Evaluation of the pathways of tropospheric nitrophenol formation using a multiphase model

International audiencePhenols are a major class of volatile organic compounds (VOC) whose reaction within, and partitioning between, the gas and liquid phases affects their lifetime within the atmosphere, the local oxidising capacity, and the extent of production of nitrophenols, which are toxic chemicals. In this work, a zero-dimension box model was constructed to quantify the relative nitration pathways, and partitioning into the liquid phase, of mono-aromatic compounds in order to help elucidate the formation pathways of 2- and 4-nitrophenol in the troposphere. The liquid phase contributed significantly to the production of nitrophenols for liquid water content (Lc) values exceeding 3×10-9, and for a range of assumed liquid droplet diameter, even though the resultant equilibrium partitioning to the liquid phase was much lower. For example, in a ''typical'' model scenario, with Lc=3×10-7, 58% of nitrophenol production occurred in the liquid phase but only 2% of nitrophenol remained there, i.e. a significant proportion of nitrophenol observed in the gas phase may actually be produced via the liquid phase. The importance of the liquid phase was enhanced at lower temperatures, by a factor ~1.5?2 at 278 K cf. 298 K. The model showed that nitrophenol production was particularly sensitive to the values of the rate coefficients for the liquid phase reactions between phenol and OH or NO3 reactions, but insensitive to the rate coefficient for the reaction between benzene and OH, thus identifying where further experimental data are required

Operation of EMEP ‘supersites’ in the United Kingdom. Annual report for 2008.

As part of its commitment to the UN-ECE Convention on Long-range Transboundary Air Pollution the United Kingdom operates two ‘supersites’ reporting data to the Co-operative Programme for Monitoring and Evaluation of the Long-range Transmission of Air Pollutants in Europe (EMEP). This report provides the annual summary for 2008, the second full calendar year of operation of the first EMEP ‘supersite’ to be established in the United Kingdom. Detailed operational reports have been submitted to Defra every 3 months, with unratified data. This annual report contains a summary of the ratified data for 2008. The EMEP ‘supersite’ is located in central southern Scotland at Auchencorth (3.2oW, 55.8oN), a remote rural moorland site ~20 km south-west of Edinburgh. Monitoring operations started formally on 1 June 2006. In addition to measurements made specifically under this contract, the Centre for Ecology & Hydrology also acts as local site operator for measurements made under other UK monitoring networks: the Automated Urban and Rural Network (AURN), the UK Eutrophication and Acidification Network (UKEAP), the UK Hydrocarbons Network, and the UK Heavy Metals Rural Network. Some measurements were also made under the auspices of the ‘Air Pollution Deposition Processes’ contract. All these associated networks are funded by Defra. This report summarises the measurements made between January and December 2008, and presents summary statistics on average concentrations. The site is dominated by winds from the south-west, but wind direction data highlight potential sources of airborne pollutants (power stations, conurbations). The average diurnal patterns of gases and particles are consistent with those expected for a remote rural site. The frequency distributions are presented for data where there was good data capture throughout the whole period. Some components (e.g. black carbon) show log-normal frequency distributions, while other components (e.g. ozone) have more nearly normal frequency distributions. A case study is presented for a period in June 2008, showing the influence of regional air pollutants at this remote rural site. All the data reported under the contract are shown graphically in the Appendix

Evaluation of the pathways of tropospheric nitrophenol formation from benzene and phenol using a multiphase model

International audiencePhenols are a major class of volatile organic compounds (VOC) whose reaction within, and partitioning between, the gas and liquid phases affects their lifetime within the atmosphere, the local oxidising capacity, and the extent of production of nitrophenols, which are toxic chemicals. In this work, a zero-dimension box model was constructed to quantify the relative importance of different nitration pathways, and partitioning into the liquid phase, of mono-aromatic compounds in order to help elucidate the formation pathways of 2- and 4-nitrophenol in the troposphere. The liquid phase contributed significantly to the production of nitrophenols for liquid water content (Lc) values exceeding 3x10-9, and for a range of assumed liquid droplet diameter, even though the resultant equilibrium partitioning to the liquid phase was much lower. For example, in a "typical" model scenario, with Lc=3x10-7, 58% of nitrophenol production occurred in the liquid phase but only 2% of nitrophenol remained there, i.e. a significant proportion of nitrophenol observed in the gas phase may actually be produced via the liquid phase. The importance of the liquid phase was enhanced at lower temperatures, by a factor ~1.5-2 at 278K c.f. 298K. The model showed that nitrophenol production was particularly sensitive to the values of the rate coefficients for the liquid phase reactions between phenol and OH or NO3 reactions, but insensitive to the rate coefficient for the reaction between benzene and OH, thus identifying where further experimental data are required

Improvement in IAPT outcomes over time: are they driven by changes in clinical practice?

