Formation and occurrence of organic hydroperoxides in the troposphere: Laboratory and field observations

The formation and occurrence of hydroperoxides in the troposphere have been studied by laboratory experiments and by preliminary field measurements. Nine alkenes were reacted individually with ozone in a reaction chamber in the presence of excess water, and the amounts of hydrogen peroxide and of nine organic hydroperoxides produced in the gas and aerosol phases and deposited on the chamber walls determined by HPLC. The reactions of ethene, propene, 1-butene and isoprene gave hydroxymethyl hydroperoxide as the major product with no hydrogen peroxide observed. In the case of - and -pinene, 2-carene and limonene the major product was hydrogen peroxide. Cis-2-butene produced hydrogen peroxide and methyl hydroperoxide. Preliminary measurements of hydrogen peroxide and five organic hydroperoxides in ambient air were made at Niwot Ridge, Colorado from 24 July–4 August 1989. The gas-phase species were preconcentrated by cryotrapping with subsequent HPLC separation. The gas-phase concentrations of H₂O₂ ranged from 0.5–2 ppbv with the lowest concentrations being measured at night and the highest under conditions of strong photochemical activity. The maximum concentrations of hydroxymethyl hydroperoxide approximated those of H₂O₂. Methyl hydroperoxide concentrations ranged from <50 to 800 pptv and three other organic hydroperoxides were detected at concentrations below 200 pptv. High volume aerosol samples yielded H₂O₂ and methyl hydroperoxide concentrations <10 ng m^-3 while H₂O₂ and six organic species were detected in rainwater at concentrations in the range <0.01–50 M.     

Effects of Rainwater Iron and Hydrogen Peroxide on Iron Speciation and Phytoplankton Growth in Seawater near Bermuda

Rainwater is a major source of dissolved iron to much of the world's oceans, including regions where iron may be a limiting nutrient for marine phytoplankton primary production. Rainwater iron is therefore potentially important in regulating global photosynthetic uptake of CO₂, and hence climate. Two rainwater addition bioassay experiments (2% rain) conducted at the Bermuda Atlantic Time-series Station (BATS) during March 2000 using 50 or 100 nM FeCl₂ or FeCl₃ in synthetic rain (pH 4.5 H₂SO₄) showed an increase in chlorophyll a 50% greater than controls after three days. Addition of 20 μM hydrogen peroxide, a typical rainwater concentration at BATS, completely removed the chlorophyll a increase with both forms of iron additions, suggesting stimulation of phytoplankton growth by rainwater iron can be limited by rainwater H₂O₂. In laboratory experiments using Gulf Stream seawater, iron-enriched (100 nM Fe(III)) synthetic rain was mixed with seawater in a 5% rain 95% seawater ratio. Dissolved iron concentrations increased two times above concentrations predicted based on dilution alone. The increase in soluble iron probably resulted from release from seawater particles and was maintained for more than 24 hours. No increase was observed in controls that did not have iron added to the synthetic rain, or with synthetic rainwater containing both added iron and H₂O₂. The increase in iron concentration above that predicted by dilution indicates rain may have a larger effect on seawater iron concentrations than that calculated for rainwater iron addition alone.     

Hydrogen Peroxide at the Bermuda Atlantic Time Series Station. Part 1: Temporal Variability of Atmospheric Hydrogen Peroxide and Its Influence on Seawater Concentrations

