Stable isotopes as an effective tool for N nutrient source identification in a heavily urbanized and agriculturally intensive tropical lowland basin

© 2020, Springer Nature Switzerland AG. We present the application of dual stable isotope analyses of NO3 (δ15N-NO3 and δ18O-NO3) to provide a comprehensive assessment of the provenance, partitioning, and conversion of nitrate across the Day River Basin (DRB), Vietnam, which is heavily impacted by agriculture and urbanization. Stable isotope compositions of river water δ18O-H2O, in addition to their δ15N-NO3 and δ18O-NO3 signatures, were sampled at 12 locations in the DRB. Sample collection was conducted during three different periods to capture changes in regional weather and agricultural fertilization regimes; April (the dry season and key fertilization period), July (the rainy season and another key fertilization period) and October (the rainy season with no regional fertilization). Ranges of NO3 stable isotopes are − 7.1 to + 9.2‰ and − 3.9 to + 13.2‰ for δ18O and δ15N, respectively. Interpretation of the stable isotope data characterizes 4 main sources of NO3 in the DRB; (1) nitrified urea fertilizer derived from an intensive agricultural irrigation network, (2) soil and groundwater leaching from within the basin (3) manure and sewage inputs (which is more prevalent in downstream river sections) and (4) upstream inflow from the Red River which discharges into the Day River through the Dao River. We applied a mixing model for the DRB consisting of 4 variables, representing these 4 different sources. The partition calculation shows that during the fertilization and rainy period of July, more than 45% of river NO3 is derived from nitrified urea sources. During the other sampling periods (April and October), manure and sewage contribute more than 50% of river NO3 and are derived from the middle portion of the DRB, where the Day River receives domestic wastewater from the Vietnamese capital, Hanoi. Stable isotope data of O and N reveal that nitrification processes are more prevalent in the rainy season than in dry season and that this predominantly takes place in paddy field agricultural zones. In general, data demonstrate that nitrate loss in the DRB is due to denitrification which takes place in polluted stretches of the river and dominates in the dry season. This study highlights that (i) domestic waste should be treated prior to its discharge into the Day River and (ii) the need for better catchment agricultural fertilization practices as large portions of fertilizer currently discharge into the river, which greatly impacts regional water quality

Insights into the transfer of silicon isotopes into the sediment record

The first δ30Sidiatom data from lacustrine sediment traps are presented from Lake Baikal, Siberia. Data are compared with March surface water (upper 180 m) δ30SiDSi compositions for which a mean value of +2.28‰ ±  0.09 (95 % confidence) is derived. This value acts as the pre-diatom bloom baseline silicic acid isotopic composition of waters (δ30SiDSi initial). Open traps were deployed along the depth of the Lake Baikal south basin water column between 2012 and 2013. Diatom assemblages display a dominance ( > 85 %) of the spring/summer bloom species Synedra acus var radians, so that δ30Sidiatom compositions reflect predominantly spring/summer bloom utilisation. Diatoms were isolated from open traps and, in addition, from 3-monthly (sequencing) traps (May, July and August 2012) for δ30Sidiatom analyses. Mean δ30Sidiatom values for open traps are +1.23‰ ±  0.06 (at 95 % confidence and MSWD of 2.9, n = 10). Total dry mass sediment fluxes are highest in June 2012, which we attribute to the initial export of the dominant spring diatom bloom. We therefore argue that May δ30Sidiatom signatures (+0.67‰ ±  0.06, 2σ) when compared with mean upper water δ30SiDSi initial (e.g. pre-bloom) signatures can be used to provide a snapshot estimation of diatom uptake fractionation factors (ϵuptake) in Lake Baikal. A ϵuptake estimation of −1.61 ‰ is therefore derived, although we emphasise that synchronous monthly δ30SiDSi and δ30Sidiatom data would be needed to provide more robust estimations and therefore more rigorously test this, particularly when taking into consideration any progressive enrichment of the DSi pool as blooms persist. The near-constant δ30Sidiatom composition in open traps demonstrates the full preservation of the signal through the water column and thereby justifies the use and application of the technique in biogeochemical and palaeoenvironmental research. Data are finally compared with lake sediment core samples, collected from the south basin. Values of +1.30‰ ±  0.08 (2σ) and +1.43‰ ±  0.13 (2σ) were derived for cores BAIK13-1C (0.6–0.8 cm core depth) and at BAIK13-4F (0.2–0.4 cm core depth) respectively. Trap data highlight the absence of a fractionation factor associated with diatom dissolution (ϵdissolution) (particularly as Synedra acus var radians, the dominant taxa in the traps, is very susceptible to dissolution) down the water column and in the lake surface sediments, thus validating the application of δ30Sidiatom analyses in Lake Baikal and other freshwater systems, in palaeoreconstructions

Diatoms in a sediment core from a flood pulse wetland in Malaysia record strong responses to human impacts and hydro‐climate over the past 150 years

