Effects of field-applied composted cattle manure and chemical fertilizer on ammonia and particulate ammonium exchanges at an upland field

The present study aimed to investigate the NH₃ volatilization loss from field-applied compost and chemical fertilizer and evaluate the atmosphere–land exchange of NH₃ and particulate NH₄⁺ (pNH₄) at an upland field with volcanic ash soil (Andosol) in Hokkaido, northern Japan. Two-step basal fertilization was conducted on the bare soil surface. First, a moderately fermented compost of cattle manure was applied by surface incorporation (mixing depth, 0–15 cm) at a rate of 117 kg N ha⁻¹ as total nitrogen (T-N) corresponding to 9.9 kg N ha⁻¹ as ammoniacal nitrogen (NH₄–N). Twelve days later, a chemical fertilizer containing 10% (w/w) of NH₄–N as a mixture of ammonium sulfate and ammonium phosphates was applied by row placement (cover depth, 3 cm) at a rate of 100 kg N ha⁻¹ as NH₄–N. The study period was divided into the first-half, beginning after the compost application (CCM period), and the second-half, beginning after the chemical fertilizer application (CF period). The mean air concentrations of NH₃ and pNH₄ (1.5 m height) were 7.6 and 3.0 μg N m⁻³, respectively, in the CCM period; the values were 3.7 and 3.9 μg N m⁻³, respectively, in the CF period. The composition ratios of NH₃ to the sum of NH₃ and pNH₄ (1.5 m height) were 72% and 49% in the CCM and CF periods, respectively. The NH₃ volatilization loss from the compost was 0.8% of the applied T-N (or 9.3% of the applied NH₄–N) and that from the chemical fertilizer was near zero. Excluding the period immediately after the compost application, the upland field acted as a net sink for NH₃ and pNH₄.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Exposure of acid aerosol for schoolchildren in metropolitan Taipei

Metropolitan Taipei, which is located in the subtropical area, is characterized by high population and automobile densities. For convenience, most primary schools are located near major roads. This study explores the exposure of acid aerosols for schoolchildren in areas in Taipei with different traffic densities. Acid aerosols were collected by using a honeycomb denuder filter pack sampling system (HDS). Experimental results indicated that the air pollutants were significantly correlated with traffic densities. The ambient air NO₂, SO₂, HNO₃, NO₃⁻, SO₄²⁻, and aerosol acidity concentrations were 31.3 ppb, 4.7 ppb, 1.3 ppb, 1.9 μg m⁻³, 18.5 μg m⁻³, and 49.5 nmol m⁻³ in high traffic density areas, and 6.1 ppb, 1.8 ppb, 0.9 ppb, 0.7 μg m⁻³, 8.8 μg m⁻³ and 14.7 nmol m⁻³ in low traffic density areas. The exposure levels of acid aerosols for schoolchildren would be higher than the measurements because the sampling height was 5 m above the ground. The SO₂ levels were low (0.13–8.03 ppb) in the metropolitan Taipei. However, the SO₄²⁻ concentrations were relatively high, and might be attributed to natural emissions of sulfur-rich geothermal sources. The seasonal variations of acid aerosol concentrations were also observed. The high levels of acidic particles in spring time may be attributed to the Asian dust storm and low height of the mixture layer. We conclude that automobile contributed not only the primary pollutants but also the secondary acid aerosols through the photochemical reaction. Schoolchildren were exposed to twice the acid aerosol concentrations in high traffic density areas compared to those in low traffic density areas. The incidence of allergic rhinitis of schoolchildren in the high traffic density areas was the highest in spring time. Accompanied by high temperature variation and high levels of air pollution in spring, the health risk of schoolchildren had been observed.     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

The influence of forest fires on CO, HCN, C2H6, and C2H2 over northern Japan measured by infrared solar spectroscopy