Diurnal and seasonal variations in atmospheric hydrogen peroxideconcentrations wereinvestigated during a summer and winter cruise aboard the R.V. `Endeavor' atthe BermudaAtlantic Time Series Station. Rainwater peroxide concentrations in Augustdisplayed dielvariability while no temporal H₂O₂ pattern was evidentin March rain. Averageconcentrations in March were also significantly lower than August whichindicates photochemicalprocesses are involved in controlling hydrogen peroxide concentrations inmarine rainwaterfalling over the open ocean. The range of gas phase hydrogen peroxideconcentrations wasbetween 1 and 6 ppbv and also exhibited a strong diurnal pattern during bothAugust and Marchwith concentration maxima in the early evening. The influence of atmosphericdeposition onsurface seawater hydrogen peroxide levels was also evaluated. Hydrogenperoxide depth profileswere measured on four separate occasions before and after rain events duringthe Augustsampling period. The input of rainfall hydrogen peroxide was observedthroughout the 25 metermixed layer with surface concentrations two fold larger in the morning aftera rain event. Theintegrated increase in hydrogen peroxide after the rain from 0 to 90 meterswas 1,720 molalmost all of which could be accounted for by the peroxide added from rain.The data presentedin this study represent the first detailed, simultaneous measurements ofhydrogen peroxide inmarine air, rain and surface seawater.     

Gas phase measurements of hydrogen peroxide in Greenland and their meaning for the interpretation of H2O2 records in ice cores

The gas phase concentration of hydrogen peroxide at Summit, Central Greenland, has been measured continuously during June/July 1990 using a coil scrubber technique combined with liquid phase fluorometry. The concentrations ranged between 0.3 ppbv and 3.5 ppbv, which is considerably higher than expected from model calculations and can be explained by low deposition rates. The record shows pronounced diurnal variations with minimum concentrations during night and maximum concentrations in the afternoon. The nocturnal minima can be explained by scavenging of H₂O₂ by hoarfrost. The scavenging mechanisms of H₂O₂ by snow and the redistribution of H₂O₂ during firnification are discussed. There is indirect evidence, that H₂O₂ is uniformly distributed in the ice lattice and that the fractionation between H₂O₂ and H₂O is small during diffusional crystal growth from the vapor phase (co-condensation).     

Observation of hydrogen peroxide concentrations in a Japanese red pine forest

In order to study the concentrations of hydrogen peroxide (H₂O₂) and the factors controlling its concentrations, we monitored concentrations of H₂O₂ and other gases such as sulfur dioxide, ozone, and NO _x as well as meteorological factors such as air temperature, relative humidity, and wind direction/speed during eight measurement periods from 2000 to 2002 in a Japanese red pine forest in Japan. The H₂O₂ concentrations ranged from below 0.01 to 1.64 ppb, and analysis of the diurnal variation in H₂O₂ concentration showed high concentrations around noon, and low concentrations in the morning and late afternoon. The H₂O₂ concentrations were high in early summer, when O₃ concentration, temperature, and solar radiation were high, and were low in fall, when O₃ concentration, temperature, and solar radiation were low. We propose that O₃ concentration affects the production of H₂O₂ in the monitored region during the period under study, but that high H₂O₂ concentrations were sometimes caused by the transport of polluted air from urban regions. H₂O₂ concentrations decreased remarkably when SO₂ concentrations increased by transported volcanic emission on Miyake Island. In the absence of the effects of SO₂, H₂O₂ concentrations increased with increasing O₃ concentration and temperature.     

Tropospheric ozone chemistry. The impact of cloud chemistry

The effect of clouds and cloud chemistry on tropospheric ozone chemistry is tested out in a two-dimensional channel model covering a latitudinal band from 30 to 60° N. Three different methods describing how clouds affect gaseous species are applied, and the results are compared. The three methods are:

?A first order parameterization scheme for the removal of sulphur and other soluble gases by liquid droplets.

?A parameterization scheme for SO₂, O₃, and H₂O₂ removal is constructed. The scheme is based on the solubility of gases in liquid droplets, cycling times of air masses between clouds and cloud free areas and on the chemical interaction of SO₂ with H₂O₂ and O₃ in the liquid phase.

?Gas-aqueous-phase interactions and aqueous-phase chemical reactions are included in the reaction scheme for a number of components in areas where clouds are present.

