Nanocomposite microbeads made of recycled polylactic acid for the magnetic solid phase extraction of xenobiotics from human urine.

Nanocomposite microbeads (average diameter = 10-100 µm) were prepared by a microemulsion-solidification method and applied to the magnetic solid-phase extraction (m-SPE) of fourteen analytes, among pesticides, drugs, and hormones, from human urine samples. The microbeads, perfectly spherical in shape to maximize the surface contact with the analytes, were composed of magnetic nanoparticles dispersed in a polylactic acid (PLA) solid bulk, decorated with multi-walled carbon nanotubes (mPLA@MWCNTs). In particular, PLA was recovered from filters of smoked electronic cigarettes after an adequate cleaning protocol. A complete morphological characterization of the microbeads was performed via Fourier-transform infrared (FTIR) spectroscopy, UV-Vis spectroscopy, thermogravimetric and differential scanning calorimetry analysis (TGA and DSC), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The recovery study of the m-SPE procedure showed yields ≥ 64%, with the exception of 4-chloro-2-methylphenol (57%) at the lowest spike level (3 µg L-1). The method was validated according to the main FDA guidelines for the validation of bioanalytical methods. Using liquid chromatography-tandem mass spectrometry, precision and accuracy were below 11% and 15%, respectively, and detection limits of 0.1-1.8 µg L-1. Linearity was studied in the range of interest 1-15 µg L-1 with determination coefficients greater than 0.99. In light of the obtained results, the nanocomposite microbeads have proved to be a valid and sustainable alternative to traditional sorbents, offering good analytical standards and being synthetized from recycled plastic material. One of the main objectives of the current work is to provide an innovative and optimized procedure for the recycling of a plastic waste, to obtain a regular and reliable microstructure, whose application is here presented in the field of analytical chemistry. The simplicity and greenness of the method endows the procedure with a versatile applicability in different research and industrial fields.

Recovery of cellulose acetate bioplastic from cigarette butts: realization of a sustainable sorbent for water remediation.

Cigarette butts, one of the most common forms of litter in the world, represent a source of chemical and plastic pollution releasing thousands of toxic compounds and microfibers of cellulose acetate (CA). Besides the correct waste management, the recovery of CA from cigarette filters is a way to cushion their negative effects on the environment. Thus far, recycling strategies have been limited to industrial applications, while not many solutions have designed for water remediation. This work describes a strategy to valorize this harmful waste and to reverse its environmental impact, proposing a simple and effective procedure of reclamation of CA and its reuse to prepare a composite sorbent for the treatment of polluted water. The first step entails the washing of filters with hot water (T = 90 °C) and hot ethanol (T = 58-68 °C) to remove the impurities produced during cigarette burning, as verified by means of UV and attenuated total reflection-Fourier-transform infrared (ATR-FTIR) spectroscopy, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The second step involves the use of the regenerated CA to prepare porous cylinder-shaped cryogels (15 mm × 10 mm) whose sorption properties are enhanced by the combination with AC (15 % w/w). The synthesis takes advantage of the sol-gel transition of the polymer dispersion (5 % w/V) in a solution acetone/water 5 mM in NH3 (60/40, v/v). After characterization by dynamic mechanical analysis (DMA), TGA, FT-IR, and scanning electron microscopy (SEM), the adsorption capability of the physical cryogel was studied in terms of treated environmental water volume, contact time and concentration of the selected pollutants. The results have shown that the proposed strategy is a low-cost way to recycle CA from cigarette butts and that the designed sorbent is a promising material for water treatment, allowing quick removal times and yields >79.6 %.

Direct Solar Oven with and without UV Filter vs. Traditional Oven: Effect on Polyphenolic Antioxidants, Vitamins and Carotenoids of Food.

