Iron and pH regulating the photochemical mineralization of dissolved organic carbon

Solar radiation mineralizes dissolved organic matter (DOM) to dissolved inorganic carbon through photochemical reactions (DIC photoproduction) that are influenced by iron (Fe) and pH. This study addressed as to what extent Fe contributes to the optical properties of the chromophoric DOM (CDOM) and DIC photoproduction at different pH values. We created the associations of Fe and DOM (Fe-DOM) that cover the range of loadings of Fe on DOM and pH values found in freshwaters. The introduced Fe enhanced the light absorption by CDOM independent of pH. Simulated solar irradiation decreased the light absorption by CDOM (i.e., caused photobleaching). Fe raised the rate of photobleaching and steepened…

Primary production calculations for sea ice from bio-optical observations in the Baltic Sea

Abstract Bio-optics is a powerful approach for estimating photosynthesis rates, but has seldom been applied to sea ice, where measuring photosynthesis is a challenge. We measured absorption coefficients of chromophoric dissolved organic matter (CDOM), algae, and non-algal particles along with solar radiation, albedo and transmittance at four sea-ice stations in the Gulf of Finland, Baltic Sea. This unique compilation of optical and biological data for Baltic Sea ice was used to build a radiative transfer model describing the light field and the light absorption by algae in 1-cm increments. The maximum quantum yields and photoadaptation of photosynthesis were determined from 14C-incorporatio…

Interannual variation and long-term trends in proportions of resident individuals in partially migratory birds

Partial migration - a part of a population migrates and another part stays resident year-round on the breeding site - is probably the most common type of migration in the animal kingdom, yet it has only lately garnered more attention. Theoretical studies indicate that in partially migratory populations, the proportion of resident individuals (PoR) should increase in high latitudes in response to the warming climate, but empirical evidence exists for few species. We provide the first comprehensive overview of the environmental factors affecting PoR and the long-term trends in PoR by studying 27 common partially migratory bird species in Finland. The annual PoR values were calculated by divid…

Revisiting the disappearance of terrestrial dissolved organic matter in the ocean: a <i>δ</i><sup>13</sup>C study

Abstract. Organic carbon (OC) depleted in 13C is a widely used tracer for terrestrial organic matter (OM) in aquatic systems. Photochemical reactions can, however, change δ13C of dissolved organic carbon (DOC) when chromophoric, aromatic-rich terrestrial OC is selectively mineralized. We assessed the robustness of the δ13C signature of DOC (δ13CDOC) as a tracer for terrestrial OM by estimating its change during the photobleaching of chromophoric DOM (CDOM) from 10 large rivers. These rivers cumulatively account for approximately one-third of the world's freshwater discharge to the global ocean. Photobleaching of CDOM by simulated solar radiation was associated with the photochemical mineral…

The effect of iron on the biodegradation of natural dissolved organic matter

Iron (Fe) may alter the biodegradation of dissolved organic matter (DOM), by interacting with (DOM), phosphorus (P) and microbes. We isolated DOM and a bacterial community from boreal lake water and examined bacterial growth on DOM in laboratory experiments. Fe was introduced either together with DOM (DOM-Fe) or into bacterial suspension, which led to the formation of insoluble Fe-precipitates on bacterial surfaces (Fe coating). In the latter case, the density of planktonic bacteria was an order of magnitude lower than that in the corresponding treatment without introduced Fe. The association of Fe with DOM decreased bacterial growth, respiration, and growth efficiency compared with DOM alo…

Biogenic Fenton process - A possible mechanism for the mineralization of organic carbon in fresh waters.

To explore the mechanisms that mineralize poorly bioavailable natural organic carbon (OC), we measured the mineralization of OC in two lake waters over long-term experiments (up to 623 days) at different pH and iron (Fe) levels. Both the microbial and photochemical mineralization of OC was higher at pH acidified to 4 than at the ambient pH 5 or an elevated pH 6. During 244 days, microbes mineralized up to 60% of OC in the 10-mu m filtrates of lake water and more than 27% in the 1-mu m filtrates indicating that large-sized microbes/grazers enhance the mineralization of OC. A reactivity continuum model indicated that the acidification stimulated the microbial mineralization of OC especially i…

Photochemical mineralization of terrigenous DOC to dissolved inorganic carbon in ocean

When terrigenous dissolved organic carbon (tDOC) rich in chromophoric dissolved organic matter (tCDOM) enters the ocean, solar radiation mineralizes it partially into dissolved inorganic carbon (DIC). This study addresses the amount and the rates of DIC photoproduction from tDOC and the area of ocean required to photomineralize tDOC. We collected water samples from 10 major rivers, mixed them with artificial seawater, and irradiated them with simulated solar radiation to measure DIC photoproduction and the photobleaching of tCDOM. The linear relationship between DIC photoproduction and tCDOM photobleaching was used to estimate the amount of photoproduced DIC from the tCDOM fluxes of the stu…

