A methodological approach to internal antifire crew optimization. An oil refinery case history

This paper deals with the problem of defining the operational tasks, modelling and optimizing of antifire crew and their attempts. Unwanted events are generally modest and easily controlled in their starting phase. This obviously leads to considering that quickness and coordination enhance the possibility of successful fire control. Hence the importance that the first intervention of the factory antifire crew is supported by strong organization and efficiency. Immediate and appropriate response to emergency is essential to minimize severity of accidents, life losses, as well as the potential reduction in the plant future productivity. In approaching internal antifire crew optimization, it is convenient to distinguish a traditional inventory phase, a subsequent optimization and a graphic modelling phase. Optimization criterion is developed according to graph theory, with regard to intervention pathways and to consistency of antifire crew. The proposed graphic model provides, in an immediately readable way, the sequence of operator actions to be followed in order to cope with emergency situations.     

Human intoxication by agrochemicals in the region of South Brazil between 1999 and 2014

The objective of this study was to evaluate pesticide poisonings in the southern region of Brazil between years 1999 and 2014. Data were collected from the database Sinitox. Intoxications and deaths were evaluated according to the distribution by gender (female and male), age group (≤14, 15–59 and ≥60 years), area of occurrence (urban and rural), circumstance (accident, occupational and suicide attempt) and evolution of the cases over time (cure, unconfirmed cure, death and sequelae). In the evaluated period, 21,305 cases of intoxication were registered. The results show that males between the ages of 15 and 59 years are more affected; and there is a greater representativeness in the urban area. These results are related to the application of agrochemicals being carried out by individuals between 15 and 59 years of age. The great correlation of urban area possibly occurs in function of the air currents brought from the field and as a result, population has been more affected and the consumption of contaminated food. It was observed that women handling pesticides more cautiously, in this way the accidents with male gender are more frequent, however, many women use the product intentionally to provoke suicide.     

Removal of the emerging contaminant bisphenol A by an ureasil–PEO hybrid membrane: experimental study and molecular dynamic simulation

This work reports the use of a cross-linked ureasil–PEO hybrid matrix (designated PEO800) as an efficient adsorbent to retain the emerging contaminant bisphenol A (BPA) from an aqueous medium. The in-deep experimental and theoretical results provide information about the interactions between PEO800 and BPA. The in situ UV-vis spectroscopy data and the pseudo-first order, pseudo-second order, Elovich, and Morris–Webber intraparticle diffusion models allowed us to propose a three-step mechanism for the adsorption of BPA onto PEO800. The results indicate that the pseudo-first-order kinetic model effectively describes the adsorption of BPA onto PEO800. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy confirmed the interaction of PEO800 with BPA, showing an alteration in the chemical environment of the polymer ether oxygen atoms present in the hybrid matrix. The molecular dynamic simulation provides further evidence that the BPA molecules interact preferentially with PEO. The amount of desorbed BPA depended on the pH and solvent used in the assays. This work provides new opportunities for using the hydrophilic ureasil–PEO matrix which has demonstrated its abilities in being a fast and easy alternative to successfully removing organic contaminants from aqueous mediums and therefore having potential applications in water remediation.

Graphical abstract

     

Turbulent jet modelling for hazardous area classification

Hazardous area classification, as per EN 60079-10, is based on the explosive gas volume of the clouds in which the average gas concentration is related to the Low Explosion Limit (LEL). The higher Reynolds number, the less this approach is valid, because of the development of a concentration gradient due to the momentum driven flow. The resulting areas and volumes may be overestimated by two or three orders of magnitude, which is often critical in equipment design and selection. This paper proposes and technically justifies an overview of turbulent jet flow modelling, with the aim at developing a more realistic calculation method of the hazardous areas, within the ATEX approach.     

Persistent organic pollutants (POPs) in populations of the clam Chione californiensis in coastal lagoons of the Gulf of California

This study examines the potential public health risk due to the massive use of organochlorine pesticides (OCs) in agriculture in the Gulf of California. Specimens of the clam Chione californiensis were collected from three coastal lagoons (Yavaros, Altata and Reforma). Sites were classified as polluted/nonpolluted based on the presence/absence of OCs as an indicator of the persistence of these pollutants; in polluted sites, the time elapsed since pesticide application (past or recent) was estimated. Screening values (SV) for protecting human health as per the U.S. Environmental Protection Agency (EPA) were used for risk assessment. OCs detected were ranked according to frequency of occurrence as follows: γ-chlordane (75%) > endrin (54%) > aldrin (48%) > heptachlor, and dichlorodiphenyl-trichloroethane (DDE) (37%) > β-heptachlor epoxide (30%) > lindane (α-BHC, δ-BHC) and endosulphan I (≤ 6%). Specifically, OCs detected at the highest concentration were heptachlor in Yavaros (0.0168 µgg^?1) and Altata (0.0046 µgg^?1), and aldrin in Reforma (0.0019 µgg^?1). β-Heptachlor epoxide in Altata and Reforma was the only OC with a concentration exceeding the EPA Screening Value. From our results and based on the monthly consumption limit set forth by EPA, the maximum safe consumption of clams to avoid a carcinogenic risk derived from β-heptachlor epoxide in the fishing villages of Yavaros and Altata is 4 servings per month (1 serving = 0.227 kg) by a 70-kg person. These findings suggest that concentrations of OCs and their isomers in C. californiensis populations reflect environmental persistence as well as recent inputs of OCs into coastal lagoons in the Gulf of California.     

