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1.
In this study, the results of four different field experiments concerning the speciation of iron and the concentrations of some other chemical compounds in cloudwater samples are compared to one-another. Hydrogen peroxide concentrations were higher during campaigns, conducted at sites not much influenced by anthropogenic emissions as compared to those conducted at more polluted areas. In contrast, percentages of S(IV) in the cloudwater were lowest at the rural sites and highest at the sites polluted by human activities, indicating a consumption of hydrogen peroxide in the oxidation reaction with S(IV). The concentration of dissolved iron was observed to correlate with the percentage of S(IV), which may be an essential point for the reductive dissolution of oxidic iron compounds of the aerosol particles. As far as the speciation of the dissolved iron is concerned, it became obvious that the percentage of Fe(III) is anticorrelated to the concentration of dissolved iron. This clearly shows the important effect of the chemical and/or photo reductive ways of dissolving the iron(III)-compounds from the aerosol particles. However, a correlation between the pH-value and hydrogen peroxide was observed.  相似文献   

2.
Iron is the most abundant transition metal in the atmosphere and can play a significant role in cloudwater chemistry where its reactivity is closely related to the partitioning between Fe(II) and Fe(III). The objective of this work is to determine the total iron content and the iron speciation in a free tropospheric site, and to understand which factors influence these parameters. We collected 147 samples of cloudwater during 34 cloud events over a period of four years at the puy de Dôme summit. Besides iron we measured other chemical compounds, solar radiation, physico-chemical and meteorological parameters potentially connected with iron reactivity. The total iron concentrations ranged from 0.1 to 9.1 μM with the major frequency occurring at low levels. The pH and presence of organic complexants seem to be the most significant factors connected with total dissolved iron; while the iron oxidation state seems to be an independent factor. Light intensity, presence of complexants or oxidants (H2O2) do not influence the Fe(II)/Fe(Total) ratio, that was quite constant at about 0.75. This could be due to the potential redox that forces the Fe(II)-Fe(III) couple to the reduced form or, more probably to the complexation by Natural Organic Matter, that can stabilize iron in its reduced form and prevent further oxidation. Our field measurements did not show the diurnal cycle observed in surface water and predicted by models of atmospheric chemistry. This result prompts a more careful review of the role of iron and, by analogy, all the transition metals in atmospheric liquid phase, often over-estimated in the literature.  相似文献   

3.
The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.  相似文献   

4.
Iron occurs in rain as particulateand dissolved Fe and includes both Fe(II) and Fe(III)species. Model calculations and correlation analysisindicate Fe(II)(aq) occurs almost exclusively as thefree ion whereas Fe(III)(aq) occurs as both ironoxalate and Fe(OH)2 +(aq) with largevariations over the pH range from 4.0 to 5.0. Complexation with humic-like compounds may also beimportant for Fe(III)(aq); however, the concentrationand structural characteristics of these compounds haveyet to be determined. 112 rain samples were collectedfor iron analysis in Wilmington, North Carolina,between 1 July 1997, and 30 June 1999. Total iron,particulate iron and Fe(III)(aq) were higher inconcentration in summer and spring rain relative towinter and autumn rain. Fe(II)(aq) concentrations, incontrast, did not vary seasonally. Particulate iron,which was approximately half the total rainwater iron,was highest between noon and 6 p.m. (EST), probably dueto more intense regional convection including land-seabreezes during that time. The ratio ofFe(II)(aq)/Fe(III)(aq) was also highest in rainreceived between noon and 6 p.m., which most likelyreflects photochemical reduction of Fe(III)(aq)complexes to form Fe(II)(aq). A conceptual modeldepicting the interplay between iron species, lightintensity and organic ligands in rainwater ispresented.  相似文献   

