Unaccounted CO2 leaks downstream of a large tropical hydroelectric reservoir.

Recent studies show that tropical hydroelectric reservoirs may be responsible for substantial greenhouse gas emissions to the atmosphere, yet emissions from the surface of released water downstream of the dam are poorly characterized if not neglected entirely from most assessments. We found that carbon dioxide (CO2) emission downstream of Kariba Dam (southern Africa) varied widely over different timescales and that accounting for downstream emissions and their fluctuations is critically important to the reservoir carbon budget. Seasonal variation was driven by reservoir stratification and the accumulation of CO2 in hypolimnetic waters, while subdaily variation was driven by hydropeaking events caused by dam operation in response to daily electricity demand. This "carbopeaking" resulted in hourly variations of CO2 emission up to 200% during stratification. Failing to account for seasonal or subdaily variations in downstream carbon emissions could lead to errors of up to 90% when estimating the reservoir's annual emissions. These results demonstrate the critical need to include both limnological seasonality and dam operation at subdaily time steps in the assessment of carbon budgeting of reservoirs and carbon cycling along the aquatic continuum.

Citizen scientist monitoring accurately reveals nutrient pollution dynamics in Lake Tanganyika coastal waters.

Several studies in Lake Tanganyika have effectively employed traditional methods to explore changes in water quality in open waters; however, coastal monitoring has been restricted and sporadic, relying on costly sample and analytical methods that require skilled technical staff. This study aims in validating citizen science water quality collected data (nitrate, phosphate and turbidity) with those collected and measured by professional scientists in the laboratory. A second objective of the study is to use citizen scientist data to identify the patterns of seasonal and spatial variations in nutrient conditions and forecast potential changes based on expected changes in population and climate (to 2050). The results showed that the concentrations of nitrate and phosphate measured by citizen scientists nearly matched those established by professional scientists, with overall accuracy of 91% and 74%, respectively. For total suspended solids measured by professional and turbidity measured by citizen scientists, results show that, using 14 NTU as a cut-off, citizen scientist measurements of Secchi tube depth to identify lake TSS below 7.0 mg/L showed an accuracy of 88%. In both laboratory and citizen scientist-based studies, all measured water quality variables were significantly higher during the wet season compared to the dry season. Climate factors were discovered to have a major impact on the likelihood of exceeding water quality restrictions in the next decades (2050), which could deteriorate lake conditions. Upscaling citizen science to more communities on the lake and other African Great Lakes would raise environmental awareness, inform management and mitigation activities, and aid long-term decision-making.

Structural genomic variation leads to genetic differentiation in Lake Tanganyika's sardines.

Identifying patterns in genetic structure and the genetic basis of ecological adaptation is a core goal of evolutionary biology and can inform the management and conservation of species that are vulnerable to population declines exacerbated by climate change. We used reduced-representation genomic sequencing methods to gain a better understanding of genetic structure among and within populations of Lake Tanganyika's two sardine species, Limnothrissa miodon and Stolothrissa tanganicae. Samples of these ecologically and economically important species were collected across the length of Lake Tanganyika, as well as from nearby Lake Kivu, where L. miodon was introduced in 1959. Our results reveal differentiation within both S. tanganicae and L. miodon that is not explained by geography. Instead, this genetic differentiation is due to the presence of large sex-specific regions in the genomes of both species, but involving different polymorphic sites in each species. Our results therefore indicate rapidly evolving XY sex determination in the two species. Additionally, we found evidence of a large chromosomal rearrangement in L. miodon, creating two homokaryotypes and one heterokaryotype. We found all karyotypes throughout Lake Tanganyika, but the frequencies vary along a north-south gradient and differ substantially in the introduced Lake Kivu population. We do not find evidence for significant isolation by distance, even over the hundreds of kilometres covered by our sampling, but we do find shallow population structure.

Nutrient Behavior in Hydrothermal Carbonization Aqueous Phase Following Recirculation and Reuse.

