in the 6 locations consider. These results are eight times higher than normally obtained in indoor settings. Considering fungi results, two species were identified in air, being the genera Penicillium found in all the samples in uncountable colonies and Rhizopus only in one sample (40 UFC/m3). These fungi are known as MVOCs producers, namely terpenoids, ketones, alcohols and others. Until now, there has been no evidence that MVOCs are toxicologically relevant, but further epidemiological research is necessary to elucidate their role on human’s health, particularly in occupational settings where microbiological contamination is common. Additionally, further research should concentrate on quantitative analyses of specific MVOCs.

Development of a biosensor for urea assay based on amidase inhibition, using an ion-selective electrode

A biosensor for urea has been developed based on the observation that urea is a powerful active-site inhibitor of amidase, which catalyzes the hydrolysis of amides such as acetamide to produce ammonia and the corresponding organic acid. Cell-free extract from Pseudomonas aeruginosa was the source of amidase (acylamide hydrolase, EC 3.5.1.4) which was immobilized on a polyethersulfone membrane in the presence of glutaraldehyde; anion-selective electrode for ammonium ions was used for biosensor development. Analysis of variance was used for optimization of the biosensorresponse and showed that 30 mu L of cell-free extract containing 7.47 mg protein mL(-1), 2 mu L of glutaraldehyde (5%, v/v) and 10 mu L of gelatin (15%, w/v) exhibited the highest response. Optimization of other parameters showed that pH 7.2 and 30 min incubation time were optimum for incubation ofmembranes in urea. The biosensor exhibited a linear response in the range of 4.0-10.0 mu M urea, a detection limit of 2.0 mu M for urea, a response timeof 20 s, a sensitivity of 58.245 % per mu M urea and a storage stability of over 4 months. It was successfully used for quantification of urea in samples such as wine and milk; recovery experiments were carried out which revealed an average substrate recovery of 94.9%. The urea analogs hydroxyurea, methylurea and thiourea inhibited amidase activity by about 90%, 10% and 0%, respectively, compared with urea inhibition.

OC/EC ratio observations in Europe: Re-thinking the approach for apportionment between primary and secondary organic carbon

This study explores a large set of OC and EC measurements in PM(10) and PM(2.5) aerosol samples, undertaken with a long term constant analytical methodology, to evaluate the capability of the OC/EC minimum ratio to represent the ratio between the OC and EC aerosol components resulting from fossil fuel combustion (OC(ff)/EC(ff)). The data set covers a wide geographical area in Europe, but with a particular focus upon Portugal, Spain and the United Kingdom, and includes a great variety of sites: urban (background, kerbside and tunnel), industrial, rural and remote. The highest minimum ratios were found in samples from remote and rural sites. Urban background sites have shown spatially and temporally consistent minimum ratios, of around 1.0 for PM(10) and 0.7 for PM(2.5).The consistency of results has suggested that the method could be used as a tool to derive the ratio between OC and EC from fossil fuel combustion and consequently to differentiate OC from primary and secondary sources. To explore this capability, OC and EC measurements were performed in a busy roadway tunnel in central Lisbon. The OC/EC ratio, which reflected the composition of vehicle combustion emissions, was in the range of 03-0.4. Ratios of OC/EC in roadside increment air (roadside minus urban background) in Birmingham, UK also lie within the range 03-0.4. Additional measurements were performed under heavy traffic conditions at two double kerbside sites located in the centre of Lisbon and Madrid. The OC/EC minimum ratios observed at both sites were found to be between those of the tunnel and those of urban background air, suggesting that minimum values commonly obtained for this parameter in open urban atmospheres over-predict the direct emissions of OC(ff) from road transport. Possible reasons for this discrepancy are explored. (C) 2011 Elsevier Ltd. All rights reserved.

QSAR modeling of antitubercular activity of diverse organic compounds

Tuberculosis (TB) is a worldwide infectious disease that has shown over time extremely high mortality levels. The urgent need to develop new antitubercular drugs is due to the increasing rate of appearance of multi-drug resistant strains to the commonly used drugs, and the longer durations of therapy and recovery, particularly in immuno-compromised patients. The major goal of the present study is the exploration of data from different families of compounds through the use of a variety of machine learning techniques so that robust QSAR-based models can be developed to further guide in the quest for new potent anti-TB compounds. Eight QSAR models were built using various types of descriptors (from ADRIANA.Code and Dragon software) with two publicly available structurally diverse data sets, including recent data deposited in PubChem. QSAR methodologies used Random Forests and Associative Neural Networks. Predictions for the external evaluation sets obtained accuracies in the range of 0.76-0.88 (for active/inactive classifications) and Q(2)=0.66-0.89 for regressions. Models developed in this study can be used to estimate the anti-TB activity of drug candidates at early stages of drug development (C) 2011 Elsevier B.V. All rights reserved.

