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The distribution of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn and their fraction characteristics (except Hg) were investigated in surface sediments of the Mwanza Gulf, Lake Victoria. The ecological risks, bioavailability, and mobility of the metals were also evaluated by using enrichment factor (EF), contamination factor (Cf), geo-accumulation index (Igeo), potential ecological risk index (RI), risk assessment code (RAC), individual contamination factor (ICF), and global contamination factor (GCF). Results showed that there were moderate accumulations of heavy metals in sediments from the southern part of the gulf. The mean Cf of heavy metals ranged from 1.19 (Ni) to 2.85 (Hg) suggesting moderate contamination of heavy metals in the sediments while Igeo results showed that the sediments are mainly contaminated by As, Cr, and Hg. The average potential ecological risk of heavy metals in sediments of the Mwanza Gulf is at moderate level (RI 205.49). Hg and Cd posed considerable or moderated risks with mean ecological risk of 114.18 and 44.16, which accounted for 51.08% and 21.54% of the total RI, respectively. High bioavailability and mobility of heavy metals were found in sediments near Mwanza city, particularly Zn and Cd, of which the bioavailability risks were at medium to high levels. Given the biological and environmental importance of the Mwanza Gulf and Lake Victoria, emission paths and bioaccumulation of heavy metals through food webs should be studied carefully to ensure the safety of food and the health and well-being of humans.
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Mercurio , Metales Pesados , Contaminantes Químicos del Agua , Cadmio , China , Monitoreo del Ambiente/métodos , Sedimentos Geológicos , Humanos , Lagos , Metales Pesados/análisis , Medición de Riesgo , Tanzanía , Contaminantes Químicos del Agua/análisisRESUMEN
Dissolved organic matter plays an important role in aquatic ecosystems and poses a major problem for drinking water production. However, our understanding of DOM reactivity in natural systems is hampered by its complex molecular composition. Here, we used Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and data from two independent studies to disentangle DOM reactivity based on photochemical and microbial-induced transformations. Robust correlations of FT-ICR-MS peak intensities with chlorophyll a and solar irradiation were used to define 9 reactivity classes for 1277 common molecular formulas. Germany's largest drinking water reservoir was sampled for 1 year, and DOM processing in stratified surface waters could be attributed to photochemical transformations during summer months. Microbial DOM alterations could be distinguished based on correlation coefficients with chlorophyll a and often shared molecular features (elemental ratios and mass) with photoreactive compounds. In particular, many photoproducts and some microbial products were identified as potential precursors of disinfection byproducts. Molecular DOM features were used to further predict molecular reactivity for the remaining compounds in the data set based on a random forest model. Our method offers an expandable classification approach to integrate the reactivity of DOM from specific environments and link it to molecular properties and chemistry.
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Agua Potable , Ecosistema , Clorofila A , Agua Dulce , Aprendizaje AutomáticoRESUMEN
Molecular formula assignment is one of the key challenges in processing high-field Fourier transform ion cyclotron resonance mass spectrometric (FT-ICR-MS) datasets. The number of potential solutions for an elemental formula increases exponentially with increasing molecular mass, especially when non-oxygen heteroatoms like N, S or P are included. A method was developed from the chemical perspective and validated using a Suwannee River Fulvic Acid (SRFA) dataset which is dominated by components consisting exclusively of C, H and O (78 % CHO). In order to get information on the application range and robustness of this method, we investigated a FT-ICR-MS dataset which was merged from 18 mine pit lake pore waters and 3 river floodplain soil waters. This dataset contained 50 % CHO and 18 % CHOS on average, whereas the former SRFA dataset contained only 1.5 % CHOS. The mass calculator was configured to allow up to five nitrogen atoms and up to one sulphur atom in assigning formulas to mass peaks. More than 50 % multiple-formula assignments were found for peaks with masses > 650 Da. Based on DBE - O frequency diagrams, many CHO, CHOS1, CHON1 and CHON1S1 molecular series were ultimately assigned to many m/z and considered to be reliable solutions. The unequivocal data pool could thus be enlarged by 523 (6.8 %) CHOS1 components. In contrast to the method validation with CHO-rich SRFA, validation with sulphur-rich pit lake samples showed that formulas with a higher number of non-oxygen heteroatoms can be more reliable assignments in many cases. As an example: CHOS molecular series were reliable and the CHO classes were unreliable amongst other molecular classes in many multiple-formula assignments from the sulphur-rich pit lake samples. Graphical abstract An exemplary frequency versus DBE - O diagram. CHOS components but not CHO (and not CHON2 or CHON2S) components were considered here reliable.
