Short-Term Groundwater Level Fluctuations Drive Subsurface Redox Variability.

As global change processes modify the extent and functions of terrestrial-aquatic interfaces, the variability of critical and dynamic transitional zones between wetlands and uplands increases. However, it is still unclear how fluctuating water levels at these dynamic boundaries alter groundwater biogeochemical cycling. Here, we used high-temporal resolution data along gradients from wetlands to uplands and during fluctuating water levels at freshwater coastal areas to capture spatiotemporal patterns of groundwater redox potential (Eh). We observed that topography influences groundwater Eh that is higher in uplands than in wetlands; however, the high variability within TAI zones challenged the establishment of distinct redox zonation. Declining water levels generally decreased Eh, but most locations exhibited significant Eh variability, which is associated with rare instances of short-term water level fluctuations, introducing oxygen. The Eh-oxygen relationship showed distinct hysteresis patterns, reflecting redox poising capacity at higher Eh, maintaining more oxidizing states longer than the dissolved oxygen presence. Surprisingly, we observed more frequent oxidizing states in transitional areas and wetlands than in uplands. We infer that occasional oxygen entering specific wetland-upland boundaries acts as critical biogeochemical control points. High-resolution data can capture such rare yet significant biogeochemical instances, supporting redox-informed models and advancing the predictability of climate change feedback.

Distinct Non-conservative Behavior of Dissolved Organic Matter after Mixing Solimões/Negro and Amazon/Tapajós River Waters.

Positive and negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and 1H NMR revealed major compositional and structural changes of dissolved organic matter (DOM) after mixing two sets of river waters in Amazon confluences: the Solimões and Negro Rivers (S + N) and the Amazon and Tapajós Rivers (A + T). We also studied the effects of water mixing ratios and incubation time on the composition and structure of DOM molecules. NMR spectra demonstrated large-scale structural transformations in the case of S + N mixing, with gain of pure and functionalized aliphatic units and loss of all other structures after 1d incubation. A + T mixing resulted in comparatively minor structural alterations, with a major gain of small aliphatic biomolecular binding motifs. Remarkably, structural alterations from mixing to 1d incubation were in essence reversed from 1d to 5d incubation for both S + N and A + T mixing experiments. Heterotrophic bacterial production (HBP) in endmembers S, N, and S + N mixtures remained near 0.03 µgC L-1 h-1, whereas HBP in A, T, and A + T were about five times higher. High rates of dark carbon fixation took place at S + N mixing in particular. In-depth biogeochemical characterization revealed major distinctions between DOM biogeochemical changes and temporal evolution at these key confluence sites within the Amazon basin.

Comprehensive assessment of dissolved organic matter processing in the Amazon River and its major tributaries revealed by positive and negative electrospray mass spectrometry and NMR spectroscopy.

Rivers are natural biogeochemical systems shaping the fates of dissolved organic matter (DOM) from leaving soils to reaching the oceans. This study focuses on Amazon basin DOM processing employing negative and positive electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI[±] FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR) to reveal effects of major processes on the compositional space and structural characteristics of black, white and clear water systems. These include non-conservative mixing at the confluences of (1) Solimões and the Negro River, (2) the Amazon River and the Madeira River, and (3) in-stream processing of Amazon River DOM between the Madeira River and the Tapajós River. The Negro River (black water) supplies more highly oxygenated and high molecular weight compounds, whereas the Solimões and Madeira Rivers (white water) contribute more CHNO and CHOS molecules to the Amazon River main stem. Aliphatic CHO and abundant CHNO compounds prevail in Tapajos River DOM (clear water), likely originating from primary production. Sorption onto particles and heterotrophic microbial degradation are probably the principal mechanisms for the observed changes in DOM composition in the Amazon River and its tributaries.

Forest cover controls the nitrogen and carbon stable isotopes of rivers.

Deforestation affects the ecological integrity of rivers and streams, threatening biodiversity and ecosystem services worldwide. However, few studies have strictly analyzed the effect of the functional responses of tropical streams to changes in forest cover since deforested basins are usually also influenced by confounding anthropogenic inputs. Here we address tropical streams and test whether the stable isotopic ratios of nitrogen (N, δ15N) and carbon (C, δ13C) and the ratio of C:N of ecosystem components vary along a forest cover gradient. We also assess the ecological integrity of streams by in situ measurements using physical features commonly used in stream quality assessments. The results showed that the δ15N of most aquatic components, δ13C of particulate matter and omnivorous fish, and C:N of particulate matter and algae vary significantly with forest cover, indicating the role of terrestrial vegetation in regulating stream biogeochemistry. The dual stable isotope analysis satisfactorily indicated the changes in terrestrial-aquatic connections regarding both N and C cycles, thus showing the role of algae and particulate matter in influencing stream fauna through food web transfers. Our results support the use of stable isotopes to monitor watershed deforestation and highlight the need for reassessment of the effects of anthropogenic inputs on δ15N increase in globally distributed inland waters since the loss of forest is a significant cause in itself.

Tropical forests as drivers of lake carbon burial.

A significant proportion of carbon (C) captured by terrestrial primary production is buried in lacustrine ecosystems, which have been substantially affected by anthropogenic activities globally. However, there is a scarcity of sedimentary organic carbon (OC) accumulation information for lakes surrounded by highly productive rainforests at warm tropical latitudes, or in response to land cover and climate change. Here, we combine new data from intensive campaigns spanning 13 lakes across remote Amazonian regions with a broad literature compilation, to produce the first spatially-weighted global analysis of recent OC burial in lakes (over ~50-100-years) that integrates both biome type and forest cover. We find that humid tropical forest lake sediments are a disproportionately important global OC sink of ~80 Tg C yr-1 with implications for climate change. Further, we demonstrate that temperature and forest conservation are key factors in maintaining massive organic carbon pools in tropical lacustrine sediments.

Spatial versus day-to-day within-lake variability in tropical floodplain lake CH4 emissions--developing optimized approaches to representative flux measurements.

Inland waters (lakes, rivers and reservoirs) are now understood to contribute large amounts of methane (CH4) to the atmosphere. However, fluxes are poorly constrained and there is a need for improved knowledge on spatiotemporal variability and on ways of optimizing sampling efforts to yield representative emission estimates for different types of aquatic ecosystems. Low-latitude floodplain lakes and wetlands are among the most high-emitting environments, and here we provide a detailed investigation of spatial and day-to-day variability in a shallow floodplain lake in the Pantanal in Brazil over a five-day period. CH4 flux was dominated by frequent and ubiquitous ebullition. A strong but predictable spatial variability (decreasing flux with increasing distance to the shore or to littoral vegetation) was found, and this pattern can be addressed by sampling along transects from the shore to the center. Although no distinct day-to-day variability were found, a significant increase in flux was identified from measurement day 1 to measurement day 5, which was likely attributable to a simultaneous increase in temperature. Our study demonstrates that representative emission assessments requires consideration of spatial variability, but also that spatial variability patterns are predictable for lakes of this type and may therefore be addressed through limited sampling efforts if designed properly (e.g., fewer chambers may be used if organized along transects). Such optimized assessments of spatial variability are beneficial by allowing more of the available sampling resources to focus on assessing temporal variability, thereby improving overall flux assessments.