Inter-laboratory differences in the apparent quantum yield for the photochemical production of dissolved inorganic carbon in inland waters and implications for photochemical rate modeling

Solar radiation initiates photochemical oxidation of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) in inland waters, contributing to their carbon dioxide emissions to the atmosphere. Models can determine photochemical DIC production over large spatiotemporal scales and assess its role in aquatic C cycling. The apparent quantum yield (AQY) spectrum for photochemical DIC production, defined as mol DIC produced per mol chromophoric dissolved organic matter-absorbed photons, is a critical model parameter. In previous studies, the principle for the determination of AQY spectra is the same but methodological specifics differ, and the extent to which these differences influenc…

Photochemical Mineralization of Terrigenous DOC to Dissolved Inorganic Carbon in Ocean

Linking the Molecular Signature of Heteroatomic Dissolved Organic Matter to Watershed Characteristics in World Rivers

Large world rivers are significant sources of dissolved organic matter (DOM) to the oceans. Watershed geomorphology and land use can drive the quality and reactivity of DOM. Determining the molecular composition of riverine DOM is essential for understanding its source, mobility and fate across landscapes. In this study, DOM from the main stem of 10 global rivers covering a wide climatic range and land use features was molecularly characterized via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). FT-ICR mass spectral data revealed an overall similarity in molecular components among the rivers. However, when focusing specifically on the contributi…

Bleaching of color of kraft pulp mill effluents and natural organic matter in lakes

In situ changes in the color of lake water and biologically treated kraft pulp mill effluents mixed in lake water were examined in three lakes. In 1.7 m3 enclosures, the color (400–700 g Pt·m–3) of the mixture of pulp mill effluent and lake water remained similar for 4 months in darkness, whereas exposure to solar radiation resulted in 17–42% bleaching of color. During the summer stratification of a humic lake, the color (160 g Pt·m–3) of hypolimnetic water remained similar to that found during spring turnover, but the color of epilimnion decreased 13%. The measured rates of photochemical bleaching of color by solar radiation could explain the decrease of epilimnetic color. Attenuation of …

Superoxide-driven autocatalytic dark production of hydroxyl radicals in the presence of complexes of natural dissolved organic matter and iron.

Abstract We introduced superoxide as potassium superoxide (KO2) to artificial lake water containing dissolved organic matter (DOM) without or with introduced ferric iron complexes (DOM-Fe(III)), and monitored the production rate of hydroxyl radicals as well as changes in the absorption and fluorescence properties of DOM. The introduction of KO2 decreased the absorption by DOM but increased the spectral slope coefficient of DOM more with complexed ferric Fe than without it. The introduction of KO2 increased the fluorescence of humic-like components in DOM without introduced ferric Fe but resulted in the loss of fluorescence in DOM with introduced ferric Fe. A single introduction of 13 μmol L…

Solar PAR and UVR modify the community composition and photosynthetic activity of sea ice algae

The effects of increased photosynthetically active radiation (PAR) and ultraviolet radiation (UVR) on species diversity, biomass and photosynthetic activity were studied in fast ice algal communities. The experimental set-up consisted of nine 1.44 m(2) squares with three treatments: untreated with natural snow cover (UNT), snow-free (PAR + UVR) and snow-free ice covered with a UV screen (PAR). The total algal biomass, dominated by diatoms and dinoflagellates, increased in all treatments during the experiment. However, the smaller biomass growth in the top 10-cm layer of the PAR + UVR treatment compared with the PAR treatment indicated the negative effect of UVR. Scrippsiella complex (mainly…

Molecular composition of dissolved organic matter from a wetland plant (Juncus effusus) after photochemical and microbial decomposition (1.25 yr): Common features with deep sea dissolved organic matter

We hypothesized that microbial and photochemical processing of dissolved organic matter (DOM) determines its molecular formula composition in aquatic systems to a greater degree than does the original source of the DOM. To test this hypothesis, we exposed DOM from a leachate of a wetland plant (Juncus effusus) to solar radiation or incubated it in the dark for 1.25 yr. Analysis of the extracted DOM of the leachates via Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) identified 2800 molecular formulae. Of the formulae in the initial DOM, 11% were lost during microbial decomposition in the dark and 54% under solar radiation. Solar radiation also produced a large number…

Superoxide-driven autocatalytic dark production of hydroxyl radicals in the presence of complexes of natural dissolved organic matter and iron

We introduced superoxide as potassium superoxide (KO2) to artificial lake water containing dissolved organic matter (DOM) without or with introduced ferric iron complexes (DOM-Fe), and monitored the production rate of hydroxyl radicals as well as changes in the absorption and fluorescence properties of DOM. The introduction of KO2 decreased the absorption by DOM but increased the spectral slope coefficient of DOM more with complexed ferric Fe than without it. The introduction of KO2 increased the fluorescence of humic-like components in DOM without introduced ferric Fe but resulted in the loss of fluorescence in DOM with introduced ferric Fe. A single introduction of 13 μmol L−1 KO2 produce…