Treatment outcomes across Improving Access to Psychological Therapies (IAPT) services in England have improved year-on-year, with the national average proportion of patients in recovery at the end of treatment now exceeding the 50% target. This is despite the number of referrals and numbers of treated patients also increasing year-on-year, suggesting that services have evolved local practices and treatment delivery to meet needs whilst improving performance. This study explores whether there have been changes in clinical practice with regard to: (1) the number of sessions and length of treatments; (2) the number of cancellations and non-attendance; and (3) the recording of problem descriptor information, and the association with treatment outcomes in IAPT. Routinely collected data from seven IAPT services involved in the North and Central East London (NCEL) IAPT Service Improvement and Research Network (SIRN) were brought together to form a dataset of nearly 88,000 patients who completed a course of IAPT treatment. Results showed that there was a slight increase in the average number of sessions, and decreases in the length of time in treatment, as well as decreases in both the number of non-attended appointments and the use of inappropriate problem descriptors. These findings highlight a number of areas where potentially small changes to clinical practice may have had positive effects on patient outcomes. The value of using IAPT data to inform service improvement evaluations is discussed

Understanding the psychological therapy treatment outcomes for young adults who are not in education, employment, or training (NEET), moderators of outcomes, and what might be done to improve them

Background: To determine: whether young adults (aged 18–24) not in education, employment or training (NEET) have different psychological treatment outcomes to other young adults; any socio-demographic or treatment-related moderators of differential outcomes; and whether service-level changes are associated with better outcomes for those who are NEET. Methods: A cohort was formed of 20 293 young adults treated with psychological therapies in eight Improving Access to Psychological Therapies services. Pre-treatment characteristics, outcomes, and moderators of differential outcomes were compared for those who were and were not NEET. Associations between outcomes and the following were assessed for those that were NEET: missing fewer sessions, attending more sessions, having a recorded diagnosis, and waiting fewer days between referral and starting treatment. Results: Those who were NEET had worse outcomes: odds ratio (OR) [95% confidence interval (CI)] for reliable recovery = 0.68 (0.63–0.74), for deterioration = 1.41 (1.25–1.60), and for attrition = 1.31 (1.19–1.43). Ethnic minority participants that were NEET had better outcomes than those that were White and NEET. Living in deprived areas was associated with worse outcomes. The intensity of treatment (high or low) did not moderate outcomes, but having more sessions was associated with improved outcomes for those that were NEET: odds (per one-session increase) of reliable recovery = 1.10 (1.08–1.12), deterioration = 0.94 (0.91–0.98), and attrition = 0.68 (0.66–0.71). Conclusions: Earlier treatment, supporting those that are NEET to attend sessions, and in particular, offering them more sessions before ending treatment might be effective in improving clinical outcomes. Additional support when working with White young adults that are NEET and those in more deprived areas may also be important

Computer Simulations of Supercooled Liquids and Glasses

After a brief introduction to the dynamics of supercooled liquids, we discuss some of the advantages and drawbacks of computer simulations of such systems. Subsequently we present the results of computer simulations in which the dynamics of a fragile glass former, a binary Lennard-Jones system, is compared to the one of a strong glass former, SiO_2. This comparison gives evidence that the reason for the different temperature dependence of these two types of glass formers lies in the transport mechanism for the particles in the vicinity of T_c, the critical temperature of mode-coupling theory. Whereas the one of the fragile glass former is described very well by the ideal version of mode-coupling theory, the one for the strong glass former is dominated by activated processes. In the last part of the article we review some simulations of glass formers in which the dynamics below the glass transition temperature was investigated. We show that such simulations might help to establish a connection between systems with self generated disorder (e.g. structural glasses) and quenched disorder (e.g. spin glasses).Comment: 37 pages of Latex, 11 figures, to appear as a Topical Review article in J. Phys.: Condens. Matte

Elemental and Organic Carbon in PM10: a One Year Measurement Campaign within the European Monitoring and Evaluation Programme EMEP

In the present study, ambient aerosol (PM10) concentrations of elemental carbon (EC), organic carbon (OC), and total carbon (TC) are reported for 12 European rural background sites and two urban background sites following a one-year (1 July 2002¿1 July 2003) sampling campaign within the European Monitoring and Evaluation Programme, EMEP (http://www.emep.int/). The purpose of the campaign was to assess the feasibility of performing EC and OC monitoring on a regular basis and to obtain an overview of the spatial and seasonal variability on a regional scale in Europe. Analyses were performed using the thermal-optical transmission (TOT) instrument from Sunset Lab Inc., operating according to a NIOSH derived temperature program. The annual mean mass concentration of EC ranged from 0.17±0.19µgm-3 (mean ± SD) at Birkenes (Norway) to 1.83±1.32µgm-3 at Ispra (Italy). The corresponding range for OC was 1.20±1.29µgm-3 at Mace Head (Ireland) to 7.79±6.80µgm-3 at Ispra. On average, annual concentrations of EC, OC, and TC were three times higher for rural background sites in Central, Eastern and Southern Europe compared to those situated in the Northern andWestern parts of Europe. Wintertime concentrations of EC and OC were higher than those recorded during summer for the majority of the sites. Moderate to high Pearson correlation coefficients (rp) (0.50¿0.94) were observed for EC versus OC for the sites investigated. The lowest correlation coefficients were noted for the three Scandinavian sites: Aspvreten (SE), Birkenes (NO), and Virolahti (FI), and the Slovakian site Stara Lesna, and are suggested to reflect biogenic sources, wild and prescribed fires. This suggestion is supported by the fact that higher concentrations of OC are observed for summer compared to winter for these sites. For the rural background sites, total carbonaceous material accounted for 30±9% of PM10, of which 27±9% could be attributed to organic matter (OM) and 3.4±1.0% to elemental matter (EM). OM was found to be more abundant than SO2- 4 for sites reporting both parametersJRC.H.2-Climate chang

Concentrations and fluxes of biogenic volatile organic compounds above a Mediterranean macchia ecosystem in western Italy

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