Characterization of Atrazine-Loaded Biodegradable Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Microspheres

Polyhydroxybutyrate-co-hydroxyvalerate microspheres (PHBV-MS) were prepared as a delivery system for the herbicide atrazine (ATZ). Characterization of the system included investigation of in vitro release properties and genotoxicity. ATZ − PHBV-MS particle diameters showed a size distribution range of 1–13 μm. Differential scanning calorimetry analyses indicated that ATZ was associated with the PHBV microparticles. The release profiles showed a different release behavior for the pure herbicide in solution, as compared with that containing ATZ-loaded PHBV-MS. Korsmeyer–Peppas model analyses showed that atrazine release from the microparticles occurred by a combination of diffusion through the matrix and partial diffusion through water-filled pores of the PHBV microparticles. A Lactuca sativa test result showed that the genotoxicity of ATZ-loaded PHBV-MP was decreased in relation to ATZ alone. The results demonstrate a viable biodegradable herbicide release system using atrazine for agrochemical purposes.     

Photomineralization of n-alkanoic acids in aqueous solution by photocatalytic membranes. Influence of trialkyl vanadates as catalytic promoters of immobilized titanium dioxide

The Ti0₂-mediated photomineralization of 8–1000 ppm of methanoic acid, of 6–100 ppm of ethanoic acid, of 6–180 ppm of propanoic acid, and of 6–90 ppm of n-decanoic acid in aqueous solutions was studied at 296± 2 K or 308 ± 2 K, with low and high pressure mercury arc lamps (radiant power in the absorption range 8 and 145 W respectively), using PHOTOPERM® CPP/313 membranes containing immobilized 30±3 wt.% Ti0₂, and, in parallel runs, 7 wt.% of a synergic mixture of tri(t-butyl)- and tri-(i-propyl) vanadate(V) as photocatalytic promoter. Stoichiometric H₂0₂ was used or, in some of the runs, 0₃, at saturation, as oxygen suppliers. Disappearance of total organic carbon (TOC) was followed as a function of time. To fit kinetic curves up to complete photomineralization, a kinetic model was employed, already used successfully in previous studies, which considers appearance and disappearance of all intermediates, as if they were represented by a hypothetical single molecule, mediating all of them. The photocatalytic activity of trialkyl vanadates was evaluated from quantum yields at “infinite” concentration, with respect to the maximum allowable efficiencies. When using O₃, a dark catalysis effect clearly appeared towards intermediate species produced during the photocatalysed degradation.     

Diffuse source apportionment of the Po river eutrophying load to the Adriatic sea: assessment of Lombardy contribution to Po river nutrient load apportionment by means of an integrated modelling approach

The source apportionment of the annual nutrient load carried by the Po river to the Adriatic sea has been studied.

An integrated modelling approach was applied to the Lombardy plain area, which covers about 34% of the Po river watershed area and accounts for about 50% of the point sources’ loads carried by the river. To extract all the information available from direct instream measurements, two different modelling tools were alternatively used. The source apportionment was investigated considering both dry and wet weather scenarios. In order to quantify the apportionment in dry-weather conditions, the Lombardy portion of the Po river basin was modelled by using the US-EPA QUAL2E model. Such a simulation allowed to assess a significant contribution (about 50% of the total dry-weather load) of a not rain-driven diffuse pollution component (i.e. groundwater, springs, lake emissaries). Moreover, to estimate the rain-driven surface runoff contribution to the instream total load, the Lombardy plain area was also modelled by means of the US-DA SWAT model. SWAT results indicate a runoff contribution to the Po river instream total load of about 10 000 t N yr⁻¹ and 1300 t P yr⁻¹ (i.e. approximately the 10–20% of the total annual Lombardy nutrient load). At the event scale (i.e. the single rainstorm event) the runoff contribution may rise up to 30–80% of the total instream load. Finally, the total annual nitrogen load at the Po basin closure was estimated for the period 1985–2001. Out of a total annual load of 140 000 t N yr⁻¹, Lombardy accounts for 43% (point plus diffuse sources). The rain-driven diffuse sources constitute the 20% of the overall total load, the point sources account for 40%, whereas the remaining 40% is mainly constituted by “dry-weather diffuse sources” (i.e. groundwater, springs, lake emissaries).     

Use of the digestive gland of the oyster Crassostrea rhizophorae (Guilding, 1828) as a bioindicator of Zn,Cd and Cu contamination in estuarine sediments (south-east Brazil)

This study demonstrates the accumulation of Zn, Cd and Cu in the digestive gland of the oyster Crassostrea rhizophorae in response to the contamination of sediments and discusses the potential use of this specific organ in monitoring metal contamination in tropical areas. Sediment and oyster samples were collected from coastal Rio de Janeiro sites with different levels of human impact: Sepetiba Bay, Guanabara Bay and the Paraty coast. Metal concentrations were measured using inductively coupled plasma optical emission spectrometry (ICP OES). Significant statistical differences (p<0.001; p<0.05) were observed for Zn and Cd concentrations in the digestive gland; the highest Zn concentrations were found at Sepetiba, followed by Guanabara and Paraty. The highest digestive gland Cd concentrations were found at Paraty, followed by Sepetiba and Guanabara. These concentrations were proportional to those found in the sediments. There was no significant difference (p>0.05) in Cu among the sampling sites. The highest digestive-gland Cu concentration was also found at Sepetiba, followed by Guanabara. The biosediment accumulation factor indicated a gradient of sediment contamination for Zn and Cd. The digestive gland of C. rhizophorae can be a potential indicator of trace metal contamination in sediments from tropical estuarine environments.