Crossed-beam and theoretical studies of multichannel nonadiabatic reactions: branching fractions and role of intersystem crossing for O(3P) + 1,3-butadiene.

Atomic oxygen reactions can contribute significantly to the oxidation of unsaturated aliphatic and aromatic hydrocarbons. The reaction mechanism is started by electrophilic O atom addition to the unsaturated bond(s) to form "chemically activated" triplet oxy-intermediate(s), which can evolve adiabatically on the triplet potential energy surface (PES) and nonadiabatically via intersystem crossing on the singlet PES, forming intermediates that undergo unimolecular decomposition to a variety of bimolecular product channels. Here, we apply a combined crossed molecular beam (CMB)-theoretical approach to the study of the O(3P) + 1,3-butadiene reaction. Although the kinetics of this reaction have been extensively investigated, little is known about the primary products and their branching fractions (BFs). In the present work, a total of eight product channels were observed and characterized in a CMB experiment at a collision energy of 32.6 kJ mol-1. Synergic ab initio transition-state theory-based master equation simulations coupled with nonadiabatic transition-state theory on coupled triplet/singlet PESs were employed to compute the product BFs and assist the interpretation of the CMB experimental results. The good agreement found between the theoretical predictions and CMB experiments supported the use of the adopted methodology for the prediction of channel-specific rate constants as a function of temperature and pressure suitable to be used for the kinetic modeling of 1,3-butadiene oxidation and of systems where 1,3-butadiene is an important intermediate.

Environmental risk assessment of the anionic surfactant sodium lauryl ether sulphate in site-specific conditions arising from mechanized tunnelling.

Sodium lauryl ether sulphate (SLES) is the anionic surfactant commonly utilized as the main synthetic chemical component in most foaming agents used in mechanized tunnelling. This produces huge amounts of soil debris which can contain residual concentrations of SLES. The absence of environmental quality standards for soil and water and the limited information about SLES persistence in real excavated soils do not facilitate any re-use of soil debris as by-products. The environmental risk assessment (ERA) of foaming agents containing SLES can be a valid tool for this purpose. In this study, an ERA analysis of SLES in 12 commercial formulations (cf) used for tunnelling excavation was performed. Various soils from different tunnel excavation sites were conditioned with the selected foaming agents containing SLES. Predicted or measured environmental concentrations (PECs, MECs) were determined and then compared with the Predicted No Effect Concentrations (PNECs) for both the terrestrial and aquatic compartments. The results indicate a reduction of the potential risk over time for these ecosystems, with differences depending on both the commercial foaming formulation and the spoil material characteristics. However, because potential threats to the natural environment cannot be excluded, some risk management and mitigation actions are discussed.

Dissipation of the antibiotic sulfamethoxazole in a soil amended with anaerobically digested cattle manure.

The application of anaerobically digested cattle manure on agricultural land for both improving its quality and recycling a farm waste is an increasingly frequent practice in line with the circular economy. However, knowledge on the potential risk of spreading antibiotic resistance through this specific practice is quite scarce. The antibiotic sulfamethoxazole (SMX) is one of the most heavily prescribed in veterinary medicine. In this study, SMX dissipation and the possible effects on natural microorganisms were investigated in a soil amended with an anaerobically digested cattle manure produced from a biogas plant inside a livestock farm. Microcosm experiments were performed using amended soil treated with SMX (20 mg/kg soil). During the experimental time (61 days), soil samples were analysed for SMX and N4-acetylsulfamethoxazole, microbial abundance, activity and structure. Furthermore, the prevalence of the intI1 gene was also determined. The overall results showed that, although there was an initial negative effect on microbial abundance, SMX halved in about 7 days in the digestate-amended soil. The intI1 gene found in both the digestate and amended soil suggested that the use of anaerobically digested cattle manure as fertilizer can be a source of antibiotic resistant bacteria (ARBs) and genes (ARGs) in agroecosystems.

Assessment of biodegradation of the anionic surfactant sodium lauryl ether sulphate used in two foaming agents for mechanized tunnelling excavation.

