Redox Speciation of Copper in Rainwater:  Temporal Variability and Atmospheric Deposition

Kieber, Robert J.; Skrabal, Stephen A.; Smith, Cliff; Willey, Joan D.

doi:10.1021/es030698r

Cited by 45 publications

(48 citation statements)

References 59 publications

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“…3) similar to what has been observed for other analytes in rainwater at this location (Kieber, 2004;Kieber et al, 2001aKieber et al, , 2001b. Events were excluded from classification if they occurred during more than one time period.…”

Section: Diurnal Variationssupporting

confidence: 61%

Temporal variations in rainwater methanol

et al. 2014

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Abstract. This work reports the first comprehensive analysis of methanol concentrations in rainwater. Methanol concentrations measured in 49 rain events collected between 28 August 2007 and 10 July 2008 in Wilmington, NC, USA, ranged from below the detection limit of 6 nM to 9.3 µM with a volume-weighted average concentration of 1 ± 0.2 µM. Methanol concentrations in rainwater were up to ∼ 200 times greater than concentrations reported previously in marine waters, indicating wet deposition as a potentially significant source of methanol to marine waters. Assuming that these methanol concentrations are an appropriate proxy for global methanol rainwater concentrations, the global methanol wet deposition sink is estimated as 20 Tg yr −1 , which implies that previous methanol budgets underestimate removal by precipitation. Methanol concentrations in rainwater did not correlate significantly with H + , NO − 3 , and NSS, which suggests that the dominant source of the alcohol to rainwater is not anthropogenic. However, methanol concentrations were strongly correlated with acetaldehyde, which has a primarily biogenic input. The methanol volume-weighted concentration during the summer (2.7 ± 0.9 µM) was ∼ 3 times that of the winter (0.9 ± 0.2 µM), further promoting biogenic emissions as the primary cause of temporal variations of methanol concentrations. Methanol concentrations peaked in rainwater collected during the time period 12 p.m.-6 p.m. Peaking during this period of optimal sunlight implies a possible relationship with photochemical methanol production, but there are also increases in biogenic activity during this time period. Rain events with terrestrial origin had greater concentrations than those of marine origin, demonstrating the significance of the continental source of methanol in rainwater.

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Section: Diurnal Variationssupporting

confidence: 61%

Temporal variations in rainwater methanol

et al. 2014

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“…For example, the photolysis of organic Cu-complexes and interactions with superoxide ion radical O 2 − may be anticipated to increase the Cu bioavailability and hence Cu toxicity to phytoplankton [66]. The reduction of the Cu(II) to Cu(I) in oxic aquatic systems occurred to a large extend via UV-induced chemical reactions of Cu(II) complexed to strong ligands [51,68,69]. The photochemical properties of the organic exudate secreted by a toxic strain of cyanobacterium Microcystis aeruginosa were studied by measuring ROS generation and redox transformations of Fe in the presence of the organic exudate under acidic (pH 4) and alkaline (pH 8) conditions.…”

Section: Light-induced Enhancement Of the Oxidative Activity In Ambiementioning

confidence: 99%

Combined Effects of Trace Metals and Light on Photosynthetic Microorganisms in Aquatic Environment

Cheloni

2018

Environments

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Abstract:In the present review, we critically examine the state-of-the-art of the research on combined effects of trace metals and light on photosynthetic microorganisms in aquatic environment. Light of different intensity and spectral composition affects the interactions between trace metals and photosynthetic microorganisms directly, by affecting vital cellular functions and metal toxicokinetics and toxicodynamics, and indirectly, by changing ambient medium characteristics. Light radiation and in particular, the ultraviolet radiation component (UVR) alters the structure and reactivity of dissolved organic matter in natural water, which in most of the cases decreases its metal binding capacity and enhances metal bioavailability. The increase of cellular metal concentrations is generally associated with increasing light intensity, however further studies are necessary to better understand the underlying mechanisms. Studies on the combined exposures of photosynthetic microorganisms to metals and UVR reveal antagonistic, additive or synergistic interactions depending on light intensity, spectral composition or light pre-exposure history. Among the light spectrum components, most of the research was performed with UVR, while the knowledge on the role of high-intensity visible light and environmentally relevant solar light radiation is still limited. The extent of combined effects also depends on the exposure sequence and duration, as well as the species-specific sensitivity of the tested microorganisms and the activation of stress defense responses.