Hydrothermal carbonization (HTC) has received much attention in recent years as a process to convert wet organic waste into carbon-rich hydrochar. The process also generates an aqueous phase that is still largely considered a burden. The success of HTC is dependent on finding solutions for the aqueous phase. In the present study, we provide the first investigation of recirculation of the aqueous phase from HTC of poultry litter as a means to concentrate nutrients and its subsequent application to agriculture as a fertilizer. Aqueous-phase recirculation generally resulted in an increase in nitrogen, phosphorus, and potassium concentrations up to cycle 3 with maximum concentrations reaching up to 5400, 397, and 23300 mg L-1 for N, P, and K, respectively. Recirculation did not adversely affect hydrochar composition or calorific value. The recirculated and nonrecirculated aqueous phases were able to support lettuce growth similar to a commercial fertilizer. Results from this study indicate that the combination of aqueous-phase recirculation and use as a fertilizer could be a suitable method to reutilize the aqueous phase and recycle nutrients back into agriculture, thus increasing HTC efficiency and economic feasibility.

Fast Potentiometric CO2 Sensor for High-Resolution in Situ Measurements in Fresh Water Systems.

We present a new potentiometric sensor principle and a calibration protocol for in situ profiling of dissolved CO2 with high temporal and spatial resolution in fresh water lakes. The sensor system is based on the measurement of EMF between two solid-contact ion selective electrodes (SC-ISEs), a hydrogen ion selective and a carbonate selective sensor. Since it relies on SC-ISEs, it is insensitive to changes in pressure, thus suitable for in situ studies. Also, as it offers a response time ( t95%) of <10 s, it allows for profiling applications at high spatial resolution. The proposed optimum in situ protocol accounts for the continuous drift and change in offset that remains a challenge during profiling in natural waters. The fast response resolves features that are usually missed by standard methods like the classical Severinghaus CO2 probe. In addition, the insensitivity of the presented setup to dissolved sulfide allows also for measurements in anoxic zones of eutrophic systems. Highly resolved CO2 concentration profiles obtained by the novel and robust SC-ISE setup along with the developed optimum in situ protocol allow investigating hotspots of biogeochemical processes, such as mineralization and primary production in the water column and help improving estimates for CO2 turnover in freshwater systems.

Thermostatted dual-channel portable capillary electrophoresis instrument.

A new portable CE instrument is presented. The instrument features the concurrent separation of anions and cations in parallel channels. Each channel has a separate buffer container to allow independent optimization of separation conditions. The microfluidics circuit is based on off-the-shelf parts, and can be easily replicated; only four valves are present in the design. The system employs a miniature automated syringe pump, which can apply both positive and negative pressures (-100 to 800 kPa). The application of negative pressure allows a semi-automatic mode of operation for introducing volume-limited samples. The separations are performed in a thermostatted compartment for improved reproducibility in field conditions. The instrument has a compact design, with all components, save for batteries and power supplies, arranged in a briefcase with dimensions of 52 × 34 × 18 cm and a weight of less than 15 kg. The system runs automatically and is controlled by a purpose-made graphical user interface on a connected computer. For demonstration, the system was successfully employed for the concurrent separation and analysis of inorganic cations and anions in sediment porewater samples from Lake Baldegg in Switzerland and of metal ions in a sample from the tailing pond of an abandoned mine in Argentina.

In Situ Ammonium Profiling Using Solid-Contact Ion-Selective Electrodes in Eutrophic Lakes.

