Pan-Arctic soil moisture control on tundra carbon sequestration and plant productivity.

Long-term atmospheric CO2 concentration records have suggested a reduction in the positive effect of warming on high-latitude carbon uptake since the 1990s. A variety of mechanisms have been proposed to explain the reduced net carbon sink of northern ecosystems with increased air temperature, including water stress on vegetation and increased respiration over recent decades. However, the lack of consistent long-term carbon flux and in situ soil moisture data has severely limited our ability to identify the mechanisms responsible for the recent reduced carbon sink strength. In this study, we used a record of nearly 100 site-years of eddy covariance data from 11 continuous permafrost tundra sites distributed across the circumpolar Arctic to test the temperature (expressed as growing degree days, GDD) responses of gross primary production (GPP), net ecosystem exchange (NEE), and ecosystem respiration (ER) at different periods of the summer (early, peak, and late summer) including dominant tundra vegetation classes (graminoids and mosses, and shrubs). We further tested GPP, NEE, and ER relationships with soil moisture and vapor pressure deficit to identify potential moisture limitations on plant productivity and net carbon exchange. Our results show a decrease in GPP with rising GDD during the peak summer (July) for both vegetation classes, and a significant relationship between the peak summer GPP and soil moisture after statistically controlling for GDD in a partial correlation analysis. These results suggest that tundra ecosystems might not benefit from increased temperature as much as suggested by several terrestrial biosphere models, if decreased soil moisture limits the peak summer plant productivity, reducing the ability of these ecosystems to sequester carbon during the summer.

Mismatch of N release from the permafrost and vegetative uptake opens pathways of increasing nitrous oxide emissions in the high Arctic.

Biogeochemical cycling in permafrost-affected ecosystems remains associated with large uncertainties, which could impact the Earth's greenhouse gas budget and future climate policies. In particular, increased nutrient availability following permafrost thaw could perturb the greenhouse gas exchange in these systems, an effect largely unexplored until now. Here, we enhance the terrestrial ecosystem model QUINCY (QUantifying Interactions between terrestrial Nutrient CYcles and the climate system), which simulates fully coupled carbon (C), nitrogen (N) and phosphorus (P) cycles in vegetation and soil, with processes relevant in high latitudes (e.g., soil freezing and snow dynamics). In combination with site-level and satellite-based observations, we use the model to investigate impacts of increased nutrient availability from permafrost thawing in comparison to other climate-induced effects and CO2 fertilization over 1960 to 2018 across the high Arctic. Our simulations show that enhanced availability of nutrients following permafrost thaw account for less than 15% of the total Gross primary productivity increase over the time period, despite simulated N limitation over the high Arctic scale. As an explanation for this weak fertilization effect, observational and model data indicate a mismatch between the timing of peak vegetative growth (week 26-27 of the year, corresponding to the beginning of July) and peak thaw depth (week 32-35, mid-to-late August), resulting in incomplete plant use of nutrients near the permafrost table. The resulting increasing N availability approaching the permafrost table enhances N loss pathways, which leads to rising nitrous oxide (N2 O) emissions in our model. Site-level emission trends of 2 mg N m-2  year-1 on average over the historical time period could therefore predict an emerging increasing source of N2 O emissions following future permafrost thaw in the high Arctic.

Earlier snowmelt may lead to late season declines in plant productivity and carbon sequestration in Arctic tundra ecosystems.

Arctic warming is affecting snow cover and soil hydrology, with consequences for carbon sequestration in tundra ecosystems. The scarcity of observations in the Arctic has limited our understanding of the impact of covarying environmental drivers on the carbon balance of tundra ecosystems. In this study, we address some of these uncertainties through a novel record of 119 site-years of summer data from eddy covariance towers representing dominant tundra vegetation types located on continuous permafrost in the Arctic. Here we found that earlier snowmelt was associated with more tundra net CO2 sequestration and higher gross primary productivity (GPP) only in June and July, but with lower net carbon sequestration and lower GPP in August. Although higher evapotranspiration (ET) can result in soil drying with the progression of the summer, we did not find significantly lower soil moisture with earlier snowmelt, nor evidence that water stress affected GPP in the late growing season. Our results suggest that the expected increased CO2 sequestration arising from Arctic warming and the associated increase in growing season length may not materialize if tundra ecosystems are not able to continue sequestering CO2 later in the season.

Statistical upscaling of ecosystem CO2 fluxes across the terrestrial tundra and boreal domain: Regional patterns and uncertainties.

The regional variability in tundra and boreal carbon dioxide (CO2 ) fluxes can be high, complicating efforts to quantify sink-source patterns across the entire region. Statistical models are increasingly used to predict (i.e., upscale) CO2 fluxes across large spatial domains, but the reliability of different modeling techniques, each with different specifications and assumptions, has not been assessed in detail. Here, we compile eddy covariance and chamber measurements of annual and growing season CO2 fluxes of gross primary productivity (GPP), ecosystem respiration (ER), and net ecosystem exchange (NEE) during 1990-2015 from 148 terrestrial high-latitude (i.e., tundra and boreal) sites to analyze the spatial patterns and drivers of CO2 fluxes and test the accuracy and uncertainty of different statistical models. CO2 fluxes were upscaled at relatively high spatial resolution (1 km2 ) across the high-latitude region using five commonly used statistical models and their ensemble, that is, the median of all five models, using climatic, vegetation, and soil predictors. We found the performance of machine learning and ensemble predictions to outperform traditional regression methods. We also found the predictive performance of NEE-focused models to be low, relative to models predicting GPP and ER. Our data compilation and ensemble predictions showed that CO2 sink strength was larger in the boreal biome (observed and predicted average annual NEE -46 and -29 g C m-2  yr-1 , respectively) compared to tundra (average annual NEE +10 and -2 g C m-2  yr-1 ). This pattern was associated with large spatial variability, reflecting local heterogeneity in soil organic carbon stocks, climate, and vegetation productivity. The terrestrial ecosystem CO2 budget, estimated using the annual NEE ensemble prediction, suggests the high-latitude region was on average an annual CO2 sink during 1990-2015, although uncertainty remains high.

Controlled growth of Cu and CuOx thin films from subvalent copper precursors.

A new Cu(i) precursor, [(COD)Cu(TFB-TFEA)] (COD = 1,5-cyclooctadiene and TFB-TFEA = N-(4,4,4-trifluorobut-1-en-3-on)-6,6,6-trifluoroethylamine) with high volatility and a clean thermal decomposition pattern was tested for thermal and plasma-assisted chemical vapor deposition (CVD). The heteroleptic configuration based on an anionic and a chelating neutral ligand unified both reactivity and sufficient stability resulting in an intrinsic molecular control over the composition of the resulting CVD deposits. The electronic influence of the ligand on the metal site was studied by 1D and 2D NMR spectroscopy, while EI mass spectrometry revealed the ligand elimination cascade. Thermal and plasma CVD experiments demonstrated the suitability of the copper compound for an atom-efficient (high molecule-to-material yield) deposition of copper(0) and copper(i) oxide films that could be converted into crystalline copper(ii) oxide upon heat treatment at 500 °C.