Natalie Mladenov

Dissolved organic matter sources and consequences for iron and arsenic mobilization in Bangladesh aquifers.

Iron (Fe) and dissolved organic matter (DOM) cycling have been implicated in arsenic mobilization via microbially mediated Fe oxide reduction. To evaluate the sources and multiple roles of DOM in Bangladesh aquifers, we conducted spectroscopic analyses on various types of surface water and groundwater samples from a site representative of aquifer chemistry and hydrology. Surface water contained humic substances with oxidized quinone-like moieties and high concentrations of labile microbially derived DOM. In contrast, in shallow groundwater where dissolved iron and arsenic concentrations were high, the quinone-like moieties of humic substances were more reduced, with less abundant labile DOM than that of surface water. Instead, DOM at these depths was characterized by terrestrial (plant/soil) signatures. A sediment microcosm experiment demonstrated that Fe(II) and terrestrially derived DOM were released from sediment over time. The results provide new evidence to support a dual role of natural DOM in Bangladesh aquifers (1) as a labile substrate for Fe- and humic-reducing bacteria and (2) as an electron shuttle via humic substances to enhance microbial iron reduction. Fluorescence index, amino acid-like fluorescence, and redox index may serve as useful indicators of the type of DOM likely to be involved in Fe solubilization and potentially As mobilization reactions.

Effects of annual flooding on dissolved organic carbon dynamics within a pristine wetland, the Okavango Delta, Botswana

In the Okavango Delta in Botswana, dissolved organic matter (DOM) transport is controlled by the slow movement of an annual flood ‘pulse’ across permanently and seasonally flooded wetlands, known respectively as the Permanent Swamp and Seasonal Swamp. We studied temporal and spatial variations in fluorescence index (FI) and specific UV absorbance (SUVA) of DOM to identify DOM sources and fate during the flood. Dissolved organic carbon (DOC) concentrations ranged from 2 to 25 mg C L−1 in channels of the Delta, with seasonal floodplains having consistently higher concentrations. Chemical indices, such as DOC concentrations, conductivity, specific UV absorbance (SUVA), fluorescence, total dissolved nitrogen, and chlorophyll a, were analyzed for channel and floodplain sites in the Seasonal Swamp. DOC concentrations increased during the rising limb of the flood in the Seasonal Swamp. SUVA of whole water samples and fluorescence index (FI) of fulvic acids isolated from channel and floodplain sites changed in a manner indicating the release of DOM by leaching of plant litter during the flood. After the flood receded, DOC concentrations and fulvic acid content decreased, and microbially-derived sources of organic matter dominated. Along two river reaches, measuring over 400 km each, variations in DOC concentrations were primarily due to geomorphology, with the effects of the annual flood overprinted atop the spatial controls. Increasing downstream DOC concentrations were found to be a product of inundation of DOC-rich seasonal floodplains and evaporation-enriched waters downstream. Increasing SUVA, dissolved nitrogen, and fulvic acid content, and decreasing FI downstream suggested microbial processing of terrestrial DOM and possible release of nutrients incorporated in the DOM.

Dissolved Organic Matter Biogeochemistry Along a Transect of the Okavango Delta, Botswana

Biogeochemical processing of dissolved organic matter (DOM) in aquatic environments can alter its chemical quality and its bioavailability to the microbial loop. In this study, we evaluated the relative importance to DOM character of allochthonous and autochthonous DOM inputs and photo-degradation in a large, pristine wetland, the Okavango Delta of Botswana. We performed an intensive spatial sampling of surface water and analyzed for chemical and physical parameters (pH, conductivity, dissolved oxygen saturation, temperature, and channel depth), dissolved organic matter (DOM), and particulate organic matter (POM). We used UV–vis absorbance, fluorescence spectroscopy, and parallel factor analysis of excitation emission matrix data (EEM-PARAFAC) to characterize DOM. Our findings from principal component analysis (PCA) show downstream changes in DOM chemistry to be dominated by photo-degradation, suggesting that DOM in the Okavango Delta is transformed photo-chemically in shallower downstream reaches after being mobilized from the permanent swamp and seasonal floodplains. Additionally, we found that the PARAFAC model developed for the Everglades, a large, anthropogenically-altered wetland in North America, was well suited to tracking DOM dynamics in the Okavango Delta and may be useful for characterizing DOM in other sub-tropical, seasonally flooded wetlands.