RESUMEN
The analysis of dissolved organic matter (DOM) using high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) poses challenges in molecular formula assignment. The consideration of (13)C isotopes provides new insights into the consistent elemental formula solutions. Modern software helps to overcome misinterpretation, but false assignments of molecular classes to mass peaks have rarely been elucidated until now. It will be demonstrated that this can be important with formula assignments comprising exactly five nitrogen and two sulfur atoms in DOM data sets: the molecular class CHON5S2. The existence of such components in DOM under tripeptide Met-His-Cys formed with the formula C14H23O4N5S2 cannot be excluded; however, components containing 5 N and 2 S should be suspected to not be highly abundant. The true elemental compositions of such unusual "N5S2 moieties" were calculated using Suwannee River fulvic acid (SRFA) data from the literature and one data set from acidic pit lake pore water. The replacement of a H3N5S2 moiety with a (13)C1(12)C5O4 moiety explained more than 95% of the questionable "N5S2 moieties". This finding was proved by calculation of δ(13)C values from relative peak intensities.
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Formula assignment is one of the key challenges in evaluation of dissolved organic matter analyses using ultrahigh resolution mass spectrometry (FTICR MS). The number of possible solutions for elemental formulas grows exponentially with increasing nominal mass, especially when non-oxygen heteroatoms like N, S or P are considered. Until now, no definitive solution for finding the correct elemental formula has been given. For that reason an approach from the viewpoint of chemical feasibility was elucidated. To illustrate the new chemical formula assignment principle, a literature data set was used and evaluated by simplified chemical constraints. Only formulas containing a maximum of one sulphur and five nitrogen atoms were selected for further data processing. The resulting data table was then divided into mass peaks with unique component solutions (singlets, representing unequivocal formula assignments) and those with two or more solutions (multiple formula assignments, representing equivocal formula assignments). Based on a [double bond equivalent (DBE) versus the number of oxygen atoms (o)] frequency contour plot and a frequency versus [DBE minus o] diagram, a new assessment and decision strategy was developed to differentiate multiple formula assignments into chemically reliable and less reliable molecular formulas. Using this approach a considerable number of reliable components were identified within the equivocal part of the data set. As a control, a considerable proportion of the assigned formulas deemed to be reliable correspond to those which would have been obtained by CH 2 -based Kendrick mass defect analysis. We conclude that formula assignment in complex mixtures can be improved by group-wise decisions based on the frequency and the [DBE minus o] values of multiple formula assignments.
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Mezclas Complejas/análisis , Espectrometría de Masas/métodos , Compuestos Orgánicos/análisis , Ciclotrones , Análisis de FourierRESUMEN
Aluminum salts are widely used to immobilize phosphorus (P) in lakes suffering from internal loading. However, longevity of treatments varies among lakes; some lakes eutrophy faster than others. We conducted biogeochemical investigations of sediments of a closed artificial Lake Barleber, Germany that was successfully remediated with aluminum sulfate in 1986. The lake became mesotrophic for almost 30 years; a rather rapid re-eutrophication took place in 2016 leading to massive cyanobacterial blooms. We quantified internal loading from sediment and analyzed two environmental factors that might have contributed to the sudden shift in trophic state. Increase in lake P concentration started in 2016, reaching 0.3 mg L-1, and remained elevated into the spring of 2018. Reducible P fraction in the sediment was 37 - 58% of total P, indicating a high potential for mobilization of benthic P during anoxia. Estimated P release from sediments for 2017 was approximately 600 kg for the whole lake. This is consistent with sediment incubation results; higher temperature (20°C) and anoxia contributed to release of P (27.9 ± 7.1 mg m-2 d-1, 0.94 ± 0.23 mmol m-2 d-1) to the lake, triggering re-eutrophication. Loss of aluminum P adsorption capacity together with anoxia and high water temperatures (organic matter mineralization) are major drivers of re-eutrophication. Accordingly, treated lakes at some time require a repeated aluminum treatment for sustaining acceptable water quality and we recommend regular sediment monitoring in treated lakes. This is crucial given the effects of climate warming on duration of stratification in lakes which may result in the need for treatment of many lakes.
