Airborne benzene in workplaces has progressively decreased due to preventive actions and the redesigning of facility processes. Professionals who assess occupational exposure should select techniques ...to detect benzene levels comparable to ambient air exposure. Thus, sensitive biomarkers are needed to discriminate the effects of confounding factors, such as smoking or sorbic acid (SA). In order to identify sensitive biomarkers and to study their correlation with confounding factors, 23 oil refinery workers were enrolled in the study; their airborne benzene exposures and biomarkers were monitored. Urinary benzene (U-B), t,t-muconic acid (t,t-MA), and S-phenylmercapturic acid (SPMA) were quantified. Urinary cotinine (U-C) and t,t-sorbic acid (t,t-SA) were evaluated to flag smoking and SA intake, respectively. The benzene measured in personal inhalation sampling ranged from 0.6 to 83.5 (median 1.7) µg/m3. The concentration range of the biomarkers, U-B, t,t-MA, and SPMA, were 18–4893 ng/m3, <10–79.4 µg/g creatinine, and <0.5–3.96 µg/g creatinine, respectively. Pearson tests were carried out; the best correlations were between airborne benzene and U-B (µg/L r = 0.820, p < 0.001) and between benzene and SPMA (g/L r = 0.812, p < 0.001), followed by benzene and t,t-MA (mg/L r = 0.465, p = 0.039). From our study, U-B and SPMA result to be the most reliable biomarkers to assess the internal number of low doses of benzene exposure, thanks to their specificity and sensitivity.
Platinum-based antineoplastic drugs (PtADs) are among the most important and used families of chemotherapy drugs, which, even showing severe side effects and being hindered by drug resistance, are ...not likely to be replaced clinically any time soon. The growing interest in the occupational health community in antineoplastic drug (AD) surface contamination requires the development of increasingly fast and easy high-throughput monitoring methods, even considering the lack of harmonized legally binding regulation criteria. Thus, a wipe sampling method together with zwitterionic hydrophilic interaction liquid chromatography (HILIC-Z)–tandem mass spectrometry (MS/MS) analysis was developed for the simultaneous evaluation of oxaliplatin, cisplatin, and carboplatin surface contaminations. A design of experiments approach was used to optimize the chromatographic conditions. Limits of quantification ranging from 2 to 5 ng/mL were obtained from interday and intraday repetitions for oxaliplatin and carboplatin, and between 170 and 240 ng/mL for cisplatin. The wipe desorption procedure is equivalent to other AD sampling methods, enabling a fast sample preparation, with an LC-MS/MS analysis time of less than 7 min.
Antineoplastic drugs are a wide and heterogeneous group of substances that, as universally known, can cause highly severe toxic effects to whoever is exposed. From an occupational safety point of ...view, surface contaminations inside preparation and administration units are a growing issue and therefore require the development and implementation of sensible and fast monitoring methods. The unlikelihood of a unique all-embracing chromatography, able to correctly retain and separate each analyte led to the need to create an orthogonal normal phase analysis, which might be able to fill the gaps in the more common reversed-phase ones. An existing hydrophilic interaction method has thus been expanded to 6 other drugs and applied to real samples after an evaluation of its performances. The experimental data were then used to evaluate the possibility of estimating reliable relationships between the chromatographic retention and the chemical-structural features of the drugs under analysis.
This review is an update of a previous review in 2009 and covers publications from 2009 to 2019. The review focuses on experimental design, referred to as the design of experiments (DoE), used in ...developing bioanalytical solid-phase microextraction (SPME) methods. Characteristics of different SPME approaches are illustrated and critically discussed. The literature selection evidences that two-level full factorial designs, with a limited number of factors (<5), are most frequently used for preliminary factors screening. When applying the response surface methodology for the quantitative assessment of factorial effects, few quadratic models were used. The most popular were the rotatable central composite and Box-Benkhen designs. Models including more than four factors, such as fractional factorial designs (including the Plackett-Burman and Taguchi designs), were rarely used. Definitive screening and D-Optimal designs were not reported anywhere in the literature selection.
When examining the diagnostic criteria used to evaluate different model’s quality and validity, it was apparent the researchers relied heavily on commercial software for experimental design, analysis, and reporting of the results.
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•Survey of reports of DoE-based SPME procedures for bioanalysis.•Trends in the use of DoE and SPME tools in bioanalysis.•Analytes, matrices, SPME modes of use, methodological approaches.•Critical discussion of the data analysis and completeness of information published.