5.
Precipitation samples collected at Erdemli, Turkey, during February 1996–June 1997 were analysed to determine iron content and speciation. The purpose of the measurements was to examine the atmospheric abundance of iron and to quantify its solubility in the region. Spectrophotometric analyses of Fe(II) and reducible Fe(III) in precipitation samples, along with measurements of pH, conductivity, filterable iron (Fefilt), particulate aluminium (Alpar) and particulateiron (Fepar) were performed to determine iron solubility, which principally affects its bioavailability. Backward trajectories corresponding to the sampling dates were analysed to determine the sources of atmospheric constituents arriving at the site. Among these, the mineral dust transported from the Great Sahara to the region is considered to be a rich source of iron. The concentration of Fe(II) varied from below detection limit (0.02 M) up to 0.42 M,while the maximum concentration of total reactive Fe (referred as Fe(II) + reducible Fe(III) = Fereac) was found to be 1.0 M in precipitation. A strong correlation was found between particulate Fe and Al fractions, both of crustal origin. No correlation was observed between the soluble and insoluble fractions of iron. The soluble iron fraction, Fe(II) concentration varied independently from the concentrations of reducible Fe(III), Fefilt, Fepar, and from the pH of the precipitation. The Fefilt fraction (size < 0.45 m), measuredby Atomic Absorption Spectrophotometer, and frequently interpreted to be the soluble iron fraction in the literature, was found to be significantly higher than the corresponding Fereac fraction inprecipitation samples, most likely due to the colloidal iron content of the Fefilt fraction passing through the 0.45 m pore size filter. The volume weighted mean Fefilt concentration of the precipitation samples collected during the episodic `red rain' events was found to be relatively higher. The geometric mean ratios of soluble Fe(II) and of Fereac to Total Fe (Fefilt + Fepar), werefound to be 1.6% and 2.1%, respectively, while the mean ratioof Fefilt to Total Fe was 9.6%. The flux of bioavailable iron (Fereac)fraction in most atmospheric wet deposition events was found to be sufficient for supporting the maximum primary production rates that are typical for the Eastern Mediterranean Sea.  相似文献   

6.
This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 103 M-1 s-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.  相似文献   

7.
The influence of sunlight and dissolved organic carbon (DOC) on the photochemically mediated cycling of hydrogen peroxide (H2O2) was investigated in rainwater samples collected in Wilmington, North Carolina USA. Upon exposure to simulated sunlight 14 of 19 authentic rainwater samples exhibited significant decreases in H2O2. The concentration of hydrogen peroxide did not change significantly in organic-free synthetic rainwater spiked with H2O2 in the light or in dark controls suggesting that the loss was not due to direct photolysis or dark mediated reactions. There was a significant correlation between pseudo-first order rate constants of H2O2 decay and initial H2O2 concentrations. There was also a significant correlation between the rate constant and the abundance of DOC suggesting that rainwater organic carbon plays an important role during photolytic decay either via direct reaction or indirectly through production of peroxide reactive species or scavenging of peroxide generating radicals. Several rain samples exhibited an initial increase in H2O2 during the first 2 h of irradiation. These increases were generally small and most likely do not represent a significant input of peroxide in precipitation. The photo-induced destruction of H2O2 is important because it may partly explain the late afternoon decrease of peroxide concentrations observed in earlier field studies and the substantial under saturation (<10%) of this oxidant in rainwater compared with gas phase concentrations.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
The reaction kinetics of S(IV) autoxidation catalyzed by single metal ions of Mn(II) and Fe(II) or Fe(III) and by a mixture of Mn(II) and Fe(II) under the conditions representative for acidified atmospheric liquid water was investigated. A simple power law kinetic model based on the stability constants for metal-sulfito complexes formed during the first step of a radical chain mechanism predicts well the kinetics for the reactions catalyzed by single metal ions. The calculated stability constants for iron (5.7×103 dm3 mol–1) and manganese (10×104 dm3 mol–1) sulfito complexes are close to those reported in the literature. The catalytic synergism between Mn(II) and Fe(II) was confirmed. For this system the following power law rate equation was suggested:rtot = SFe · rFe + SMn · rMn ,where rFe and rMn are the reaction rates in the presence of Fe(II) and Mn(II), respectively. SFe and SMn are proportional factors, which account for the synergistic effect. The proposed power law rate equation predicts the reaction kinetics very well. The values of SFe (1.35) and SMn (15) indicate that the influence of Fe(II)/Fe(III) on Mn(II)/Mn(III) cycling is larger than, vice versa, agreeing with the reaction mechanism proposed for the S(IV) autoxidation catalyzed by mixed metal ions.  相似文献   

