Production of HO2 and OH radicals from near-UV irradiated airborne TiO2 nanoparticles.

The production of gas-phase hydroperoxyl radicals, HO2, is observed directly from sub-micron airborne TiO2 nanoparticles irradiated by 300-400 nm radiation. The rate of HO2 production as a function of O2 pressure follows Langmuir isotherm behaviour suggesting O2 is involved in the production of HO2 following its adsorption onto the surface of the TiO2 aerosol. Reduction of adsorbed O2 by photogenerated electrons is likely to be the initial step followed by reaction with a proton produced via oxidation of adsorbed water with a photogenerated hole. The rate of HO2 production decreased significantly over the range of relative humidities between 8.7 and 36.9%, suggesting competitive adsorption of water vapour inhibits HO2 production. From the data, the adsorption equilibrium constants were calculated to be: KO2 = 0.27 ± 0.02 Pa-1 and KH2O = 2.16 ± 0.12 Pa-1 for RH = 8.7%, decreasing to KO2 = 0.18 ± 0.01 Pa-1 and KH2O = 1.33 ± 0.04 Pa-1 at RH = 22.1%. The increased coverage of H2O onto the TiO2 aerosol surface may inhibit HO2 production by decreasing the effective surface area of the TiO2 particle and lowering the binding energy of O2 on the aerosol surface, hence shortening its desorption lifetime. The maximum yield (i.e. when [O2] is projected to atmospherically relevant levels) for production of gas-phase HO2, normalised for surface area and light intensity, was found to be at a RH of 8.7% for the 80% anatase and 20% rutile formulation of TiO2 used here. This yield decreased to as the RH was increased to 22.1%. Using this value, the rate of production of HO2 from TiO2 surfaces under atmospheric conditions was estimated to be in the range 5 × 104-1 × 106 molecule cm-3 s-1 using observed surface areas of mineral dust at Cape Verde, and assuming a TiO2 fraction of 4.5%. For the largest loadings of dust in the troposphere, the rate of this novel heterogeneous production mechanism begins to approach that of HO2 production from the gas-phase reaction of OH with CO in unpolluted regions. The production of gas-phase OH radicals could only be observed conclusively at high aerosol surface areas, and was attributed to the decomposition of H2O2 at the surface by photogenerated electrons.

Significant OH production under surface cleaning and air cleaning conditions: Impact on indoor air quality.

We report measurements of hydroxyl (OH) and hydroperoxy (HO2 ) radicals made by laser-induced fluorescence spectroscopy in a computer classroom (i) in the absence of indoor activities (ii) during desk cleaning with a limonene-containing cleaner (iii) during operation of a commercially available "air cleaning" device. In the unmanipulated environment, the one-minute averaged OH concentration remained close to or below the limit of detection (6.5×105  molecule cm-3 ), whilst that of HO2 was 1.3×107  molecule cm-3 . These concentrations increased to ~4×106 and 4×108  molecule cm-3 , respectively during desk cleaning. During operation of the air cleaning device, OH and HO2 concentrations reached ~2×107 and ~6×108  molecule cm-3 respectively. The potential of these OH concentrations to initiate chemical processing is explored using a detailed chemical model for indoor air (the INDCM). The model can reproduce the measured OH and HO2 concentrations to within 50% and often within a few % and demonstrates that the resulting secondary chemistry varies with the cleaning activity. Whilst terpene reaction products dominate the product composition following surface cleaning, those from aromatics and other VOCs are much more important during the use of the air cleaning device.

Randomized controlled trial of asthma risk with paracetamol use in infancy--a feasibility study.

