Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg^?1, respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Leaching of S-metolachlor,terbuthylazine, desethyl-terbuthylazine,mesotrione, flufenacet,isoxaflutole, and diketonitrile in field lysimeters as affected by the time elapsed between spraying and first leaching event

The effect of elapsed time between spraying and first leaching event on the leaching behavior of five herbicides (terbuthylazine, S-metolachlor, mesotrione, flufenacet, and isoxaflutole) and two metabolites (desethyl-terbuthylazine and diketonitrile) was evaluated in a 2011–2012 study in northwest Italy. A battery of 12 lysimeters (8.4 m² long with a depth of 1.8 m) were used in the study, each filled with silty-loam soil and treated during pre-emergence with the selected herbicides by applying a mixture of commercial products Lumax (4 L ha^?1) and Merlin Gold (1 L ha^?1). During treatment periods, no gravity water was present in lysimeters. Irrigation events capable of producing leaching (40 mm) were conducted on independent groups of three lysimeters on 1 day after treatment (1 DAT), 7 DAT, 14 DAT, and 28 DAT. The series was then repeated 14 days later. Leachate samples were collected a few days after irrigation; compounds were extracted by solid phase extraction and analyzed by high-performance liquid chromatography and gas chromatography–mass spectrometry. Under study conditions, terbuthylazine and S-metolachlor showed the highest leaching potentials. Specifically, S-metolachlor concentrations were always found above 0.25 µg L^?1. Desethyl-terbuthylazine was often detected in leached waters, in most cases at concentrations above 0.1 µg L^?1. Flufenacet leached only when irrigation occurred close to the time of herbicide spraying. Isoxaflutole and mesotrione were not measured (<0.1 µg L^?1), while diketonitrile was detected in concentrations above 0.1 µg L^?1 on 1 DAT in 2011 only.     

Persistent Organic Pollutants in gull eggs of two species (Larus michahellis and Larus audouinii) from the Ebro delta Natural Park

The aim of this study was to determine the impact of priority and emerging Persistent Organic Pollutants (POPs) in gull eggs from two species, the scavenger Larus michahellis and the protected species, Larus audouinii. These two species share habitat in the Natural Park of the Ebro delta (Catalonia, Spain). Compounds studied are included or under consideration in the Stockholm Convention and comprise polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated compounds (OCs), perfluorinated compounds (PFCs) and short chain chlorinated paraffins (SCCPs). Four methods based in selective extraction and gas or liquid chromatography coupled to mass spectrometry were used and quality parameters are provided. OC pesticides and marker PCBs were the most abundant chemical families detected in eggs from the two species, followed by PFCs, PBDEs (especially BDE 209) and SCCPs. Dioxin-like PCBs and PCDD/Fs were also detected in all samples. The overall widespread presence of POPs is discussed in terms of feeding habits, bird ecology and anthropogenic pressures in the protected Ebro delta breeding area.     

Identification of heavy metal sources by multivariable analysis in a typical Mediterranean city (SE Spain)

Problems associated with heavy metal characterization in the majority of sites are often due to multiple sources of pollution. This work presents the results through the use of advanced statistical techniques to identify sources of soil heavy metals in a typical Mediterranean city. The multivariable analysis performed on seven metals identified four sources controlling their variability. Cr, Mn, and Ni contents were associated to soil parent materials; Cd and Pb contents were related to anthropogenic activities, specifically industrial activities and traffic; Cu content is controlled by long-term application of inorganic fertilizers in agricultural areas. Finally, zinc concentration is associated to commercial and outdoor activities in the area. These results were supported by the fact that metals associated to parent material (Cr, Mn, and Ni) were better correlated with soil lithogenic properties, while anthropogenic metals were correlated with more variable soil constituents.     

Evaluation of a simultaneous sampling method of PAHs, PCDD/Fs and dl-PCBs in ambient air

The Stockholm Convention on Persistent Organic Pollutants (POPs) was signed in May 2001 by 127 countries. Currently, 12 substances are regulated by the convention, and the work on finding new candidate chemicals to the convention has started. Among these 12 substances, dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are the objects of this study. There are no European standard methods for the simultaneous determination of these microorganic compounds, together with polycyclic aromatic hydrocarbons (PAHs) in ambient air--they must be referred to three different methods developed by the U.S. Environmental Protection Agency (EPA). The quali-quantitative analysis of these microorganic pollutants is an important challenge due to the low concentrations at which they may be present. In this study, the development of a simplified, alternative, fast and affordable sampling method for the determination of PAHs, PCDDs, PCDFs and PCBs in ambient air was performed. The sampling time was extended from 24 h to 7 d in order to enrich the sample, to fall within the instrumental limits of detection and to reduce the number of samples to be processed and, therefore, errors that may arise. First of all, experiments with labelled standards were conducted in the research area of Montelibretti (rural station, which is sited about 20 km northeast of Rome), with the purpose of optimizing sampling efficiency. Finally, the method was applied to the analysis of these compounds in the air of a suburban area with small industrial plants in order to evaluate the feasibility of the proposed sampling method system, by comparing concentrations of native compounds acquired during simultaneous daily and weekly sampling.     