In all three methods, a full gas-phase chemistry scheme is used. Particular emphasis is given to the study of how the ozone and hydrogen peroxide levels are affected. Significant changes in the distributions are found when aqueous-phase chemical reactions are included. The result is loss of ozone in the aqueous phase, with pronounced reductions in ozone levels in the middle and lower troposphere. Ozone levels are reduced by 10 to 30% with the largest reductions in the remote middle troposphere, bringing the values in better agreement with observations. Changes in H₂O₂ are harder to predict. Although, in one case study, hydrogen peroxide is produced within the aqueous phase, concentrations are mostly comparable or even lower than in the other cases. Hydrogen peroxide levels are, however, shown to be very pH sensitive. pH values around 5 seem to favour high H₂O₂ levels. High H₂O₂ concentrations may be found particularly in the upper part of the clouds under favourable conditions.     

Photochemistry of Cu complexed with chromophoric dissolved organic matter: implications for Cu speciation in rainwater

Significant quenching of fluorescence by Cu in rainwater samples from southeastern North Carolina demonstrates that chromophoric dissolved organic matter (CDOM) is an effective ligand for Cu in rainwater. A strong inverse correlation between the decrease in fluorescence upon Cu addition and CDOM abundance suggests the presence of excess binding sites for Cu in high CDOM samples. Electroanalytical studies indicate that CDOM extracted from C₁₈ cartridges formed Cu complexes with concentrations and conditional stability constants similar to ligands found in ambient rainwater. When authentic rainwater samples were photolyzed with simulated sunlight both photoproduction and photodestruction of ligands were observed, suggesting the photochemical response of Cu-complexing ligands in rainwater is the result of two competing reactions. The rate of CDOM photobleaching was directly related to changes in strong ligands (K_CuL ∼ 10¹⁵) whereas weaker ligands (K_CuL < 10¹³) were not correlated, suggesting the photolabile CDOM resides in the strong ligand class. A photolysis study comparing filtered and unfiltered rainwater samples indicated that Cu-complexing ligands adsorbed onto or otherwise associated with particles are photodegraded much more rapidly than dissolved ligands. Photolysis with UV radiation appears to be most effective at engendering changes in Cu ligands, however a significant photochemical response was also observed when samples were exposed to photosynthetically active radiation with wavelengths greater than 400 nm. Results from this study demonstrate that complexation of Cu by CDOM has important ramifications for controlling both the speciation of the metal and the reactivity of CDOM in rainwater.     

Thymol as a Biocide in Japanese Rainwater

Rainwater samples (wet-only; event samples) collected in Niigata in late autumn 1996 and springtime 1997 were used to assess the effectiveness of thymol as a biocide in Japanese rainwater. Upon collection each rainwater sample was divided into sub-samples, with thymol added to one sub-sample. Sub-samples with and without thymol were shipped to CSIRO, Australia, for chemical analysis. Comparison of analytical results for each pair of sub-samples proved the effectiveness of thymol in preventing biological action in this region where effects of rainwater microflaura and fauna on rainwater composition have not before been studied. Sub-samples without thymol exhibited lowered electrical conductivity, loss of the cations H⁺ and NH ₄ ^- , and loss of the anions HCOO^-, CH₃COO^-, C₂O ₄ ^2- , CH₃SO ₃ ^- and PO ₄ ^3- . Nitrate showed no change in all but one of the samples, indicating that ammonia was the preferred source of nitrogen for the biological processes that consumed the rainwater organic acids and phosphate. These results suggest that thymol is a suitable rainwater biocide for use under Japanese conditions.     

Measurements of atmospheric hydroperoxides at a rural site in central Japan

Measurements of hydroperoxides (H₂O₂ and MHP) at ground level were made from 2012 to 2015 in Imizu City, Toyama Prefecture in central Japan. H₂O₂ and MHP concentrations ranged from 0.01 to 3.5 ppb and from below the level of detection (< 0.01 ppb) to 1.4 ppb, respectively. The concentrations of H₂O₂ and MHP were high in the summer and low in the winter. The H₂O₂ concentration was at its maximum in July and August, whereas the concentration of O₃ in the daytime was highest in May and June. The ratio of [H₂O₂]/[SO₂] presented clear seasonal variations. Many cases showed the condition of [H₂O₂] < [SO₂], called oxidant limitation especially in the cold months. Hydroperoxide concentrations in the rainwater were also high in the summer. The concentrations of MHP were much lower than those of H₂O₂ in the rain water. High concentrations of H₂O₂ (> 2.5 ppb) were detected in the summer during the inflow of air pollution. The concentrations of H₂O₂ were significantly high in July and August of 2013. The H₂O₂ was well correlated with the O₃ in July and August whereas there was no correlation between O₃ and H₂O₂ in May and June. There was a negative correlation between NO_X and H₂O₂.     