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Aluminio , Lagos , Humanos , Fósforo/análisis , Sedimentos Geológicos , Compuestos de Alumbre , Eutrofización , Hipoxia , Monitoreo del AmbienteRESUMEN
The molecular composition of dissolved organic matter (DOM) is of relevance for global carbon cycling and important for drinking water processing also. The detection of variation of DOM composition as function of time and space from a methodological viewpoint is essential to observe DOM processing and was addressed so far. High resolution concerning DOM quality was achieved with Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). However almost none of the existing FTICR-MS data sets were evaluated addressing the fate of single mass features / molecular formulas (MFs) abundance during experiments. In contrast to former studies we analyze the function of MF abundance of time and space for such MFs which are present in all samples and which were formerly claimed as recalcitrant in not all but a great number of studies. For the first time the reactivity of MFs was directly compared by their abundance differences using a simple equation, the relative intensity difference (δRI). Search strategies to find out the maximum δRI values are introduced. The corresponding MFs will be regarded as key MFs (KEY-MFs). In order to test this new approach data from a recent photo degradation experiment were combined with monitoring surveys conducted in two drinking water reservoirs. The δRI values varied over one order of magnitude (more than five-fold). MFs like C9H12O6 and C10H14O6 revealed high biogeochemical reactivity as photo products. Some of the KEY-MFs were identical with MFs identified as disinfection byproducts precursors in recent studies. Other KEY-MFs were oxygen-rich and relatively unsaturated (poly-phenol-like) and hence relevant to flocculation procedures.
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Materia Orgánica Disuelta , Agua Potable , Espectrometría de Masas , Oxígeno , FenolesRESUMEN
Elevated concentrations of dissolved organic matter (DOM) such as humic substances in raw water pose significant challenges during the processing of the commercial drinking water supplies. This is a relevant issue in Saxony, Central East Germany, and many other regions worldwide, where drinking water is produced from raw waters with noticeable presence of chromophoric DOM (CDOM), which is assumed to originate from forested watersheds in spring regions of the catchment area. For improved comprehension of DOM molecular composition, the seasonal and spatial variations of humic-like fluorescence and elemental formulas in the catchment area of the Muldenberg reservoir were recorded by excitation emission matrix fluorescence (EEMF) and ultrahigh-resolution mass spectrometry (FT-ICR-MS). The Spearman rank correlation was applied to link the EEMF intensities with exact molecular formulas and their corresponding relative mass peak abundances. Thereby, humic-like fluorescence could be allocated to the pool of oxygen-rich and relatively unsaturated components with stoichiometries similar to those of tannic acids, which are suspected to have a comparatively high disinfection byproduct formation potential associated with the chlorination of raw water. Analogous relationships were established for UV absorption at 254 nm (UV(254)) and dissolved organic carbon (DOC) and compared to the EEMF correlation.
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Agua Potable/química , Modelos Químicos , Compuestos Orgánicos/análisis , Espectrometría de Fluorescencia/métodos , Movimientos del Agua , Carbono/análisis , Elementos Químicos , Alemania , Sustancias Húmicas/análisis , Ríos/química , Estaciones del Año , Solubilidad , Estadísticas no Paramétricas , Rayos UltravioletaRESUMEN
Heavy metal pollution in sediments is a common environmental issue in small- and medium-sized reservoirs not only in China but also worldwide; however, few interpretations of the pollution pattern exist. Based on the analyses of accumulation characteristics, ecological risks, and source apportionments of eight heavy metals (As, Cd, Cr, Cu, Hg, Pb, Ni, and Zn) in sediments, we derived a paradigm to describe the pollution pattern of heavy metals in sediments of a typical small- and medium-sized Tongjiqiao Reservoir. The results showed high levels of Cd, Hg, and As pollutants in the surface and upper sediment layers of the pre-dam area. Additionally, As, Cd, Hg, and Pb pollutants peaked in the middle layers of the inflow area, indicating a high ecological risk in these areas. The positive matrix factorization results implied that industrial, agricultural, and transportation activities were the main sources of heavy metals. The heavy metal pollution pattern exhibited three distinct stages: low contamination, rapid pollution, and pollution control. This pattern explains the heavy metal pollution process in the sediments and will provide scientific guidance for realizing the green and sustainable operation and development of the reservoir.