Chemical characterization of DOM in channels of a seasonal wetland

Abstract.Although wetlands are known to be important sources of dissolved organic matter (DOM) within watersheds, production of DOM within wetlands is not well understood. In the Okavango Delta, a large wetland located in Botswana, large amounts of DOM produced in the wetland are transported in the river network and to the subsurface. The purpose of this study was to gain insight into environmental processing of DOM in wetland surface waters by examining chemical characteristics of plant litter leachates and fulvic acids isolated from two surface water sites in the Panhandle (PHFA) and Seasonal Swamp (SSFA) of the Okavango Delta. Spectroscopic properties measured over the course of leaching experiments indicated a greater abundance of plant-derived DOM over time. Results of elemental and 13CNMR analyses showed that aromaticities and C:N ratios of PHFA and SSFA and a Cyperus papyrus leachate fulvic acid (CPLFA) were in the range typical for fulvic acids derived from vascular plants. Fluorescence analyses of fulvic acids using parallel factor analysis (PARAFAC) further indicated the importance of plant litter sources in surface water DOM. Environmental processing of DOM in downstream surface waters by bacterial and photodegradation was suggested by higher N and S content for SSFA compared to CPLFA and by differences in δ15N, δ34S, δ13C and fluorescence signatures among the 3 fulvic acid samples. These chemical characterization results suggest that a progressive enrichment of DOM by plant-derived material occurs with distance downstream and that this DOM undergoes some environmental processing within the surface water system.

Dissolved Organic Matter Quality in a Shallow Aquifer of Bangladesh: Implications for Arsenic Mobility

In some high arsenic (As) groundwater systems, correlations are observed between dissolved organic matter (DOM) and As concentrations, but in other systems, such relationships are absent. The role of labile DOM as the main driver of microbial reductive dissolution is not sufficient to explain the variation in DOM-As relationships. Other processes that may also influence As mobility include complexation of As by dissolved humic substances, and competitive sorption and electron shuttling reactions mediated by humics. To evaluate such humic DOM influences, we characterized the optical properties of filtered surface water (n = 10) and groundwater (n = 24) samples spanning an age gradient in Araihazar, Bangladesh. Further, we analyzed large volume fulvic acid (FA) isolates (n = 6) for optical properties, C and N content, and (13)C NMR spectroscopic distribution. Old groundwater (>30 years old) contained primarily sediment-derived DOM and had significantly higher (p < 0.001) dissolved As concentration than groundwater that was younger than 5 years old. Younger groundwater had DOM spectroscopic signatures similar to surface water DOM and characteristic of a sewage pollution influence. Associations between dissolved As, iron (Fe), and FA concentration and fluorescence properties of isolated FA in this field study suggest that aromatic, terrestrially derived FAs promote As-Fe-FA complexation reactions that may enhance As mobility.

Spatiotemporal drivers of dissolved organic matter in high alpine lakes: Role of Saharan dust inputs and bacterial activity

The effects of many environmental stressors such as UV radiation are mediated by dissolved organic matter (DOM) properties. Therefore, determining the factors shaping spatial and temporal patterns is particularly essential in the most susceptible, low dissolved organic carbon (DOC) lakes. We analyzed spatiotemporal variations in dissolved organic carbon concentration and dissolved organic matter optical properties (absorption and fluorescence) in 11 transparent lakes located above tree line in the Sierra Nevada Mountains (Spain), and we assessed potential external (evaporation and atmospheric deposition) and internal (bacterial abundance, bacterial production, chlorophyll a, and catchment vegetation) drivers of DOM patterns. At spatial and temporal scales, bacteria were related to chromophoric DOM (CDOM). At the temporal scale, water soluble organic carbon (WSOC) in dust deposition and evaporation were found to have a significant influence on DOC and CDOM in two Sierra Nevada lakes studied during the ice-free periods of 2000-2002. DOC concentrations and absorption coefficients at 320 nm were strongly correlated over the spatial scale (n = 11, R(2) = 0.86; p < 0.01), but inconsistently correlated over time, indicating seasonal and interannual variability in external factors and a differential response of DOC concentration and CDOM to these factors. At the continental scale, higher mean DOC concentrations and more CDOM in lakes of the Sierra Nevada than in lakes of the Pyrenees and Alps may be due to a combination of more extreme evaporation, and greater atmospheric dust deposition.

Dissolved Organic Matter Accumulation, Reactivity, and Redox State in Ground Water of a Recharge Wetland

Ground water beneath the seasonal swamp of the Okavango Delta, a recharge wetland in northwestern Botswana, is known to be a sink for solutes. In this study, measurements of organic carbon and inorganic ion concentrations, as well as UV-visible and fluorescence spectroscopy, were used to examine dissolved organic matter (DOM) storage and redox state of fulvic acids in ground water beneath an island and riparian woodland. Increasing dissolved organic carbon (DOC) concentrations along the ground-water flowpath suggests an accumulation of DOM in ground water, especially beneath island centers. However, the increase in DOC concentration was relatively less than the increase in chloride and sulfate concentrations, indicating non-conservative behavior of DOM in ground water beneath wetland islands. In combination with a decrease in fulvic acid content and specific UV absorbance, this result suggests that preferential sorption or destabilization of more aromatic organic compounds may be occurring under conditions of high pH and salinity. Finally, the increase in reduced fluorescence components (semiquinone- and hydroquinone-like components) along the ground-water flowpath strongly supports the transition to reduced fulvic acids in ground water of island centers. The reactivity and potential electron-shuttling function of fulvic acids may play an important role in the dissolution of metal oxides and associated DOM-iron-arsenic interactions in ground water of this recharge wetland.