Coastal rainwater hydrogen peroxide: Concentration and deposition

Correlation analysis between rainwater component concentrations (hydrogen peroxide, hydrogen ion, nitrate, nonseasalt sulfate and chloride ion) was used to investigate patterns of variation in hydrogen peroxide concentrations in rain collected in Wilmington, North Carolina, a coastal southeastern United States location, between October 1992, and October 1994. Rainwater hydrogen peroxide concentrations in general correlated positively with the pollutant components (hydrogen ion, nitrate and non-seasalt sulfate). This pattern suggests that destruction of hydrogen peroxide by sulfur dioxide is not the dominant factor controlling the concentration of hydrogen peroxide in this rainwater, with the possible exception of winter rain from coastal storms where an inverse correlation between hydrogen peroxide and nonseasalt sulfate was observed. Sequential sampling indicates rapid production of hydrogen peroxide and incorporation into rain within time periods of hours during summer daytime rains.Rain is an important transport mechanism for removal of atmospheric hydrogen peroxide, which may affect the oxidizing capacity of surface waters that receive the rain. During this study time, the annual deposition of hydrogen peroxide by rain was 12 mmole m^-2 yr^-1. An average rain event added approximately half of the resident amount of hydrogen peroxide to the shallow lakes typical of eastern North Carolina; extreme rain events can triple the amount normally present. The episodic nature of rain contributes to the variability in hydrogen peroxide concentration in surface waters. Higher hydrogen peroxide concentrations and greater rainfall amounts cause wet deposition of hydrogen peroxide to be approximately seven times greater during the warm season than the cold season.     

Effects of Monochromatic UV-Visible Light and Sunlight on Fe(III)-Catalyzed Oxidation of Dissolved Sulfur Dioxide

The effect of UV-visible light and natural sunlight on the Fe(III)-catalyzed oxidation of dissolved sulfur dioxide has been studied under the conditions representative for those of acidified atmospheric liquids. The experimental results have shown that both sunlight and UV-visible light enhance the rate of Fe(III)-catalyzed oxidation of aqueous sulfite with wavelength ranging from 300 to 575 nm. The light enhanced oxidation is mainly due to photochemical formation of OH radicals from Fe(OH)²⁺ complexes in the wavelength region below 420 nm and SO₃^•− free radicals from Fe(III) sulfite complexes above 420 nm in the absence of organic ligands. Like the Fe(III)-catalyzed thermal chemical oxidation, the Fe(III)-catalyzed photochemical oxidation is also first order with respect to sulfite ion concentration. The sunlight irradiation can increase the Fe(III)-catalyzed oxidation of S(IV) over 45%. The presence of organic complex ligands, such as oxalate, can completely inhibit the Fe-catalyzed oxidation of S(IV) in the dark. However, the photolysis of Fe(III)-oxalato complexes generates oxalate free radicals, leading to the formation of H₂O₂ and OH radicals and the oxidation of S(IV). The rate of Fe(III)-catalyzed oxidation of S(IV) species is found to increase with increasing light intensity. The effects of sunlight on the Fe(III)-catalyzed oxidation of S(IV) should be taken into account when predicting the daytime rates of sulfuric acid formation in atmospheric water droplets.     