BACKGROUND: There is non-experimental evidence that paracetamol (acetaminophen) use may increase the risk of developing asthma. However, numerous methodological issues need to be resolved before undertaking a randomized controlled trial to investigate this hypothesis. OBJECTIVE: To establish the feasibility of a randomized controlled trial of liberal paracetamol as usually given by parents/guardians vs. a comparator (restricted paracetamol in accordance with WHO guidelines, ibuprofen or placebo), and childhood asthma risk. METHODS: Questionnaires were completed by parents/guardians of infants admitted to Wellington Hospital with bronchiolitis to assess views about comparator treatments. Subsequently, infants of parents/guardians who provided informed consent were randomized to restricted or liberal paracetamol use for 3 months with paracetamol use recorded. RESULTS: Of 120 eligible participants, 72 (60%) parents/guardians completed the questionnaire. Ibuprofen, restricted paracetamol and placebo were acceptable to 42 (58%), 29 (40%) and 9 (12%) parents/guardians, respectively. 36 (30%) infants were randomized to restricted or liberal paracetamol. Paracetamol use was greater for the liberal vs. restricted group for reported [Hodges-Lehmann estimator of difference 0.94 mg/kg/day (95% CI 0.2-3.52), P = 0.02] and measured use [Hodges-Lehmann estimator of difference 2.11 mg/kg/day (95% CI 0.9-4.18), P = 0.004]. The median reported and measured use of paracetamol was 2.0-fold and 3.5-fold greater in the liberal vs. restricted group. CONCLUSIONS AND CLINICAL RELEVANCE: Although separation in paracetamol dosing is likely to be achieved with a liberal vs. restricted paracetamol regime, ibuprofen is the preferred comparator treatment in the proposed RCT of paracetamol use and risk of asthma in childhood.

On the mechanism of iodine oxide particle formation.

The formation of atmospherically relevant iodine oxides IxOy (x = 1,…,3, y = 1,…,7) has been studied experimentally using time-of-flight mass spectrometry combined with a soft ionisation source, complemented with ab initio electronic structure calculations of ionisation potentials and bond energies at a high level of theory presented in detail in the accompanying paper (Galvez et al., 2013). For the first time, direct experimental evidence of the I2Oy (y = 1,…,5) molecules in the gas phase has been obtained. These chemical species are observed alongside their precursors (IO and OIO) in experiments where large amounts of aerosol are also generated. The measured relative concentrations of the IxOy molecules and their dependence on ozone concentration have been investigated by using chemical modelling and rate theory calculations. It is concluded that I2O4 is the most plausible candidate to initiate nucleation, while the contribution of I2O5 in the initial steps is likely to be marginal. The absence of large I3Oy (y = 3,…,6) peaks in the mass spectra and the high stability of the I2O4-I2O4 dimer indicate that dimerisation of I2O4 is the key step in iodine oxide particle nucleation.

Selenium status and allergic disease in a cohort of New Zealand children.

BACKGROUND: New Zealand has one of the highest rates of asthma and atopy. Selenium has been implicated in the aetiology of asthma, and associations between low selenium status and asthma in New Zealand children have been reported. OBJECTIVE: The aim was to investigate the association between selenium status and allergic disease in a birth cohort of New Zealand children. METHODS: The New Zealand Asthma and Allergy Cohort Study is a prospective birth cohort in Wellington and Christchurch, involving 1105 infants born 1997-2001. During the 6-year assessment (n = 635), associations were investigated between plasma selenium (PlSe) and whole blood glutathione peroxidase activity (WBGPx) and allergy-related health outcomes including asthma, wheeze, hayfever, rhinitis, eczema and rash. RESULTS: Wellington children had greater PlSe and WBGPx than Christchurch children (P < 0.001 for both). PlSe (P = 0.004) and WBGPx (P = 0.03) were lower in children exposed to environmental smoke, but differences were no longer significant after adjustment for study location, current household smoking (5-6 years), maternal smoking during pregnancy, family history (either parent with asthma, eczema or hayfever), prioritized ethnicity (Maori, Pacific peoples, Other, European), gender, season born, number of siblings, New Zealand Deprivation Index and body mass index at 6 years. Analysis of PlSe or WBGPx as continuous variables or of quartiles of PlSe with health outcomes showed no significant associations after adjustment. Univariate analysis of quartiles of PlSe and WBGPx with persistent wheeze showed significant inverse trends (P = 0.005 for both), but these reduced after adjustment. CONCLUSIONS AND CLINICAL RELEVANCE: Our results do not support a strong association between selenium status and the high incidence of asthma in New Zealand. However, there was a modest association between lower PlSe and WBGPx activity and higher incidence of persistent wheeze.

The effects of early and late paracetamol exposure on asthma and atopy: a birth cohort.