Total column abundances of CO, HCN, C₂H₆, and C₂H₂ have been retrieved from infrared solar spectra observed at Moshiri (44.4°N) and Rikubetsu (43.5°N) in northern Japan from 1997 to 2005. The spectra were recorded with high spectral resolution ground-based Fourier transform infrared (FTIR) spectrometers and total column abundances were calculated by SFIT1 version 1.09e. Deviations of these species relative to their seasonal mean values (ΔCO, ΔHCN, ΔC₂H₆, and ΔC₂H₂) were derived, which showed short-time enhancements in 1998, 2002, and 2003. Good correlations among ΔCO, ΔHCN, ΔC₂H₆, and ΔC₂H₂ in a few months of each year were seen. Since the number of forest fires in Siberia had large enhancements in 1998, 2002, and 2003, trajectory analyses were performed in order to assess the influence of forest fires and it was confirmed that air masses passing over the location of burning points in Siberia reached Moshiri and Rikubetsu. This paper shows that enhancements of these species were driven by biomass burning in Siberia.     

Characteristics of ambient C2–C11 non-methane hydrocarbons in metropolitan Nagoya,Japan

To understand the characteristics of non-methane hydrocarbon (NMHC) abundance in an urban air of Nagoya, one of the metropolitan areas of Japan, 48 species of C₂–C₁₁ NMHCs were measured with a measurement system, developed in this study, by using gas chromatography with flame ionization detection (GC/FID) continuously for one year from December 2003 to November 2004.Annual mean concentration of NMHCs in normal and propylene equivalent (PE) in Nagoya was compared with those in four urban areas of Seoul, London, Lille, and Dallas to extract characteristics of urban air. While the absolute values of the normal and PE concentrations of alkanes, alkenes, alkyne, and aromatics were significantly different among these urban areas, the proportions of each chemical group to the total NMHC were not so different.In Nagoya, the total normal concentration was high from November to February and low from June to August. The pattern of the seasonal variation was influenced mainly by that of alkanes. On the other hand, the total PE concentration was high from July to December and low from January to June. The pattern of the seasonal variation was influenced mainly by those of alkenes and aromatics. Particularly the normal concentration of isoprene was high from May to September because of large emission associated with activity of plants. As the results, in summer, the PE concentration of isoprene was especially high, and its contribution to the total NMHCs measured in this study was approximately 40%. The total PE concentrations were high in summer when the concentration of OH radicals is also high, suggesting that the productions of ozone and secondary organic aerosol (SOA) are likely to be promoted in summer of Nagoya.     

Carbonyls and non-methane hydrocarbons at a rural mountain site in northeastern United States

Measurements of carbonyls and C₂–C₆ non-methane hydrocarbons (NMHCs) were made in ambient air at a rural site at the summit of Whiteface Mountain (WFM) in New York State. Alkanes dominated in the samples, with ethane and propane making up about 55% of the total on a carbon-atom basis. Ethane, the longest-lived of the NMHCs, showed a mixing ratio in the range of 0.86–2.1 ppbv. Photochemical ageing analysis indicated an anthropogenic influence on the NMHC levels. The photochemical reactivity of the hydrocarbons, calculated in terms of propylene-equivalent concentration, was dominated by alkenes (propene and ethene), which accounted for 74% of the total NMHC sum. Air mass back-trajectories have been used to investigate the origin of the observed NMHCs and carbonyls. Higher concentrations were found when air masses arrived from the midwestern US corridor. Acetone was the most abundant species, comprising from 31% to 53% of the total detected carbonyls, followed by MEK (15–53%), HCHO (7–39%), and CH₃CHO (7–19%). Average concentrations were determined to be 1.61 ppbv for CH₃C(O)CH₃, 1.40 ppbv for MEK, 1.16 ppbv for HCHO, and 0.49 ppbv for CH₃CHO. The variations in carbonyl concentrations were observed to follow patterns similar to variations in O₃ concentrations, typical of secondary products. Correlations and statistical analysis of the carbonyls and NMHCs were performed, and showed that most of the compounds derived from mixing and photochemical transformation of long-range transported pollutants from the major source areas. Ranking of the carbonyls with respect to removal of the OH radical showed HCHO to be the most important species, followed by CH₃CHO, MEK, and CH₃C(O)CH₃.     