Speciation and Photochemistry of Mercury in Rainwater

Mercury speciation was determined in rainwater from 76 storms in southeastern North Carolina between September 1, 2003 and September 30, 2005. Volume-weighted average concentrations of total Hg (THg), total dissolved Hg (TDHg), particulate Hg (Hg_part) and dissolved monomethyl Hg (MMHg) were 45.5 pM, 34.8 pM, 12.0 pM and 1.1 pM respectively. TDHg accounted for 77% of THg in precipitation which is similar to Cu but significantly higher than Cr or Fe. Concentrations of the various Hg species were very similar during summer and winter indicating that there was not a dominant seasonal influence on Hg speciation in rainwater at this location. THg, TDHg, and MMHg concentrations were also not significantly impacted by storm origin suggesting that they are relatively well mixed regionally and that air mass back trajectory is not the dominant factor controlling their concentration at this location. Concentrations of TDHg and Hg_part were inversely correlated in rainwater samples subjected to irradiation with simulated sunlight, suggesting the distribution between dissolved and particulate Hg may be controlled by photochemical transformations. Unlike TDHg and Hg_part, no significant changes in MMHg were observed upon photolysis of rainwater indicating that its distribution is not significantly driven by sunlight-mediated reactions, in contrast to what has been observed in surface waters. Results presented in this study indicate that the speciation of Hg in rainwater is dynamic and is driven by a complex combination of natural and anthropogenic processes as well as interactions with sunlight.     

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth

One-dimensional radiative-convective and photochemical models are used to examine the effects of enhanced CO₂ concentrations on the surface temperature of the early Earth and the composition of the prebiotic atmosphere. Carbon dioxide concentrations of the order of 100–1000 times the present level are required to compensate for an expected solar luminosity decrease of 25–30%, if CO₂ and H₂O were the only greenhouse gases present. The primitive stratosphere was cold and dry, with a maximum H₂O volume mixing ratio of 10^–6. The atmospheric oxidation state was controlled by the balance between volcanic emission of reduced gases, photo-stimulated oxidation of dissolved Fe⁺² in the oceans, escape of hydrogen to space, and rainout of H₂O₂ and H₂CO. At high CO₂ levels, production of hydrogen owing to rainout of H₂O₂ would have kept the H₂ mixing ratio above 2×10^–4 and the ground-level O₂ mixing ratio below 10^–11, even if no other sources of hydrogen were present. Increased solar UV fluxes could have led to small changes in the ground-level mixing ratios of both O₂ and H₂.     

Ground Based Gas Phase Measurements in Surinam during the LBA-Claire 98 Experiment

As part of the LBA-CLAIRE-98 experiment, ground level atmosphericconcentrations of O₃, CO, hydroperoxides and organic acids weremeasured in the rainforest region in Surinam. Measurements of CO andO₃ were also made at a coastal site.The results suggest that a significant consumption of `boundary layer' ozoneoccurs over the forested region of Surinam, with an estimated net ozoneconsumption of about 5% hr^–1 during daytime. Thiswould be mainly explained by a low photochemical production and high drydeposition to the forest vegetation. Compared to other tropical sites, lowerlevels of H₂O₂ were observed at the rainforest site,with an average boundary layer concentration of 0.55± 0.2 nmolmol^–1. Also acetic and formic acids showed relatively lowaverage boundary layer mixing ratios; 1.1± 0.4 nmolmol^–1 and 1.4± 0.5 nmol mol^–1,respectively. Significant correlations were found between both acids andbetween the acids and hydrogen peroxide, suggesting an atmospheric source forthe acids.From the available observations we discuss possible implications of ourmeasurements for the O₃, HO₂, and NO_x budgetsand concentrations in the boundary layer. We conclude that, despite the highsolar irradiation, relatively low levels of O₃,H₂O₂, HCOOH and CH₃COOH are observed in theboundary layer of the rainforest of Surinam, probably due to low levels ofNO_x and high levels of VOCs, which leads to loss of OH andHO₂ radicals. Additionally, high deposition rates of these gasesoccur to the forest vegetation.     

