Iron-montmorillonite clays as active sorbents for the decontamination of hazardous chemical warfare agents.

A class of heterogeneous catalysts based on commercial bentonite from natural origin, containing at least 80 wt% of montmorillonite clay, was designed to transform selectively and under mild conditions toxic organosulfur and organophosphorus chemical warfare agents into non-noxious products with a reduced impact on health and environment. The bentonite from the natural origin was modified by introducing iron species and acid sites in the interlayer space, aiming to obtain a sorbent with strong catalytic oxidising and hydrolytic properties. The catalytic performance of these materials was evaluated in the oxidative abatement of (2-chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, in the presence of aqueous hydrogen peroxide as an oxidant. A new decontamination formulation was, moreover, proposed and obtained by mixing sodium perborate, as a solid oxidant, to iron-bentonite catalysts. Solid-phase decontamination tests, performed on a cotton textile support contaminated with organosulfide and organophosphonate simulant agents revealed the good activity of the solid formulation, especially in the in situ detoxification of blistering agents. Tests carried out on the real blistering warfare agent, sulfur mustard (HD agent), showed that, thanks to the co-presence of the iron-based clay together with the solid oxidant component, a good decontamination of the test surface from the real warfare agent could be achieved (80% contaminant degradation, under ambient conditions, in 24 h).

Headache in cerebral venous thrombosis associated with extracranial tumors: a clinical series.

Cerebral venous thrombosis (CVT) may represent the clinical onset of malignancies or complicate their course, also in phase of quiescence. In literature, there are several case reports on the association between CVT and tumors, but there are few articles on its clinical characteristics in cancer patients (Pts). Our aim was to analyze the clinical characteristics of CVT associated with extracranial tumors. We identified nine cases of CVT in adults affected by extracranial tumors in 6 years from six hospitals. The median age was 40 years; eight Pts were female. Associated tumors were: lymphoma (4/9); breast (2/9), rhinopharynges (1/9) and gastric (1/9) carcinomas. One patient presented a kidney tumor and a melanoma at the same time. Multiple sinuses were affected in seven Pts. MRI showed parenchymal lesions in most cases (7/9). Clinical manifestations were: focal deficits (7/9), headache (6/9), early seizures (4/9) and consciousness disorders (3/9). Headache was the onset symptom in six Pts. In four of these Pts, headache preceded the onset of the focal deficit and/or seizures than 2-15 days. The characteristics of the headache were variable in intensity, location and type but all the Pts agreed in saying that it was an unusual headache, unresponsive to common pain medications. Five of the six Pts complaining of headache in the course of CVT presented focal deficits and parenchymal lesions at admission to the emergency room. All nine Pts were anticoagulated without further haemorrhagic complications. At discharge, the Pts presented a complete recovery in four cases, mild sequelae in four and moderate sequelae in one. In conclusion, we would like to underline the importance of particular care to cancer Pts complaining of headache, since the early diagnosis and the appropriate anticoagulant treatment could prevent the appearance of parenchymal lesions and the consequent neurological deficits. Also in the cases of normal brain CT, a brain MRI/MR venography should be performed in emergency setting if CVT is suspected.

Polycyclic aromatic hydrocarbons and metals in transplanted lichen (Pseudovernia furfuracea) at sites adjacent to a solid-waste landfill in central Italy.

The aim of the study was to evaluate the airborne contamination by polycyclic aromatic hydrocarbons (PAHs) and some heavy metals (arsenic [As], cadmium [Cd], chromium [Cr], copper [Cu], nickel [Ni], lead [Pb], and zinc [Zn]) of different pollution scenarios around a solid-waste landfill in central Italy using the lichen Pseudovernia furfuracea as a monitoring tool. For this purpose, eight stations around a landfill characterized by different air pollution sources (industrial, agricultural, residential areas, and roads with different traffic intensities), together with three stations far from the landfill (control areas), were monitored using a set of 22 lichen samples (11 samples analysed for PAHs and metals after 4 months, and 11 samples analysed for metals after 8 months). After 4 months of exposure, the lichen content of all of the analysed elements was greater than that in the pre-exposed lichens. In addition, the Cu and Pb concentration after 8 months was greater than the level after 4 months. The order of metal concentration was Zn > Pb > Cu (or Cu > Pb) > Cr > Ni > As > Cd in all cases. The range of ∑11PAHs concentration was 634-1,371 ng/g dw (three to seven times greater than the amount in the pre-exposed lichens). The ∑11PAHs were dominated (>70 %) by compounds with three aromatic rings. The comparison of the levels of air pollutants among the monitored stations shows nonrelevant spatial patterns between the landfill stations and the control areas; the levels of PAHs and metals found in the lichen samples around the landfill seemed to be more related to the general diffusion of these pollutants in that area.

