Despite the considerable steps taken in the last decade in the context of antineoplastic drug (AD) handling procedures, their mutagenic effect still poses a threat to healthcare personnel actively ...involved in compounding and administration units. Biological monitoring procedures usually require large volumes of sample and extraction solvents, or do not provide adequate sensitivity. It is here proposed a fast and automated method to evaluate the urinary levels of cyclophosphamide and iphosphamide, composed of a miniaturized solid phase extraction (µSPE) followed by ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. The extraction procedure, developed through design of experiments (DoE) on the ePrep One Workstation, required a total time of 9.5 min per sample, with recoveries of 77-79% and a solvent consumption lower than 1.5 mL per 1 mL of urine sample. Thanks to the UHPLC-MS/MS method, the limits of quantification (LOQ) obtained were lower than 10 pg/mL. The analytical procedure was successfully applied to 23 urine samples from compounding wards of four Italian hospitals, which resulted in contaminations between 27 and 182 pg/mL.
Formaldehyde (FA) is a toxic compound and a human carcinogen. Regulating FA-releasing substances in commercial goods is a growing and interesting topic: worldwide production sectors, like food ...industries, textiles, wood manufacture, and cosmetics, are involved. Thus, there is a need for sensitive, economical, and specific FA monitoring tools. Solid-phase microextraction (SPME), with
-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) on-sample derivatization and gas chromatography, is proposed for FA monitoring of real-life samples. This study reports the use of polydimethylsiloxane (PDMS) as a sorbent phase combined with innovative commercial methods, such as multiple SPME (MSPME) and cooling-assisted SPME, for FA determination. Critical steps, such as extraction and sampling, were evaluated in method development. The derivatization was performed at 60 °C for 30 min, followed by 15 min sampling at 10 °C, in three cycles (SPME Arrow) or six cycles (SPME). The sensitivity was satisfactory for the method's purposes (LOD-LOQ at 11-36 ng L
, and 8-26 ng L
, for SPME and SPME Arrow, respectively). The method's linearity ranges from the lower LOQ at trace level (ng L
) to the upper LOQ at 40 mg L
. The precision range was 5.7-10.2% and 4.8-9.6% and the accuracy was 97.4% and 96.3% for SPME and SPME Arrow, respectively. The cooling MSPME set-up applied to real commercial goods provided results of quality comparable to previously published data.
Crop models are used to estimate crop productivity under future climate projections, and modellers manage uncertainty by considering different scenarios and GCMs, using a range of crop simulators. ...Five crop models and 20 users were arranged in a randomized block design with four replicates. Parameters for maize (well studied by modellers) and rapeseed (almost ignored) were calibrated. While all models were accurate for maize (RRMSE from 16.5% to 25.9%), they were, to some extent, unsuitable for rapeseed. Although differences between biomass simulated by the models were generally significant for rapeseed, they were significant only in 30% of the cases for maize. This could suggest that in case of models well suited to a crop, user subjectivity (which explained 14% of total variance in maize outputs) can hide differences in model algorithms and, consequently, the uncertainty due to parameterization should be better investigated.
•Five crop models and 20 users were arranged in four randomized blocks.•The significance of model factor for maize and rapeseed was evaluated.•All models achieved good performance for maize and poor for rapeseed.•Differences between models were significant only in 30% of the cases for maize.•Parameterization uncertainty should be explicitly managed also in model ensembles.
High-throughput screening of samples is the strategy of choice to detect occupational exposure biomarkers, yet it requires a user-friendly apparatus that gives relatively prompt results while ...ensuring high degrees of selectivity, precision, accuracy and automation, particularly in the preparation process. Miniaturization has attracted much attention in analytical chemistry and has driven solvent and sample savings as easier automation, the latter thanks to the introduction on the market of the three axis autosampler. In light of the above, this contribution describes a novel user-friendly solid-phase microextraction (SPME) off- and on-line platform coupled with gas chromatography and triple quadrupole-mass spectrometry to determine urinary metabolites of polycyclic aromatic hydrocarbons 1- and 2-hydroxy-naphthalene, 9-hydroxy-phenanthrene, 1-hydroxy-pyrene, 3- and 9-hydroxy-benzoantracene, and 3-hydroxy-benzoapyrene. In this new procedure, chromatography's sensitivity is combined with the user-friendliness of
-butyldimethylsilyl-
-methyltrifluoroacetamide on-fiber SPME derivatization using direct immersion sampling; moreover, specific isotope-labelled internal standards provide quantitative accuracy. The detection limits for the seven OH-PAHs ranged from 0.25 to 4.52 ng/L. Intra-(from 2.5 to 3.0%) and inter-session (from 2.4 to 3.9%) repeatability was also evaluated. This method serves to identify suitable risk-control strategies for occupational hygiene conservation programs.