Hydroperoxides in the marine troposphere over the Atlantic Ocean

Hydrogen peroxide (H₂O₂) and organic hydroperoxides (ROOH) were measured on board of theRV Polarstern during its cruise across the Atlantic Ocean from 20 October to 12 November 1990 (54° N to 51° S latitude) by the enzyme fluorometric method. The H₂O₂ mixing ratio varied from below the detection limit of about 0.12 ppbv up to 3.89 ppbv, showing a latitudinal dependence with generally higher values around the equator and decreasing values poleward. The shape of the latitudinal H₂O₂ distribution agrees well with an analytical steady state expression for H₂O₂ using the measured H₂O and O₃ distribution and a wind dependent H₂O₂ deposition rate. The ROOH mixing ratio varied from below the detection limit of about 0.08 ppbv up to 1.25 ppbv with qualitatively the same latitudinal dependence as H₂O₂. The observed ratio ROOH/(ROOH + H₂O₂) varied between 0.17 and 0.98 showing higher values at the lowest H₂O₂ mixing ratios at high latitudes. The measured H₂O₂ mixing ratio shows a significant diurnal variation with a maximum around 14:00 local time, explicable by a superposition of the photochemical H₂O₂ production with a constant H₂O₂ deposition rate. Four independent estimations of the average effective H₂O₂ deposition rate inferred from the H₂O₂ decrease in the night, from the midday H₂O₂ production deficit (as derived from comparison with a photochemical model and from the daily ozone loss), and from the offset in the latitudinal H₂O₂ distribution, were consistent. An episode of maximum H₂O₂ concentration suggests the possibility of its formation in clouds.     

Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

Gas-phase H₂O₂, organic peroxides and carbonyl compoundswere determined at various sites from Mid-July to early August 1998 during the BERLIOZ campaign in Germany. The sites were located northwest of Berlin and were chosen to determine pollutants downwind of the city emissions during a summer smog episode. Hydrogen peroxide (H₂O₂),methyl hydroperoxide (MHP, CH₃OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH₂OOH) were quantified in air samples by commercial fluorimetric methods and classical HPLC with post-column derivatisation by horseradish peroxidase/p-hydroxyphenyl acetic acid and fluorimetric detection. Carbonyl compounds were determined in ambient air by a novel method based onO-pentafluorobenzyl hydroxylamine as derivatisation agent.Mixing ratio profiles of the hydroperoxides and the carbonyl compounds are reported for the intensive phase of the campaign, 20–21 July, 1998. Peroxides showed pronounced diurnal variations with peak mixing ratios in the early afternoon. At times, a second maximum was observed in the late afternoon. The major part of the H₂O₂ was formed throughrecombination reactions of HO₂ radicals, but there is some evidencethat H₂O₂ is also formed from ozonolysis ofanthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C₂ to C₁₀,isobutanal), unsaturated carbonyl compounds (methacrolein, methylvinylketone, acrolein), hydroxycarbonyl (glycolaldehyde, hydroxyacetone) and dicarbonyl compounds (glyoxal, methylglyoxal, biacetyl), aromatic compounds (benzaldehyde, o- and m-tolylaldehyde) and pinonaldehyde.     

SO2 Oxidation in a rainband: Effects of in‐cloud H2O2 Production

Abstract

Aqueous‐phase H₂O₂ production in a rainband and its possible effect on sulphate production are studied by means of a two‐dimensional numerical model. In‐cloud peroxide production is incorporated into this chemistry model and its simulation results are compared with those in which aqueous‐phase H₂O₂ came only from the dissolution of gaseous H₂O₂ from the cloud interstitial air.

Results are presented for two different polluted situations ‐ Case 1 having initial SO₂ and sulphate aerosol profiles representative of a moderately polluted air mass, and Case 2 having chemical profiles expected to increase the relative importance of oxidation to nucleation as a means of contributing sulphate to cloud and rain. Sulphate production increased in both cases, although in Case 1 the effect of this increase on the concentration of sulphate in rain is negligible because nucleation and scavenging of aerosol are the major processes by which sulphate enters cloud and rain. In Case 2, sulphate concentrations in rain increase by 5–10%. Under environmental conditions of low sulphate aerosol, where oxidation reactions are the dominant means for sulphate to enter cloud and rain, the neglect of sulphate produced by the additional H₂O₂ may lead to error. The usual uncertainties in the initial SO₂ and sulphate aerosol vertical profiles, however, could be a more significant source of error in simulations of the chemistry of cloud and precipitation than the neglect of aqueous‐phase peroxide production during the lifetime of even a long‐lived system.     