Giant reed is a promising perennial grass providing ligno-cellulosic biomass suitable to be cultivated in marginal lands (MLs) and converted into several forms of renewable energy. This study ...investigates how much energy, in the form of biomethane, bioethanol, and combustible solid, can be obtained by the cultivation of this species in marginal land of two Italian regions, via the spatially explicit application of the Arungro crop model. Arungro was calibrated in both rainfed/well-irrigated systems, under non-limiting conditions for nutrient availability. The model was then linked to a georeferenced database, with data on (i) current/future climate, (ii) agro-management, (iii) soil physics/hydrology, (iv) land marginality, and (v) crop suitability to environment. Simulations were run at 500 × 500 m spatial resolution in MLs of Catania (CT, Southern Italy) and Bologna (BO, Northern Italy) provinces, characterized by contrasting pedo-climates. At field scale, Arungro explained 85% of the year-to-year variability of measured carbon accumulation in aerial biomass. At the provincial level, simulated energy yields progressively increased from bioethanol, to biomethane, and finally to combustible solid, with average values of 92-115-264 GJ ha−1 in BO and 105-133-304 GJ ha−1 in CT. Mean energy yields estimated for 2030 remained unchanged compared to the baseline, although showing large heterogeneity across the study area (changes between −6/+15% in BO and −16/+15% in CT). This study provides site-specific indications on giant reed current productions, energy yields, and natural water consumption, as well as on their future trends and stability, ready-to-use for multiple stakeholders of the agricultural sector involved in bioenergy planning.
A model was developed to simulate fatty acid accumulation in oleaginous seeds.The model structure was based on a Petri Net description of the biochemical pathway.Four published experimental datasets ...were used to calibrate and validate the model.The model reproduced the dynamics of fatty acids in various experimental conditions.Environmental stress scenarios were simulated obtaining results consistent with literature.
A simulation model was developed to study the accumulation dynamics of seed oil fatty acids (FAs) in response to environmental stimuli. The Petri Net (PN) formalism was used to encode a virtual analogue of the FA biosynthetic pathway, where the process is governed by rules targeting enzymatic regulatory mechanisms. Four alternative types of rules were conceived: i) constant enzymatic activity throughout seed development; ii) enzymatic activity regulated by temperature; iii) enzymatic activity regulated by time-dependent gene expression; iv) combination of temperature- and time-dependent regulatory mechanisms. A set of 10 PN-based candidate models were built upon these rules to be evaluated against real oil composition data gathered during seed development.
Camelina sativa (L.) Crantz was chosen as a case-study crop to test model performance. Published experimental datasets from Italy, Spain and the USA were used to calibrate and validate the models through a cross-validation procedure.
Models incorporating endogenous time-based regulation showed higher predictive power than those built upon temperature-based rules, but the best results were obtained when combinations of both types of rules were used. The highest scoring model used the beta function to model endogenously regulated time-dependency of enzymatic activity, and the response to temperature. The fitted model correctly reproduced time-course FA accumulation. In order to assess its behaviour under climate change, sample simulations were run under two artificial scenarios, one characterized by increased air temperature, and the other by imposed restriction to photosynthetic carbon supply to the seed. The latter scenario was intended to mimic drought stress in particular. At higher temperatures the model predicted an increase in saturated and monounsaturated FAs, with a concomitant decrease of the polyunsaturated fraction.
Under simulated carbon restrictions the prevailing behaviour was a lowering of monounsaturated FAs whereas the polyunsaturated fraction markedly increased. In both case-studies the predicted responses were found to be consistent with previous literature reports.
•Extreme weather events are expected to increase their impact on crop productions.•New modelling solutions were developed to better account for weather extremes.•Many crops were simulated in Europe ...under current climate and future projections.•Behavior of new modelling solutions was analyzed using sensitivity analysis methods.
The formalization of novel equations explicitly modelling the impact of extreme weather events into the crop model WOFOST (EMS: existing modelling solution; MMS: modified modelling solution) is proposed as a way to reduce the uncertainty in estimations of crop yield. A sensitivity analysis (SA) was performed to assess the effect of changing parameters values on the yield simulated by the model (both EMS and MMS) for different crops (winter and durum wheat, winter barley, maize, sunflower) grown under a variety of conditions (including future climate realisations) in Europe. A two-step SA was performed using global techniques: the Morris screening method for qualitative ranking of parameters was first used, followed by the eFAST variance-based method, which attributes portions of variance in the model output to each parameter.
The results showed that the parameters related to the partitioning of assimilates to storage organs (FOTB) and to the conversion efficiency of photosynthates into storage organs (CVO) generally affected considerably the simulated yield (also underlying tight correlation with this output), whereas the parameters involved with respiration rate (Q10) or specific leaf area (SLA) became influential in case of unfavourable weather conditions. Major differences between EMS and MMS (which includes a component simulating the impact of extreme weather events) emerged in extreme cases of crop failure triggered by markedly negative minimum temperatures. With few exceptions, the two SA methods revealed the same parameter ranking. We argue that the SA performed in this study can be useful in the design of crop modelling studies and in the implementation of crop yield forecasting systems in Europe.
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.
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