Surfactant therapy for acute respiratory distress in children.

In children with acute lung injury the endogenous surfactant system is altered via a variety of different mechanisms, including inflammation, vascular dysfunction, oxidant injury, cellular injury and oedema. This article examines the pathophysiology of acute lung injury and surfactant use for treatment of acute respiratory failure in infants and children.

Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: a spectroscopic study.

Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir4(CO)10(SnCl3)2] and NEt4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9)4 onto pre-formed Ir metal particles. These solids possess promising properties, in terms of selectivity, as catalysts for propane dehydrogenation to propene. Detailed CO-adsorption DRIFTS, XANES and EXAFS characterization studies have been performed on these systems in order to compare the structural and electronic evolution of systems in relation to the nature of the Ir-Sn bonds present in the precursor compounds and to propose a structural model of the Ir-Sn species present at the silica surface of the final catalyst.

Air pollution positively correlates with daily stroke admission and in hospital mortality: a study in the urban area of Como, Italy.

Some current evidences suggest that stroke incidence and mortality may be higher in elevated air pollution areas. Our study examined the hypothesis of a correlation between air pollution level and ischemic stroke admission and in Hospital mortality in an urban population. Data on a total of 759 stroke admissions and 180 deaths have been obtained over a 4-year period (2000-2003). Five air ambient particles have been studied. A general additive model estimating Poisson distribution has been used, adding meteorological variables as covariates. NO(2) and PM(10) were significantly associated with admission and mortality (P value < 0.05) and with estimated RR of 1.039 (95% CI 1.066-1.013) and 1.078 (95% CI 1.104-1.052) for hospital admission at 2- and 4-day lags, respectively. In conclusion, this study suggests an association between short-term outdoor air pollution exposure and ischemic stroke admission and mortality.

Acute encephalopathies.

In daily hospital activity a frequent observation is that of patients in conditions of acute global suffering of the central nervous system due to a primary cause or symptomatic of other diseases. This condition shows an alteration of the state of consciousness, which involves three possible semeiologic manifestations: delirium (acute confusional state), acute confusional state associated with psychomotor underactivity and coma. The possible causes of an acute encephalopathy (AE) are: metabolic, iatrogenic and toxic, infective, primary neurologic, surgery-related and others. Diagnostic-therapeutic routes to be followed by emergency room doctors and neurologists dealing with AE are defined.

A multi-biomarker analysis of DNA damage in automobile painters.

The genotoxic effects associated with automobile painting were analyzed using a panel of biomarkers. Chromosomal aberrations (CAs), sister chromatid exchange (SCE), and micronuclei were evaluated in 25 car painters (12 smokers, 13 nonsmokers) working in different automobile paint-shops in Italy and in 37 control subjects. The controls were healthy blood donors (14 smokers, 23 non-smokers) that were matched with the experimental population for gender and age. Air samples were analyzed regularly at the work places, and elevated concentrations of benzene and toluene were detected consistently. The exposed group had higher frequencies of CAs (both chromosome- and chromatid-type), micronuclei, and SCE (P < 0.5 - P < 0.001). Furthermore, exposed and control subjects were also genotyped for GSTM1 and GSTT1 polymorphism. No significant associations were detected between the biomarker responses and either the GSTM1 or GSTT1 genotype of the subjects, but the small sample size does not allow definite conclusions on the relationship between the genetic polymorphism and the biomarkers. The results indicate that automobile painters have increased levels of clastogenic and possible aneugenic damage and that smoking may be a confounding factor for the responses.

A case of short-lasting unilateral neuralgiform headache with conjunctival injection and tearing (SUNCT). Discussion of clinical features and differential diagnosis.

Chronic short-lasting headaches, in which trigeminal autonomic cephalalgias (TACs) are included, are relatively rare syndromes and not always well recognised. We present a case highly suggestive of short-lasting unilateral neuralgiform headache with conjunctival injection and tearing (SUNCT) and we try to affirm essential points to distinguish the diagnosis from other TACs and chronic short-lasting headaches. We conclude that the qualifying points for differential diagnosis are number and duration of attacks in a day, presence of autonomic features and lack of indomethacin effect.

Lichens as polycyclic aromatic hydrocarbon bioaccumulators used in atmospheric pollution studies.