The anionic surfactant sodium lauryl ether sulphate (SLES) is the main component in most foaming agents used for mechanized tunneling excavation. The process produces huge amounts of soil debris that can have a potential impact on ecosystems. The lack of accurate information about SLES persistence in excavated soil has aroused increasing concern about how it is recycled. The objective of this study was to assess SLES biodegradability in two commercial foaming agents (P1 and P2). Microcosm experiments were performed with two different soils collected from a tunnel construction site and conditioned with P1 or P2 (85.0 or 83.0 mg kg -1 of SLES, respectively). At selected times soil samples were collected for assessing the SLES residual concentration using Pressured Liquid Extraction followed by methylene blue active substance analysis (MBAS). Simultaneously, soil microbial abundance (DAPI counts), viability (Live/Dead method), activity (dehydrogenase analysis) and phylogenetic structure (Fluorescent In Situ Hybridization) were evaluated. SLES halved faster in the silty-clay soil (6 d) than in the gravel in a clay-silty-sand matrix (8-9 days). At day 28 it was degraded in both soils. Its biodegradation was ascribed to the significant increase in Gamma-Proteobacteria. At this time, the spoil material can be considered as a by-product.

The impact of anthropogenic pressure on the virological quality of water from the Tiber River, Italy.

The objective of the present study was to assess the occurrence of major waterborne enteric viruses (enterovirus, norovirus, adenovirus, rotavirus, hepatitis A and E virus) along the Tiber River in Italy, in areas affected by different kinds of anthropogenic pressure (agricultural, urban, industrial and pristine). Moreover, in light of the recent abundant detection of human bocavirus in urban wastewater samples in Italy, the occurrence of this virus was also assessed. Virus detection was based on nested PCR followed by sequencing, and on real-time PCR. A correlation with anthropogenic pressure was observed. The urban and industrial areas were the most contaminated (100 and 75% of samples were positive for at least one virus respectively). The agricultural area was less contaminated, with 50% of samples positive. None of the samples collected in a pristine area were positive for viruses. The most frequently detected virus was human bocavirus, identified in 37·5% of samples, followed by norovirus and enterovirus (28% each) and adenovirus (21·6%). Rotavirus, and hepatitis A and E viruses were less common (<9%). Although Human Bocavirus is not considered a waterborne pathogen, the widespread contamination of river waters suggests that virus transmission via the water route should not be neglected. SIGNIFICANCE AND IMPACT OF THE STUDY: To the best of our knowledge, this study constitutes the first attempt to assess the occurrence of enteric viruses in river waters, in areas differentially influenced by anthropogenic pressure. Enteric viruses (enterovirus, norovirus, adenovirus, rotavirus, hepatitis A and E viruses, and bocavirus) were widespread in the industrial and urban areas, and were less frequently detected in the agricultural area. Interestingly, human bocavirus was the most frequently detected virus, outnumbering even adenoviruses, known to be widespread in water environments. The widespread presence of bocavirus in surface waters suggests that a potential role of water in its transmission should not be excluded.

Unravelling the risk factors that underlie laryngeal surgery in elderly.

Older patients are not considered good candidates to undergo more challenging therapeutic treatments, e.g. highly invasive surgery and complex chemotherapy. However, their exclusion from standard therapeutic options is not justifiable. Herein, we reviewed 212 patients aged ≥ 70, affected with laryngeal squamous cell carcinoma, and treated with transoral laser microsurgery or open neck (partial / total) laryngectomy with radical intent. The main aim was to compare patient outcomes to identify predictive factors that can be used by surgeons to choose the most appropriate treatment option. In our cohort, patients affected with more advanced tumour and hence treated by invasive open neck surgeries (above all TL) are more prone to develop complications and undergo fatal outcome than those with early disease treated by laser microsurgery, independently of age at surgery. In conclusion, elderly patients affected by laryngeal cancer can be treated similarly to younger patients, keeping in mind that more invasive surgeries are associated with a higher risk of developing complications. The advantages of mini-invasive surgery make it a possible first choice treatment in very old and frail patients suffering from laryngeal cancer, especially considering the recent success in treatment of some advanced stage tumours. Furthermore, comorbidities, by themselves, should not be used as exclusion criteria for subjecting an elderly patient to a different treatment that is from standard therapy.

Reclassification of the members of the genus Tetrathiobacter Ghosh et al. 2005 to the genus Advenella Coenye et al. 2005.