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Contaminantes Ambientales , Mercurio , Metales Pesados , Contaminantes Químicos del Agua , Monitoreo del Ambiente/métodos , Cadmio/análisis , Plomo/análisis , Contaminantes Químicos del Agua/análisis , Sedimentos Geológicos , Medición de Riesgo , Metales Pesados/análisis , Mercurio/análisis , China , Contaminantes Ambientales/análisisRESUMEN
Deforestation is currently a widespread phenomenon and a growing environmental concern in the era of rapid climate change. In temperate regions, it is challenging to quantify the impacts of deforestation on the catchment dynamics and downstream aquatic ecosystems such as reservoirs and disentangle these from direct climate change impacts, let alone project future changes to inform management. Here, we tackled this issue by investigating a unique catchment-reservoir system with two reservoirs in distinct trophic states (meso and eutrophic), both of which drain into the largest drinking water reservoir in Germany. Due to the prolonged droughts in 2015-2018, the catchment of the mesotrophic reservoir lost an unprecedented area of forest (exponential increase since 2015 and ca. 17.1% loss in 2020 alone). We coupled catchment nutrient exports (HYPE) and reservoir ecosystem dynamics (GOTM-WET) models using a process-based modeling approach. The coupled model was validated with datasets spanning periods of rapid deforestation, which makes our future projections highly robust. Results show that in a short-term time scale (by 2035), increasing nutrient flux from the catchment due to vast deforestation (80% loss) can turn the mesotrophic reservoir into a eutrophic state as its counterpart. Our results emphasize the more prominent impacts of deforestation than the direct impact of climate warming in impairment of water quality and ecological services to downstream aquatic ecosystems. Therefore, we propose to evaluate the impact of climate change on temperate reservoirs by incorporating a time scale-dependent context, highlighting the indirect impact of deforestation in the short-term scale. In the long-term scale (e.g. to 2100), a guiding hypothesis for future research may be that indirect effects (e.g., as mediated by catchment dynamics) are as important as the direct effects of climate warming on aquatic ecosystems.
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Ecosistema , Calidad del Agua , Cambio Climático , Conservación de los Recursos Naturales , BosquesRESUMEN
The knowledge of size-distribution and lability of metals and nutrients in freshwater systems is important for estimation of the ecological effects of mining. However, it is still limited in several mining areas such as the Quadrilátero Ferrífero (Brazil) which was severely polluted by the collapse of the Fundão tailings dam in November 2015. In this study, results of an investigation from 2014 using a neural network named self-organising map (SO-Map) into the conditions of selected trace metals that are of particular importance to mining areas (Cr, Cu, Co, Mn, Ni, Pb, Zn) are presented. Additionally, P was considered by its high importance as a nutrient and sites later affected by the dam burst were also included by chance. Water samples were collected at six sites in dry and rainy seasons and filtered and ultrafiltered for determination of total dissolved (<0.45 µm) and truly dissolved (<1 kDa) fractions. Diffusive gradients in thin films (DGT) devices were deployed in situ for determination of the DGT-labile fraction. All data were analysed using SO-Map and Spearman's rank correlation. Phosphorus in the Carmo River occurred mainly in the truly dissolved and DGT-labile fractions. The higher amounts of this element in the river water (up to 263 µg L-1 of total P) might be related to untreated sewage discharge. Moreover, the concentrations of other trace metals (Mn, Cu, Co, Ni, Zn) were high, even under the "natural" conditions (before the dam failure) due to natural and anthropogenic factors such as local lithology and mining.