Concentrations and elemental composition of particulate matter in the Buenos Aires underground system

Total suspended particulate (TSP) samples have been collected at six stations in the C and B lines of the Buenos Aires underground system and, almost simultaneously, at six ground level sites outside and nearby the corresponding underground stations, in the Oct 2005/Oct 2006 period. All these samples were analyzed for mass and elemental Fe, Cu, and Zn concentrations by using the Particle Induced X-ray Emission (PIXE) technique. Mostly, TSP concentrations were found to be between 152 μg m⁻³ (25% percentile) and 270 μg m⁻³ (75% percentile) in the platform of the stations, while those in outside ambient air oscillated from 55 μg m⁻³ (25% percentile) to 137 μg m⁻³ (75% percentile). Moreover, experimental results indicate that TSP levels are comparable to those measured for other underground systems worldwide. Statistical results demonstrate that subway TSP levels are about 3 times larger on average than those for urban ambient air. The TSP levels inside stations and outdoors are poorly correlated, indicating that TSP levels in the metro system are mainly influenced by internal sources.Regarding metal concentrations, the most enriched element in TSP samples was Fe, the levels of which ranged from 36 (25% percentile) to 86 μg m⁻³ (75% percentile) in Line C stations, while in Line B ones they varied between 8 μg m⁻³ (25% percentile) and 46 μg m⁻³ (75% percentile). As a comparison, Fe concentrations in ambient air oscillated between 0.7 μg m⁻³ (25% percentile) and 1.2 μg m⁻³ (75% percentile). Other enriched elements include Cu and Zn. With regard to their sources, Fe and Cu have been related to processes taking place inside the subway system, while Zn has been associated with outdoor vehicular traffic. Additionally, concerns about possible health implications based on comparisons to various indoor air quality limits and available toxicological information are discussed.     

Spatial gradients and source apportionment of volatile organic compounds near roadways

Concentrations of 55 volatile organic compounds (VOCs) (C₂–C₁₂) are reported near a highway in Raleigh, NC. Thirty-minute samples were collected at eight locations, ranging from approximately 10–100 m perpendicular from the roadway. The highest concentrations of VOCs were generally measured closest to the roadway, and concentrations decreased exponentially with increasing distance from the roadway. The highest mean concentration for individual VOCs were for ethylene (3.10 ppbv) (mean concentration at x = 13 m), propane (2.27 ppbv), ethane (1.91 ppbv), isopentane (1.54 ppbv), toluene (0.95 ppbv), and n-butane (0.89 ppbv). Concentrations at the nearest roadway location (x = 13 m) were generally between 2.0 and 1.5 times those from the farthest roadway location (x = 92 m). The data were apportioned into four source categories using the EPA Chemical Mass Balance Model (CMB8.2): motor vehicle exhaust, compressed natural gas, propane gas, and evaporative gasoline. The majority of the VOCs resulted from motor vehicle exhaust (67 ± 12%) (% of total VOC at x = 13 m ± S.D.). Compressed natural gas, propane gas, and evaporative gasoline accounted for approximately 15%, 7% and 1% of the total VOC emissions, respectively, at x = 13 m.     

Effects of reactive hydrocarbons on ozone formation in southern Taiwan

Ambient air samples were collected at 13 air quality monitoring stations in Kaohsiung city, Kaohsiung county, and Pingtung county (KKP) to investigate the composition and spatial distribution of C₂–C₁₀ non-methane hydrocarbons (NMHCs) in southern Taiwan. Ozone formation potentials (OFPs) of NMHCs were estimated using maximum incremental reactivity (MIR) and k_OH method (reactivity of NMHC with OH radical) to assess the relative effects of hydrocarbons on ozone formation. The measurements showed that mixing ratios of toluene, ethene, ethyne, ethane, isopantane and propane were the highest among all measured species at most of the sampling sites. Nevertheless, considering both the photochemical reactivities and mixing ratios of all the measured species, toluene, xylene, ethene and propene were calculated to have the highest OFPs and reactivities. The OFPs and reactivities assessed by the MIR and k_OH methods for the four compounds accounted for 54.5% and 39.3% of all the measured species. Larger benefit margin of ozone abatement may be obtained by reducing emissions of a group of key species with high OFPs.2,2-dimethylbutane (22DMC4) was used as an indicator of traffic emissions to distinguish traffic from non-traffic contributions of key species in Kaohsiung metropolitan area. It revealed that the contribution of non-traffic source was significant for toluene, whereas xylene was found to be primarily from the traffic source in Kaohsiung metropolitan area during the sampling periods.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