The use of efficient solar ovens can be a way for progressing ecofriendly technologies in the field of food preparation. In most performing direct solar ovens, the sun rays reach the foods directly, therefore, it becomes essential to check whether, in these conditions, foods can retain theirnutraceutical properties (antioxidants, vitamins and carotenoids). In the present research work, to investigate this issue, several foods (vegetables, meats, and a fish sample) were analyzed before and after cooking (traditional oven, solar oven, and solar oven with a UV filter). The content of lipophilic vitamins and carotenoids (analyzed via HPLC-MS) and the variation of total phenolic content (TPC), and antioxidant capacity (via Folin-Ciocalteu and DPPH assays) have evidenced that cooking with the direct solar oven allows to preserve some nutrients (i.e., tocopherols) and, sometimes, to enhance nutraceutical properties of vegetables (for example, solar oven-cooked eggplants showed 38% higher TPC compared to electric oven cooked sample) and meats. The specific isomerization of all-trans-ß-carotene to 9-cis was also detected. The use of a UV filter is advisable to avoid UV drawbacks (for instance, a significant carotenoid degradation) without losing the beneficial effects of the other radiations.

Biomonitoring of pesticides in urine by using isoamyl acetate as a sustainable extraction solvent.

The protection of the health and safety of workers in the agricultural sector requires the assessment of human exposure to pesticides through biomonitoring programs. In doing this, the health and safety of laboratory analysts should be also protected through the use of analytical procedures as safe as possible. According to Green Analytical Chemistry and Green Sample Preparation principles, the use of miniaturized extraction techniques such as dispersive liquid-liquid microextraction (DLLME) should be encouraged, with the aim of limiting the consumption of chemicals (solvents and reagents) and energy, as well as the production of wastes. Moreover, safer and more environmentally friendly alternatives to petroleum-derived solvents must be found. In this regard, the effort of researchers is focused on the development/identification of sustainable solvents, some of which have been ranked according to their disposal, environmental, safety, and health features. Here, we introduce the alternative use of isoamyl acetate ("banana oil") as sustainable extraction solvent. Compared with the trendy class of eutectic solvents (ESs), isoamyl acetate is advantageous because it is already in the liquid state, which fasters operations, and because it can be evaporated to dryness and reconstituted in a solvent compatible with the mobile chromatographic phase, which is not an option for ESs. The applicability of isoamyl acetate has been here evaluated for the first time to extract 12 pesticides of different polarities from urine matrix, by using a DLLME approach. The HPLC/MS validated method has proven to possess the sensitivity, precision and accuracy required to reliable bioanalytical methods. Its cheapness, simplicity and quickness make it an ideal sustainable choice for the screening of large numbers of samples in health monitoring programs involving people occupationally-exposed to pesticides.

Enantioselective high-performance liquid chromatographic separations to study occurrence and fate of chiral pesticides in soil, water, and agricultural products.

As many as 40% of all plant protection products currently used contain chiral active ingredients. Enantiomers of the same pesticide have identical physicochemical properties in an isotropic medium, but they may display different activity and toxicity because of their interaction with enzymes or other naturally occurring asymmetric molecules. This difference may also lead to variations in biotic degradation rates, making one enantiomer more persistent than the other in natural and agricultural environments. In terms of methodological aspects, this critical review describes the most used chiral stationary phases for HPLC enantioseparations of chiral pesticides, pinpointing their strengths and weaknesses. As far as their applicability is concerned, most research has been carried out by means of columns based on derivatized amylose/cellulose due to their rather universal analyte coverage. The chromatographic compatibility with sensitive detection techniques, such as mass spectrometry, has allowed the trace analysis of stereoisomers, revealing ubiquitous occurrence of some chiral pesticides in surface waters, sediments, plants, agricultural soils, roots, fruit and vegetables. The study of their distribution and degradation in various environmental compartments and agricultural soil-plant systems has highlighted the enrichment with one enantiomer over the other in certain matrices following the enantioselective dissipation catalysed by microorganisms or plant enzymes as well as the phenomenon of chiral inversion in some cases. Irrespective of the reliability of a chiral method, such investigations are often hindered by the lack of pure standards of single enantiomers, which makes it difficult to identify their stereochemical configuration and requires precise strategies of quantification. Surely, the research in this field has been grown over the last few years due to the necessity of assessing and limiting risks related to exposure to chiral pesticides, which can be considered emerging contaminants in all aspects.