Rapid development and climate change in southeast Asia is placing unprecedented pressures on freshwater ecosystems, but long term records of the ecological consequences are rare. Here we examine one basin of Tasik Chini (Malaysia), a UNESCO?designated flood pulse wetland, where human disturbances (dam installation, iron ore mining, oil palm and rubber cultivation) have escalated since the 1980s. Diatom analysis and organic matter geochemistry (?13Corg and C/N ratios) were applied to a sediment sequence to infer ecological changes in the basin since c. 1900 CE. As the Tasik Chini wetland is a rare ecosystem with an unknown diatom ecology, contemporary diatom habitats (plant surfaces, mud surfaces, rocks, plankton) were sampled from across the lake to help interpret the sedimentary record. Habitat specificity of diatoms was not strongly defined and, although planktonic and benthic groupings were distinctive, there was no difference in assemblages among the benthic habitat surfaces. An increase in the proportion of benthic diatom taxa suggests that a substantial decrease in water level occurred between c. 1938 and 1995 CE, initiated by a decline in rainfall (supported by regional meteorological data), which increased the hydrological isolation of the sub?basin. Changes in the diatom assemblages were most marked after 1995 CE when the Chini dam was installed. After this time both ?13Corg and C/N decreased, suggesting an increase in autochthonous production relative to allochthonous river flood pulse inputs. Oil palm plantations and mining continued to expand after c. 1995 CE and we speculate that inputs of pollutants from these activities may have contributed to the marked ecological change. Together, our work shows that this sub?basin of Tasik Chini has been particularly sensitive to, and impacted by, a combination of human and climatically induced changes due to its hydrologically isolated position

Using stable isotopes to estimate young water fractions in a heavily regulated, tropical lowland river basin

The young water fraction of streamflow (Fyw), an important hydrological variable, has been calculated for the first time, for a monsoon‐fed coastal catchment in northern Vietnam. Oxygen stable isotopes (δ18O) from six river sites in the Day River Basin (DRB) were analysed monthly, between January 2015 and December 2018. River δ18O signatures showed sine wave variability, reflecting the amount effect and tropical (dry‐rainy) seasonality of the region. The δ18O composition of precipitation ranged from −12.67 to +1.68‰, with a mean value of −5.14‰, and in‐streamflow signatures ranged from −11.63 to −1.37‰ with a mean of −5.02‰. Fractions of young water (Fyw) were calculated from the unweighted and flow‐weighted δ18O composition of samples. Unweighted Fyw ranged between 29 ± 8% and 82 ± 21% with a mean value of 51 ± 19%, and was not significantly different from flow‐weighted Fyw (range between 33 ± 25% and 92 ± 73%, mean 52 ± 36%). Both unweighted and flow‐weighted Fyw were highest in the middle of stream and lowest in downstream sites, capturing the impacts of landuse changes, hydrology and human activities in the catchment. Our calculations imply that more than a half of rainwater reaches the DRB river mainstream within the first 3 months. The Fyw is much higher than the global average (of one‐third) and insensitive to discharge due to the combination of a humid catchment with high rainfall, low storage capacity, flat landscape and an intensive drainage system in the DRB. Also the low discharge sensitivity of Fyw in the DRB implies that the regional hydrology is severely altered by humans

Spatial differences in dissolved silicon utilisation in Lake Baikal, Siberia: examining the impact of high diatom biomass events and eutrophication

Recent research has highlighted how Lake Baikal, Siberia, has responded to the direct and indirect effects of climate change (e.g., ice-cover duration), nutrient loading, and pollution, manifesting as changes in phytoplankton/zooplankton populations, community structure, and seasonal succession. Here, we combine and compare= analyses of chlorophyll a (an estimate of total algal biomass), carotenoid pigments (biomarkers of algal groups), and lake water silicon isotope geochemistry (d30SiDSi) to differentiate spatial patterns in dissolved silicon (DSi) uptake at Lake Baikal. A total of 15 sites across the three basins (south, central, and north) of Lake Baikal were sampled in August 2013 along a depth gradient of 0–180 m. Strong, significant correlations were found between vertical profiles of photic zone DSi concentrations and d30SiDSi compositions (r 5 20.81, p < 0.001), although these are strongest in the central basin aphotic zone (r 5 20.98, p < 0.001). Data refute the hypothesis of DSi uptake by picocyanobacteria. Algal biomass profiles and high surface d30SiDSi compositions suggest greater productivity in the south basin and more oligotrophic conditions in the north basin. d30SiDSi signatures are highest at depth (20 m) in central basin sites, indicating greater (10–40%) DSi utilization at deep chlorophyll maxima. DSi limitation occurs in the pelagic central basin, probably reflecting a high diatom biomass bloom event (Aulacoseira baicalensis). Meanwhile in the more hydrologically restricted, shallow Maloe More region (central basin), both high d30SiDSi compositions and picocyanobacteria (zeaxanthin) concentrations, respectively point to the legacy of an “Aulacoseira bloom year” and continuous nutrient supply in summer months (e.g., localized eutrophication)

The stable isotope composition of organic and inorganic fossils in lake sediment records: current understanding, challenges, and future directions