Particle size distribution of airborne Aspergillus fumigatus spores emitted from compost using membrane filtration

Information on the particle size distribution of bioaerosols emitted from open air composting operations is valuable in evaluating potential health impacts and is a requirement for improved dispersion simulation modelling. The membrane filter method was used to study the particle size distribution of Aspergillus fumigatus spores in air 50 m downwind of a green waste compost screening operation at a commercial facility. The highest concentrations (approximately 8 × 10⁴ CFU m⁻³) of culturable spores were found on filters with pore diameters in the range 1–2 μm which suggests that the majority of spores are emitted as single cells. The findings were compared to published data collected using an Andersen sampler. Results were significantly correlated (p < 0.01) indicating that the two methods are directly comparable across all particles sizes for Aspergillus spores.     

High concentrations and dry deposition of reactive nitrogen species at two sites in the North China Plain

Atmospheric concentrations of major reactive nitrogen (N_r) species were quantified using passive samplers, denuders, and particulate samplers at Dongbeiwang and Quzhou, North China Plain (NCP) in a two-year study. Average concentrations of NH₃, NO₂, HNO₃, pNH₄⁺ and pNO₃⁻ were 12.0, 12.9, 0.6, 10.3, and 4.7 μg N m⁻³ across the two sites, showing different seasonal patterns of these N_r species. For example, the highest NH₃ concentration occurred in summer while NO₂ concentrations were greater in winter, both of which reflected impacts of N fertilization (summer) and coal-fueled home heating (winter). Based on measured N_r concentrations and their deposition velocities taken from the literature, annual N dry deposition was up to 55 kg N ha⁻¹. Such high concentrations and deposition rates of N_r species in the NCP indicate very serious air pollution from anthropogenic sources and significant atmospheric N input to crops.     

Assessment of traffic-related air pollution in the urban streets before and during the 2008 Beijing Olympic Games traffic control period

In order to investigate the air quality and the abatement of traffic-related pollution during the 2008 Olympic Games, we select 12 avenues in the urban area of Beijing to calculate the concentrations of PM₁₀, CO, NO₂ and O₃ before and during the Olympic traffic controlling days, with the OSPM model.Through comparing the modeled results with the measurement results on a representative street, the OSPM model is validated as sufficient to predict the average concentrations of these pollutants at street level, and also reflects their daily variations well, i.e. CO presents the similar double peaks as the traffic flow, PM₁₀ concentration is influenced by other sources. Meanwhile, the model predicts O₃ to stay less during the daytime and ascend in the night, just opposite to NO₂, which reveals the impact of photochemical reactions. In addition, the predicted concentrations on the windward side often exceed the leeward side, indicating the impact of the special street shape, as well as the wind.The comparison between the predicted street concentrations before and during the Olympic traffic control period shows that the overall on-road air quality was improved effectively, due to the 32.3% traffic flow reduction. The concentrations of PM₁₀, CO and NO₂ have reduced from 142.6 μg m⁻³, 3.02 mg m⁻³ and 118.7 μg m⁻³ to 102.0 μg m⁻³, 2.43 mg m⁻³ and 104.1 μg m⁻³. However, the different pollutants show diverse changes after the traffic control. PM₁₀ decreases most, and the reduction effect focusing on the first half-day even clears the morning peak, whereas CO and NO₂ have even reductions to minify the daily fluctuations on the whole. Opposite to the other pollutants, ozone shows an increase of concentration. The average reduction rate of PM₁₀, CO, NO₂ and O₃ are respectively 28%, 19.3%, 12.3% and −25.2%. Furthermore, the streets in east, west, south and north areas present different air quality improvements, probably induced by the varied background pollution in different regions around Beijing, along with the impact of wind force. This finding suggests the pollution control in the surrounding regions, not only in the urban area.     