BACKGROUND: Despite reports of positive associations between paracetamol and asthma, the nature of these associations is unclear. OBJECTIVE: We aimed to investigate the associations between infant and childhood paracetamol use and atopy and allergic disease at 5-6 years. METHODS: In a birth cohort study, we collected reported paracetamol exposure between birth and 15 months in Christchurch (n=505) and between 5 and 6 years for all participants (Christchurch and Wellington) (n=914). Outcome data for reported current asthma, reported wheeze and atopy (measured using skin prick tests) were collected at 6 years for all participants. Logistic regression models were adjusted for potential confounders, including the number of chest infections and antibiotic use. RESULTS: Paracetamol exposure before the age of 15 months was associated with atopy at 6 years [adjusted odds ratio (OR)=3.61, 95% confidence interval (CI) 1.33-9.77]. Paracetamol exposure between 5 and 6 years showed dose-dependent associations with reported wheeze and current asthma but there was no association with atopy. Compared with use 0-2 times, the adjusted OR (95% CI) were wheeze 1.83 (1.04-3.23) for use 3-10 times, and 2.30 (1.28-4.16) for use >10 times: current asthma 1.63 (0.92-2.89) for use 3-10 times and 2.16 (1.19-3.92) for use >10 times: atopy 0.96 (0.59-1.56) for use 3-10 times, and 1.05 (0.62-1.77) for use >10 times. CONCLUSION AND CLINICAL RELEVANCE: Our findings suggest that paracetamol has a role in the development of atopy, and the maintenance of asthma symptoms. Before recommendations for clinical practice can be made, randomized-controlled trials are needed to determine whether these associations are causal.

The association of early life exposure to antibiotics and the development of asthma, eczema and atopy in a birth cohort: confounding or causality?

BACKGROUND: In general, studies reporting positive associations between antibiotic exposure and respiratory and allergic disease have been unable to determine the nature of this association. OBJECTIVE: To examine the association between antibiotic exposure in infancy and the development of asthma, eczema and atopy in early childhood. METHODS: In a birth cohort study, we collected reported antibiotic exposure before 3 months and before 15 months along with outcomes (wheeze, asthma, eczema, rash, inhaler use) at 15 months (n=1011) and 4 years (n=986). Atopy was measured using skin prick tests at 15 months. RESULTS: We found significant univariate associations of antibiotic exposure before 3 months with asthma developing between birth and 15 months [OR 2.32 (95% CI 1.45-3.69)]. After adjustment for chest infections, this association reduced (OR=1.58, 95% CI 0.96-2.60) becoming marginally significant (P=0.07). A marginally significant association of antibiotics with atopy (OR=1.44, 95% CI 0.96-2.14) in the univariate analysis also reduced after adjustment for chest infections (OR=1.36, 95% CI 0.91-2.05). There was no effect of antibiotic exposure before 15 months on asthma developing after 15 months and present between 3 and 4 years (OR=1.35 95% CI 0.85-2.14). Antibiotic exposure before 3 months was not associated with eczema and rash developing between birth and 15 months but exposure before 15 months was related to eczema [OR 1.83 (95% CI 1.10-3.05)] and rash [OR 1.61 (95% CI 1.02-2.53)] developing after 15 months and remaining present at 4 years. These effects reduced in the multivariate analysis. CONCLUSIONS: Our findings suggest that the effect of antibiotics on respiratory disease may be due to confounding by chest infections at an early age when asthma may be indistinguishable from infection.

Monitoring the use of amiodarone: compliance with guidelines.

AIM: Careful monitoring of amiodarone is recommended because it produces a range of potentially severe adverse effects. The aim of this study was to compare existing practice at our hospitals with the current international guidelines for the use of this drug. METHODS: A retrospective audit was carried out on all patients aged 15 years or older, with a primary discharge diagnosis of tachyarrhythmia and who were commenced and discharged alive on amiodarone between 1 January 2000 and 30 June 2002 from Wellington and Kenepuru Hospitals, Capital and Coast District Health Board, Wellington, New Zealand. The medical records were examined for baseline measurements of renal, liver, thyroid and pulmonary function, the electrocardiogram and chest X-ray. Follow-up arrangements were sought postdischarge. A questionnaire was sent to the general practitioner requesting information on follow-up testing. RESULTS: During the trial period, 743 patients were admitted with a primary diagnosis of tachyarrhythmia. Eighty-six patients satisfied the entry criteria, and of these 58 were followed for at least 1 year postdischarge. Baseline testing of the electrocardiogram, full blood count and renal function testing was excellent (95-100%). Chest X-rays were carried out in 80% of patients. Baseline testing of thyroid (61%) and liver (44%) function was suboptimal. Two percent of patients had pulmonary function testing and no patient had a formal eye examination. At 6 months, only 32% had thyroid function tests and 41% had liver function tests. At 1 year, of those still on treatment, 35% had both liver and thyroid function tests. CONCLUSION: Monitoring of thyroid, liver and pulmonary function tests in patients on amiodarone is less than ideal. This is probably because of lack of awareness of current guidelines.

