Barbara Sulzberger

Environmental effects of ozone depletion and its interactions with climate change: progress report, 2011

The Environmental Effects Assessment Panel (EEAP) is one of three Panels that regularly informs the Parties (countries) to the Montreal Protocol on the effects of ozone depletion and the consequences of climate change interactions with respect to human health, animals, plants, biogeochemistry, air quality, and materials. The Panels provide a detailed assessment report every four years. The most recent 2014 Quadrennial Assessment by the EEAP was published as a special issue of seven papers in 2015 (Photochem. Photobiol. Sci., 2015, 14, 1-184). The next Quadrennial Assessment will be published in 2018/2019. In the interim, the EEAP generally produces an annual update or progress report of the relevant scientific findings. The present progress report for 2015 assesses some of the highlights and new insights with regard to the interactive nature of the effects of UV radiation, atmospheric processes, and climate change.

Interactive effects of solar UV radiation and climate change on biogeochemical cycling

This report assesses research on the interactions of UV radiation (280-400 nm) and global climate change with global biogeochemical cycles at the Earths surface. The effects of UV-B (280-315 nm), which are dependent on the stratospheric ozone layer, on biogeochemical cycles are often linked to concurrent exposure to UV-A radiation (315-400 nm), which is influenced by global climate change. These interactions involving UV radiation (the combination of UV-B and UV-A) are central to the prediction and evaluation of future Earth environmental conditions. There is increasing evidence that elevated UV-B radiation has significant effects on the terrestrial biosphere with implications for the cycling of carbon, nitrogen and other elements. The cycling of carbon and inorganic nutrients such as nitrogen can be affected by UV-B-mediated changes in communities of soil organisms, probably due to the effects of UV-B radiation on plant root exudation and/or the chemistry of dead plant material falling to the soil. In arid environments direct photodegradation can play a major role in the decay of plant litter, and UV-B radiation is responsible for a significant part of this photodegradation. UV-B radiation strongly influences aquatic carbon, nitrogen, sulfur and metals cycling that affect a wide range of life processes. UV-B radiation changes the biological availability of dissolved organic matter to microorganisms, and accelerates its transformation into dissolved inorganic carbon and nitrogen, including carbon dioxide and ammonium. The coloured part of dissolved organic matter (CDOM) controls the penetration of UV radiation into water bodies, but CDOM is also photodegraded by solar UV radiation. Changes in CDOM influence the penetration of UV radiation into water bodies with major consequences for aquatic biogeochemical processes. Changes in aquatic primary productivity and decomposition due to climate-related changes in circulation and nutrient supply occur concurrently with exposure to increased UV-B radiation, and have synergistic effects on the penetration of light into aquatic ecosystems. Future changes in climate will enhance stratification of lakes and the ocean, which will intensify photodegradation of CDOM by UV radiation. The resultant increase in the transparency of water bodies may increase UV-B effects on aquatic biogeochemistry in the surface layer. Changing solar UV radiation and climate also interact to influence exchanges of trace gases, such as halocarbons (e.g., methyl bromide) which influence ozone depletion, and sulfur gases (e.g., dimethylsulfide) that oxidize to produce sulfate aerosols that cool the marine atmosphere. UV radiation affects the biological availability of iron, copper and other trace metals in aquatic environments thus potentially affecting metal toxicity and the growth of phytoplankton and other microorganisms that are involved in carbon and nitrogen cycling. Future changes in ecosystem distribution due to alterations in the physical and chemical climate interact with ozone-modulated changes in UV-B radiation. These interactions between the effects of climate change and UV-B radiation on biogeochemical cycles in terrestrial and aquatic systems may partially offset the beneficial effects of an ozone recovery.

Chemical characterization of dissolved organic matter (DOM): A prerequisite for understanding UV-induced changes of DOM absorption properties and bioavailability