The taxonomic position of the genera Advenella and Tetrathiobacter was examined. 16S rRNA gene sequence analysis revealed that the two genera are closely related, representing a monophyletic cluster with high sequence similarity (98.1-99.7%) within the family Alcaligenaceae. The phenotypic characteristics of the type strains of Advenella incenata, Tetrathiobacter kashmirensis and Tetrathiobacter mimigardefordensis were re-examined using the API 20NE, API ZYM and API 50CH systems. Phylogenetic data together with similarities in phenotypic characteristics, G+C content and cellular acid composition suggest that they should be classified in the same genus. On the basis of the data presented, the two species of the genus Tetrathiobacter should be transferred to the genus Advenella, since this genus has nomenclatural priority. Therefore, Tetrathiobacter kashmirensis and Tetrathiobacter mimigardefordensis should be transferred to the genus Advenella as Advenella kashmirensis comb. nov. (type strain WT001T=LMG 22695T=MTCC7002T) and Advenella mimigardefordensis comb. nov. (type strain DPN7T=DSM 17166T=LMG 22922T). Emended descriptions of Advenella incenata and the genus Advenella are also presented.

Fate of diuron and linuron in a field lysimeter experiment.

The environmental fate of herbicides can be studied at different levels: in the lab with disturbed or undisturbed soil columns or in the field with suction cup lysimeters or soil enclosure lysimeters. A field lysimeter experiment with 10 soil enclosures was performed to evaluate the mass balance in different environmental compartments of the phenylurea herbicides diuron [3-(3,4-diclorophenyl)-1,1-dimethyl-urea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea]. After application on the agricultural soil, the herbicides were searched for in soil, pore water, and air samples. Soil and water samples were collected at different depths of the soil profile and analyzed to determine residual concentrations of both the parent compounds and of their main transformation products, to verify their persistence and their leaching capacity. Air volatilization was calculated using the theoretical profile shape method. The herbicides were detected only in the surface layer (0-10 cm) of soil. In this layer, diuron was reduced to 50% of its initial concentration at the end of the experiment, while linuron was still 70% present after 245 d. The main metabolites detected were DCPMU [3-(3,4-dichlorophenyl)-1-methylurea] and DCA (3,4-dichloroaniline). In soil pore water, diuron and linuron were detected at depths of 20 and 40 cm, although in very low concentrations. Therefore the leaching of these herbicides was quite low in this experiment. Moreover, volatilization losses were inconsequential. The calculated total mass balance showed a high persistence of linuron and diuron in the soil, a low mobility in soil pore water (less than 0.5% in leachate water), and a negligible volatilization effect. The application of the Pesticide Leaching Model (PELMO) showed similar low mobility of the chemicals in soil and water, but overestimated their volatilization and their degradation to the metabolite DCPMU. In conclusion, the use of soil enclosure lysimeters proved to be a good experimental design for studying mobility and transport processes of herbicides in field conditions.

Degradation and leaching of the herbicides metolachlor and diuron: a case study in an area of Northern Italy.

In this work the degradation of the herbicides metolachlor, diuron, monuron and of the metabolites 2-ethyl-6-methylaniline (EMA), and 3,4-dichloroaniline (DCA) was assessed in laboratory experiments on microbiologically active and sterilized soils. Their leaching potentials were calculated, using Gustafson's equation, by determining their mobility (as Koc) and persistence (expressed as DT50). Lysimeter experiments were also conducted to assess the actual leaching of the studied herbicides in a cereal crop tillage area vulnerable to groundwater contamination. The data obtained from the field were compared to the laboratory results. Moreover, some compounds of particular concern were searched for in the groundwater located near the experimental area in order to evaluate actual contamination and to test the reliability of the leaching potential. The GUS index, computed on data from microbiologically active soil, shows monuron as a leacher compound, EMA and DCA as non-leachers, metolachlor and diuron as transient ones. The presence of metolachlor in the groundwater monitored, even at concentrations up to 0.1 mug/l, confirms the possibility that transient compounds can be leached if microbial activity has not completely occurred in active surface soil.

Assessment of leaching potential of aldicarb and its metabolites using laboratory studies.