The atmospheric chemistry of trace gases and particulate matter emitted by different land uses in Borneo.

We report measurements of atmospheric composition over a tropical rainforest and over a nearby oil palm plantation in Sabah, Borneo. The primary vegetation in each of the two landscapes emits very different amounts and kinds of volatile organic compounds (VOCs), resulting in distinctive VOC fingerprints in the atmospheric boundary layer for both landscapes. VOCs over the Borneo rainforest are dominated by isoprene and its oxidation products, with a significant additional contribution from monoterpenes. Rather than consuming the main atmospheric oxidant, OH, these high concentrations of VOCs appear to maintain OH, as has been observed previously over Amazonia. The boundary-layer characteristics and mixing ratios of VOCs observed over the Borneo rainforest are different to those measured previously over Amazonia. Compared with the Bornean rainforest, air over the oil palm plantation contains much more isoprene, monoterpenes are relatively less important, and the flower scent, estragole, is prominent. Concentrations of nitrogen oxides are greater above the agro-industrial oil palm landscape than over the rainforest, and this leads to changes in some secondary pollutant mixing ratios (but not, currently, differences in ozone). Secondary organic aerosol over both landscapes shows a significant contribution from isoprene. Primary biological aerosol dominates the super-micrometre aerosol over the rainforest and is likely to be sensitive to land-use change, since the fungal source of the bioaerosol is closely linked to above-ground biodiversity.

Comparison of two dust collection methods for reservoir indoor allergens and endotoxin on carpets and mattresses.

Variable methods of dust collection may lead to uncertainty in the measurement of biomarkers. The purpose of this study was to examine the effect of two different dust collection devices on dust weight, Der p 1, Fel d 1, and endotoxin levels. We compared: (1) a nylon mesh sock inserted between the furniture attachment and the vacuum hose (the reference method) and (2) the ALK device. Duplicate dust samples were collected for 2 min from 2 m(2) of 37 living room floors and from each longitudinal half of 37 mattresses. Measurement of Der p 1 and Fel d 1 were by double monoclonal antibody enzyme-linked immunosorbent assay (ELISA) and endotoxin by a Limulus Amobocyte Lysate assay. Geometric mean ratios (95% confidence intervals) were calculated to show the differences between sampling devices for each measurement. Compared with the ALK device, the reference method collected significantly more dust from floors (sevenfold) and mattresses (threefold) and more total Der p 1, Fel d 1, and endotoxin in both sites. Floor, but not mattress, Der p 1 concentrations were also significantly higher (threefold) using our reference method. We recommend that, in order to minimize sampling device bias, allergen and endotoxin are expressed as a concentration, and that the bed is considered the major source of allergen exposure. Practical Implications Dust sampling equipment can influence the dust yield. In order to have confidence in comparisons of allergen and endotoxin reservoir levels between centers, standardization in the use of sampling equipment is important.

A comparison of the ProSeal and classic laryngeal mask airways for airway management by inexperienced personnel after manikin-only training.

We compared the ProSeal (PLMA) and Classic (LMA) laryngeal mask airway for airway management by inexperienced personnel. Nine nurses from the post-anaesthesia care unit, with no prior experience of LMA or PLMA insertion, were observed inserting the LMA and PLMA in 60 ASA 1 to 2 anaesthetized, paralyzed adults following manikin-only training. The time to achieve an effective airway (2 consecutive expired tidal volumes (6 ml/kg; maximum 2 minutes allowed), the number of insertion attempts and the reasons for failure (inability to insert into pharynx or inadequate ventilation) were determined by analysis of digital video recordings. The first attempt success rate (LMA, 85%; PLMA, 83%), overall success rate (LMA, 88%; PLMA, 90%) and effective airway time (LMA, 39 +/- 13 s; PLMA, 43 +/- 19 s) were similar. Failure was from an inability to insert into the pharynx in five with the LMA and three with the PLMA, and inadequate ventilation with two from the LMA and three from the PLMA. Effective airway time and the number of failures were similar for the first and second device. Failure of both devices occurred in four patients. We conclude that airway management in anaesthetized, paralyzed adults is equally successful for the LMA and PLMA by inexperienced personnel following manikin-only training. The PLMA is worthy of consideration as a tool for emergency airway management by inexperienced personnel.