Greenhouse gas and air pollutant emissions from power barges (powerships)

Power barges or powerships that operate on natural gas (NG) are an increasingly appealing easy-to-use solution to electricity deficits in Africa, Asia, the Middle East, and the Caribbean. Global generating capacity has increased from 0.1 to 2.6 GW, and 4.4 GW is under construction. South Africa has licensed three powerships to provide 1.2 GW generating capacity with foreign liquefied NG (LNG) over 20 years. To understand the importance of this source, we estimate lifecycle emissions of GHGs and air pollutants for South Africa and extend this to the global fleet. Annual lifecycle GHG emissions for 1.2 GW generating capacity total 2.6–3.8 Tg carbon dioxide equivalents (CO2e) using 100 year global warming potentials (GWPs). This increases to 4.0–7.1 Tg CO_{2} e using 20 year GWPs, due to the potency of fugitive methane (CH4). Adoption of air pollutant emission control technology will need to be enforced to achieve compliance with national standards for fine particles (PM) and nitrogen oxides (NO_{x}). A global fleet of 7.0 GW generating capacity reliant on domestic NG could emit 12 Tg CO_{2}, 2.2–8.6 Tg CH_{4}, 4.3 Gg NO_{x}, and 2.6 Gg PM. Additional NOx and SO2 emissions would result from imported LNG, as LNG tankers burn dirty fuel oil, though SO_{2} emissions may be curtailed with recent stricter limits on the fuel sulfur content. These powerships could have important regional impacts, but emission estimates are uncertain. Characteristic emission factors, detailed operating conditions, and NG composition data are urgently needed to address uncertainties in emissions for air quality and climate modelling of this emergent source

Removal and photocatalysis of 4-Nitrophenol using metallophthalocyanines

Photodegradation of 4-nitrophenol (4-Np) in the presence of water-soluble zinc phthalocyanines and water-insoluble metallophthalocyanines is reported. The water-soluble phthalocyanines employed include zinc tetrasulphophthalocyanine (ZnPcS[subscript 4]), zinc octacarboxyphthalocyanine (ZnPc(COOH)[subscript 8]) and a sulphonated ZnPc containing a mixture of differently sulphonated derivatives (ZnPcS[subscript mix]), while the water-insoluble phthalocyanines used include unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring-substituted zinc tetranitro (ZnPc(NO[subscript 2])[subscript 4]), zinc tetraamino (ZnPc(NH[subscript 2])[subscript 4]), zinc hexadecafluoro (ZnPcF[subscript 16]) and zinc hexadecachloro (ZnPcCl[subscript 16]) phthalocyanines. The most effective water-soluble photocatalyst is ZnPcS[subscript mix] in terms of the high quantum yield obtained for 4-Np degradation (Φ[subscript 4-Np]) as well as its photostability. While ZnPc(COOH)[subscript 8] has the highest Φ[subscript 4-Np] value relative to the other water-soluble complexes, it degrades readily during photocatalysis. The Φ[subscript 4-Np] values were closely related to the singlet oxygen quantum yields Φ[subscript Δ] and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPcS[subscript mix] and 7.7 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPc(COOH)[subscript 8]. ClAlPc is the most effective photocatalyst relative to the other heterogeneous photocatalysts for the phototransformation of 4-Np, with 89 ± 8.4 % degradation of 4-Np achieved after 100 min. The least effective catalysts were ZnPcCl[subscript 16] and MgPc. The final products of the photocatalysis of 4-Np in the presence of the homogeneous photocatalysts include 4-nitrocatechol and hydroquinone, while degradation of 4-Np in the presence of the heterogeneous photocatalysts resulted in fumaric acid and 4-nitrocatechol. ClAlPc was employed for the heterogeneous photocatalysis of the non-systemic insecticide, methyl paraoxon. Complete degradation of the pesticide was confirmed by the disappearance of the HPLC trace for methyl paraoxon after 100 min of irradiation with visible light. The removal of 4-Np from an aqueous medium using commercially available Amberlite[superscript ®] IRA-900 modified with metal phthalocyanines was also investigated. The metallophthalocyanines immobilised onto the surface of Amberlite[superscript ®] IRA-900 include Fe (FePcS[subscript 4]), Co (CoPcS[subscript 4]) and Ni (NiPcS[subscript 4]) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcS[subscript mix]), Co (CoPcS[subscript mix]) and Ni (NiPcS[subscript mix]). Adsorption rates were fastest for the modified adsorbents at pH 9. Using the Langmuir-Hinshelwood kinetic model, the complexes showed the following order of 4-Np adsorption: CoPcS[subscript mix] > NiPcS[subscript 4] > NiPcS[subscript mix] > FePcS[subscript 4] > FePcS[subscript mix] > CoPcS[subscript 4]. The adsorbents were regenerated using dilute HNO[subscript 3], with 76 % (7.6 x 10[superscript -5] mol) of 4-Np recovered within 150 min

Non-methane volatile organic compounds in Africa: a vew from space

Isoprene emissions affect human health, air quality, and the oxidative capacity of the atmosphere. Globally anthropogenic non-methane volatile organic compounds (NMVOC) emissions are lower than that of isoprene, but local hotspots are hazardous to human health and air quality. In Africa the tropics are a large source of isoprene, while Nigeria appears as a large contributor to regional anthropogenic NMVOC emissions. I make extensive use of space-based formaldehyde (HCHO) observations from the Ozone Monitoring Instrument (OMI) and the chemical transport model (CTM) GEOS-Chem to estimate and examine seasonality of isoprene emissions across Africa, and identify sources and air quality consequences of anthropogenic NMVOC emissions in Nigeria.Earth and Planetary Science

