Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

Construction safety: An analysis of systems failure: The case of the multifunctional Bos & Lommerplein estate,Amsterdam

Bos & Lommer is a district in the west of Amsterdam. The new centre, consisting of the district office, 96 apartments, a few dozen businesses and shops, a two-storey parking lot with capacity for more than 500 cars, and a market place, was completed in 2004. Less than 2 years later, in July 2006, this whole multifunctional complex had to be urgently cleared, because its safety could not be guaranteed.The investigations revealed that the planning and realisation of the Bos & Lommer complex were anything but exceptional. What happened there could have happened anywhere in the Netherlands and possibly elsewhere.This paper analyses the decision-making process in the planning and construction of the Bos & Lommerplein estate on the basis of accident causation theories. It will ascertain which safety science methodology is best equipped to describe and analyse the events in this multifunctional estate. The analysis forms the basis for a reflection on a set of concrete guidelines for designing and constructing complex projects. Construction safety would be enhanced if the scope for improvement in decision-making on complex building projects were properly utilised.     

I-Risk: development of an integrated technical and management risk methodology for chemical installations

This paper presents an integrated quantitative risk assessment method for hazardous installations, taking into account management as well as technical design and producing risk level measures. The key components of the I-Risk methodology are the technical model, the management model and their interface. The technical model consists of developing a master logic diagram (MLD) delineating the major immediate causes of loss of containment (LOC) and associated quantitative models for assessing their frequency. The management model consists of the tasks, which must be carried out systematically in the primary business functions (such as operations, emergency operations, maintenance and modifications). A management audit quantifies the quality of these management tasks. The management–technical interface modifies certain parameters of the technical model on the basis of the quality of the safety management system of the specific installation. The methodology is exemplified through its application to the risk assessment of an ammonia storage facility. A detailed technical model simulating the response of the system to various initiating events is developed along with a detailed management model simulating the influence of the plant-specific management and organisational practices. The overall effect is quantified through the frequency of release of ammonia as a result of a loss of containment in a storage tank and in a pipeline.     

Metabolic transformations of acquired lucibufagins by firefly “femmes fatales”

Summary. Female Photuris fireflies sequester defensive steroidal pyrones (lucibufagins) from male fireflies of the genus Photinus. Lucibufagin analyses of Photuris females and Photinus ignitus males show that the lucibufagin mixtures of predator and prey differ in their composition. Analyses of whole body extracts showed that P. ignitus males contain a mixture of eight non-glycosylated lucibufagins, composed mostly of compounds with two oxygenated positions in the steroidal A-ring (C-3, C-5). After feeding on P. ignitus males, Photuris females contain six major lucibufagins. Three of these compounds are not present in the prey, including the novel lucibufagin glycoside 5β,11α-dihydroxy-12-oxo-3β-O-β-D-xylopyranosylbufalin, and two other lucibufagins with a trioxygenated A-ring (C-2, C-3, C-5). These results indicate that Photuris females transform the sequestered lucibufagins both by glycosylation and oxidation, which could affect the systemic transportability of these compounds due to an increase in their polarity. Received 18 February 1999; accepted 19 April 1999.     

Controlled readability of Seveso II company safety documents,the design of a new KPI

Companies often use a substantial quantity of safety-related documents such as the front gate safety flyer, emergency evacuation instructions, work permits, safety procedures, work instructions and policy statements. In many cases the personnel magazines and message board notes also contain safety information. The authors and readers may not be in the same department, premises or cultural group. Both authors and readers are diverse groups when it comes to reading, writing and language skills. Previous research has found that Seveso II companies produce documents that are difficult for their workforce and visitors to understand. Authors do not write systematically to match the reader’s skill level. This may be due in part to the quality and effectiveness of layout guidance, expert linguistic advice and document appraisal systems. These do not in general provide the immediate support needed. Layout suggestions are of limited effectiveness, and availability and usability limits the value of expert advice and appraisal systems. So, without useful feedback, many authors cannot write sufficiently readable documents; to overcome this threshold, they need a quick document readability assessment tool. With such a tool, readability can become a controlled property of safety documents. Large companies may use hundreds or thousands of documents containing safety information. This paper presents a practical approach for the transition to, and monitoring of, controlled readability for all documents related to safety. A new Key Performance Indicator design on readability is proposed.     

Seasonal and particle size-dependent variations in gas/particle partitioning of PCDD/Fs

This study monitored particle size-dependent variations in atmospheric polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Two gas/particle partitioning models, the subcooled liquid vapor pressure (P(L)(0)) and the octanol-air partition coefficient (K(OA)) model, were applied to each particle sizes. The regression coefficients of each fraction against the gas/particle partition coefficient (K(P)) were similar for separated particles within the same sample set but differed for particles collected during different periods. Gas/particle partitioning calculated from the integral of fractions was similar to that of size-segregated particles and previously measured bulk values. Despite the different behaviors and production mechanisms of atmospheric particles of different sizes, PCDD/F partitioning of each size range was controlled by meteorological conditions such as atmospheric temperature, O(3) and UV, which reflects no source related with certain particle size ranges but mixed urban sources within this city. Our observations emphasize that when assessing environmental and health effects, the movement of PCDD/Fs in air should be considered in conjunction with particle size in addition to the bulk aerosol.     

Technical modeling in integrated risk assessment of chemical installations

This paper presents the technical model of an Integrated Quantitative Risk Assessment method, taking into account management as well as technical design and producing risk level measures. The basic steps of the technical model consist in developing a Master Logic Diagram (MLD) delineating the major immediate causes of Loss of Containment and associated quantitative models for assessing their frequency. Appropriate management models quantify the parameters of the technical model on the basis of the safety management system of the installation. The methodology is exemplified through its application on the risk assessment of a LPG scrubbing tower of an oil refinery. A detailed technical model simulating the response of the system to various initiating events is developed, along with a detailed model simulating the influence of the plant-specific management and organizational practices. The overall effect is quantified through the frequency of release of LPG as a result of a Loss of Containment in scrubbing towers of the refinery.     

Root uptake of atenolol,sulfamethoxazole and carbamazepine,and their transformation in three soils and four plants

Soils can be contaminated by pharmaceuticals. The aim of this study was to evaluate the impact of soil conditions (influencing sorption and persistence of pharmaceuticals in soils) and plant type on the root uptake of selected pharmaceuticals and their transformation in plant-soil systems. Four plants (lamb’s lettuce, spinach, arugula, radish) planted in 3 soils were irrigated for 20 days (26) with water contaminated by one of 3 pharmaceuticals (carbamazepine, atenolol, sulfamethoxazole) or their mixture. The concentrations of pharmaceuticals and their metabolites in soils and plant tissues were evaluated after the harvest. Sulfamethoxazole and atenolol dissipated rapidly from soils. The larger concentrations of both compounds and an atenolol metabolite were found in roots than in leaves. Sulfamethoxazole metabolites were below the limits of quantifications. Carbamazepine was stable in soils, easily uptaken, accumulated, and metabolized in plant leaves. The efficiency of radish and arugula (both family Brassicaceae) in metabolizing was very low contrary to the high and moderate efficiencies of lamb’s lettuce and spinach, respectively. Compounds’ transformations mostly masked the soil impact on their accumulation in plant tissues. The negative relationships were found between the carbamazepine sorption coefficients and its concentrations in roots of radish, lamb’s lettuce, and spinach.