Environmental study of two significant solid samples: gravitation dust sediment and soil

In this work are presented results of the complex study of two significant solid environmental samples: gravitation dust sediments (industrial pollutants, potential source of risk elements input to soils) and soils (component of the environment, potential source of risk elements input to food web). The first phase of this study was focused on the study of the significant chemical properties (phase composition, content of organic and inorganic carbon) of the dust and soil samples. In the second phase, the fractionation analysis was used on the evaluation of the mobility of chosen risk elements (Cu, Ni, Pb, Zn) in the studied samples. The single-step extractions were applied in the order of the isolation of the element forms (fractions), with different mobilities during defined ecological conditions by utilization of the following reagents: 1 mol dm^− 3 NH₄NO₃ for isolation of the “mobile” fraction, 0.05 mol dm^− 3 ethylenediaminetetraacetic acid and 0.43 mol dm^− 3 CH₃COOH for isolation of the “mobilizable” fraction, and 2 mol dm^− 3 HNO₃ for isolation of all releasable forms. On the basis of the results obtained in this study, it is possible to state that different origins and positions of solid environmental samples in the environment reflect in different chemical properties of their matrix. The different properties of the sample matrix result in different mobilities of risk elements in these kinds of samples. The fractionation analysis with single-step extraction for isolation element fractions is the method most suitable for easy checking of environmental pollution and for evaluation of risk elements cycle in the environment.     

PAHs in the urban air of Sarajevo: levels,sources, day/night variation,and human inhalation risk

Polycyclic aromatic hydrocarbons (PAHs) are organic pollutants derived from pyrolysis and pyrosynthesis processes. Industrial activity, motor vehicle emission, and domestic combustion are the main sources of PAHs in the urban atmosphere. In this work, samples collected during the day and night in the urban area of Sarajevo are analyzed separately for gaseous and particle-bound PAHs; the possible origin of PAHs at the receptor site was suggested using different methods applied to the solid phase and to the total PAHs (gaseous + particulate phase). Finally, the risk level in Sarajevo associated to the carcinogenic character of the studied PAHs has been assessed. The result of this study suggests that (a) the total PAH concentrations were higher than those reported in other European cities; (b) the PAH daytime concentrations are higher than nocturnal concentrations: the sum of the PAH day/night ratios is 1.52 (gas) and 1.45 (particle phase); (c) stationary combustion and traffic were suggested to be the main sources of PAHs; (d) the average particle-bound benzo(a)pyrene (BaP) concentration (5.4 ng/m³) is higher than EU target annual value (1 ng/m³); and (e) PAH cancer risk exceeds the carcinogenic benchmark level recommended by the EPA mainly due to BaP during both the day and night periods.     

Characterisation of the airborne pollen spectrum in Guadalajara (central Spain) and estimation of the potential allergy risk

Aerobiological research into airborne pollen diversity and seasonal variations in pollen counts has become increasingly important over recent decades due to the growing incidence of asthma, rhinitis and other pollen-related allergic conditions. Airborne pollen in Guadalajara (Castilla-La Mancha, Spain) was studied over a 6-year period (2008–2013) using a Hirst-type volumetric spore trap. The highest pollen concentrations were recorded from February to June, coinciding with the pollen season of the pollen types that most contribute to the local airborne pollen spectrum: Cupressaceae (32.2 %), Quercus (15.1 %), Platanus (13.2 %), Olea (8.3 %), Populus (7.8 %) and Poaceae (7.2 %). These are therefore critical months for allergy sufferers. The pollen calendar was typically Mediterranean and comprised 25 pollen types. Between January and March, Cupressaceae pollen concentrations exceeded allergy risk thresholds on 38 days. Other woody species such as Olea and Platanus have a shorter pollen season, and airborne concentrations exceeded allergy risk thresholds on around 13 days in each case. Poaceae pollen concentrations attained allergy risk levels on 26 days between May and July. Other highly allergenic pollen types included Urticaceae and Chenopodiaceae-Amaranthaceae, though these are less abundant than other pollen types in Guadalajara and did not exceed risk thresholds on more than 3 and 5 days, respectively.     

The digital representation of safety systems at “Seveso” plants and its potential for improving risk management

At Seveso plants, duty holders must have a complex system for assessing and managing risks. The pillars of this system are the safety report and the safety management system, with a number of underlying documents. The strength of the system is the high standardization of these documents. Regulations, standard codes and guidelines define content, structure and formats. The weakness is the high complexity. Managers and workers perceive documents as difficult to understand and far from actual operations. Major threats for the credibility of documents (and therefore for the safety systems) come from the continuous organizational and technical changes, which in a short time can make most documents obsolete; as well as by near misses, which continuously show the holes in safety systems. A big effort is required to follow up the plant changes and the near misses. In order to help safety managers, a new software has been developed. At Seveso plants, it has been possible build an integrated digital representation, because all documents are perfectly structured. This representation may be used both for updating the relevant documents after a change and to improve documents after a near miss or an accident. In this way, safety documents are always up to date and trustworthy and the huge knowledge, which is usually hidden inside safety documents, is clearly revealed and revived. The approach is basically “knowledge based” and the intention is to provide safety managers with an easy and simple tool. IRISonLine is a software that has been developed by ISPESL to provide safety managers of “Seveso” establishments with a tool for improving the management of change and of near misses.