The metabolites of pesticides can contaminate groundwater and pose a risk to human health when this water is used for drinking. This paper reports the results of a laboratory study on aldicarb and its main metabolites, aldicarb sulfone and aldicarb sulfoxide. Aldicarb and its metabolites showed Koc values (6-31) which were lower than that of atrazine (55), indicating that they are very mobile in soil. They are less persistent than atrazine (DT50 = 25 days), with DT50 values from less than 1 day and up to 12 days. Aldicarb behaved as a non-leacher, whereas its metabolites clearly showed the characteristics of leachers. Aged residue leaching experiments showed that aldicarb can occur at high concentrations in the leachate, together with its two metabolites. The leachate composition depends on the incubation time of the parent compound. Aldicarb and its metabolites can form various mixtures in groundwater on the basis of the time elapsing between the application of the insecticide and the first significant rainfall. This study confirms the characteristics of contaminants of aldicarb and especially its metabolites, as reported in the literature.

Identification and developmental expression of three Distal-less homeobox containing genes in the ascidian Ciona intestinalis.

Several homeobox-containing genes related to Drosophila Distal-less (Dll) have been isolated from a wide variety of organisms and have been shown to function as developmental regulators. While in Drosophila only one Dll gene has been described so far, in Vertebrates many components of the Dlx multigenic family have been characterized. This suggests that, during the evolution of the Chordate phylum, the Dlx genes arose from an ancestral Dll/Dlx gene via gene duplication. We have previously reported the isolation of two Dll-related homeoboxes from the protochordate Ciona intestinalis, and described their clustered arrangement (Gene 156 (1995) 253). Here we present the detailed genomic organization and spatial-temporal expression of these two genes, Ci-Dll-A and Ci-Dll-B, and describe the isolation and characterization of another member of the ascidian family of Dll-related genes, which we tentatively named Ci-Dll-C.

Role of distinct mitogen-activated protein kinase pathways and cooperation between Ets-2, ATF-2, and Jun family members in human urokinase-type plasminogen activator gene induction by interleukin-1 and tetradecanoyl phorbol acetate.

We have investigated the in vivo and in vitro regulation of the human urokinase-type plasminogen activator (uPA) gene by interleukin-1 (IL-1) and analyzed the transcription factors and signalling pathways involved in the response of the -2.0-kb uPA enhancer to IL-1 induction and to tetradecanoyl phorbol acetate (TPA) induction. Mutational analysis showed the cooperative activity of the Ets-binding site (EBS) and the two AP-1 elements of the enhancer. The results reveal that the EBS is required for the response to both inducers mediated by Ets-2, which is regulated at a level subsequent to DNA binding, by an IL-1- and phorbol ester-inducible transactivation domain. Both the IL-1 and the TPA-mediated induction result in a drastic increase of AP-1 binding to the downstream site of the enhancer (uPA 3' TPA-responsive element), while a mostly qualitative change, resulting from the interplay between ATF-2 homodimers and c-Jun-ATF-2 heterodimers, takes place at the upstream AP-1 element. The analysis of two distinct mitogen-activated protein kinase pathways shows that stress-activated protein kinase-Jun N-terminal kinase activation, resulting in the phosphorylation of ATF-2, c-Jun, and JunD, is required not only for the IL-1- but also for the TPA-dependent induction, while the extracellular signal-related kinase 1 (ERK-1) and ERK-2 activation is involved in the TPA- but not in the IL-1-dependent stimulation of the uPA enhancer.

Specific cellular localization of tyrosinase mRNA during Ciona intestinalis larval development.

A Ciona intestinalis cDNA clone that encodes a protein highly homologous to other tyrosinases was isolated. Northern blot analysis showed that expression of Ciona tyrosinase starts at the early neurula stage and continues throughout the tail-bud and tadpole larval stages. The earliest tyrosinase expression was detected, by in situ hybridization, at the neural plate stage, in pigment precursor cells located along the two neural folds, in the animal region of the embryo. In the course of embryonic development the strong hybridization signal was always localized, within the rostral part of the developing brain, in the pigment precursor cells and was later detected in the otolith and ocellus. These results are discussed in relation to tyrosinase as an early marker of neural induction.

Heterodimerization of c-Jun with ATF-2 and c-Fos is required for positive and negative regulation of the human urokinase enhancer.

