Simple analytical method for determination of pesticide residues in human serum by liquid chromatography tandem mass spectrometry

The aim of this study was to develop an analytical method for the determination of residues of organophosphorus and carbamate pesticides which are widely used in Tunisia. This method involves a liquid-liquid extraction procedure followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for the identification and quantification of compounds. Ionization of molecules was performed by the electrospray mode. Multiple reactions monitoring (MRM) was the acquisition mode used for the monitoring of two MS/MS transitions for each compound. The average recoveries obtained, at three different fortification levels, ranged between 65% and 106% for most of the pesticides studied, except for methamidophos (lower than 25%).The linearity of the method was in the range of 5 to 50 μ g/L with a correlation coefficient from 0.995 to 0.999, depending on the analyte. The estimated limit of detection and limit of quantification were 2 μ g/L and 5 μ g/L, respectively. The precision of the analytical procedure was satisfactory and the coefficients of variation, evaluated at three concentration levels were lower than 15% for most pesticides studied. The application of the method was investigated in a population of agricultural workers chronically exposed to various pesticides some of which, such as carbofuran, carbendazim, methomyl and pirimicarb, were detected in some serum samples.     

Urinary dialkyl phosphate levels before and after first season chlorpyrifos spraying amongst farm workers in the Western Cape,South Africa

The study investigated urinary levels of dialkyl phosphates resulting from pesticide exposure amongst 40 farm workers. Workers were tested (urinary dialkyl phosphate levels, anthropometry, short exposure questionnaire) before and after the first day of seasonal chlorpyrifos spraying. Median baseline urinary dialkyl phosphates was high amongst both non-applicators (1587.5 μg/g creatinine, n = 8) and applicators (365.6 μg/g creatinine, n = 9). There was not much evidence of an increase in post-spray dialkyl phosphates levels from pre-spray levels amongst both applicators and non-applicators. Hours mixing, spraying, driving a tractor and hours worked by non-applicators were not significantly associated with an increase in post-spray dialkyl phosphate levels, adjusting for age, height, weight, gender, use of empty pesticide containers and self-reported kidney problems. Past applicator status was weakly positively associated with pre-spray dialkyl phosphate levels adjusting for age, height, weight, and gender, self-reported kidney problems, smoking and alcohol (β= 1019.5, p = 0.307, R²= 0.28). The high dialkyl phosphate levels call for an epidemiological investigation into the health effects of organophosphorous pesticides.     

Effects of increasing temperatures on biomarker responses and accumulation of hazardous substances in rope mussels (Mytilus galloprovincialis) from Bizerte lagoon

This study examined the influence of increasing temperatures in spring and summer on biochemical biomarkers in Mytilus galloprovincialis mussels sampled from Bizerte lagoon (northern Tunisia). Spatial and seasonal variations in a battery of seven biomarkers were analyzed in relation to environmental parameters (temperature, salinity, and pH), physiological status (condition and gonad indexes), stress on stress (SoS), and chemical contaminant levels (heavy metals, polycyclic aromatic hydrocarbons (PAHs), and PCBs) in digestive glands. Integrated biological response (IBR) was calculated using seven biomarkers (acetylcholinesterase (AChE), benzo[a]pyrene hydroxylase (BPH), multixenobiotic resistance (MXR), glutathione S-transferase (GST), catalase (CAT), malondialdehyde (MDA), and metallothioneins (MT). Seasonal variations in biological response were determined during a critical period between spring and summer at two sites, where chemical contamination varies by a factor of 2 for heavy metals and a factor 2.5 for PAHs. The analysis of a battery of biomarkers was combined with the measurement of physiological parameters at both sites, in order to quantify a maximum range of metabolic regulation with a temperature increase of 11 °C between May and August. According to our results, the MT, MDA, CAT, and AChE biomarkers showed the highest amplitude during the 11 °C rise, while the BPH, GST, and MXR biomarkers showed the lowest amplitude. Metabolic amplitude measured with the IBR at Menzel Abdelrahmen—the most severely contaminated station—revealed the highest metabolic stress in Bizerte lagoon in August, when temperatures were highest 29.1 °C. This high metabolic rate was quantified for each biomarker in the North African lagoon area and confirmed in August, when the highest IBR index values were obtained at the least contaminated site 2 (IBR = 9.6) and the most contaminated site 1 (IBR = 19.6). The combined effects of chemical contamination and increased salinity and temperatures in summer appear to induce a highest metabolic adaptation response and can therefore be used to determine thresholds of effectiveness and facilitate the interpretation of monitoring biomarkers. This approach, applied during substantial temperature increases at two sites with differing chemical contamination, is a first step toward determining an environmental assessment criteria (EAC) threshold in a North African lagoon.     