Removal of Copper Corrosion Products by Using Green Deep Eutectic Solvent and Bio-Derivative Cellulose Membrane.

A safe and environmentally friendly material for corrosion removal from metals is proposed in this article. Electrochemically corroded copper was selected as a target material, and a deep eutectic solvent (DES) composed of choline chloride and ascorbic acid, in a molar ratio of 2:1, was developed to this end. Aqueous solutions of the DES with a concentration above 70 wt% were found to be effective in the dissolution of patina and less aggressive towards other materials such as CaCO3, which is the main component of limestone. These concentrated DES solutions were integrated with either cotton swabs or cellulose-based membranes and used for the cleaning of electrochemically corroded copper. The membrane containing 80 wt% DES aqueous solution exhibited the most desirable cleaning ability in terms of speed and area selectivity. X-ray diffraction analysis of the corroded copper before and after the application of the membrane was performed to demonstrate the successful corrosion removal.

Hydrophobic Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction Applied to the Analysis of Pesticides in Wine.

A green solvent-based DLLME/HPLC-MS method for the determination of 19 pesticides in wine samples has been developed. The extractant solvent is a hydrophobic eutectic mixture composed of L-menthol and butylated hydroxytoluene in a molar ratio of 3:1. The endogenous ethanol of wine has been used as dispersive solvent, in order to avoid the solidification of the extracts under 19 °C. The mobile phase composition, the elution gradient and the sample injection volume were optimized in order to make this hydrophobic mixture compatible with conventional reversed phase chromatography and electrospray ionization. The method was validated in matrix, using a wine free from the target compounds. Average recovery as high as 80%, precision between 3 and 14%, and limits of detection and quantification much lower than the maximum residue levels (MRLs) for grapes and wines fixed by the EU regulation, make this multiresidue method fitted for the purpose, with the further advantages of being quick, cheap and in compliance with the green analytical chemistry. From the analysis of 11 commercial wines it was found that just in a bio sample the target compounds were not detectable or lower than quantification limit; as for the other samples, the most widespread and abundant pesticides were methoxyfenozide and boscalid, but their levels were much lower than the relative MRLs.

Chiral Nano-Liquid Chromatography and Dispersive Liquid-Liquid Microextraction Applied to the Analysis of Antifungal Drugs in Milk.

A novel chromatographic application in chiral separation by using the nano-LC technique is here reported. The chiral recognition of 12 antifungal drugs was obtained through a 75 µm I.D. fused-silica capillary, which was packed with a CSP-cellulose 3,5-dichlorophenylcarbamate (CDCPC), by means of a lab-made slurry packing procedure. The mobile phase composition and the experimental conditions were optimized in order to find the optimum chiral separation for some selected racemic mixtures of imidazole and triazole derivatives. Some important parameters, such as retention faction, enantioresolution, peak efficiency, and peak shape, were investigated as a function of the mobile phase (pH, water content, type and concentration of both the buffer and the organic modifier, and solvent dilution composition). Within one run lasting 25 min, at a flow rate of approximately 400 nL min-1, eight couples of enantiomers were baseline-resolved and four of them were separated in less than 25 min. The method was then applied to milk samples, which were pretreated using a classical dispersive liquid-liquid microextraction technique preceded by protein precipitation. Finally, the DLLME-nano-LC-UV method was validated in a matrix following the main FDA guidelines for bioanalytical methods.

Glyphosate-Eating Fungi: Study on Fungal Saprotrophic Strains' Ability to Tolerate and Utilise Glyphosate as a Nutritional Source and on the Ability of Purpureocillium lilacinum to Degrade It.