A promising profiling setup for in situ measurements in lakes with potentiometric solid-contact ion-selective electrodes (SC-ISEs) and a data processing method for sensor calibration and drift correction are presented. The profiling setup consists of a logging system, which is equipped with a syringe sampler and sensors for the measurement of standard parameters including temperature, conductivity, oxygen and photosynthetically active radiation (PAR). The setup was expanded with SC-ISEs in galvanically separated amplifiers. The potential for high-resolution profiling is investigated by deploying the setup in the eutrophic Lake Rotsee (Lucerne, Switzerland), using two different designs of ammonium sensing SC-ISEs. Ammonium was chosen as a target analyte, since it is the most common reduced inorganic nitrogen species involved in various pathways of the nitrogen cycle and is therefore indicative of numerous biogeochemical processes that occur in lakes such as denitrification and primary production. One of the designs, which uses a composite carbon-nanotube-PVC-based membrane, suffered from sulfide poisoning in the deeper, sulfidic regions of the lake. In contrast, electrodes containing a plasticizer-free methacrylate copolymer-based sensing layer on top of a conducting polymer layer as a transducer did not show this poisoning effect. The syringe samples drawn during continuous profiling were utilized to calibrate the electrode response. Reaction hotspots and steep gradients of ammonium concentrations were identified on-site by monitoring the electrode potential online. Upon conversion to high-resolution concentration profiles, fine scale features between the calibration points were displayed, which would have been missed by conventional limnological sampling and subsequent laboratory analyses. Thus, the presented setup with SC-ISEs tuned to analytes of interest can facilitate the study of biogeochemical processes that occur at the centimeter scale.

Improving crop yield and water productivity by ecological sanitation and water harvesting in South Africa.

This study quantifies the potential effects of a set of technologies to address water and fertility constraints in rain-fed smallholder agriculture in South Africa, namely in situ water harvesting (WH), external WH, and ecological sanitation (Ecosan, fertilization with human urine). We used the Soil and Water Assessment Tool to model spatiotemporally differentiated effects on maize yield, river flow, evaporation, and transpiration. Ecosan met some of the plant nitrogen demands, which significantly increased maize yields by 12% and transpiration by 2% on average across South Africa. In situ and external WH did not significantly affect the yield, transpiration or river flow on the South Africa scale. However, external WH more than doubled the yields for specific seasons and locations. WH particularly increased the lowest yields. Significant water and nutrient demands remained even with WH and Ecosan management. Additional fertility enhancements raised the yield levels but also the yield variability, whereas soil moisture enhancements improved the yield stability. Hence, coupled policies addressing both constraints will likely be most effective for improving food security.

Fe(II) sorption on a synthetic montmorillonite. A combined macroscopic and spectroscopic study.

Extended X-ray absorption fine structure (EXAFS) and Mössbauer spectroscopy combined with macroscopic sorption experiments were employed to investigate the sorption mechanism of Fe(II) on an iron-free synthetic montmorillonite (Na-IFM). Batch sorption experiments were performed to measure the Fe(II) uptake on Na-IFM at trace concentrations as a function of pH and as a function of sorbate concentration at pH 6.2 and 6.7 under anoxic conditions (O2 < 0.1 ppm). A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model was used to quantitatively describe the uptake of Fe(II) on Na-IFM. Two types of clay surface binding sites were required to model the Fe(II) sorption, the so-called strong (≡S(S)OH) and weak (≡S(W)OH) sites. EXAFS data show spectroscopic differences between Fe sorbed at low and medium absorber concentrations that were chosen to be characteristic for sorption on strong and weak sites, respectively. Data analysis indicates that Fe is located in the continuity of the octahedral sheet at trans-symmetric sites. Mössbauer spectroscopy measurements confirmed that iron sorbed on the weak edge sites is predominantly present as Fe(II), whereas a significant part of surface-bound Fe(III) was produced on the strong sites (∼12% vs ∼37% Fe(III) species to total sorbed Fe).

Isotopic signatures induced by upwelling reveal regional fish stocks in Lake Tanganyika.

