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.

Basin-scale control on the phytoplankton biomass in Lake Victoria, Africa.

The relative bio-optical variability within Lake Victoria was analyzed through the spatio-temporal decomposition of a 1997-2004 dataset of remotely-sensed reflectance ratios in the visible spectral range. Results show a regular seasonal pattern with a phase shift (around 2 months) between the south and north parts of the lake. Interannual trends suggested a teleconnection between the lake dynamics and El-Niño phenomena. Both seasonal and interannual patterns were associated to conditions of light limitation for phytoplankton growth and basin-scale hydrodynamics on phytoplankton access to light. Phytoplankton blooms developed during the periods of lake surface warming and water column stability. The temporal shift apparent in the bio-optical seasonal cycles was related to the differential cooling of the lake surface by southeastern monsoon winds. North-south differences in the exposure to trade winds are supported by the orography of the Eastern Great Rift Valley. The result is that surface layer warming begins in the northern part of the lake while the formation of cool and dense water continues in the southern part. The resulting buoyancy field is sufficient to induce a lake-wide convective circulation and the tilting of the isotherms along the north-south axis. Once surface warming spreads over the whole lake, the phytoplankton bloom dynamics are subjected to the internal seiche derived from the relaxation of thermocline tilting. In 1997-98, El-Niño phenomenon weakened the monsoon wind flow which led to an increase in water column stability and a higher phytoplankton optical signal throughout the lake. This suggests that phytoplankton response to expected climate scenarios will be opposite to that proposed for nutrient-limited great lakes. The present analysis of remotely-sensed bio-optical properties in combination with environmental data provides a novel basin-scale framework for research and management strategies in Lake Victoria.

Effective upwelling irradiance depths in turbid waters: a spectral analysis of origins and fate.

The spectral distribution of upwelling and downwelling irradiance were used to estimate the effective upwelling irradiance depth as well as examine the angular distribution of the downwelling radiance. The effective upwelling depth was seen to undergo spectral "shifts" in wavelength maxima in relation to elevated particulate concentrations. Wavelengths of the UVA minimum and mid visible maximum depths were found to be shifted to higher wavelengths (red shifted) at high particulate concentrations, while expected minimums at chlorophyll and phycocyanin absorption peaks and in the NIR were shifted to lower wavelengths (blue shifted). By comparing upwelling and downwelling irradiance profiles, the wavelength limits of the asymptotic angular radiance distribution were found to correspond to the visible spectral domain (390-740 nm).

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.

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.

Spatial and seasonal changes in optical properties of autochthonous and allochthonous chromophoric dissolved organic matter in a stratified mountain lake.

In this study, we present results on seasonal and spatial changes in CDOM absorption and fluorescence (fCDOM) in a deep mountain lake (Salto Lake, Italy). A novel approach was used to describe the shape of CDOM absorption between 250-700 nm (distribution of the spectral slope, S(lambda)) and a new fluorescence ratio is used to distinguish between humic and amino acid-like components. Solar ultraviolet irradiance, dissolved organic carbon (DOC), DOM fluorescence and absorption measurements were analysed and compared to other physicochemical parameters. We show that in the UV-exposed mixed layer: (i) fluorescence by autochthonous amino acid-like CDOM, (ii) values of S(lambda) across UV-C and UV-B wavebands increased during the summer months, whereas (i) average molar absorption coefficient and (ii) fluorescence by allochthonous humic CDOM decreased. In the unexposed deep layer of the water column (and in the entire water column in winter), humic-like CDOM presented high values of molar absorption coefficients and low values of S(lambda). UV attenuation coefficients correlated with both chlorophyll a concentrations and CDOM absorption. In agreement with changes in CDOM, minimal values in UV attenuation were found in summer. The S(lambda) curve was used as a signature of the mixture between photobleached and algal-derived CDOM with respect to the unexposed chromophoric dissolved compounds in this thermal stratified lake. Furthermore, S(lambda) curves were useful to distinguish between low and high molecular weight CDOM.

Variability in photobleaching yields and their related impacts on optical conditions in subtropical lakes.

Changes in the concentration and spectral absorption of chromophoric dissolved organic matter (CDOM) may strongly condition the optical properties of tropical and subtropical water bodies. We examined the spatial distribution of CDOM-related absorption, spectral slope and vertical attenuation of solar radiation in two shallow lakes in the Esteros del Iberá wetland system. In situ measurements were made to examine spatial variations in photobleaching yields in natural lake conditions. The results showed that "fresh" allochthonous CDOM is more susceptible to phototransformations than either "aged" allochthonous organic matter or autochthonous sources, if the distances from sources are considered as proxies for residence time. Based on measured changes in absorption spectral slope in relation to solar ultraviolet irradiance, a model was developed which used CDOM as a non-conservative tracer of water masses. Spatial changes in CDOM absorption within the lake were then used to compare photo related transformations to those associated with conservative mixing.

Satellite-based indices in the analysis of land cover for municipalities in the province of Siena, Italy.