This paper provides an overview of stable isotope analysis (H, C, N, O, Si) of the macro and microscopic remains from aquatic organisms found in lake sediment records and their application in (palaeo)environmental science. Aquatic organisms, including diatoms, macrophytes, invertebrates, and fish, can produce sufficiently robust remains that preserve well as fossils and can be identified in lake sediment records. Stable isotope analyses of these remains can then provide valuable insights into habitat-specific biogeochemistry, feeding ecology, but also on climatic and hydrological changes in and around lakes. Since these analyses focus on the remains of known and identified organisms, they can provide more specific and detailed information on past ecosystem, food web and environmental changes affecting different compartments of lake ecosystems than analyses on bulk sedimentary organic matter or carbonate samples. We review applications of these types of analyses in palaeoclimatology, palaeohydrology, and palaeoecology. Interpretation of the environmental ‘signal’ provided by taxon-specific stable isotope analysis requires a thorough understanding of the ecology and phenology of the organism groups involved. Growth, metabolism, diet, feeding strategy, migration, taphonomy and several other processes can lead to isotope fractionation or otherwise influence the stable isotope signatures of the remains from aquatic organisms. This paper includes a review of the (modern) calibration, culturing and modeling studies used to quantify the extent to which these factors influence stable isotope values and provides an outlook for future research and methodological developments for the different examined fossil groups

Influence of the ratio of planktonic to benthic diatoms on lacustrine organic matter δ13C from Erlongwan maar lake, northeast China

Carbon isotope ratio (δ13Corg) values of organic matter in lake sediments are commonly used to reconstruct environmental change, but the factors which influence change are varied and complex. Here we report δ13C values for sediments from Erlongwan maar lake in northeast China. In this record, changes in δ13C cannot be explained by simple changes in aquatic productivity. Instead, values were likely influenced by differences in the ratio between planktonic and benthic algae, as indicated by the remains of diatoms. This is because the variation of δ13Corg in algae from different habitats is controlled by the thickness of the diffusive boundary layer, which is dependent on the turbulence of the water. Compared with benthic algae, which grow in relatively still water, pelagic algae are exposed to greater water movement. This is known to dramatically reduce the thickness of the boundary layer and was found to cause even more severe δ13C depletion. In Erlongwan maar lake, low values were linked to the dominance of planktonic diatoms during the period commonly known as the Medieval Warm Period. Values gradually increased with the onset of the Little Ice Age, which we interpret as being driven by an increase in the proportion of benthic taxa, due to effect of the colder climate. The increase in planktonic diatoms at the end of the Little Ice Age, linked to higher temperature and a reduction in ice cover, resulted in a further decline in δ13Corg

Investigating the role of hydrological connectivity on the processing of organic carbon in tropical aquatic ecosystems

Inland waters are highways of carbon and nutrient flows between the land and ocean. Aquatic environments integrate multiple sources and processes over space and time that influence ecosystem functionality. The complexity of these systems and their multiple interactions with the surrounding environment are conceptualised, but often lack empirical scrutiny that allows further understanding of how inland waters mobilise, transport, and utilise carbon and nutrients. This is particularly evident in tropical waters. Here, we apply advanced geochemical analyses of dissolved organic matter (DOM) composition in conjunction with algal pigment biomarkers, to determine the seasonal variability of organic matter production, processing and export for a tropical, floodpulse wetland, Tasik Chini (Malaysia). We identify two phases in the hydrological cycle: Phase 1 signifying a transition from the wet season with high suspended sediment and dissolved organic carbon concentrations. DOM is composed of humic substances, building blocks and lower molecular weight compounds. Towards the end this phase then are periods of increased water clarity and algal productivity. This is followed by Phase 2, which has a greater contribution of autochthonous DOM, composed of proteinaceous material, concomitant with lower dissolved nutrient concentrations, increased mixotrophic algae and emergent vegetation. Based on this framework, we highlight the role of such tropical wetland lakes as hydrological “bottlenecks,” through a lentic/lotic switch that shifts aquatic transport of carbon and nutrients from lateral river continuum supply to flood pulses. We highlight the need to consider inherent biases of spatial and temporal scaling when examining freshwater ecosystems along the land-ocean aquatic continuum

Using lake sediments to assess the long-term impacts of anthropogenic activity in tropical river deltas

Tropical river deltas, and the social-ecological systems they sustain, are changing rapidly due to anthropogenic activity and climatic change. Baseline data to inform sustainable management options for resilient deltas is urgently needed and palaeolimnology (reconstructing past conditions from lake or wetland deposits) can provide crucial long-term perspectives needed to identify drivers and rates of change. We review how palaeolimnology can be a valuable tool for resource managers using three current issues facing tropical delta regions: hydrology and sediment supply, salinisation and nutrient pollution. The unique ability of palaeolimnological methods to untangle multiple stressors is also discussed. We demonstrate how palaeolimnology has been used to understand each of these issues, in other aquatic environments, to be incorporated into policy. Palaeolimnology is a key tool to understanding how anthropogenic influences interact with other environmental stressors, providing policymakers and resource managers with a ‘big picture’ view and possible holistic solutions that can be implemented