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“…Unfortunately, the information on the oxidation state of copper (Cu(I)/Cu(II)) in atmospheric waters is rather scarce. Although copper in its reduced form is not thermodynamically stable in the atmospheric liquid phase because of the presence of different oxidants, there are evidences that dissolved copper can exist as Cu(I) [4,66]. Redox speciation of copper in rainwater samples was studied by Kieber et al [66].…”

Section: Redox Speciationmentioning

confidence: 99%

“…Although copper in its reduced form is not thermodynamically stable in the atmospheric liquid phase because of the presence of different oxidants, there are evidences that dissolved copper can exist as Cu(I) [4,66]. Redox speciation of copper in rainwater samples was studied by Kieber et al [66]. They determined relatively high concentrations of dissolved Cu(I) (on average about 25% of the total Cu) with an average ratio, Cu(II)/Cu(I), of about 2.3.…”

Section: Redox Speciationmentioning

confidence: 99%

“…Even if the O 2 /H 2 O couple controls the redox conditions, substantial amounts of reduced metals can exist because of photoreduction of metals complexed with different organic ligands [67]. It was found that concentrations of strong Cu-complexing ligands were consistently lower than dissolved copper concentrations, indicating that some proportion of dissolved copper is likely to be complexed [66]. A portion of these ligands may be Cu(I)-complexing ligands.…”

Section: Redox Speciationmentioning

confidence: 99%

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Metals in Aerosols

Grgić

2008

Environmental Chemistry of Aerosols

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Atmospheric aerosols have important role in the biogeochemistry and transportation of metals in the atmosphere. On a mass basis, so-called trace metals represent a relatively small proportion of the atmospheric aerosol (generally less than 1%). Among them are transition metals (TM) (e.g. vanadium, chromium, manganese, iron, cobalt, nickel, copper, etc.), which have several oxidation states, and thus can participate in many important atmospheric redox reactions. Field measurements provide strong evidence that TM are common components in aerosol particles as well as in atmospheric liquid water [1][2][3][4][5].The concentrations of trace metals in atmospheric aerosols are a function of their sources. Natural emissions of trace metals result from different processes acting on crustal minerals (e.g. erosion, surface winds and volcanic eruptions), as well as from natural burning and from the oceans. On a global scale, resuspended surface dusts make a large contribution to the total natural emission of trace metals to the atmosphere (e.g. more than 50% of Cr, Mn and V, and more than 20% of Cu, Mo, Ni, Pb, Sb and Zn), whereas volcanism presumably generates about 20% of Cd, Hg, As, Cr, Cu, Ni, Pb and Sb [6]. Sea-salt aerosols generated by spray and wave action may contribute to about 10% of total trace metals emissions. Biomass combustion can contribute to emissions of Cu, Pb and Zn [7]. The predominant anthropogenic sources are due to high-temperature processes, biomass burning, fossil-fuel combustion, industrial activity, incineration, etc. Anthropogenic high-temperature processes result in the release of volatile metals as vapours forming particles by condensation or gas-to-particle reactions. Combustion of fossil fuels is the most important anthropogenic source of atmospheric Be, Co, Hg, Mo, Ni, Sb, Se, Sn and V; it also contributes to emissions of As, Cr, Cu, Mn and Zn [6]. Industrial metallurgical processes produce the largest emissions of As, Cd, Cu, Ni and Zn. Exhaust emissions from gasoline-and diesel-fuelled vehicles contribute to atmospheric Pb, Fe, Cu, Zn, Ni and Cd, while tyre-rubber abrasion to Zn [8]. In the last decade, the use of new automobile catalytic converters also contributes to the emissions of Pt, Pd and Rh [9, 10]. The composition of aerosols depends on the occurrence of metals in combustion processes and their volatility as well as on their amount produced by decomposition of continental and oceanic surfaces. Thus, the size distributions of different metals depend on the balance of different sources.Environmental Chemistry of Aerosols Edited by Ian Colbeck

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Redox Speciation of Copper in Rainwater: Temporal Variability and Atmospheric Deposition

Cited by 45 publications

References 59 publications

Temporal variations in rainwater methanol

Temporal variations in rainwater methanol

Combined Effects of Trace Metals and Light on Photosynthetic Microorganisms in Aquatic Environment

Metals in Aerosols

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