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Oligoelementos , Contaminantes Químicos del Agua , Monitoreo del Ambiente/métodos , Metales/análisis , Minería , Fósforo/análisis , Oligoelementos/análisis , Agua/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
Tanzania is the only country bordering all three transboundary East African Great Lakes, i.e., Lake Victoria, Lake Tanganyika, and Lake Nyasa (Lake Malawi). This study investigated the spatiotemporal variability of basic physicochemical parameters of nearshore surface waters in Mwanza Gulf (Lake Victoria), Kigoma Bay (Lake Tanganyika), and Wissmann Bay (Lake Nyasa). Water quality was evaluated using the water quality index (WQI) method. Results showed that N and P nutrient pollution was relatively severe in central and southern parts of Mwanza Gulf owing to external agricultural emissions and internal release associated with physically disturbed sediment resuspension. External inputs from inflowing surface runoffs from the city of Mwanza typically enhanced N loading in northern parts of the gulf during the rainy season. Poor water quality was found in central and southern parts of Mwanza Gulf, especially in the rainy season. Algal blooms and NH4+-N (total P and total N) were the main factors driving water quality degradation in the rainy (dry) season. Kigoma Bay and Wissmann Bay both had good water quality, except in river mouth areas in Lake Nyasa during the rainy season. The degradation in water quality was caused primarily by increased land-based nutrient and turbidity inputs. To respond to challenges associated with climate change and local socioeconomic development, long-term monitoring of the lacustrine environment and systematic limnological studies will be required, not only in the three bays but also more widely throughout the three lakes and their basins.
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Lagos , Calidad del Agua , China , Monitoreo del Ambiente , Eutrofización , Nitrógeno/análisis , Fósforo/análisis , TanzaníaRESUMEN
Toxic cyanobacteria blooms are a frequent problem in subtropical reservoirs and freshwater systems. The purpose of this study was to investigate the occurrence of potentially toxic cyanobacteria and the environmental conditions associated with the presence of cyanotoxins in a Brazilian subtropical reservoir. Five collections were carried out at seven sampling locations in the reservoir, during the rainy and dry seasons, between the years 2016 and 2017. There was permanent occurrence of Raphidiopsis raciborskii (Woloszynska) Aguilera, Berrendero Gómez, Kastovsky, Echenique & Salerno (Phycologia 57(2):130-146, 2018), ranging between dominant and abundant, with an average biomass of 38.8 ± 29.9 mg L-1. Also abundant were Dolichospermum solitarium, D. planctonicum, Planktothrix isothrix, and Aphanizomenon gracile. Saxitoxin (STX) was detected in all the collected samples (0.11 ± 0.05 µg L-1). Microcystin (MC) was also detected, but at lower concentrations (0.01 ± 0.0 µg L-1). Low availability of NO3- and phosphorus limitation had significant effects on the R. raciborskii biomass and the levels of STX and MC. It was observed that R. raciborskii was sensitive to thermal stratification, at the same time that STX levels were higher. This suggested that STX was produced under conditions that restricted the growth of R. raciborskii. These are important findings, because they add information about the permanent occurrence of STX and R. raciborskii in an aquatic ecosystem limited by phosphorus, vulnerable to climatic variations, and polluted by domestic effluents.
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Toxinas de Cianobacterias , Cylindrospermopsis , Brasil , EcosistemaRESUMEN
In temperate lakes, it is generally assumed that light rather than temperature constrains phytoplankton growth in winter. Rapid winter warming and increasing observations of winter blooms warrant more investigation of these controls. We investigated the mechanisms regulating a massive winter diatom bloom in a temperate lake. High frequency data and process-based lake modeling demonstrated that phytoplankton growth in winter was dually controlled by light and temperature, rather than by light alone. Water temperature played a further indirect role in initiating the bloom through ice-thaw, which increased light exposure. The bloom was ultimately terminated by silicon limitation and sedimentation. These mechanisms differ from those typically responsible for spring diatom blooms and contributed to the high peak biomass. Our findings show that phytoplankton growth in winter is more sensitive to temperature, and consequently to climate change, than previously assumed. This has implications for nutrient cycling and seasonal succession of lake phytoplankton communities. The present study exemplifies the strength in integrating data analysis with different temporal resolutions and lake modeling. The new lake ecological model serves as an effective tool in analyzing and predicting winter phytoplankton dynamics for temperate lakes.