Glyphosate is the most commonly used herbicide worldwide. Its improper use during recent decades has resulted in glyphosate contamination of soils and waters. Fungal bioremediation is an environmentally friendly, cost effective, and feasible solution to glyphosate contamination in soils. In this study, several saprotrophic fungi isolated from agricultural environments were screened for their ability to tolerate and utilise Roundup in different cultural conditions as a nutritional source. Purpureocillium lilacinum was further screened to evaluate the ability to break down and utilise glyphosate as a P source in a liquid medium. The dose-response effect for Roundup, and the difference in toxicity between pure glyphosate and Roundup were also studied. This study reports the ability of several strains to tolerate 1 mM and 10 mM Roundup and to utilise it as nutritional source. P. lilacinum was reported for the first time for its ability to degrade glyphosate to a considerable extent (80%) and to utilise it as a P source, without showing dose-dependent negative effects on growth. Pure glyphosate was found to be more toxic than Roundup for P. lilacinum. Our results showed that pure glyphosate toxicity can be only partially addressed by the pH decrease determined in the culture medium. In conclusion, our study emphasises the noteworthy potential of P. lilacinum in glyphosate degradation.

Application of a Low Transition Temperature Mixture for the Dispersive Liquid-Liquid Microextraction of Illicit Drugs from Urine Samples.

The use of psychoactive substances is a serious problem in today's society and reliable methods of analysis are necessary to confirm their occurrence in biological matrices. In this work, a green sample preparation technique prior to HPLC-MS analysis was successfully applied to the extraction of 14 illicit drugs from urine samples. The isolation procedure was a dispersive liquid-liquid microextraction based on the use of a low transition temperature mixture (LTTM), composed of choline chloride and sesamol in a molar ratio 1:3 as the extracting solvent. This mixture was classified as LTTM after a thorough investigation carried out by FTIR and DSC, which recorded a glass transition temperature at -71 °C. The extraction procedure was optimized and validated according to the main Food and Drug Administration (FDA) guidelines for bioanalytical methods, obtaining good figures of merit for all parameters: the estimated lower limit of quantitation (LLOQ) values were between 0.01 µg L-1 (bk-MMBDB) and 0.37 µg L-1 (PMA); recoveries, evaluated at very low spike levels (in the ng-µg L-1 range), spanned from 55% (MBDB) to 100% (bk-MMBDB and MDPV); finally, both within-run and between-run precisions were lower than 20% (LLOQ) and 15% (10xLLOQ).

Chitosan-Graphene Oxide Composite Membranes for Solid-Phase Extraction of Pesticides.

Solid-phase extraction (SPE) coupled to LC/MS/MS analysis is a valid approach for the determination of organic micropollutants (OMPs) in liquid samples. To remove the greatest number of OMPs from environmental matrices, the development of innovative sorbent materials is crucial. Recently, much attention has been paid to inorganic nanosystems such as graphite-derived materials. Graphene oxide has been employed in water-purification processes, including the removal of several micropollutants such as dyes, flame retardants, or pharmaceutical products. Polysaccharides have also been widely used as convenient media for the dispersion of sorbent materials, thanks to their unique properties such as biodegradability, biocompatibility, nontoxicity, and low cost. In this work, chitosan-graphene oxide (CS_GO) composite membranes containing different amounts of GO were prepared and used as sorbents for the SPE of pesticides. To improve their dimensional stability in aqueous medium, the CS_GO membranes were surface crosslinked with glutaraldehyde. The composite systems were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, swelling degree, contact angle, and mechanical measurements. As the GO content increased, a decrease in surface homogeneity, an improvement of mechanical properties, and a reduction of thermal stability of the CS-based membranes were observed. The increased dimensional stability in water, together with the presence of high GO amounts, made the prepared composite membranes more efficacious than the ones based just on CS in isolating and preconcentrating different hydrophilic/hydrophobic pollutants.

Remediation of hexavalent chromium contaminated water through zero-valent iron nanoparticles and effects on tomato plant growth performance.