Atmospheric concentrations,gaseous–particulate distribution,and carcinogenic potential of polycyclic aromatic hydrocarbons in Assiut,Egypt

The concentrations of 15 priority PAHs were determined in the atmospheric gaseous and particulate phases from nine sites across Assiut City, Egypt. While naphthalene, acenaphthene, and fluorene were the most abundant in the gaseous phase with average concentrations of 377, 184, and 181 ng/m³, benzo[b]fluoranthene, chrysene, and benzo[g,h,i]perylene showed the highest levels in the particulate phase with average concentrations of 76, 6, and 52 ng/m³. The average total atmospheric concentration of target PAHs (1,590 ng/m³) indicates that Assiut is one of the highest PAH-contaminated areas in the world. Statistical analysis revealed a significant difference between the levels of PAHs in the atmosphere of urban and suburban sites (P?=?0.029 and 0.043 for gaseous and particulate phases, respectively). Investigation of diagnostic PAH concentration ratios revealed vehicular combustion and traffic exhaust emissions as the major sources of PAHs with a higher contribution of gasoline rather than diesel vehicles in the sampled areas. Benzo[a]pyrene has the highest contribution (average?=?32, 4 % for gaseous and particulate phases) to the total carcinogenic activity (TCA) of atmospheric PAHs. While particulate phase PAHs have higher contribution to the TCA, gaseous phase PAHs present at higher concentrations in the atmosphere are more capable of undergoing atmospheric reactions to form more toxic derivatives.     

Climatic drivers of potential hazards in Mediterranean coasts

This paper studies climatic drivers (air and water temperature, precipitation rates, river discharge, sea level and storm patterns) in four Mediterranean regions: the Catalan-Valencia Coast (Spain), the Oran (Algeria) and Gabès (Tunisia) Gulfs and the western Nile Delta (Egypt). The paper also considers the potential hazards that these drivers can induce. It first analyses climatic trends in the drivers, taking into account the available time series of recorded and simulated meteo-oceanographic data from different sources. Next, it presents the general framework to assess biogeophysical hazards (flooding, erosion, droughts and water quality), followed by a simple and yet robust evaluation of those hazards for the four studied coastal sites. Assuming climate change projections under different scenarios and considering the observed trends in drivers, the resulting erosion rates due to sea-level rise and wave storm effects have been estimated. The Nile and Ebro Deltas, together with the Oran Gulf, are more vulnerable than the Gulfs of Valencia and Gabès. Regarding water quality in terms of (a) precipitation and dissolved oxygen in the water column and (b) sea surface temperature, the results show that the most vulnerable zones for the projected conditions (a) are the Gulfs of Oran, Valencia and Gabès, while the Nile Delta is the region where the decrease in water quality will be less pronounced. For the projected conditions (b), the most vulnerable zone is the Ebro Delta, while the impact in the other three cases will be smaller and of comparable magnitude. Finally, the overall future impact of these hazards (associated to climatic change) in the four sites is discussed in comparative terms, deriving some conclusions.     

1D and 2D absorption-rate/kinetic modeling and simulation of carbon dioxide absorption into mixed aqueous solutions of MDEA and PZ in a laminar jet apparatus

