Atmosphere Exchange Research Articles

What Determines Water Temperature Dynamics in the San Francisco Bay‐Delta System?

AbstractWater temperature is an important factor determining estuarine species habitat conditions. Water temperature is mainly governed by advection (e.g., from rivers) and atmospheric exchange processes varying strongly over time (day‐night, seasonally) and the spatial domain. On a long time scale, climate change will impact water temperature in estuarine systems due to changes in river flow regimes, air temperature, and sea level rise. To determine which factors govern estuarine water temperature and its sensitivity to changes in its forcing, we developed a process‐based numerical model (Delft3D Flexible Mesh) and applied it to a well‐monitored estuarine system (the San Francisco Estuary) for validation. The process‐based approach allows for detailed process description and a physics‐based analysis of governing processes. The model was calibrated for water year 2011 and incorporated 3‐D hydrodynamics, salinity intrusion, water temperature dynamics, and atmospheric coupling. Results show significant skill in reproducing temperature observations on daily, seasonal, and yearly time scales. In North San Francisco Bay, thermal stratification is present, enhanced by salinity stratification. The temperature of the upstream, fresh water Delta area is captured well in 2‐D mode, although locally—on a small scale—vertical processes (e.g., stratification) may be important. The impact of upstream river temperature and discharge and atmospheric forcing on water temperatures differs throughout the Delta, possibly depending on dispersion and residence times. Our modeling effort provides a sound basis for future modeling studies including climate change impact on water temperature and associated ecological modeling, e.g., clam and fish habitat and phytoplankton dynamics.

Adverse effects of increasing drought on air quality via natural processes

Abstract. Drought is a recurring extreme of the climate system with well-documented impacts on agriculture and water resources. The strong perturbation of drought to the land biosphere and atmospheric water cycle will affect atmospheric composition, the nature and extent of which are not well understood. Here we present observational evidence that US air quality is significantly correlated with drought severity. Severe droughts during the period of 1990–2014 were found associated with growth-season (March–October) mean enhancements in surface ozone and PM2.5 of 3.5 ppbv (8 %) and 1.6 µg m−3 (17 %), respectively. The pollutant enhancements associated with droughts do not appear to be affected by the decreasing trend of US anthropogenic emissions, indicating natural processes as the primary cause. Elevated ozone and PM2.5 are attributed to the combined effects of drought on deposition, natural emissions (wildfires, biogenic volatile organic compounds (BVOCs), and dust), and chemistry. Most climate–chemistry models are not able to reproduce the observed correlations of ozone and PM2.5 to drought severity. The model deficiencies are partly attributed to the lack of drought-induced changes in land–atmosphere exchanges of reactive gases and particles and misrepresentation of cloud changes under drought conditions. By applying the observed relationships between drought and air pollutants to climate model projected drought occurrences, we estimate an increase of 1–6 % for ground-level O3 and 1–16 % for PM2.5 in the US by 2100 compared to the 2000s due to increasing drought alone. Drought thus poses an important aspect of climate change penalty on air quality, and a better prediction of such effects would require improvements in model processes.

Contamination of short-chain chlorinated paraffins to the biotic and abiotic environments in the Bohai Sea.

Short-chain chlorinated paraffins (SCCPs) have been produced and emitted intensively around the Bohai Sea, potentially causing risks to this unique ecosystem and one of primary fishery resources in China and busiest seaways in the world. Little is known about fate, cycling, and sources of SCCPs in the Bohai Sea biotic and abiotic environment. In this study, we combined a marine food web model with a comprehensive atmospheric transport-multiple phase exchange model to quantify SCCPs in the biotic and abiotic environment in the Bohai Sea. We performed multiple modeling scenario investigations to examine SCCP levels in water, sediment, and phytoplankton. We assessed numerically dry and wet depositions, biomagnification and bioaccumulation of SCCPs in the Bohai Sea marine food web. Results showed declining SCCP levels in water and sediment with increasing distance from the coastline, and so do dry and wet depositions. The net deposition overwhelmed the water-air exchange of SCCPs due to their current use in China, though the diffusive gas deposition fluctuated monthly subject to mean wind speed and temperature. A risk assessment manifests that SCCPs levels in the Bohai Sea fish species are at present not posing risks to the residents in the Bohai Sea Rim region. We identified that the SCCP emission sources in the south of the Bohai Sea made a primary contribution to its loadings to the seawater and fish contamination associated with the East Asian summer monsoon. In contrast, the SCCP emissions from the north and northwest regions of the Bohai Sea were major sources contributing to their loading and contamination to Bohai Sea food web during the wintertime, potentially driven by the East Asian winter monsoon.