The potential carcinogenicity of formaldehyde (FA) has prompted increasing preventive measures in anatomic pathology (AP) laboratories and new strategies aimed at innovating airborne FA monitoring ...systems. This review provides an updated overview of the most recent improvements in preventive measures, safe practices, and exposure monitoring tools in the FA usage and handling. A computer-based search of scientific and non-scientific sources was performed on PubMed, Web of Science, Google and Google Patents databases, querying the main topics of real-time, in-continuous FA monitoring instruments for sale, and commercially available tools for improving preventive measures in formalin management. In order to simplify the sampling process and to choose a better analytic solution to FA assessment, the main characteristics of each FA monitoring instrument were described. The novel technical tools recently introduced on the global market, aimed at reducing FA emissions in AP laboratories, were summarized. This review is directed at anatomic pathologists to draw their attention to the rapidly growing field of safe formalin practices. A repeated exposure assessment is recommended to evaluate technical changes in air monitoring programs to keep FA emissions low, in compliance with the limit value; thus, evolved monitoring devices are needed. Key words: formaldehyde, mitigation, formalin, exposure monitoring, anatomic pathology, occupational exposure
Trimellitic anhydride (TMAn) is an essential starting material of the chemical manufacturing industry; it is widely used in saturated polyester resins (SPR) manufacturing to produce plasticizers for ...different purposes. TMAn was recently added, as a new substance of very high concern, to the candidate list by the European Chemicals Agency, since it can lead to sensitization, respiratory tract irritation and lung disease. Any substance from the list of candidates if present in manufactured products at concentrations above 0.1% (w/w) obliges the manufacturer to communicate this to customers down the supply chain and to consumers. We propose here a method that allows the fully automated determination of TMAn in SPR samples by using large volume injection (LVI), with programmed temperature vaporization (PTV) injection, in a gas chromatographic (GC) system equipped with ion trap mass spectrometer (IT) operating in tandem mass spectrometry (MS/MS). The method optimization was obtained by a chemometric model, using the experimental design. Introducing the use of short chromatographic column, triethyloxonium tetrafluoroborate (TEO) as derivatization agent and IS granted specificity, sensitivity and robustness. The detection and quantification limits for TMAn were 0.01% and 0.03% w/w, respectively. Trueness (between 94 and 98%) and precision (RSD lower than 10%,
n
= 6) were also assessed.
Antineoplastic drugs (ADs) are essential tools in cancer treatment, but their cytotoxicity poses a risk to workers involved in their handling. In a hospital environment fundamental strategies for ...minimising exposure involve proper use of safety cabinets and closed-circuit transfer devices, along with personnel training and increased awareness of risks. However, medical gloves remain the first line of defence. In this respect the evaluation of glove materials and best choices can improve hospital safety management and prevent potential hazards and long-term consequences. The aim of this study was to assess contamination of gloves in samples taken from AD administration and preparation units of nine Italian hospitals and to raise awareness of the importance of evaluating chemico-physical properties of gloves. Our findings show that 33 % of the analysed gloves were positive for at least one AD, with contaminations ranging from 0.6 to 20,729 pg/ cm
. We proposed the
(AGVs) for each AD as a limit value for contamination assessment and good practice evaluation. Our findings also point to multiple AD contamination (43 % of positive findings in preparation units), calculated as total AGV (AGV-T), and confirm that gloves should be replaced after 30 min of AD handling, based on cumulative permeation and area under the curve (AUC), to maintain safety and limit dermal exposure.
Solid-phase microextraction (SPME) via on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) and gas chromatographic determination is considered a technique of choice in ...many analytical fields for formaldehyde (FA) monitoring. Vapor phase adsorption models of experimentally loaded PFBHA on porous divinylbenzene (DVB) SPME were investigated at 60 °C, 35 cm s-1 of air velocity, in a 1-64 min range: with the fiber completely exposed, loaded PFBHA was about 276 µg. Among the models tested, i.e. heat transfer, pseudo-second-order (PSO), Elovich, intra-particle diffusion, extra-particle diffusion and Langmuir, PFBHA adsorption was best fit by the PSO model, showing agreement with experimental data (272 µg). The sampling rate of FA in our conditions, obtained with a permeation tube system, was in agreement with literature (17.4 and 18.3 mL min-1, respectively). Thus, an overall standardization of the sampling phase is presented, leaving the sampling time as the most crucial parameter to be set for future applications.
Crop simulation models are used to forecast the impacts of climate change on yield levels and to identify adaptation strategies. Nevertheless, crop quality has been almost neglected in available ...studies, despite its relevance on the economic and nutritional value of agricultural products. We present here a modeling study to evaluate the future trends of rice quality in the main European rice district, placed in Northern Italy. A rice growth model was coupled with a library of models of rice milling and cooking suitability, using current farmer management and baseline/future climatic scenarios as input for the simulations. Four general circulation models (NOResm, MIROC‐ESM, HadGEM2‐ES, and GISS‐ES) and two CO2 representative concentration pathways (2.6, 8.5) were used to generate 20‐year future climatic data centered on 2030 and 2070. Spatially distributed simulations were run at 2 × 2 km spatial resolution considering a Japonica (Loto) and a Tropical Japonica (Gladio) rice cultivar. The results depicted an overall decline in rice quality, especially for Loto (−5% of milling suitability considering GISS‐ES‐2.6 in all time frames; −8% in 2030 and −20% in 2070 under HadGEM2‐ES‐8.5). While the revenues of millers are expected to decrease of about 50 € t−1 in 2030 and 100 € t−1 in 2070 for Loto, minor changes are projected on Gladio milling and cooking suitability, except in the worst scenario in 2070 (−10 to −5% of cooking suitability, corresponding to −30 to −72 € t−1). Despite the need of reducing models uncertainty, this study provides variety‐specific indications on rice grain quality ready‐to‐use for crop specialists, farmers, and millers and that could raise the interest of different stakeholders of the agri‐food sector, including food scientists, geneticists, and policy makers.
We performed a model‐based evaluation of future trends of rice milling and cooking suitability, considering two widely cultivated cultivars in the main European rice‐producing area, an ensemble of climate change projections and remote sensing techniques to detect crop presence and sowing dates. Our study indicates a general decline in milling suitability with a large heterogeneity between cultivars and spatial areas, whereas cooking suitability is predicted to remain almost stable in the future. Despite the explicit limitations and assumptions, our work provides plausible indications on rice quality trends and connected economic projections to preserve the sustainability of European rice systems.
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