Antonio Tognazzi

Chemical and optical phototransformation of dissolved organic matter

Dissolved organic matter represents the main reservoir of organic carbon in most aquatic ecosystems. In the present study, we determined the optical changes and the quantum yields of transient species formation for chromophoric dissolved organic matter (CDOM) samples undergoing photodegradation. The results show that the triplet states (3)CDOM* are potentially key players in CDOM photodegradation and that such transformations are strongly influenced by small differences in CDOM sources and sinks. In contrast, ·OH radicals are very unlikely to play a key role in phototransformation. These results represent an important first step in combining optical and transient species analyses to understand photodegradation processes of dissolved organic matter.

Assessing the optical changes in dissolved organic matter in humic lakes by spectral slope distributions

The impact of photodegradation and mixing processes on the optical properties of dissolved organic matter (DOM) was examined using a distribution of absorption spectral slopes and fluorescence measurements in two Argentine lakes. By examining the variability of the absorption spectral slopes throughout the ultraviolet and visible wavelengths, it was possible to determine which wavelength intervals were most sensitive to dominant loss processes. For DOM photodegradation, results show that increases in the absorption spectral slope between 265 and 305 nm were highly sensitive to increased exposure to solar ultraviolet radiation. A slightly larger wavelength range (265-340 nm) was found to be influenced when both mixing and photodegradation processes were considered, in terms DOM residence time, DOM absorption and UV diffuse attenuation coefficients. This same interval of spectral slopes (265-340 nm) was found to highly correlate with changes in fluorescence emission/excitation in wavelengths that are typically associated with terrestrial humic-like DOM. The identification of specific wavelength intervals, rather than the use of standard wavelength intervals or ratios, improved our ability to identify the dominant dissolved organic matter (humic-like) and major loss mechanisms (photodegradation) in these lakes.

Chemical characterisation of a new estuarine pollutant (2,4-Dichloro-6-Nitrophenol) and assessment of the acute toxicity of its quinoid form for Artemia salina

It is known that the compound 2,4-dichloro-6-nitrophenol (2,4DC6NP) is formed upon nitration of 2,4-dichlorophenol, which in turn is a transformation intermediate of the herbicide dichlorprop. However, the chemical and spectroscopic characteristics of 2,4DC6NP, as well as its toxicity, are poorly known. This work shows that 2,4DC6NP behaves as a diprotic acid in aqueous solutions, with pKa values of 3.0 ± 0.9 and 4.9 ± 0.5. At pH < 3, 2,4DC6NP would undergo protonation. The absorption spectra suggest that anionic 2,4DC6NP, which prevails at pH > 5 would have an ortho-quinoid structure that is responsible for the absorption peak centred at 428 nm. Considering that 2,4DC6NP has been detected in the brackish lagoons of the Rhône delta (southern France), where its levels are comparable to those of the parent herbicide, it is necessary to examine the possible effects of 2,4DC6NP on the species living in that environment. For this reason, the acute toxicity of the anionic form of 2,4DC6NP was assessed for the brine shrimp Artemia salina, a zooplankton species that lives both in brackish and in saline aquatic environments. The toxicity test yielded a LC20 value of 8 ± 2 mg L−1 and a LC50 value of 18.7 ± 0.8 mg L−1. Such values are safely higher than the maximum detected concentration of 2,4DC6NP in the Rhône delta lagoons. Further studies should be concentrated on the long-term effects of 2,4DC6NP, and in particular on its potential genotoxicity.

Competition for spectral irradiance between epilimnetic optically active dissolved and suspended matter and phytoplankton in the metalimnion. Consequences for limnology and chemistry

In deep lakes, water column stratification isolates the surface water from the deeper bottom layers, creating a three dimensional differentiation of the chemical, physical, biological and optical characteristics of the waters. Chromophoric dissolved organic matter (CDOM) and total suspended solids (TSS) play an important role in the attenuation of ultraviolet and photosynthetically active radiation. In the present analysis of spectral irradiance, we show that the wavelength composition of the metalimnetic visible irradiance was influenced by epilimnetic spatial distribution of CDOM. We found a low occurrence of blue-green photons in the metalimnion where epilimnetic concentrations of CDOM are high. In this field study, the spatial variation of the spectral irradiance in the metalimnion correlates with the observed metalimnetic concentrations of chlorophyll a as well as chlorophyll a : chlorophyll b/c ratios. Dissolved oxygen, pH, and nutrients trends suggest that chlorophyll a concentrations were representative of the phytoplankton biomass and primary production. Thus, metalimnetic changes of spectral irradiance may have a direct impact on primary production and an indirect effect on the spatial trends of pH, dissolved oxygen, and inorganic nutrients in the metalimnion.

Spatial dynamics of chromophoric dissolved organic matter in nearshore waters of Lake Victoria.

The underwater light conditions in the African Great Lakes depend on the complex dynamics of ecological and hydrological forces, and are strongly influenced by local environmental conditions and global biogeochemical cycles. Changes in the optical conditions in these lakes have direct impacts on ecosystem productivity, carbon dynamics and nutrient availability. A central role in the underwater light climate is played by dissolved organic matter which is present in all aquatic ecosystems. The chromophoric fraction of these compounds can mediate ecosystem change through its influence on the attenuation of ultraviolet and PAR radiation, microbial carbon cycling and radiative transfer. In the African Great Lakes, little information is available regarding the dynamics of dissolved organic matter and those sources and sinks which control its presence in the water column. We present an extensive spatial analysis of three major bays on the Kenyan and Ugandan shores of Lake Victoria. We use these data to examine the dynamics of chromophoric dissolved organic matter in different bays and we develop a model to estimate its flow from these bays to the Lake, considering both conservative mixing and photodegradation processes. While some bays release chromophoric dissolved organic matter practically unmodified into the Lake, increased residence time and exposure to solar ultraviolet radiation create conditions where chromophores are lost before entering the open lake.

The optical qualities of shallow wetland lined bays in Lake Victoria

In tropical lakes, the characteristics and dimension of the coastal wetlands can have a strong influence on the quality of the inshore waters. The interaction between littoral wetlands and the open water environment is complex and requires an understanding of the material and energy exchanges between these compartments. In the present analysis, we examine the impact of wetlands on the optical properties (underwater light environment) of two adjacent bays on the Ugandan side of Lake Victoria. We use both irradiance profiles within the water column as well as measurements of the dissolved and particulate fractions of the water column. By introducing a new term to identify that part of the solar spectrum most affected by wetland released dissolved organic matter, it is possible to determine the area of each bay that is influenced by the wetland. Depending on the period of analysis, wetland released chromophoric dissolved organic matter can play a dominating role in the attenuation of UV and visible radiation in the underwater environment.

The Role of TOF-SIMS in the Characterisation of Inorganic and Organic Components in Paint Samples

The conservation of cultural heritage requires a profound knowledge of the materials and technologies used for its production. In particular, the analysis of the surface of an object of art is of primary importance, considering that it constitutes a basic tool for the understanding of the history of the object and of its ageing processes. In fact, the surface is not only the visible part of the artwork, but it also represents the interface between the object and the environment, where the interactions with physical, biological and chemical agents occur. In order to provide chemical information regarding the surface of the artwork under study and to understand its interactions with the environment, the employment of ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) appears of fundamental importance. ToF-SIMS provides elemental data and a certain degree of molecular information, while also allowing depth profiling, mapping or imaging to be carried out (Spoto 2000). As a result, this procedure was successfully applied for the characterisation of inorganic and organic components of a wide range of cultural heritage objects (Keune and Boon 2004; Adriaens and Dowsett 2006; Mazel et al. 2006).