Lake Tanganyika's pelagic fish sustain the second largest inland fishery in Africa and are under pressure from heavy fishing and global warming related increases in stratification. The strength of water column stratification varies regionally, with a more stratified north and an upwelling-driven, biologically more productive south. Only little is known about whether such regional hydrodynamic regimes induce ecological or genetic differences among populations of highly mobile, pelagic fish inhabiting these different areas. Here, we examine whether the regional contrasts leave distinct isotopic imprints in the pelagic fish of Lake Tanganyika, which may reveal differences in diet or lipid content. We conducted two lake-wide campaigns during different seasons and collected physical, nutrient, chlorophyll, phytoplankton and zooplankton data. Additionally, we analyzed the pelagic fish-the clupeids Stolothrissa tanganicae, Limnothrissa miodon and four Lates species-for their isotopic and elemental carbon (C) and nitrogen (N) compositions. The δ13C values were significantly higher in the productive south after the upwelling/mixing period across all trophic levels, implying that the fish have regional foraging grounds, and thus record these latitudinal isotope gradients. By combining our isotope data with previous genetic results showing little geographic structure, we demonstrate that the fish reside in a region for a season or longer. Between specimens from the north and south we found no strong evidence for varying trophic levels or lipid contents, based on their bulk δ15N and C:N ratios. We suggest that the development of regional trophic or physiological differences may be inhibited by the lake-wide gene flow on the long term. Overall, our findings show that the pelagic fish species, despite not showing evidence for genetic structure at the basin scale, form regional stocks at the seasonal timescales. This implies that sustainable management strategies may consider adopting regional fishing quotas.

Hydrodynamic regimes modulate nitrogen fixation and the mode of diazotrophy in Lake Tanganyika.

The factors that govern the geographical distribution of nitrogen fixation are fundamental to providing accurate nitrogen budgets in aquatic environments. Model-based insights have demonstrated that regional hydrodynamics strongly impact nitrogen fixation. However, the mechanisms establishing this physical-biological coupling have yet to be constrained in field surveys. Here, we examine the distribution of nitrogen fixation in Lake Tanganyika - a model system with well-defined hydrodynamic regimes. We report that nitrogen fixation is five times higher under stratified than under upwelling conditions. Under stratified conditions, the limited resupply of inorganic nitrogen to surface waters, combined with greater light penetration, promotes the activity of bloom-forming photoautotrophic diazotrophs. In contrast, upwelling conditions support predominantly heterotrophic diazotrophs, which are uniquely suited to chemotactic foraging in a more dynamic nutrient landscape. We suggest that these hydrodynamic regimes (stratification versus mixing) play an important role in governing both the rates and the mode of nitrogen fixation.

Adsorption of arsenic on polyaluminum granulate.

The kinetics and efficiencies of arsenite and arsenate removal from water were evaluated using polyaluminum granulates (PAG) with high content of aluminum nanoclusters. PAG was characterized to be meso- and macroporous, with a specific surface area of 35 ± 1 m(2) g(-1). Adsorption experiments were conducted at pH 7.5 in deionized water and synthetic water with composition of As-contaminated groundwater in the Pannonian Basin. As(III) and As(V) sorption was best described by the Freundlich and Langmuir isotherm, respectively, with a maximum As(V) uptake capacity of ~200 µmol g(-1) in synthetic water. While As(III) removal reached equilibrium within 40 h, As(V) was removed almost entirely within 20 h. Micro X-ray fluorescence and electron microscopy revealed that As(III) was distributed uniformly within the grain, whereas As(V) diffused up to 81 µm into PAG. The results imply that As(V) is adsorbed 3 times faster while being transported 10(5) times slower than As(III) in Al hydroxide materials.

Tracking the legacy of early industrial activity in sediments of Lake Zurich, Switzerland: using a novel multi-proxy approach to find the source of extensive metal contamination.

Historical industrial activities at the Horn Richterwil, on the shore of Lake Zurich (Switzerland), caused widespread metal contamination on land and in the adjacent lake sediments. This study provides an estimation of the age and source of the contamination by using XRF core scanning, ICP-OES, and Hg-AFS for quantitative measurements of trace metals and MC-ICP-MS for the stable isotope analysis of mercury. Radiometric dating ([Formula: see text]Cs, [Formula: see text]Pb, and Pu dating) of two proximal cores and varve chronology in a distal core suggest two different contaminations, one stemming from around 1960 (Zn, Cd) and an earlier one from 1880 (Cr, Cu, Hg, Pb, Sn). The XRF data suggest two different contamination pathways: one by landfill of contaminated soil and another one by industrial wastewater effluents. Maximum concentrations found within all samples are in the range of per mil (dry weight) for Cr, Cu, Hg, Pb, Sn, and Zn and lie within the top 10 cm of the sediment cores. The analysis of the mercury isotopic composition ([Formula: see text]Hg and [Formula: see text]Hg) shows a significantly different signature for one of the cores, indicating a second mercury source. We could not identify the exact source or process leading to the isotopic fractionation of mercury, but the isotopic data confirm two different sources.