The aim of this work has been to determine the possibility of using lichens as polycyclic aromatic hydrocarbon (PAH) bioaccumulators for the evaluation of atmospheric pollution in the city of Rieti. A lichen sample collected in a remote unpolluted area was divided into 18 sub-samples. These were collocated in nine different stations in the city of Rieti and every 5 months the PAH concentrations were determined. Only phenanthrene, anthracene, fluoranthene, pyrene and chrysene were found at concentrations over the limit of quantification. In the meantime a continuous increase of their concentrations was observed.

Determination of Se4+ in drinkable water by solid-phase microextraction and gas chromatography/mass spectrometry.

A method was developed for the selective determination of Se4+ in drinkable water by solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS). Se4+ was selectively derivatized to ethane, 1,1'-selenobis by reaction with sodium tetraethylborate, extracted by the SPME fiber, and determined by GC/MS. Both headspace (HS)-SPME and direct SPME were studied. The method requires only a few milliliters of sample and 20 min for completion. At 2.0 microg/L concentration, the relative standard deviation was 10.1% for HS-SPME and 9.1% for direct SPME. For HS-SPME, the theoretical detection limit was 81 ng/L and 166 ng/L for direct SPME. The recovery rate was 95%. The method was used to determine Se4+ in 10 tap water samples.

Evaluation of genotoxic and cytotoxic properties of pesticides employed in Italian agricultural practices.

In a program coordinated by the Italian Ministry of Works, we tested in vitro four pesticides widely employed in a developed agricultural region of central Italy. The four commercial agents were chosen on the basis of their diffusion in agricultural practice, knowledge of their active principle(s), and scant availability of data concerning their toxic and genotoxic activity. The agents were Cirtoxin, Decis, Tramat Combi (TC), and Lasso Micromix (LM). All substances were tested in three in vitro systems: Chinese hamster ovary (CHO) cells, a metabolically competent hamster cell line (Chinese hamster epithelial liver; CHEL), and root tips of Vicia faba (VF). The cytotoxic and genotoxic end points challenged were micronuclei and root tip length (RTL) in VF and mitotic index (MI), proliferation index (PI), cell survival (CS), cell growth (CG), cell cycle length (CCL), sister chromatid exchanges, chromosomal aberrations, and single-cell gel electrophoresis, or comet assay, in CHEL and CHO cells. Tested doses ranged from the field dose up to 200x the field dose to take into account accumulation effects. On the whole, tested agents appear to induce genotoxic damage only at subtoxic or toxic doses, indicating a low clastogenic risk. MI, PI, CS, CG, RTL, and CCL appear to be the less sensitive end points, showing no effects in the presence of a clear positive response in some or all of the other tests. Using cytogenetic tests, we obtained positive results for TC and LM treatments in CHO but not in CHEL cells. These data could be accounted for by postulating a detoxifying activity exerted by this cell line. However, cytogenetic end points appear to be more sensitive than those referring to cytotoxicity.

[Laboratory diagnosis: correlated health and environmental risks]. / La diagnostica di laboratorio: rischi sanitari e ambientali correlati.

Method description and initial results of a study to assess risks to health sector workers and environment due to chemical agents used and waste products generated in diagnostic clinical chemical laboratories, and image diagnostic testing. A survey was conducted of the methods and agents used and their toxicological classification, the number of workers exposed and an analytical profile of the waste produced. The assessment of risk to workers was based on cytogenetic tests (chromosome aberrations and micronuclei); the assessment of environmental risk from waste disposal was based on tests on plant systems.

Determination of organic micropollutants in rain water for laboratory screening of air quality in urban environment.

Rain water may collect organic air pollutants, such as polycyclic aromatic hydrocarbons (PAHs), phthalate ester (PEs), pesticides, and polychrorinated biphenyls (PCBs), that could be present in air in consequence of different factors. The determination of these compounds in rain water samples consequently may be interesting for a first screening of air quality in urban and/or industrial areas. For this purpose, 3 areas of the city of Rieti (central Italy) were selected for rain water sampling: a) the city center, densely populated and with high road traffic; b) a suburban residential area; c) the industrial area, about 3 km out of the city center and along the state road. Wet-only precipitation collectors were used for sampling; solid-phase microextraction or liquid-liquid microextraction techniques followed by GC/MS determinations were applied for sample analysis. PCBs and pesticides were never found in the samples collected. On the contrary, some polycyclic aromatic hydrocarbons and phthalates were always found. Significant and seasonal differences in PAH levels were observed in the 3 different sampling areas, with higher values always found in the city center and during the winter period; on the contrary, PEs levels remained unchanged.