Dimerization plays a pivotal role in modulating the activity of the c-Jun proto-oncogene product. Heterodimerization with activating transcription factor-2 (ATF-2) alters the DNA-binding specificity of c-Jun, allowing its targeting to several cAMP responsive element (CRE)-related sequences, which control a subset of AP-1-responsive genes. Here we show that a c-Jun/ATF-2 heterodimer binds to the AP-1 site (uPA 5'-TRE) essential for the activity of the human urokinase enhancer, conferring on this element several distinctive regulatory properties. The c-Jun/ATF-2 heterodimer was identified by binding competition assays, u.v. cross linking, and monospecific antibodies. In vitro binding studies revealed that the uPA 5'-TRE sequence is recognized by the cyclic AMP-unresponsive ATF-2 factor, but not by the cyclic AMP-inducible CREB. In addition, in vivo studies suggest that ATF-2 can mediate, at the same time, the activation of the c-Jun/ATF-2 site and the repression of the canonical collagenase AP-1 site. We report that heterodimerization with c-Fos does not increase the binding of c-Jun to the uPA 5'-TRE, in contrast to the increased binding at a consensus AP-1 site. Our data further suggest that c-Fos can act as a repressor of the c-Jun/ATF-2 binding site, revealing an important functional difference, with respect to canonical AP-1 elements.

Patient-ventilator interaction during synchronized intermittent mandatory ventilation. Effects of flow triggering.

Synchronized intermittent mandatory ventilation (SIMV) intermixes assisted and spontaneous breaths. Its ability as a weaning technique has been questioned on the basis that patients show little adaptation to ventilator assistance. We studied inspiratory effort and patient-ventilator interaction at different levels (SIMV, 100, 50, and 0%) of flow-triggered SIMV versus pressure-triggered SIMV in patients during the weaning period. The two triggering systems were evaluated during constant flow and constant pressure mandatory SIMV breaths. Inspiratory effort was estimated as the esophageal pressure time product (PTP) per breath (PTP/b) and per minute (PTP/min). The PTP/b and PTP/min of both mandatory and spontaneous breaths were significantly lower during flow triggering than during pressure triggering SIMV, irrespective of the ventilatory mode. During pressure-triggered SIMV PTP/b and PTP/min were identical for mandatory and spontaneous breaths, whereas during flow-triggered SIMV PTP/b and PTP/min were significantly lower for mandatory than for spontaneous breaths. This difference was greatest when flow triggering and constant pressure ventilation were associated. These data show that flow triggering reduces inspiratory effort during both mandatory and spontaneous SIMV breaths and obtains a better patient-ventilator interaction.

A regulatory element that mediates co-operation between a PEA3-AP-1 element and an AP-1 site is required for phorbol ester induction of urokinase enhancer activity in HepG2 hepatoma cells.

We have characterized a transcriptional enhancer of the human urokinase-type plasminogen activator (uPA) gene and found a regulatory element required for co-operation between a PEA3--AP-1 element and an AP-1 site in the enhancer. We designated this regulatory element co-operation mediator (COM). Both the PEA3--AP-1 element, the AP-1 site and the COM are required for efficient phorbol ester induction of transcription from the uPA promoter in the HepG2 hepatoma cell line. We show that the COM is also required for co-operation between the PEA3--AP-1 element and a glucocorticoid response element, both in the presence or absence of TPA, indicating that the COM is generally capable of mediating synergism between inducible enhancer elements. The COM contains multiple overlapping binding sites for nuclear proteins, designated uPA enhancer factors 1-4 (UEF-1-4). We have identified putative binding sites for UEF-1, -2 and -3. The UEF-1 and -3 sites in the uPA enhancer are highly conserved between species. We demonstrate the binding of UEF-3 to the NIP element, a previously characterized regulatory element in the human interleukin-3 and stromelysin promoters, suggesting that this factor plays a role in regulation of a variety of genes.

Changes in plasma concentrations of atrial natriuretic peptide during the first ten days and the second month of life.

Atrial natriuretic peptide (ANP) was assayed on the 1st, 3rd, 7th and 10th day of extrauterine life and the levels of the hormone were checked after the 2nd month in 12 infants. After an initially rapid increase, with a peak of the 3rd day (45.7 +/- 7 pg/ml the 1st day of extrauterine life and 175 +/- 5 pg/ml on the 3rd day), we can recognise a progressive decrease until the measurement made at 2 months (61.5 +/- 5 pg/ml). The reported data show the important role of ANP in adaption of life after birth. This can be considered as a compensatory response because it represents an attempt to maintain the balance of positive sodium which is essential for the growth of the newborn.