The kinetics of the reaction between carbon dioxide (CO₂) and mixed solutions of methyldiethanolamine (MDEA) and piperazine (PZ) was investigated experimentally in a laminar jet apparatus. The experimental kinetic data were obtained under no interfacial turbulence and over a temperature range from 313 to 333 K, MDEA/PZ wt% concentration ratios of 27/3, 24/6 and 21/9, and CO₂ loadings from 0.0095 to 0.33 mol CO₂/mol amine. In addition, a new absorption-rate/kinetics model for the kinetics of the mixed of solvents was developed, which takes into account the coupling between chemical equilibrium, mass transfer, and all possible chemical reactions involved in the CO₂ reaction with MDEA/PZ solvent. The partial differential equations of this model were solved by the finite element numerical method (FEM) based on COMSOL software. The obtained experimental kinetics data were used to obtain the kinetic parameters of CO₂ absorption into MDEA/PZ solutions. The reaction-rate constant obtained for PZ blended with MDEA was kPZ = 2.572 × 10¹² exp(?5211/T). The 2D model for the blended amines MDEA/PZ has revealed the concentration profiles of all the species in both the radial and axial directions of the laminar jet which has enabled a better understanding of the correct sequence in which the reaction steps involved in the reactive absorption of CO₂ in aqueous mixed MDEA/PZ solution occur. It also revealed that PZ may be depleted by the time the solvent blend of MDEA/PZ with a loading greater than 0.015 mol/mol amine is exposed to CO₂ from the top of the laminar jet absorber.     

Heavy metal concentrations in marine molluscs from the Moroccan coastal region

Mussels (Mytilus galloprovincialis), clams (Venerupis decussatus) and oysters (Crassostrea gigas) were sampled seasonally during 2004-2005, from different coastal environments of Morocco in order to measure their accumulated heavy metal concentrations. The concentrations of Hg and Pb were determined by AFS and ICP-MS methods, respectively, whilst the remaining metals (Cd, Cr, Cu, Mn, Zn and Ni) were quantified by AAS. The soft tissue concentrations of the mussels were on average 7.2 mg kg(-1) (Cd), 9.6 mg kg(-1) (Pb), 0.6 mg kg(-1) (Hg), 26.8 mg kg(-1) (Cu), 8.8 mg kg(-1) (Cr), 292 mg kg(-1) (Zn), 20.8 mg kg(-1) (Mn) and 32.8 mg kg(-1) (Ni). The highest tissue heavy metal concentrations were recorded in the south from the industrial area of Jorf Lasfar. The relationships between metal concentration and season in each species showed very similar annual profiles with a peak observed around spring-summer. Statistical analysis indicated that different species showed different bioaccumulation of metals depending on study site and season.     

Preparation and characterization of mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> recovered from aluminum cans waste and its use in the dehydration of methanol to dimethyl ether

The present study includes synthesis of two γ-Al₂O₃ samples from waste aluminum cans using a simple precipitation method. Precipitation was carried out using two different precipitating agents (i.e. NaOH and NH₄OH). The two prepared alumina samples were characterized by means of X-ray diffraction (XRD) and N₂ adsorption–desorption techniques. Surface acidity of γ-Al₂O₃ samples was measured by adsorption of two different probe molecules (i.e. pyridine and dimethyl pyridine) followed by desorption measurements using thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Catalytic activity of the two prepared alumina samples towards the dehydration of methanol (to dimethyl ether) was studied in a fixed bed reactor at 300 °C. For comparison reasons, commercial γ-Al₂O₃ sample was, also, tested for the same catalytic reaction under the same conditions. Results showed that the alumina sample prepared using NaOH as a precipitating agent exhibited a better catalytic activity and stability compared with that prepared using NH₄OH and showed a similar activity as the commercial γ-Al₂O₃ sample.     

Computer professionals and Carpal Tunnel Syndrome (CTS).

Carpal Tunnel Syndrome (CTS) is an important problem among computer professionals. Hence the prevalence of CTS among computer professionals and risk factors were studied. 648 subjects were selected from 4,276 computer professionals from 21 companies by with simple random sampling method. CTS was diagnosed based on clinical features. The prevalence of CTS was found to be 13.1% (95% CI 10.5-15.7%). Subjects with over 8 years of computer work, over 12 hrs of work per day and system administrators were at a higher risk for CTS (OR 3.3, 4.9 and 2.5 respectively). Flexed or extended hand position had higher risk for CTS. Higher risk for CTS was found with higher exposure to computer work. Ergonomic considerations are important in facilitating proper positioning of hand while working with a computer. Further studies on CTS risk factors among computer professionals are essential for planning prevention.