Spatial heterogeneity of methane ebullition in a large tropical reservoir.

Tropical reservoirs have been identified as important methane (CH(4)) sources to the atmosphere, primarily through turbine and downstream degassing. However, the importance of ebullition (gas bubbling) remains unclear. We hypothesized that ebullition is a disproportionately large CH(4) source from reservoirs with dendritic littoral zones because of ebullition hot spots occurring where rivers supply allochthonous organic material. We explored this hypothesis in Lake Kariba (Zambia/Zimbabwe; surface area >5000 km(2)) by surveying ebullition in bays with and without river inputs using an echosounder and traditional surface chambers. The two techniques yielded similar results, and revealed substantially higher fluxes in river deltas (∼10(3) mg CH(4) m(-2) d(-1)) compared to nonriver bays (<100 mg CH(4) m(-2) d(-1)). Hydroacoustic measurements resolved at 5 m intervals showed that flux events varied over several orders of magnitude (up to 10(5) mg CH(4) m(-2) d(-1)), and also identified strong differences in ebullition frequency. Both factors contributed to emission differences between all sites. A CH(4) mass balance for the deepest basin of Lake Kariba indicated that hot spot ebullition was the largest atmospheric emission pathway, suggesting that future greenhouse gas budgets for tropical reservoirs should include a spatially well-resolved analysis of ebullition hot spots.

Arsenic dynamics in porewater of an intermittently irrigated paddy field in Bangladesh.

In Bangladesh, irrigation of dry season rice (boro) with arsenic-contaminated groundwater is leading to increased As levels in soils and rice, and to concerns about As-induced yield reduction. Arsenic concentrations and speciation in soil porewater are strongly influenced by redox conditions, and thus by water management during rice growth. We studied the dynamics of As, Fe, P, Si, and other elements in porewater of a paddy field near Sreenagar (Munshiganj), irrigated according to local practice, in which flooding was intermittent. During early rice growth, As porewater concentrations reached up to 500 µg L(-1) and were dominated by As(III), but As release was constrained to the lower portion of the soil above the plow pan. In the later part of the season, soil conditions were oxic throughout the depth range relevant to rice roots and porewater concentrations only intermittently increased to ∼150 µg L(-1) As(V) following irrigation events. Our findings suggest that intermittent irrigation, currently advocated in Bangladesh for water-saving purposes, may be a promising means of reducing As input to paddy soils and rice plant exposure to As.

Anoxic chlorophyll maximum enhances local organic matter remineralization and nitrogen loss in Lake Tanganyika.

In marine and freshwater oxygen-deficient zones, the remineralization of sinking organic matter from the photic zone is central to driving nitrogen loss. Deep blooms of photosynthetic bacteria, which form the suboxic/anoxic chlorophyll maximum (ACM), widespread in aquatic ecosystems, may also contribute to the local input of organic matter. Yet, the influence of the ACM on nitrogen and carbon cycling remains poorly understood. Using a suite of stable isotope tracer experiments, we examined the transformation of nitrogen and carbon under an ACM (comprising of Chlorobiaceae and Synechococcales) and a non-ACM scenario in the anoxic zone of Lake Tanganyika. We find that the ACM hosts a tight coupling of photo/litho-autotrophic and heterotrophic processes. In particular, the ACM was a hotspot of organic matter remineralization that controlled an important supply of ammonium driving a nitrification-anammox coupling, and thereby played a key role in regulating nitrogen loss in the oxygen-deficient zone.

Living with floating vegetation invasions.