Biologically labile photoproducts from riverine non-labile dissolved organic carbon in the coastal waters

In order to assess the production of biologically labile photoproducts (BLPs) from non-labile riverine dissolved organic carbon (DOC), we collected water samples from ten major rivers, removed labile DOC and mixed the residual non-labile DOC with artificial seawater for microbial and photochemical experiments. Bacteria grew on non-labile DOC with a growth efficiency of 11.5% (mean; range from 3.6 to 15.3%). Simulated solar radiation transformed a part of non-labile DOC into BLPs, which stimulated bacterial respiration and production, but did not change bacterial growth efficiency (BGE) compared to the non-irradiated dark controls. In the irradiated water samples, the amount of BLPs stimulat…

Effects of dissolved organic matter from a eutrophic lake on the freely dissolved concentrations of emerging organic contaminants

The authors studied the effects of dissolved organic matter (DOM) on the bioavailability of bisphenol A (BPA) and chloramphenicol by measuring the freely dissolved concentrations of the contaminants in solutions containing DOM that had been isolated from a mesocosm in a eutrophic lake. The abundance and aromaticity of the chromophoric DOM increased over the 25-d mesocosm experiment. The BPA freely dissolved concentration was 72.3% lower and the chloramphenicol freely dissolved concentration was 56.2% lower using DOM collected on day 25 than using DOM collected on day 1 of the mesocosm experiment. The freely dissolved concentrations negatively correlated with the ultraviolent absorption coef…

Iron as a source of color in river waters.

Organic chromophores of total organic carbon (TOC) and those of iron (Fe) contribute to the color of water, but the relative contributions of colored organic carbon (COC%) and Fe (Fe%) are poorly known. In this study, we unraveled Fe% and COC% in 6128 unfiltered water samples collected from 94 Finnish river sites of contrasting catchment properties. According to regression analysis focusing on TOC alone, on average 84% of the mean TOC consisted of COC, while 16% was non-colored or below the color-detection limit. COC and Fe were much more important sources of color than phytoplankton (chlorophyll a as a proxy) or non-algal particles (suspended solids as a proxy). When COC and Fe were consid…

Increasing air temperature relative to water temperature makes the mixed layer shallower, reducing phytoplankton biomass in a stratified lake

The depth of the mixed layer is a major determinant of nutrient and light availability for phytoplankton in stratified waterbodies. Ongoing climate change influences surface waters through meteorological forcing, which modifies the physical structure of fresh waters including the mixed layer, but effects on phytoplankton biomass are poorly known. To determine the responses of phytoplankton biomass to the depth of the mixed layer, light availability and associated meteorological forcing, we followed daily changes in weather and water column properties in a boreal lake over the first half of a summer stratification period. Phytoplankton biomass increased with the deepening of the mixed layer …

Global charcoal mobilization from soils via dissolution and riverine transport to the oceans

Dissolving Charcoal Biomass burning produces 40 to 250 million tons of charcoal per year worldwide. Much of this is preserved in soils and sediments for thousands of years. However, the estimated production rate of charcoal is significantly larger than that of decomposition, and Jaffe et al. (p. 345 ; see the Perspective by Masiello and Louchouarn ) calculate that a large fraction of the charcoal produced by fires is lost from the land through dissolution and transport to the oceans.

Selective incorporation of dissolved organic matter (DOM) during sea ice formation

This study investigated the incorporation of DOM from seawater into >2 day-old sea ice in tanks filled with seawater alone or amended with DOM extracted from the microalga, Chlorella vulgaris. Optical properties, including chromophoric DOM (CDOM) absorption and fluorescence, as well as concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), dissolved carbohydrates (dCHOs) and dissolved uronic acids (dUAs) were measured. Enrichment factors (EFs), calculated from salinity-normalized concentrations of DOM in bulk ice, brine and frost flowers relative to under-ice water, were generally >1. The enrichment factors varied for different DOM fractions: EFs were the lowest fo…

Data from: Primary production calculations for sea ice from bio-optical observations in the Baltic Sea

Bio-optics is a powerful approach for estimating photosynthesis rates, but has seldom been applied to sea ice, where measuring photosynthesis is a challenge. We measured absorption coefficients of chromophoric dissolved organic matter (CDOM), algae, and non-algal particles along with solar radiation, albedo and transmittance at four sea-ice stations in the Gulf of Finland, Baltic Sea. This unique compilation of optical and biological data for Baltic Sea ice was used to build a radiative transfer model describing the light field and the light absorption by algae in 1-cm increments. The maximum quantum yields and photoadaptation of photosynthesis were determined from 14C-incorporation in phot…