Territorial indicators based on the satellite measured reflected or emitted energy can provide valuable information on the spatial evolution of a territory. Information regarding land use, biomass coverage and radiant temperature were obtained from remotely obtained measurements for each municipality in the Province of Siena. Remotely sensed data were combined into different indices to compare characteristics of land cover between territories and create an information base for continued study. A classification was performed on a municipal level and land use classes were grouped together and a general index of use pressure was created. A vegetation index was used to compare biomass densities. A radiant temperature index was calculated using measure thermal infrared emissions. The results of these analyses allowed researchers to examine the intra and inter-municipal spatial heterogeneity within the Province. A comparison between the results of each index was made and the problems related to the use of such indices were examined.

The bio-optical properties of CDOM as descriptor of lake stratification.

Multivariate statistical techniques are used to demonstrate the fundamental role of CDOM optical properties in the description of water masses during the summer stratification of a deep lake. PC1 was linked with dissolved species and PC2 with suspended particles. In the first principal component that the role of CDOM bio-optical properties give a better description of the stratification of the Salto Lake with respect to temperature. The proposed multivariate approach can be used for the analysis of different stratified aquatic ecosystems in relation to interaction between bio-optical properties and stratification of the water body.

The role of wetlands in the chromophoric dissolved organic matter release and its relation to aquatic ecosystems optical properties. A case of study: Katonga and Bunjako Bays (Victoria Lake; Uganda).

Chromophoric Dissolved Organic Matter (CDOM) is an important component in freshwater and marine ecosystems and plays direct and indirect role in biogeochemical cycles. CDOM originates from the degradation process of organic materials, usually macrophytes and planktons. The present work examines the importance of wetland derived CDOM on the optical and bio-optical properties of two bays of Lake Victoria (Uganda, Africa). This was achieved by determining the attenuation and extinction coefficients of filtered and unfiltered water samples from two equatorial bays on the Ugandan coastline of Lake Victoria. Katonga Bay is a wetland lined bay that receives water from the Katonga river, while Bunjako Bay is an outer bay between Katonga Bay and Lake Victoria. The results showed that attenuation was highest in Katonga Bay and the role of CDOM is most dominant near the river inlet. The quantity and quality of CDOM is extremely different in the two bays: in Katonga Bay it is possible to hypothesize a terrestrial origin of CDOM (transported by the wetland river). On the contrary, in Bunjako Bay, spectral measurements of absorption indicate a modified CDOM and/or alternative CDOM source. The terrestrial CDOM in Katonga Bay is more capable of absorbing harmful UV radiation than the CDOM present in the Bunjako Bay. The resulting optical environment in the former bay presented a water column with a very limited penetration of harmful UV radiation, while a higher penetration was observed in the Bunjako Bay.

Spatial and temporal variations of the inherent and apparent optical properties in a shallow coastal lake.

Apparent and inherent optical properties in the coastal lagoon of Fogliano were measured in three seasonal surveys in 2002. Irradiance data from in situ measurements of ultraviolet and visible wavebands permitted to estimate the related attenuation coefficients. Laboratory extinction measurements on filtered (0.22 microm) and unfiltered water samples were also performed. The integrated approach between in situ and laboratory measurements allowed the determination of the role of the suspended and dissolved matter in the attenuation and extinction of ultraviolet and visible radiation within the water column. As noted, the impact of the suspended and dissolved matter on the lake optical quality was influenced by wind resuspension of particulate matter: the relative role of dissolved matter in the absorption of UV and visible radiation was prevailing at low wind velocity conditions (less than 2.2 m s(-1)), while at high wind velocities (3.9 m s(-1)), particulate matter resuspension strongly influenced the attenuation and the extinction measurements. The extinction in the analyzed wavelengths of filtered and unfiltered water samples and the in situ irradiance measurements allowed us to define new optical parameters and important correlations with limnological and classical optical measurements. By sampling at high spatial resolution (18 stations in 4 km2), it was possible to evidence a spatial gradient of the optical and limnological properties, these distributions showed a consistent pattern in all three surveys, and were important for the characterization of the chromophoric dissolved organic matter that was estimated with the spectral slope of the extinction curve spectra. A relatively higher spectral slope was found in the southern basin with respect to the northern, where the maximum values of the attenuation coefficients and limnological parameters were found. These results suggest different sources of dissolved organic matter and/or a different level of photobleaching.

Estimate of the effects of ultraviolet radiation on the mortality of Artemia franciscana in naupliar and adult stages.

The impact of different doses of artificial ultraviolet (UV) radiation on the growth stages of a marine zooplankton was investigated using laboratory microcosms. Mortality percentages of naupliar and adult samples of Artemia franciscana were recorded in relation to different UV doses (single exposure: 75, 150, 300, 600, 1,200, 2,400, 3,900, 7,800 J m(-2)) at specific observation times after exposure (24, 48, 72, 96 and 120 h). The relationship between mortality percentage and UV dose showed significant differences in relation to the zooplankton growth stage. The elevated susceptibility of the naupliar samples to UV radiation is described through a mortality model based on a logistic equation. The data analysis shows that the slope of mortality versus dose remains the same for the two growth stages while the lethal dose in the naupliar stage was 3.3 smaller than that determined for the adult stage. The slope of the UV mortality rate versus post-incubation time was found to be significantly different (P<0.05) at low UV doses for the two life stages examined, i.e. naupliar and adult. The lower value of LD(50) in naupliar stages compared to that for adults confirms that in the early growth stage this marine zooplankton is more susceptible to UV radiation.