Contaminated water with hexavalent chromium Cr(VI) is a serious environmental problem. This study aimed to evaluate the Cr(VI) removal by zero valent iron nanoparticles (nZVI) reduction process and the impact of Cr(VI), nZVI and combined treatment with nZVI and Cr(VI) on tomato growth performance. To evaluate the Cr(VI) toxic effect on germination capability, seeds were exposed to increasing Cr(VI) concentrations up to 1000 mg L-1. The inhibition of seed germination and the decrease of hypocotyl and root length started from Cr(VI) 5 mg L-1. Under treatment with Cr(VI) + nZVI 5 mg L-1, seed germination, hypocotyl and root length resulted significantly higher compared to Cr(VI) 5 mg L-1 treatment. The impact of only nZVI was investigated on chlorophyll and carotenoid in leaves; iron levels in leaves, roots, fruits and soil; carotenoid, fat-soluble vitamin and nicotianamine in mature fruits. A significant increase of leaf chlorophyll and carotenoids was observed after nZVI 5 mg L-1 treatment compared to controls. No significant variations were observed in carotenoids, fat-soluble vitamins and nicotianamine levels after treatment with nZVI 5 mg L-1 in mature fruits. For their ability to reduce Cr(VI) and to stimulate tomato growth, nZVI might to be considered as alternative for remediation purposes.

Extraction of Carotenoids and Fat-Soluble Vitamins from Tetradesmus Obliquus Microalgae: An Optimized Approach by Using Supercritical CO2.

In recent years, great attention has been focused on rapid, selective, and environmentally friendly extraction methods to recover pigments and antioxidants from microalgae. Among these, supercritical fluid extraction (SFE) represents one of the most important alternatives to traditional extraction methods carried out with the use of organic solvents. In this study, the influence of parameters such as pressure, temperature, and the addition of a polar co-solvent in the SFE yields of carotenoids and fat-soluble vitamins from T. obliquus biomass were evaluated. The highest extraction of alpha-tocopherol, gamma-tocopherol, and retinol was achieved at a pressure of 30 MPa and a temperature of 40 °C. It was observed that overall, the extraction yield increased considerably when a preliminary step of sample pre-treatment, based on a matrix solid phase dispersion, was applied using diatomaceous earth as a dispersing agent. The use of ethanol as a co-solvent, under certain conditions of pressure and temperature, resulted in selectively increasing the yields of only some compounds. In particular, a remarkable selectivity was observed if the extraction was carried out in the presence of ethanol at 10 MPa and 40 °C: under these conditions, it was possible to isolate menaquinone-7, a homologous of vitamin K2, which, otherwise, cannot not recovered by using traditional extraction procedures.

Large-scale profiling of carotenoids by using non aqueous reversed phase liquid chromatography - photodiode array detection - triple quadrupole linear ion trap mass spectrometry: Application to some varieties of sweet pepper (Capsicum annuum L.).

Analysis of carotenoids is very complex and demanding in terms of both separation and detection. In this article, an analytical strategy relying on high-performance liquid chromatography-photodiode array detection-tandem mass spectrometry (HPLC-PAD-MS/MS) is presented for the large-scale screening of these phytochemicals. Separation was realized by means of Non-Aqueous Reversed Phase (NARP) chromatography on a triacontyl stationary phase kept at subambient temperature, using a mobile phase compatible with atmospheric pressure chemical ionization (APCI). The standards of 14 analytes were used to optimize the method and to predict the chromatographic behaviour of untargeted carotenoids. MS and MS/MS data, obtained during Information Dependent Acquisition (IDA) experiments, were utilized to set up a sensitive HPLC- selected reaction monitoring (SRM) method. Relative abundance between SRM ion currents (ion ratio) allowed the MS distinction of structural isomers (for example, bicyclic, monocyclic and acyclic isomers), while the identification of geometrical isomers was based on Qratio and fine structure, as calculated from UV-vis spectra. The comparison of LC-PAD- SRM chromatograms, acquired after applying two different extraction procedures (matrix solid-phase dispersion and overnight cold saponification), allowed verifying that sweet peppers are a good source of xanthophylls, prevalently occurring as esterified forms. The overall strategy could identify more than 40 carotenoids in some sweet pepper varieties (Jolly, horn and sweet chili pepper) available on the Italian and European food market.