Water-soluble organic and nitrogen levels in cloud and rainwater in a background marine environment under influence of different air masses

Chemical characterization was performed on cloud and rainwater samples collected as part of the Rain In Cumulus over the Ocean Experiment (RICO). This experiment took place at a mountaintop site (East Peak) in Puerto Rico from December 2004 to March 2007 in order to determine water-soluble organic and nitrogen fractions in a marine background environment. For cloud water, similar average concentrations of 1.0 (±0.3) mg/L were found for total organic carbon (TOC) and total nitrogen (TN) and an average concentration of 0.8 (±0.2) mg/L was found for dissolved organic carbon (DOC). In rainwater, these concentrations were lower, ranging from 0.3 to 0.5 (±0.1) mg/L. Changes in the concentrations of these species were observed in periods under the influence of anthropogenic, African dust, and volcanic ash air masses. In these periods the concentrations of TOC, DOC, and TN were 2 to 4 times higher than in periods under the influence of trade winds. The insoluble organic material arriving during African dust events showed total carbon (TC) concentrations on averaging 1.5 mg/L for cloud water. The TC was composed mainly of organic carbon with polar compounds from low to high molecular weight (MW). The polar compounds with high MW were probably associated with pollution (e.g., fossil fuel combustion) from other regions. Crustal species (Al and Fe) dominated particles associated with dust episodes, confirming the soil origin. Our results suggested that a fraction (40–80%) of TOC and (<100%) of TN in Puerto Rican cloud/rainwater could be originated from long-range transport of dust, ash and/or pollution.     

Some observations on the acidity and composition of rainwater in Sydney,Australia, during the summer of 1980–81

During the summer of 1980–81, a rudimentary form of wet-only event sampling was employed to collect a total of 294 rainwater samples at 12 sites spread across the metropolitan region of Sydney, Australia's largest city. From the samples were determined conductivity, pH, ammonium, chloride and nitrate ion concentrations as well as deposited water volume. Supplementary data consisting of city-wide averaged SO₂, NO₂, NO, and O₃ concentrations and 950 mb wind speed and direction were obtained for times coinciding with the period during which each event occurred.The pH of rainwater upwind of the city and unaffected by urban/industrial emissions was found to be usually 5, whereas the volume-weighted mean pH of all the metropolitan samples was 4.4, indicating that local emissions significantly increased rainwater acidity in the near field. Time available for conversion of precursors to acids averaged 1–2 h only.Considerable day-to-day variability in rainwater composition was observed. Factors identified as contributing to this variability included precursor gas concentration, wind speed, wind direction, amount of water deposited per event and possibly time of day. These results show that physical/meteorological factors cannot be excluded from consideration if variance in rainwater composition data is to be explained.     

Precipitation Chemistry and Wet Deposition in Kruger National Park, South Africa

The chemical composition, as well as the sources contributing to rainwater chemistry have been determined at Skukuza, in the Kruger National Park, South Africa. Major inorganic and organic ions were determined in 93 rainwater samples collected using an automated wet-only sampler from July 1999 to June 2002. The results indicate that the rain is acidic and the averaged precipitation pH was 4.72. This acidity results from a mixture of mineral acids (82%, of which 50% is H₂SO₄) and organic acids (18%). Most of the H₂SO₄ component can be attributed to the emissions of sulphur dioxide from the industrial region on the Highveld. The wet deposition of S and N is 5.9 kgS⋅ha⁻¹⋅yr⁻¹ and 2.8 kgN⋅ha⁻¹⋅yr⁻¹, respectively. The N deposition was mainly in the form of NH₄ ⁺. Terrigenous, sea salt component, nitrogenous and anthropogenic pollutants have been identified as potential sources of chemical components in rainwater. The results are compared to observations from other African regions.