Morphological anomalies in pollen tubes of Actinidia deliciosa (kiwi) exposed to 50 Hz magnetic field.

The role of the pollen grain, with respect to the reproductive process of higher plants, is to deliver the spermatic cells to the embryo sac for egg fertilisation. Delivery occurs through the pollen tube, a self produced organ that is generated when the pollen grain reaches the stigma surface. The effect of magnetic fields on pollen tube growth was reported in a recent publication by Germanà et al. Pollen tube growth is an interesting candidate for the detailed study of the effects of electromagnetic fields on cytoplasmic structures and organelles. In this research Actinidia deliciosa (kiwifruit) pollen grains were germinated in the presence of an alternating magnetic field (50 Hz). Our results, although of preliminary nature, show that pollen tube growth is affected by magnetic fields. The analysis of the observed anomalies in the pollen tube appear to be the result of changes in the ionic charges within the pollen tube cytoplasm.

Penetration of solar radiation into the waters of Messina Strait (Italy).

The optical properties of the waters of five different stations, three located in the Messina Strait and two near the Strait (open sea), were analysed. Direct spectral measurements of the downward solar irradiance (290 - 800 nm) at different depths (0.5 m, 7 m, 10 m, 13 m, 20 m) were made using a cosine sensor connected to a spectroradiometer. Water samples were collected in the surface layer and their absorption spectra were analysed. The natural fluorescence profiles, along the water column, were determined using a fluorometer (SBE 911plus - Sea Teach). The spectral attenuation coefficient (K(lambda)), the variation of K(lambda) in different wavelength ranges (deltaK(deltalambda)), the wavelength corresponding to minimum value of K(lambda), the spectral depths of penetration of both 1% and 10% of the sub-surface irradiance values (P(lambda)), the depths of 1% of penetration of UVB, UVA and PAR, the depth ranges of the maxim concentration of Chl a and superficial CDOM were measured at each station. The maximum solar UVB penetration was about 65% of the photic zone and the maximum UVA penetration was nearly 100% (data of the Ionic sea station). Thus, a large part of the photic zone was exposed to UV radiation sufficient to cause a possible reduction in the photosynthetic activity of phytoplankton. The spectral penetration of solar radiation, especially UVB radiation, was significantly different in the three stations of the Strait with respect to the two stations studied in the open sea. This shows that variations in the spectral attenuation along the water column can be used as an indicator of properties of the water body.

Analysis of extinction in ultraviolet and visible spectra of water bodies of the Paraguay and Brazil wetlands.

The extinction spectra in ultraviolet and visible radiation were analyzed using filtered and unfiltered water samples obtained in 11 open water bodies in the Neembucù (Paraguay) and Pantanal (Brazil) wetlands. The role of dissolved and suspended matter in the total extinction was analyzed between 260 nm and 700 nm. The chromophoric dissolved organic matter (CDOM) was the major component in extinction of considered ultraviolet radiation (260-400 nm). The differences in CDOM concentrations explained the main pattern of extinction of the ultraviolet radiation in the samples. Nevertheless, differences between the studied water bodies were found also to depend on the rate of photodegradation and photobleaching. The methodology developed in the present study was to distinguish "humic optic waters" according to quantity and quality of dissolved and suspended matter present. In the "humic optic water", the penetration of 10% of incident UV radiation and the photoactive layer are estimated. The influence of particulate matter increases in the total extinction of the wavelengths higher than 400 nm. The integral of the extinction curve of suspended matter in the visible wavelengths (400-700 nm) was found to relate with the total suspended solids and chlorophyll concentrations.

The spatial distribution of optical properties in the ultraviolet and visible in an aquatic ecosystem.

In aquatic ecosystems, the UV and visible radiation environment is strongly influenced by variation in the chemical and physical parameters of the ecosystems. In shallow lakes, highly heterogeneous water characteristics produce a wide variety of optical environments. Such ecosystems require analysis approaches that consider a potential variability. In this study, 77 stations were used to characterize the optical properties of a shallow lake (open water surface 54 km(2)). The vertical attenuation of solar radiation at 305, 313, 320 and 340 nm and at photosynthetically active radiation was measured during the seasonal cycle. Dissolved organic matter (DOM), turbidity, fluorescence, pH, temperature, conductance and dissolved oxygen were simultaneously measured. The spatial variation of the extinction spectra of the dissolved fraction at each sampling station was also measured and analyzed between 270 and 400 nm. The spatial heterogeneity of the lake was examined by determining the distributions of the attenuation coefficients and biooptical parameters at high spatial resolution and describing the distributions in a series of maps. The methodology permitted a quantitative description of the interaction between solar radiation and aquatic ecosystems as well as a spatial classification of the dominating processes within the lake. This included the determination of the role played by DOM loading and changing chemical properties within the lake optical environment.