Nonpeptide oxytocin antagonists: analogs of L-371,257 with improved potency.

Structure-activity studies on the oxytocin antagonist 1 (L-371,257; Ki = 9.3 nM) have led to the identification of a related series of compounds containing an ortho-trifluoroethoxyphenylacetyl core which are orally bioavailable and have significantly improved potency in vitro and in vivo, e.g., compound 8 (L-374,943; Ki = 1.4 nM).

Determination of pesticide residues in wine by SPME and GC/MS for consumer risk assessment.

An analytical procedure applying solid phase microextraction (SPME) combined with gas chromatography/ mass spectrometry (GC/MS) for the detection of pesticide residues in wine was performed for the determination of 14 of the pesticides most frequently used on grapes (insecticides, fungicides, herbicides). As SPME combines the possibility of a single-step extraction with other advantages (short sampling times, solvent-free procedure, speedy extraction, low cost and simplicity) it could be successfully used either for screening or routine analysis for detecting pesticides of different chemical classes in wines, even at trace levels. The analytical procedure performed showed minimum detectable quantities ranging from 0.10 microgram/l to 6.0 micrograms/l and precision from 9.7% to 18% (as relative standard deviation of 1 microgram/l levels), assuring high sensitivity and precision of analysis. Twenty-one wine samples (10 white wines and 11 red wines) available on the Italian market were analysed with the procedure described and about 57% were positive for one or more pesticides. An approach for consumer risk assessment on the basis of the data obtained was proposed for further assessments of the daily dietary intake of pesticides through wine.

Development of orally active oxytocin antagonists: studies on 1-(1-[4-[1-(2-methyl-1-oxidopyridin-3-ylmethyl)piperidin-4-yloxy]-2- methoxybenzoyl]piperidin-4-yl)-1,4-dihydrobenz[d][1,3]oxazin-2-one (L-372,662) and related pyridines.

The previously reported oxytocin antagonist L-371,257 (2) has been modified at its acetylpiperidine terminus to incorporate various pyridine N-oxide groups. This modification has led to the identification of compounds with improved pharmacokinetics and excellent oral bioavailability. The pyridine N-oxide series is exemplified by L-372,662 (30), which possessed good potency in vitro (Ki = 4.1 nM, cloned human oxytocin receptor) and in vivo (intravenous AD50 = 0.71 mg/kg in the rat), excellent oral bioavailability (90% in the rat, 96% in the dog), good aqueous solubility (>8.5 mg/mL at pH 5.2) which should facilitate formulation for iv administration, and excellent selectivity against the human arginine vasopressin receptors. Incorporation of a 5-fluoro substituent on the central benzoyl ring of this class of oxytocin antagonists enhanced in vitro and in vivo potency but was detrimental to the pharmacokinetic profiles of these compounds. Although lipophilic substitution around the pyridine ring of compound 30 gave higher affinity in vitro, such substituents were a metabolic liability and caused shortfalls in vivo. Two approaches to prevent this metabolism, addition of a cyclic constraint and incorporation of trifluoromethyl groups, were examined. The former approach was ineffective because of metabolic hydroxylation on the constrained ring system, whereas the latter showed improvement in plasma pharmacokinetics in some cases.

Inter-laboratory validation of solid-phase microextraction for the determination of triazine herbicides and their degradation products at ng/l level in water samples.

The accuracy and precision of solid-phase microextraction (SPME) were validated in an inter-laboratory study including ten laboratories for the analysis of triazine herbicides and their metabolites at ng/l level in aqueous samples. The SPME conditions were optimised in order to obtain maximum sensitivity. Especially, salt addition and choice of the SPME fibre coated with Carbowax-divinylbenzene increased the sensitivity. The average detection limits were in the range from 4 to 24 ng/l for the triazine herbicides, and 20 and 40 ng/l for desisopropylatrazine and desethylatrazine, respectively. The average r2 values of the calibration curves were above 0.99 for all of the analytes. The statistical data treatment was performed in accordance with the International Standardisation Organisation (ISO) standard 5725. Relative repeatability standard deviations between 6 and 14% and relative reproducibility standard deviations between 10 and 17% were found. The determined concentrations of the reference sample compared well to the "true" values, thus proving the good accuracy of the method. It is concluded that SPME is a reliable technique for the quantitative analysis of water samples containing triazine herbicides in concentrations around the European limit of 100 ng/l for individual pesticides in drinking water.