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Diatomeas , Lagos , Biomasa , Eutrofización , Fitoplancton , Estaciones del AñoRESUMEN
In order to better understand the chemical diversity of dissolved organic matter (DOM) in iron-rich mine waters, a variety of sediment pore waters was analysed by means of ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). A considerable number of the DOM elemental formulae were found to contain sulfur. In a rather simplified experiment, DOM was exposed to sunlight in the presence of dissolved ferric iron, which is common in the oxygenated acidified epilimnetic waters of mine pit lakes. The photochemical alteration of the CHOS (carbon-, hydrogen-, oxygen- and sulfur-containing) compounds was then categorised by following the changes in signal intensity of mass peaks. Nearly 20,000 elemental compositions were identified and sorted into the following categories: totally degraded, partially degraded, not significantly degraded, minor new photoproducts, and newly formed photoproducts. A large proportion of the CHOS compounds were found to be entirely degraded; the degradation ratios exceeded those of the CHO compounds. The pools of totally degraded compounds and those of newly formed products were contrasted with respect to photochemically relevant mass differences. These results indicate that photochemical loss of sulfur-containing low molecular weight compounds can be considered likely. One feasible explanation is the photodegradation of sulfonic acids within the CHOS pool eventually leading to the release of sulfate.
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Hierro/química , Espectrometría de Masas/métodos , Minería , Compuestos de Azufre/química , Agua Dulce/química , Sustancias Húmicas/análisis , Compuestos Inorgánicos/química , Procesos Fotoquímicos , Espectroscopía Infrarroja por Transformada de Fourier , Compuestos de Azufre/análisis , Luz Solar , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/químicaRESUMEN
Sources of particulate organic carbon (POC) play important roles in aqueous carbon cycling because internal production can provide labile material that can easily be turned into CO2. On the other hand, more recalcitrant external POC inputs can cause increased loads to sedimentary organic matter that may ultimately cause CH4 release. In order to differentiate sources, stable isotopes offer a useful tool. We present a study on the Itupararanga Reservoir (Brazil) where origins of POC were explored by comparing its isotope ratios (δ13CPOC) to those of dissolved inorganic carbon (δ13CDIC). The δ13CPOC averaged around - 25.1 in near-surface waters, which indicates higher primary production inferred from a fractionation model that takes into account carbon transfer with a combined evaluation of δ13CPOC, δ13CDIC and aqueous CO2. However, δ13CPOC values for water depths from 3 to 15 m decreased to - 35.6 and indicated different carbon sources. Accordingly, the δ13CDIC values of the reservoir averaged around + 0.6 in the top 3 m of the water column. This indicates CO2 degassing and photosynthesis. Below this depth, DIC isotope values of as low as - 10.1 showed stronger influences of respiration. A fractionation model with both isotope parameters revealed that 24% of the POC in the reservoir originated from detritus outside the reservoir and 76% of it was produced internally by aqueous CO2 fixation.
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The aim of this study was to identify sources of carbon turnover using stable isotope mass balances. For this purpose, two pre-reservoirs in the Harz Mountains (Germany) were investigated for their dissolved and particulate carbon contents (dissolved inorganic carbon (DIC), dissolved organic carbon, particulate organic carbon) together with their stable carbon isotope ratios. DIC concentration depth profiles from March 2012 had an average of 0.33 mmol L-1. Increases in DIC concentrations later on in the year often corresponded with decreases in its carbon isotope composition (δ13CDIC) with the most negative value of -18.4 in September. This led to a carbon isotope mass balance with carbon isotope inputs of -28.5 from DOC and -23.4, -31.8 and -30.7 from algae, terrestrial and sedimentary matter, respectively. Best matches between calculated and measured DIC gains were achieved when using the isotope composition of algae. This shows that this type of organic material is most likely responsible for carbon additions to the DIC pool when its concentrations and δ13CDIC values correlate negatively. The presented isotope mass balance is transferable to other surface water and groundwater systems for quantification of organic matter turnover.