Carbon, metals, and grain size correlate with bacterial community structure in sediments of a high arsenic aquifer.

Bacterial communities can exert significant influence on the biogeochemical cycling of arsenic (As). This has globally important implications since As in drinking water affects the health of over 100 million people worldwide, including in the Ganges–Brahmaputra Delta region of Bangladesh where geogenic arsenic in groundwater can reach concentrations of more than 10 times the World Health Organization’s limit. Thus, the goal of this research was to investigate patterns in bacterial community composition across gradients in sediment texture and chemistry in an aquifer with elevated groundwater As concentrations in Araihazar, Bangladesh. We characterized the bacterial community by pyrosequencing 16S rRNA genes from aquifer sediment samples collected at three locations along a groundwater flow path at a range of depths between 1.5 and 15 m. We identified significant differences in bacterial community composition between locations in the aquifer. In addition, we found that bacterial community structure was significantly related to sediment grain size, and sediment carbon (C), manganese (Mn), and iron (Fe) concentrations. Deltaproteobacteria and Chloroflexi were found in higher proportions in silty sediments with higher concentrations of C, Fe, and Mn. By contrast, Alphaproteobacteria and Betaproteobacteria were in higher proportions in sandy sediments with lower concentrations of C and metals. Based on the phylogenetic affiliations of these taxa, these results may indicate a shift to more Fe-, Mn-, and humic substance-reducers in the high C and metal sediments. It is well-documented that C, Mn, and Fe may influence the mobility of groundwater arsenic, and it is intriguing that these constituents may also structure the bacterial community.

Deposition rates of viruses and bacteria above the atmospheric boundary layer

Aerosolization of soil-dust and organic aggregates in sea spray facilitates the long-range transport of bacteria, and likely viruses across the free atmosphere. Although long-distance transport occurs, there are many uncertainties associated with their deposition rates. Here, we demonstrate that even in pristine environments, above the atmospheric boundary layer, the downward flux of viruses ranged from 0.26 × 109 to >7 × 109 m−2 per day. These deposition rates were 9–461 times greater than the rates for bacteria, which ranged from 0.3 × 107 to >8 × 107 m−2 per day. The highest relative deposition rates for viruses were associated with atmospheric transport from marine rather than terrestrial sources. Deposition rates of bacteria were significantly higher during rain events and Saharan dust intrusions, whereas, rainfall did not significantly influence virus deposition. Virus deposition rates were positively correlated with organic aerosols <0.7 μm, whereas, bacteria were primarily associated with organic aerosols >0.7 μm, implying that viruses could have longer residence times in the atmosphere and, consequently, will be dispersed further. These results provide an explanation for enigmatic observations that viruses with very high genetic identity can be found in very distant and different environments.

Biogeochemical Controls on the Release and Accumulation of Mn and As in Shallow Aquifers, West Bengal, India

The prevalence of manganese (Mn) in Southeast Asian drinking water has recently become a topic of discussion, particularly when concurrent with elevated arsenic (As). Although Mn groundwater geochemistry has been studied, the link between dissolved organic matter (DOM) quality and Mn release is less understood. This work evaluates characteristics of DOM, redox chemistry, and the distribution of Mn within Murshidabad, West Bengal, India. Shallow aquifer samples were analyzed for cations, anions, dissolved organic carbon, and DOM properties using 3-dimensional fluorescence excitation emission matrices followed by parallel factor modeling analyses. Two biogeochemical regimes are apparent, separated geographically by the river Bhagirathi. East of the river, where Eh and nitrate (NO3-) values are low, humic-like DOM coexists with high dissolved Mn, As, and Fe. West of the river, lower dissolved As and Fe concentrations are coupled with more protein-like DOM and higher NO3- and Eh values. Dissolved Mn concentrations are elevated in both regions. Based on the distribution of available electron acceptors, it is hypothesized that groundwater east of the Bhagirathi, which are more reducing and enriched in dissolved Fe and Mn but depleted in NO3-, are chemically dominated by Mn(IV) / Fe(III) reduction processes. West of the river where NO3- is abundant yet dissolved Fe is absent, NO3- and Mn(IV) likely buffer redox conditions such that Eh values are not sufficiently reducing to release Fe into the dissolved phase. The co-occurrence of humic-like DOM with dissolved As, Fe, and Mn in the more reducing aquifers may reflect complex formation between humic DOM and metals, as well as electron shuttling processes involving humic DOM, which may enhance metal(loid) release. Saturation indices of rhodochrosite (MnCO3) suggest that precipitation is thermodynamically favorable in a greater proportion of the more reducing sites, however humic DOM–Mn complexes may be inhibiting MnCO3 precipitation. Where dissolved arsenic concentrations are low, it is postulated that Mn(IV) reduction is oxidizing As(III) to As(V), increasing the potential for re-adsorption of As(V) onto relatively stable, un-reduced or newly precipitated Fe-oxides. Manganese release appears to be independent of DOM quality, as it persists in both humic and protein-like DOM environments.