11.
Differences in total iron and manganese concentrations between large (d > 23 m) and small (4 < d < 23 m) cloud and fog drops were investigated at four locations in the United States. The study examined coastal stratus and stratocumulus clouds in southern California and northern Oregon, frontal and orographic clouds at Mt. Mitchell, North Carolina, and radiation fogs in California's San Joaquin Valley. The speciation of iron as a function of drop size was also examined in some fog samples from the San Joaquin Valley. Total iron and manganese concentrations were generally higher in large drops than in small drops in clouds sampled at Mt. Mitchell and along the southern California coast. These species were typically enriched in small drops at the Oregon coast and San Joaquin Valley sites. Ratios of dissolved Fe(III) to total dissolved Fe ranged from 0.88 to 0.93 in small fog drops. Non-uniform distributions of iron and manganese across the drop size spectrum can influence rates of metal catalyzed S(IV) autooxidation. Approximately 50% of the sampled clouds were calculated to experience autooxidation rate enhancements greater than 30% due to variations in drop acidity and catalyst concentrations with drop size.  相似文献   

12.
Coastal rainwater hydrogen peroxide: Concentration and deposition   总被引：3，自引：0，他引：3  
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.  相似文献   

13.
Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O2-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–rS(IV) = k · [S(IV)] · [Fe(III))] · e -b·[Ox]  相似文献   

14.
To explore the freezing effect on iron (Fe) solubility in natural environments, especially in Polar regions, event based freshly fallen snow samples were collected at Newark, New Jersey on the US East Coast for two consecutive winter seasons (2014–2015 and 2015–2016). These samples were analyzed for the concentrations of soluble iron (Fesol) using UV-Vis Spectroscopy and filterable iron (Fefil) and total iron (Fetot) using Atomic Absorption Spectroscopy. The average fractional solubility of the Fesol (the portion that passes through a 0.22 μm pore-size filter) with respect to the total Fe in the samples was 23.3?±?12.2%, with the majority of the soluble Fe being present as Fe(III). Approximately 48.5% of the total Fe existed as Fefil (the portion that passes through 0.45 μm pore size filter media). No significant correlation was found between the soluble ionic species and soluble Fe. Six snow events were kept frozen for 10 days, and analyzed in periodic intervals to study the post-freezing modification in Fe solubility. Events 1 and 2 showed increasing trend in the soluble Fe concentrations; however, the events 5, 6, 7, and 8 showed no noticeable increments. The pattern shown in Events 1 and 2 is associated with high fraction of Fefil and one unit pH drop, suggesting that the freeze-induced modification in Fe solubility could be linked with the amount of Fefil and the acidity change in the samples. To further investigate the freeze-induced compaction of particles, samples from three events 6, 7, and 10 were analyzed by SEM-STEM-EDS microscopy, and the results showed that due to freezing, in general, the particles in the ice-melt counterparts tend to compact and cluster and form larger aggregates compared to the particles in snow-melt. These results show, despite the freeze-induced compaction in snow was observed from STEM images, the snow freezing might not have significant effect in increasing Fe solubility from materials in the snow. These results further suggest that freezing process with fresh snow in high-latitude regions may not impose significant modification on Fe solubility in snow.  相似文献   

15.
Formaldehyde levels were determined in various forms of atmospheric precipitation (rain, snow, road and roof runoff, throughfall) and deposition (rime, hoarfrost, dew) collected over twelve months at various locations in two large urban agglomerations and along two highways. HCHO was found in 303 of 500 samples analyzed, with concentrations ranging from 0.05 to 10.7 mg/dm3. The results confirmed the significant effect of vehicular traffic on formaldehyde levels in various forms of wet deposition. Correlations of formaldehyde levels with other parameters commonly monitored in precipitation and/or deposition were also examined. No correlation was found between HCHO levels and rain volume. On the other hand, positive correlations were found for hydrogen peroxide, non-sea-salt sulphate, nitrate, ammonia, and total organic carbon (TOC). In addition, the effect of selected meteorological parameters (temperature, wind speed, wind direction, rainfall) on the concentration of formaldehyde in various forms of precipitation and runoff (road runoff, roof runoff, throughfall) was studied. The only correlation found was that between HCHO concentration and daily rainfall.  相似文献   

16.
不同天气系统下我国云雨水化学特征的研究   总被引：4，自引：0，他引：4  
根据1985－1993年我国10个省市飞机观测的云水化学资料，分析了不同天气系统对我国云、雨水化学特征的影响。平均而言，我国北方地区云水不酸，南方地区云水酸。降水天气系统对云化学组分有一定的影响。北方地区受蒙古低涡影响时，云水中Ca^2 明显增多，表现了沙尘污染的特征；南方地区静止锋降水时，云水酸，离子浓度也高。  相似文献   