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Compuestos Inorgánicos de Carbono/análisis , Isótopos de Carbono/análisis , Monitoreo del Ambiente , Agua Dulce/química , Sedimentos Geológicos/análisis , Altitud , Compuestos Inorgánicos de Carbono/química , Precipitación Química , Alemania , Agua Subterránea/análisis , Agua Subterránea/química , Lluvia/química , Solubilidad , TemperaturaRESUMEN
Peatlands can be a potential source of dissolved organic matter (DOM) in fresh water catchment areas. The quantity and quality of DOM can differ between pristine, degraded and rewetted peatlands. Due to the large scale and continuing losses of peatlands, their conservation and restoration has been increasingly emphasized. Mostly rewetting measures are required to improve the hydrology of damaged peatlands, which is a precondition for the resettlement of peat-forming plant species. Thus, in term of DOM, there is a special need to understand how rewetting measures affect DOM characteristics and concentrations. To estimate the potential leaching of humic substances from rewetted areas two natural sites were compared with four artificially rewetted sites in a peatland area of the Harz Mountains National Park, Germany. This was done with regards to DOM quality by combining the results from Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS, measured at one time in Spring) and excitation-emission-matrix fluorescence spectroscopy (EEMF, measured monthly for the period of one year). The DOM quality was significantly less variable in the pristine peatland soil water compared to the rewetted peatland soil waters, from both a spatial and a seasonal perspective. The soil water from the rewetted peatland sites showed a higher degree of humification compared to pristine peatland. DOC concentration was mostly consistent in the pristine peatland over the year. The rewetted peatlands showed higher DOC levels in Summer months and lower DOC in Winter months compared to the pristine peatland. It can be concluded that the rewetting of peatlands is coupled with high concentrations of DOC in soil water and its quality is highly aromatic (as reflected by the observed values from the humification index) during times with elevated temperature. The results may have a significant input for dynamic catchment area studies with regards to rewetting peatland sites.
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Humic substances (HS) are ubiquitous organic compounds able to affect mobility and availability of arsenic (As) in aquatic systems. Although it is known that associations between HS and As occur mainly via iron (Fe)-cationic bridges, the behaviour and distribution of this metalloid in HS- and Fe-rich environments is still not fully understood. In this paper, the quality of HS from different rivers in Brazil and Germany and its influence on the behaviour of As(V) under different Fe(III) concentrations were investigated. HS were extracted from four different rivers (Cascatinha, Holtemme, Selke and Warme Bode), characterised and fractionated into different molecular weight sizes (10, 5 and 1 kDa). Complexation tests were performed using an ultrafiltration system and 1 kDa membranes. All data was analysed using the Kohonen neural network (SOM - Self organising maps). All samples, except Selke, exhibited similar results of free As (<1 kDa). The results suggested that associations between HS, Fe and As were dependent on nitrogen (N)-aromatic carbon (C), amount of sulphur (S) and the molecular size of the HS. Although all HS appeared to be similar after looking at most variables analysed, the SOM could discriminate them into three different groups. Characterisation of the HS indicated that they had terrestrial material (from C3 plants) as precursor material. Most of the As and Fe was distributed in the fractions of higher (>10 kDa) and lower (<1 kDa) size. HS quality is an important factor to take into account when studying the behaviour of As in HS-rich environments.
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Arsénico/análisis , Compuestos Férricos/farmacología , Agua Dulce/análisis , Sustancias Húmicas/análisis , Brasil , Carbono/análisis , Agua Dulce/química , Alemania , Hierro/análisis , Nitrógeno/análisis , Tamaño de la Partícula , Azufre/análisis , Ultrafiltración/métodosRESUMEN
The mobility and bioavailability of arsenic (As) are strongly controlled by adsorption/precipitation processes involving metal oxides. However, the organic matter present in the environment, in combination with these oxides, can also play an important role in the cycle of arsenic. This work concerns the interaction between As and two samples of aquatic humic substances (AHS) from tropical rivers. The AHS were extracted as proposed by IHSS, and were characterized by (13)C NMR. The experiments were conducted with the AHS in natura and enriched with metal cations, with different concentrations of As, and complexation capacity was evaluated at three different pH levels (5.0, 7.0, and 9.0). The AHS samples showed similar chemical compositions. The results suggested that there was no interaction between As(III) and AHS in natura or enriched with Al. Low concentrations of As(V) were bound to AHS in natura. For As(III), the complexation capacity of the AHS enriched with Fe was approximately 48 µmol per g of C, while the values for As(V) were in the range 69-80 µmol per grams of C. Fluorescence spectra showed that changes in Eh affected the complexation reactions of As(V) species with AHS.