Subcritical water extraction of thyreostats from bovine muscle followed by liquid chromatography-tandem mass spectrometry.

Thyreostats can be used fraudulently to promote a rapid increase in weight of breeding animals at low cost. Their severe toxicological effects impose the development of reliable analytical methods to be used in monitoring plans. This work describes an alternative approach to isolate residues of thiouracil, methyl-thiouracil, propyl-thiouracil, phenyl-thiouracil, tapazole and mercaptobenzimidazole from bovine muscle tissue. The developed procedure is based on the following three steps: i) matrix solid-phase dispersion with C18 for the preliminary sample preparation; ii) subcritical water extraction (SWE) at 160°C and 100 bar; iii) clean-up on an Oasis HLB cartridge. The quantitative determination was performed by LC-MS/MS in dual polarity ionization by using internal standardization. The SWE-LC-MS/MS method was validated according to the identification criteria of the Commission decision 2002/657/EC. The relative recoveries ranged from 72 to 97%; within-lab reproducibility was less than 18%. The decision limit and the detection capability of all analytes were below the recommended concentration, set at 10 µg kg-1, but the validation results demonstrated that this method could only be applied for screening of thiouracil and methyl-thiouracil. Besides the analytical advantages related to the use of water as solvent extraction, the procedure allowed significant removal of lipids, whose detrimental effects on instrumentation and MS sensitivity are well-known.

Screening and Assessment of Low-Molecular-Weight Biomarkers of Milk from Cow and Water Buffalo: An Alternative Approach for the Rapid Identification of Adulterated Water Buffalo Mozzarellas.

Adulteration of Mozzarella di Bufala Campana with cow milk is a common fraud because of the high price and limited seasonal availability of water buffalo milk. To identify such adulteration, this work proposes a novel approach based on the use of species-specific, low-molecular-weight biomarkers (LMWBs). Liquid chromatography-tandem mass spectrometry screening analyses identified ß-carotene, lutein, and ß-cryptoxanthin as LMWBs of cow milk, while ergocalciferol was found only in water buffalo milk. Adulterated mozzarellas were prepared in the laboratory and analyzed for the four biomarkers. Combined quantification of ß-carotene and ergocalciferol enabled the detection of cow milk with a sensitivity threshold of 5% (w/w). The method was further tested by analyzing a certificated water buffalo mozzarella and several commercial products. This approach is alternative to conventional proteomic and genomic methods and is advantageous for routine operations as a result of its simplicity, speed, and low cost.

Synthesis and Characterization of Cellulose-Based Hydrogels to Be Used as Gel Electrolytes.

Cellulose-based hydrogels, obtained by tuned, low-cost synthetic routes, are proposed as convenient gel electrolyte membranes. Hydrogels have been prepared from different types of cellulose by optimized solubilization and crosslinking steps. The obtained gel membranes have been characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mechanical tests in order to investigate the crosslinking occurrence and modifications of cellulose resulting from the synthetic process, morphology of the hydrogels, their thermal stability, and viscoelastic-extensional properties, respectively. Hydrogels liquid uptake capability and ionic conductivity, derived from absorption of aqueous electrolytic solutions, have been evaluated, to assess the successful applicability of the proposed membranes as gel electrolytes for electrochemical devices. To this purpose, the redox behavior of electroactive species entrapped into the hydrogels has been investigated by cyclic voltammetry tests, revealing very high reversibility and ion diffusivity.

Optimal follow-up intervals in active surveillance of renal masses in patients with von Hippel-Lindau disease.