Photocatalytic transformation of 4-nitrophenol in aqueous media using suspended, water-insoluble metallophthalocyanine complexes

Unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring substituted zinc tetranitro (ZnPc(NO2)4), zinc tetraamino (ZnPc(NH2)4), zinc hexadecafluoro (ZnPcF16) and zinc hexadecachloro (ZnPcCl16), phthalocyanine complexes are employed as photocatalysts for the heterogeneous transformation of 4-nitrophenol (4-Np) to fumaric acid and 4-nitrocatechol. ClAlPc is the best catalyst, with 89 ± 8% degradation of 4-Np after 100 min. The least effective catalysts were ZnPcCl16 and MgPc

Impact of Legislated and Best Available Emission Control Measures on UK Particulate Matter Pollution, Premature Mortality, and Nitrogen-Sensitive Habitats

Past emission controls in the UK have substantially reduced precursor emissions of health-hazardous fine particles (PM2.5) and nitrogen pollution detrimental to ecosystems. Still, 79% of the UK exceeds the World Health Organization (WHO) guideline for annual mean PM2.5 of 5 μg m-3 and there is no enforcement of controls on agricultural sources of ammonia (NH3). NH3 is a phytotoxin and an increasingly large contributor to PM2.5 and nitrogen deposited to sensitive habitats. Here we use emissions projections, the GEOS-Chem model, high-resolution data sets, and contemporary exposure-risk relationships to assess potential human and ecosystem health co-benefits in 2030 relative to the present day of adopting legislated or best available emission control measures. We estimate that present-day annual adult premature mortality attributable to exposure to PM2.5 is 48,625 (95% confidence interval: 45,188-52,595), that harmful amounts of reactive nitrogen deposit to almost all (95%) sensitive habitat areas, and that 75% of ambient NH3 exceeds levels safe for bryophytes and lichens. Legal measures decrease the extent of the UK above the WHO guideline to 58% and avoid 6,800 premature deaths by 2030. This improves with best available measures to 36% of the UK and 13,300 avoided deaths. Both legal and best available measures are insufficient at reducing the extent of damage of nitrogen pollution to sensitive habitats. Far more ambitious reductions in nitrogen emissions (>80%) than is achievable with best available measures (34%) are required to halve the amount of excess nitrogen deposited to sensitive habitats

Diagnosing domestic and transboundary sources of fine particulate matter (PM2.5) in UK cities using GEOS-Chem

The UK is set to impose a stricter ambient annual mean fine particulate matter (PM2.5) standard than was first adopted fourteen years ago. This necessitates strengthened knowledge of the magnitude and sources that influence urban PM2.5 in UK cities to ensure compliance and improve public health. Here, we use a regional-scale chemical transport model (GEOS-Chem), validated with national ground-based observations, to quantify the influence of specific sources within and transported to the mid-sized UK city Leicester. Of the sources targeted, we find that agricultural emissions of ammonia (NH3) make the largest contribution (3.7 μg m−3 or 38 % of PM2.5) to annual mean PM2.5 in Leicester. Another important contributor is long-range transport of pollution from continental Europe accounting for 1.8 μg m−3 or 19 % of total annual mean PM2.5. City sources are a much smaller portion (0.2 μg m−3; 2 %). We also apply GEOS-Chem to the much larger cities Birmingham and London to find that agricultural emissions of NH3 have a greater influence than city sources for Birmingham (32 % agriculture, 19 % city) and London (25 % agriculture, 13 % city). The portion from continental Europe is 16 % for Birmingham and 28 % for London. Action plans aimed at national agricultural sources of NH3 and strengthened supranational agreements would be most effective at alleviating PM2.5 in most UK cities

Evaluation of the WRF and CHIMERE models for the simulation of PM₂.₅ in large East African urban conurbations

Urban conurbations of East Africa are affected by harmful levels of air pollution. The paucity of local air quality networks and the absence of the capacity to forecast air quality make difficult to quantify the real level of air pollution in this area. The CHIMERE chemistry transport model has been used along with the Weather Research and Forecasting (WRF) meteorological model to run high-spatial-resolution (2 × 2 km) simulations of hourly concentrations of particulate matter with an aerodynamic diameter smaller than 2.5 µm (PM2.5) for three East African urban conurbations: Addis Ababa in Ethiopia, Nairobi in Kenya, and Kampala in Uganda. Two existing emission inventories were combined to test the performance of CHIMERE as an air quality model for a target monthly period in 2017, and the results were compared against observed data from urban, roadside, and rural sites. The results show that the model is able to reproduce hourly and daily temporal variabilities in aerosol concentrations that are close to observed values from urban, roadside, and rural environments. CHIMERE's performance as a tool for managing air quality was also assessed. The analysis demonstrated that, despite the absence of high-resolution data and up-to-date biogenic and anthropogenic emissions, the model was able to reproduce 66 %–99 % of the daily PM2.5 exceedances above the World Health Organization (WHO) 24 h mean PM2.5 guideline (25 µg m−3) in the three cities. An analysis of the 24 h average PM2.5 levels was also carried out for 17 constituencies in the vicinity of Nairobi. This showed that 47 % of the constituencies in the area exhibited a poor Air Quality Index for PM2.5 that was in the unhealthy category for human health, thereby exposing between 10 000 and 30 000 people per square kilometre to harmful levels of air contamination

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO) or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2). We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5°) to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 %) than at coarser resolution (59 %). The cumulative probability distribution functions (CDFs) of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes) are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy) changing little across model resolutions. Model concentrations in the lower free troposphere are also insensitive to grid resolution. The overall low sensitivity of modeled concentrations to grid resolution implies that coarse resolution is adequate when modeling continental boundary layer chemistry for global applications