Microbial characterization of nitrification in a shallow, nitrogen-contaminated aquifer, Cape Cod, Massachusetts and detection of a novel cluster associated with nitrifying Betaproteobacteria

Groundwater nitrification is a poorly characterized process affecting the speciation and transport of nitrogen. Cores from two sites in a plume of contamination were examined using culture-based and molecular techniques targeting nitrification processes. The first site, located beneath a sewage effluent infiltration bed, received treated effluent containing O₂ (> 300 µM) and NH₄⁺ (51–800 µM). The second site was 2.5 km down-gradient near the leading edge of the ammonium zone within the contaminant plume and featured vertical gradients of O₂, NH₄⁺, and NO₃⁻ (0–300, 0–500, and 100–200 µM with depth, respectively). Ammonia- and nitrite-oxidizers enumerated by the culture-based MPN method were low in abundance at both sites (1.8 to 350 g^− 1 and 33 to 35,000 g^− 1, respectively). Potential nitrifying activity measured in core material in the laboratory was also very low, requiring several weeks for products to accumulate. Molecular analysis of aquifer DNA (nested PCR followed by cloning and 16S rDNA sequencing) detected primarily sequences associated with the Nitrosospira genus throughout the cores at the down-gradient site and a smaller proportion from the Nitrosomonas genus in the deeper anoxic, NH₄⁺ zone at the down-gradient site. Only a single Nitrosospira sequence was detected beneath the infiltration bed. Furthermore, the majority of Nitrosospira-associated sequences represent an unrecognized cluster. We conclude that an uncharacterized group associated with Nitrosospira dominate at the geochemically stable, down-gradient site, but found little evidence for Betaproteobacteria nitrifiers beneath the infiltration beds where geochemical conditions were more variable.     

Traffic generated non-exhaust particulate emissions from concrete pavement: A mass and particle size study for two-wheelers and small cars

This study aimed to understand the non-exhaust (NE) emission of particles from wear of summer tire and concrete pavement, especially for two wheelers and small cars. A fully enclosed laboratory-scale model was fabricated to simulate road tire interaction with a facility to collect particles in different sizes. A road was cast using the M-45 concrete mixture and the centrifugal casting method. It was observed that emission of large particle non exhaust emission (LPNE) as well as PM₁₀ and PM_2.5 increased with increasing load. The LPNE was 3.5 mg tire⁻¹ km⁻¹ for a two wheeler and 6.4 mg tire⁻¹ km⁻¹ for a small car. The LPNE can lead to water pollution through water run-off from the roads. The contribution of the PM₁₀ and PM_2.5 was smaller compared to the LPNE particles (less than 0.1%). About 32 percent of particle mass of PM₁₀ was present below 1 μm. The number as well as mass size distribution for PM₁₀ was observed to be bi-modal with peaks at 0.3 μm and 4–5 μm. The NE emissions did not show any significant trend with change in tire pressure.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

The ratio between nitrogen oxides and carbon monoxide total emissions as precursors of tropospheric hydroxyl content evolution

The Main Geophysical Observatory 2D channel photochemical model is used to study the behavior of tropospheric OH within the 30–60°N zonal belt in relation to changing NO_X and CO emissions. The changes of tropospheric OH as a function of the contributions by NO_X and CO emissions during the period 1850–2050 are calculated. Our estimations show that the largest annual increment of total tropospheric OH within the belt considered occurs in the 1985–1995 period, about 0.27% yr⁻¹. Based on scenarios of tropospheric pollution emissions in the first half of 21st century, the total tropospheric OH content will increase more slowly, by 0.12–0.15% yr⁻¹. The maximum growth of OH concentration occurs close to air pollution locations—in the lower troposphere during 1850–1995 but in the upper troposphere in the 21st century when the NO_X source from subsonic aircraft increases faster than the surface source.     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.