Abstract.UV-induced transformations of colored dissolved organic matter (CDOM, which is part of dissolved organic matter, DOM) affect CDOM absorption properties resulting in the loss of color (referred to as photobleaching). CDOM photobleaching increases the penetration depths of the damaging UV-B radiation into water bodies and strongly depends on the wavelength of solar radiation and on the pH of aquatic systems. UV-induced transformations also affect DOM availability to bacterioplankton, often enhancing the bioavailability of terrigenous DOM and in turn microbial respiration. The combination of UV-induced enhancement of DOM bioavailability and increased export of terrigeneous DOM into estuaries and coastal waters due to climate-related changes in continental hydrology could result in a UV-mediated positive feedback of CO2 accumulation in the atmosphere.The extent and type of CDOM photobleaching and of UV-induced changes in DOM bioavailability depend on (C)DOM chemical composition, which in turn undergoes drastic changes upon UV-induced transformations. Therefore, the chemical characterization of (C)DOM is key for rationalizing UV-induced transformations. In the second section (after the “Introduction”), we review important methods for the elucidation of the chemical composition of (C)DOM. However, this article is not intended to be comprehensive regarding (C)DOM chemical characterization. An important purpose is to provide photochemical bases for the understanding of UV-induced changes of (C)DOM absorption properties and bioavailability (mainly discussed in the sections “Pathways of DOM phototransformations” and ”UV-induced changes of the absorption properties of CDOM”).

Light‐induced redox cycling of iron in circumneutral lakes

The light-induced redox cycling of Fe II /Fe III was studied both in laboratory experiments and in the field in two circumneutral Swiss lakes: Greifensee, a eutrophic, natural water body, and Melchsee, an oligotrophic, artificial mountain lake. To determine Fe II

Reactivity of various types of iron(III) (hydr)oxides towards light-induced dissolution

Laboratory experiments were conducted on the light-induced dissolution of three well defined Fe(III) (hydr)oxide phases (γ-FeOOH, α-FeOOH, and α-Fe2O3) with oxalate as reductant/ligand. Upon irradiation of an aerated γ-FeOOH suspension of pH 3, photooxidation of oxalate and photochemical formation of dissolved Fe(II) occurred according to a 1:1 stoichiometry. This was not observed with aerated α-FeOOH and α-Fe2O3 suspensions of pH 3, where photooxidation of oxalate was not accompanied by formation of appreciable concentrations of dissolved Fe(II). We hypothesize that in aerated α-FeOOH and α-Fe2O3 suspensions, oxidation of surface Fe(II) outcompetes its detachment from the crystal lattice. Also in deaerated suspensions, α-FeOOH and α-Fe2O3 behaved differently from γ-FeOOH with regard to light-induced dissolution. We interpret our results by assuming that light-induced dissolution of α-FeOOH and α-Fe2O3 in deaerated suspensions of pH 3 occurred mainly through Fe(II)-catalyzed thermal dissolution of the solid phases, where Fe(II) was initially formed by photoreductive dissolution and then predominantly via photolysis of dissolved Fe(III) oxalate complexes. With γ-FeOOH, on the other hand, dissolved Fe(II) formation occurred probably mainly through photochemical reductive dissolution under photooxidation of adsorbed oxalate. From our results we conclude that the efficiency of detachment of reduced surface iron is a key parameter of the overall kinetics of photoreductive dissolution of Fe(III) (hydr)oxides in aquatic systems, and that thermodynamically stable phases such as α-FeOOH and α-Fe2O3 are not readily dissolved in the presence of O2, even at low pH-values and in the presence of light and reductants like oxalate. We propose that redox cycling of iron at the surface of crystalline Fe(III) (hydr)oxide phases, i.e. reduction and oxidation of surface iron without transfer into solution, may be an important pathway of transformation of thermodynamically stable atmospheric Fe(III) (hydr)oxides into less stable and thus more soluble phases.

A comparison of methods for detection of phosphate limitation in microalgae

Abstract: This paper presents the results of studies into the use of the emerging techniques of nutrient induced fluorescence transients (NIFTs) and Fourier Transform InfraRed (FTIR) spectroscopy to determine the nutrient status of microalgae. Four species of microalgae were grown under conditions where growth rate was P-limited or P-replete, and NIFT responses and FTIR spectra in response to the re-supply of P (as

Surface Complexation of Sulfate by Hematite Surfaces: FTIR and STM Observations

{\rm PO}^{3-}_4

Characterizing the properties of dissolved organic matter isolated by XAD and C-18 solid phase extraction and ultrafiltration

) measured. These responses were compared to more conventional measures of algal nutrient status such as P-uptake rates, P quotas and transient effects of

Iron oxidation kinetics in an acidic alpine lake

{\rm PO}^{3-}_4

Self-sensitization of photo-oxygen evolution in Ag+ zeolites: computer-controlled experiments

on oxygen exchange. The NIFT technique and FTIR spectroscopy gave results that were consistent with those obtained by the other techniques. Furthermore, we were able to demonstrate NIFT responses in phytoplankton samples taken from Lake Lucerne (total ambient P