17.
Cloudwater samples were collected from November 1992 to March 1995 in Vallombrosa, a mountain site of the Tuscan Apennines (central Italy). Chemical analyses show that all examined inorganic ions contributed significantly to the total ionic content (TIC). The ratio SO42−/NO4− ranged from 0.92 to 3.46 and was >1 for 86% of samples. There is a wide range in the chemical composition of the cloudwater. The total ionic content ranged from 640 to 7476 μeq l−1 and pH from 3.17 to 6.22. The liquid water content (LWC) ranged from 0.06 to 0.94 g m−3 and electrical conductivity from 47 to 485 μΩ−1. The total ionic content decreases while the liquid water content increases. Also analyzed were soluble trace metals (Fe, Pb, Cu, Mn, Cd, Al), synthetic anionic surfactants and the methanesulphonic acid. Chemical analyses evidenced in some cases a high concentration of organic matter. The meteorological analysis for a few samples of individual passages was carried out for the possibility of establishing a correspondence between meteorological events and chemical composition. The sources (marine, crustal and anthropogenic) of chemical components were deduced.  相似文献   

18.
The abundance and optical characteristics of dissolved organic matter (DOM) were determined in 120 rain samples collected in Wilmington, North Carolina, USA, between February 21, 2002 and August 11, 2003. All rainwater samples contained chromophoric dissolved organic matter (CDOM) as well as fluorescent compounds. The absorbance spectra of CDOM in the samples decreased exponentially with wavelength with little or no measurable absorbance past 550 nm. Fluorescence excitation emission spectra (EEMS) of the precipitation revealed the presence of four major peaks indicating both terrestrial and marine influences. There was a strong positive correlation between total integrated fluorescence and the absorbance coefficient at 300 nm in rainwater samples, suggesting that these optical properties are directly interrelated and that the compounds responsible for absorbance may be the same as those responsible for fluorescence. Air-mass back-trajectory analysis indicated elevated CDOM levels in continentally influenced rainwater relative to marine dominated events implying that anthropogenic and/or terrestrial sources are important contributors to CDOM levels in precipitation. The presence of highly absorbing and fluorescing CDOM in rainwater has significant ramifications in atmospheric chemistry and may play a previously unrecognized role in the wavelength dependent spectral attenuation of solar radiation by atmospheric waters.  相似文献   

19.
在一般的冰雹云参数化模式中,水凝结物粒子分布谱的截距取为常数,这样就严重地歪曲了云水和雨水以及雨水和冰雹之间的自然演变。为了改进这个图象,我们取消了这一限制,引入了雨水、冻雨和冰雹浓度连续方程,并重新给定了冻雨,冰雹的谱形式。 根据这些假定,我们导出了每个方程中的发生项表达式,建立了一个新的一维时变参数化模式,这个模式可以较好地描述各种不同类型的水凝物粒子间的相互作用,计算结果表明,云物理图象有了明显地改善。  相似文献   

20.
Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex (Fe(Ⅲ)-Ox). The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(Ⅲ)-Ox under solar irradiation. Although the photolysis mechanisms of Fe(Ⅲ)-Ox have been investigated extensively, information about the oxidation of volatile organic compounds (VOC), specifically the potential for Secondary Organic Aerosol (SOA) formation in the Fe(Ⅲ)-Ox system, is lacking. In this study, a ubiquitous VOC methacrolein (MACR) is chosen as a model VOC, and the oxidation of MACR with Fe(Ⅲ)-Ox is investigated under typical atmospheric water conditions. The effects of oxalate concentration, Fe(Ⅲ) concentration, MACR concentration, and pH on the oxidation of MACR are studied in detail. Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(Ⅲ). The oxidation rate of MACR also accelerates with increasing concentration of oxalate. The effect of Fe(Ⅲ) is found to be more complicated. The oxidation rate of MACR first increases and then decreases with increasing Fe(Ⅲ) concentration. The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration. The production of ferrous and hydrogen peroxide, pH, and aqueous absorbance are monitored throughout the reaction process. The quenching experiments verify that ·OH and (O-·2) are both responsible for the oxidation of MACR. MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight, which contributes to the yield of SOA. These results suggest that Fe(Ⅲ)-Ox plays an important role in atmospheric oxidation.  相似文献   

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