Occupational exposure to poultry dust and effects on the respiratory system in workers

Farmers are occupationally exposed to many respiratory hazards at work and display higher rates of asthma and respiratory symptoms than other workers. Dust is one of the components present in poultry production that increases risk of adverse respiratory disease occurrence. Dust originates from poultry residues, molds, and feathers and is biologically active as it contains microorganisms. Exposure to dust is known to produce a variety of clinical responses, including asthma, chronic bronchitis, chronic airways obstructive disease (COPD), allergic alveolitis, and organic dust toxic syndrome (ODTS). A study was developed to determine particle contamination in seven poultry farms and correlate this with prevalence rate of respiratory defects and record by means of a questionnaire the presence of clinical symptoms associated with asthma and other allergy diseases by European Community Respiratory Health Survey. Poultry farm dust contamination was found to contain higher concentrations of particulate matter (PM) PM5 and PM10. Prevalence rate of obstructive pulmonary disorders was higher in individuals with longer exposure regardless of smoking status. In addition, a high prevalence for asthmatic (42.5%) and nasal (51.1%) symptoms was noted in poultry workers. Data thus show that poultry farm workers are more prone to suffer from respiratory ailments and this may be attributed to higher concentrations of PM found in the dust. Intervention programs aimed at reducing exposure to dust will ameliorate occupational working conditions and enhance the health of workers.

Nanofiltration of Cork Wastewaters and Their Possible Use in Leather Industry as Tanning Agents

Cork processing wastewater is a very complex mixture of vegetal extracts and has, among other natural compounds, a very high content of phenolic/tannic colloidal matter that is responsible for severe environmental problems. In the present work, the concentration of this wastewater by nanofiltration was investigated with the aim of producing a cork tannin concentrate to be utilized in tanning. Permeation results showed that the permeate fluxes are controlled by both osmotic pressure and fouling/gel layer phenomena, leading to a rapid decrease of permeate fluxes with the concentration factor. The rejection coefficients to organic matter were higher than 95%, indicating that nanofiltration has a very good ability to concentrate the tannins and produce a permeate stream depleted from organic matter. The cork tannin concentrate obtained by nanofiltration and evaporation had total solids concentration of 34.8 g/l. The skins tanned by this concentrate were effectively converted to leather with a shrinking temperature of 7 degrees C.

Influence of ventilation type in volatile organic compounds exposure: poultry case

Agricultural workers especially poultry farmers are at increased risk of occupational respiratory diseases. Epidemiological studies showed increased prevalence of respiratory symptoms and adverse changes in pulmonary function parameters in poultry workers. In poultry production volatile organic compounds (VOCs) presence can be due to some compounds produced by molds that are volatile and are released directly into the air. These are known as microbial volatile organic compounds (MVOCs). Because these compounds often have strong and/or unpleasant odors, they can be the source of odors associated with molds. MVOC's are products of the microorganisms primary and secondary metabolism and are composed of low molecular weight alcohols, aldehydes, amines, ketones, terpenes, aromatic and chlorinated hydrocarbons, and sulfur-based compounds, all of which are variations of carbon-based molecules.

Exposure to volatile organic compounds in a composting plant

Some previous studies have suggested that some of the volatile organic compounds (VOCs) found in composting plants may have a toxic effect that can influence, besides surroundings populations, workers from the composting plants. Impact of waste management to the environment and workers is already recognised as an environment and occupational health concerns. Several studies regarding the VOCs and bioaerosols emissions from composting have been conducted all over Europe and also in Asia. However, in Portugal the studies developed are scarce and normally VOCs are not studied and recognized as a risk factor present in this occupational setting. Consudering this, a study was developed in a Portuguese composting plant aiming to clarify if there was VOCs presence in the workplaces.

Exposure to volatile organic compounds, particulate matter and fungi in a composting plant

Composting is an important process of solid waste management and it can be used for treatment of a variety of different wastes (green waste, household waste, sewage sludge and more). This process aims to: 1. Reduce the volumes of waste and; 2. Create a valuable product which can be recycled as a soil amendment in agriculture and gardening. A natural self-heating process involving the biological degradation of organic matter under aerobic conditions. The handling of waste and compost is responsible for the release of airborne microorganisms and their compounds in the air. Possible contaminants: a) Dust; b) Mesophilic and thermophilic microorganisms; c) Volatile organic compounds; d) Endotoxins and mycotoxins…. Aim: assess exposure/contamination to: a) Volatile organic compounds (VOCs); b) Particulate matter (PM); c) Fungi. In a composting plant located in Lisbon. An additional goal was to identify the workplace with higher level of contamination. In a totally indoor composting plant. The composting operations consisted: 1º Waste already sorted is unloaded in a reception area; 2º Pretreatment - remove undesirable materials from the process (glass, rocks, plastics, metals…); 3º Anaerobic digestion; 4º Dehydration; 5º Open composting with forced aeration. All the process takes thirteen weeks.

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.