A study of the reactions of Ni+ and NiO+ ions relevant to planetary upper atmospheres.

The reactions between Ni+(2D) and O3, O2, N2, CO2 and H2O were studied at 294 K using the pulsed laser ablation at 532 nm of a nickel metal target in a fast flow tube, with mass spectrometric detection of Ni+ and NiO+. The rate coefficient for the reaction of Ni+ with O3 is k(294 K) = (9.7 ± 2.1) × 10-10 cm3 molecule-1 s-1; the reaction proceeds at the ion-permanent dipole enhanced Langevin capture rate with a predicted T-0.16 dependence. Electronic structure theory calculations were combined with Rice-Ramsperger-Kassel-Markus theory to extrapolate the measured recombination rate coefficients to the temperature and pressure conditions of planetary upper atmospheres. The following low-pressure limiting rate coefficients were obtained for T = 120-400 K and He bath gas (in cm6 molecule-2 s-1, uncertainty ±σ at 180 K): log10(k, Ni+ + N2) = -27.5009 + 1.0667log10(T) - 0.74741(log10(T))2, σ = 29%; log10(k, Ni+ + O2) = -27.8098 + 1.3065log10(T) - 0.81136(log10(T))2, σ = 32%; log10(k, Ni+ + CO2) = -29.805 + 4.2282log10(T) - 1.4303(log10(T))2, σ = 28%; log10(k, Ni+ + H2O) = -24.318 + 0.20448log10(T) - 0.66676(log10(T))2, σ = 28%). Other rate coefficients measured (at 294 K, in cm3 molecule-1 s-1) were: k(NiO+ + O) = (1.7 ± 1.2) × 10-10; k(NiO+ + CO) = (7.4 ± 1.3) × 10-11; k(NiO+ + O3) = (2.7 ± 1.0) × 10-10 with (29 ± 21)% forming Ni+ as opposed to NiO2+; k(NiO2+ + O3) = (2.9 ± 1.4) × 10-10, with (16 ± 9)% forming NiO+ as opposed to ONiO2+; and k(Ni+·N2 + O) = (7 ± 4) × 10-12. The chemistry of Ni+ and NiO+ in the upper atmospheres of Earth and Mars is then discussed.

A study of the reactions of Al+ ions with O3, N2, O2, CO2 and H2O: influence on Al+ chemistry in planetary ionospheres.

The reactions between Al+(31S) and O3, O2, N2, CO2 and H2O were studied using the pulsed laser ablation at 532 nm of an aluminium metal target in a fast flow tube, with mass spectrometric detection of Al+ and AlO+. The rate coefficient for the reaction of Al+ with O3 is k(293 K) = (1.4 ± 0.1) × 10-9 cm3 molecule-1 s-1; the reaction proceeds at the ion-dipole enhanced Langevin capture frequency with a predicted T-0.16 dependence. For the recombination reactions, electronic structure theory calculations were combined with Rice-Ramsperger-Kassel-Markus theory to extrapolate the measured rate coefficients to the temperature and pressure conditions of planetary ionospheres. The following low-pressure limiting rate coefficients were obtained for T = 120-400 K and He bath gas (in cm6 molecule-2 s-1, uncertainty ±σ at 180 K): log10(k, Al+ + N2) = -27.9739 + 0.05036 log10(T) - 0.60987(log10(T))2, σ = 12%; log10(k, Al+ + CO2) = -33.6387 + 7.0522 log10(T) - 2.1467(log10(T))2, σ =13%; log10(k, Al+ + H2O) = -24.7835 + 0.018833 log10(T) - 0.6436(log10(T))2, σ = 27%. The Al+ + O2 reaction was not observed, consistent with a D°(Al+-O2) bond strength of only 12 kJ mol-1. Two reactions of AlO+ were also studied: k(AlO+ + O3, 293 K) = (1.3 ± 0.6) × 10-9 cm3 molecule-1 s-1, with (63 ± 9)% forming Al+ as opposed to OAlO+; and k(AlO+ + H2O, 293 K) = (9 ± 4) × 10-10 cm3 molecule-1 s-1. The chemistry of Al+ in the ionospheres of Earth and Mars is then discussed.

Kinetic Study of Ni and NiO Reactions Pertinent to the Earth's Upper Atmosphere.

Nickel atoms are injected into the Earth's mesosphere by meteoric ablation, producing a Ni layer between 70 and 105 km in altitude. The subsequent reactions of Ni and NiO with atmospherically relevant species were studied using the time-resolved pulsed laser photolysis-laser-induced fluorescence technique, combined with electronic structure calculations and RRKM theory where appropriate. Results for bimolecular reactions (in cm3 molecule-1 s-1): k(Ni + O3, 293 K) = (6.5 ± 0.7) × 10-10; k(NiO + O3 → Ni + 2O2, 293 K) = (1.4 ± 0.5) × 10-10; k(NiO + O3 → NiO2 + O2, 293 K) = (2.5 ± 0.7) × 10-10; k(NiO + CO, 190-377 K) = (3.2 ± 0.6) × 10-11 ( T/200)-0.19±0.05. For termolecular reactions (in cm6 molecule-2 s-1, uncertainty ± σ over the stated temperature range): log10( krec,0(Ni + O2 + N2, 190-455 K)) = -37.592 + 7.168log10( T) - 1.5650(log10( T))2, σ = 11%; log10( krec,0(NiO + O2 + N2, 293-380 K)) = -41.0913 + 10.1064log10( T) - 2.2610(log10( T))2, σ = 22%; and log10( krec,0(NiO + CO2 + N2, 191-375 K)) = -41.4265 + 10.9640log10( T) - 2.5287(log10( T))2, σ = 15%. The faster recombination reaction NiO + H2O + N2, which is clearly in the falloff region over the experimental pressure range (3-10 Torr), is best described by log10( krec,0/cm6 molecule-2 s-1) = -29.7651 + 5.2064log10( T) - 1.7118(log10( T))2, krec,∞ = 6.0 × 10-10 exp(-171/ T) cm3 molecule-1 s-1, broadening factor Fc = 0.84, σ = 16%. The implications of these results in the atmosphere are then discussed.

On-line monitoring of airborne bioaerosols released from a composting/green waste site.

This study is the first to employ the on-line WIBS-4 (Wideband Integrated Bioaerosol Sensor) technique for the monitoring of bioaerosol emissions and non-fluorescing "dust" released from a composting/green waste site. The purpose of the research was to provide a "proof of principle" for using WIBS to monitor such a location continually over days and nights in order to construct comparative "bioaerosol site profiles". The real-time data obtained was then used to assess variations of the bioaerosol counts as a function of size, "shape", site location, working activity levels, time of day, relative humidity, wind speeds and wind directions. Three short campaigns were undertaken, one classified as a "light" workload period, another as a "heavy" workload period and finally a weekend when the site was closed. One main bioaerosol size regime was found to predominate: 0.5-3µm with morphologies ranging from elongated to ellipsoidal/spherical. The real-time number-concentration data provides a long-term "video" record of the site and were consistent with the Andersen sampling protocol performed that provides only a single "snapshot" for bioaerosol release. The number-concentration of fluorescent particles as a proportion of total particle counts amounted, on average, to ∼1% for the "light" workday period, ∼7% for the "heavy" workday period and ∼18% for the weekend. The bioaerosol release profiles at the weekend were considerably different from those monitored during the working weekdays.