OBJECTIVES: To estimate an optimal follow-up (FU) interval for von Hippel-Lindau (VHL) patients with renal masses (RMs) by determining tumour growth rates from growth curves. METHODS: Thirty lesions (47.6%) were classified as solid tumours (STs) and 33 (52.4%) as complex cysts (CCs). Variations in lesion volume over time were analyzed. For 53 lesions, we calculated the growth rate during the period when the volume of the lesion changed most rapidly, and called this the fast growth rate (FGR). RESULTS: The STs initially grew fast, followed by a period of slower growth. The CCs varied in volume over time, associated with variable amounts of their fluid component. The FGR correlated better with the latest volume for STs (r = 0.905) than for CCs (r = 0.780). An optimal FU interval between 3 and 12 months was derived by combining the FGR calculated from the curve with the latest volume measured. CONCLUSIONS: Analyzing growth curves and related kinetic parameters for RMs in VHL patients could be useful with a view to optimizing the subsequent FU interval and improving the active surveillance program. KEY POINTS: • Measuring volume changes over time enables tumour growth curves to be charted. • Renal solid tumours increase in volume with a typical sigmoidal curve. • Complex cysts may increase and decrease in volume spontaneously over time. • The fast growth rate of solid tumours correlates with their latest volume. • The fast growth rate can orient the scheduling of subsequent follow-ups.

Comparison of preoperative and surgical measurements of Zenker's diverticulum.

BACKGROUND: Zenker's diverticulum (ZD) may be treated with a variety of endoscopic or open surgical techniques; the choice of treatment depends partly on the size of the diverticulum. The purpose of this study was to correlate ZD measurements obtained preoperatively and during surgery. METHODS: From March 2006 to November 2008, 20 consecutive patients (19 males; median age 64.5 (range 37-88) years) with dysphagia secondary to ZD were enrolled for this study. All patients had preoperative barium radiography of the pharynx and esophagus, and diagnostic endoscopy. Ten patients underwent transoral stapling diverticulostomy and ten had open surgery. The depth of the ZD was measured on radiographic views, at endoscopy and during surgery, focusing on the distance from the top of the septum to the bottom of the pouch. The ZD dimensions obtained radiologically and endoscopically were compared with those found during surgery. Correlations and agreements between measurements were assessed using Pearson's correlation coefficients and method-comparison analysis, respectively. RESULTS: The median depth of the ZD was 2.9 cm (mean 2.95 ± 1.12 cm; range 1.5-6 cm), 3.0 cm (mean 3.24 ± 1.27 cm; range 1.7-6.8 cm), and 3.0 cm (mean 2.99 ± 1.01 cm; range 1.5-6 cm) when measured during surgery, radiology, and endoscopy, respectively. The correlation and agreement between the radiographic and surgical ZD measurements were good, whereas those between the endoscopic and surgical measurements were poor. CONCLUSIONS: These findings confirm that preoperative barium radiography is mandatory in order to choose the most appropriate surgical treatment for ZD.

Usefulness and limits of ultrasound-guided hook-wire positioning for localisation of soft tissue lesions prior to surgery.

PURPOSE: The aim of our study was to assess the usefulness of positioning metal wires under ultrasound guidance for localising soft tissue lesions in the preoperative phase. MATERIALS AND METHODS: We studied superficial soft-tissue lesions in 12 patients, using hooked mammographic wires of different lengths. One patient had a multifocal growth of disease which required a double localisation procedure. Correct positioning of the wire was confirmed by ultrasonography. All patients underwent surgery within five hours of hook-wire positioning. RESULTS: Correct wire position was confirmed at surgery in 12 out of 13 procedures. In one case the hook-wire reached the margin of the lesion. In all cases, the preoperative localisation procedure facilitated identification and resection of the masses. CONCLUSIONS: In our experience, the main indications for hook-wire positioning before surgery are: marking of small lesions, localisation of lesions in anatomic areas structurally subverted by previous surgery and consequently difficult to detect, guidance for surgical sectioning in order safeguard the noble structures close to the lesions.