Invasions of water bodies by floating vegetation, including water hyacinth (Eichhornia crassipes), are a huge global problem for fisheries, hydropower generation, and transportation. We analyzed floating plant coverage on 20 reservoirs across the world's tropics and subtropics, using > 30 year time-series of LANDSAT remote-sensing imagery. Despite decades of costly weed control, floating invasion severity is increasing. Floating plant coverage correlates with expanding urban land cover in catchments, implicating urban nutrient sources as plausible drivers. Floating vegetation invasions have undeniable societal costs, but also provide benefits. Water hyacinths efficiently absorb nutrients from eutrophic waters, mitigating nutrient pollution problems. When washed up on shores, plants may become compost, increasing soil fertility. The biomass is increasingly used as a renewable biofuel. We propose a more nuanced perspective on these invasions moving away from futile eradication attempts towards an ecosystem management strategy that minimizes negative impacts while integrating potential social and environmental benefits.

Non-additive effects of foundation species determine the response of aquatic ecosystems to nutrient perturbation.

Eutrophication is a persistent threat to aquatic ecosystems worldwide. Foundation species, namely those that play a central role in the structuring of communities and functioning of ecosystems, are likely important for the resilience of aquatic ecosystems in the face of disturbance. However, little is known about how interactions among such species influence ecosystem responses to nutrient perturbation. Here, using an array (N = 20) of outdoor experimental pond ecosystems (15,000 L), we manipulated the presence of two foundation species, the macrophyte Myriophyllum spicatum and the mussel Dreissena polymorpha, and quantified ecosystem responses to multiple nutrient disturbances, spread over two years. In the first year, we added five nutrient pulses, ramping up from 10 to 50 µg P/L over a 10-week period from mid-July to mid-October, and in the second year, we added a single large pulse of 50 µg P/L in mid-October. We used automated sondes to measure multiple ecosystems properties at high frequency (15-minute intervals), including phytoplankton and dissolved organic matter fluorescence, and to model whole-ecosystem metabolism. Overall, both foundation species strongly affected the ecosystem responses to nutrient perturbation, and, as expected, initially suppressed the increase in phytoplankton abundance following nutrient additions. However, when both species were present, phytoplankton biomass increased substantially relative to other treatment combinations: non-additivity was evident for multiple ecosystem metrics following the nutrient perturbations in both years but was diminished in the intervening months between our perturbations. Overall, these results demonstrate how interactions between foundation species can cause surprisingly strong deviations from the expected responses of aquatic ecosystems to perturbations such as nutrient additions.

Anthropogenic influences on Zambian water quality: hydropower and land-use change.

The Zambezi River Basin in Southern Africa is undergoing rapid development and population growth. Agricultural intensification, urbanization and future development of hydropower dams will likely lead to a degradation of surface water quality, but there have been few formal assessments of where, how and why these changes impact specific water quality parameters based on in situ data spanning a large region. We sampled a large suite of biogeochemical water quality parameters at 14 locations in four field campaigns in central and southern Zambia in 2018 and 2019 to characterize seasonal changes in water quality in response to large hydropower dams and human landscape transformations. We find that the major rivers (Zambezi and Kafue) are very clean with extremely low concentrations of solutes, but suffer from thermal changes, hypoxia and loss of suspended sediment below dams. Smaller tributaries with a relatively large anthropogenic landcover footprint in their catchments show signs of pollution in the form of higher concentrations of nutrients and dissolved ions. We find significant relationships between crop and urban land cover metrics and selected water quality metrics (i.e. conductivity, phosphorus and nitrogen) across our data set. These results reflect a very high-quality waterscape exhibiting some hotspots of degradation associated with specific human activities. We anticipate that as agricultural intensification, urbanization and future hydropower development continue to accelerate in the basin, the number and extent of these hotspots of water quality degradation will grow in response. There is an opportunity for governments, managers and industry to mitigate water quality degradation via investment in sustainable infrastructure and practice, such as wastewater treatment, environmental dam operations, or riparian protection zones.