Improving CLM4.5 simulations of land–atmosphere exchange during freeze–thaw processes on the Tibetan Plateau

Soil is heterogeneous and has different thermal and hydraulic properties, causing varied behavior in heat and moisture transport. Therefore, soil has an important effect on land–atmosphere interactions. In this study, an improved soil parameterization scheme that considers gravel and organic matter in the soil was introduced into CLM4.5 (Community Land Model). By using data from the Zoige and Madoi sites on the Tibetan Plateau, the ability of the model to simultaneously simulate the duration of freeze–thaw periods, soil temperature, soil moisture, and surface energy during freeze–thaw processes, was validated. The results indicated that: (1) the new parameterization performed better in simulating the duration of the frozen, thawing, unfrozen, and freezing periods; (2) with the new scheme, the soil thermal conductivity values were decreased; (3) the new parameterization improved soil temperature simulation and effectively decreased cold biases; (4) the new parameterization scheme effectively decreased the dry biases of soil liquid water content during the freezing, completely frozen, and thawing periods, but increased the wet biases during the completely thawed period; and (5) the net radiation, latent heat flux, and soil surface heat flux of the Zoige and Madoi sites were much improved by the new organic matter and thermal conductivity parameterization.

Land–Atmosphere Exchange of Water and Heat in the Arid Mountainous Grasslands of Central Asia during the Growing Season

Arid grassland ecosystems are widely distributed across Central Asia. However, there is a lack of research and observations of the land–atmosphere exchange of water and heat in the arid grasslands in this region, particularly over complex surfaces. In this study, systematic observations were conducted from 2013 to 2015 using an HL20 Bowen ratio and TDR300 and WatchDog1400 systems to determine the characteristics of these processes during the growing season (April–October) of the arid mountainous grasslands of this region. (1) The latent heat flux (Le) was lower than the sensible heat flux (He) overall, and a small transient decrease in Le was observed before its daytime maximum; daily comparative variations in both fluxes were closely related to vegetation growth. (2) Evapotranspiration (ET) showed substantial variation across different years, seasons and months, and monthly variations in ET were closely related to vegetation growth. Water condensation (Q) was low and relatively stable. Relatively high levels of soil water were measured in spring followed by a decreasing trend. The land–atmosphere exchange of water and heat during the growing season in this region was closely associated with phenology, available precipitation and terrain. This study provides data support for the scientific management of arid mountainous grasslands.

Mineralization age and metallogenic environment of Daotuo manganese deposits in Guizhou: Evidence from Re-Os isotopes

The Neoproterozoic is a critical interval in Earth’s history, having witnessed the breakup of supercontinent Rodinia, global glaciations (or the snowball Earth), and the evolution of multicellular organisms. It is proposed that the breakup of Rodinia might have triggered the snowball Earth, while the termination of the Neoproterozoic global glaciations might have triggered the evolution of life in the Ediacaran Period. Two snowball Earth events, the Sturtian (717–663 Ma) and the Marinoan (654–635 Ma) glaciations, were separated by an interglacial interval of ~10 million years (663–654 Ma). In South China, the Sturtian and Marinoan glacial deposits are represented by the Jiangkou and Nantuo Formations. The interglacial Datangpo Formation is characterized by widespread manganese (Mn) ore deposits, such the Datangpo and Xixibao in Guizhou, Minle in Hunan, and Xiushan in Chongqing, representing the most important metallogenic period of Mn in China. The Daotuo Mn ore, a superlarge-scale deposit (approximately 200 million tons), was first discovered in 2010 in northeastern Guizhou. It is hosted in a fault-bound depression system between the Yangtze block and the Jiangnan orogenic belt. The Mn ores were discovered in black shale of the Member I of the Datangpo Formation, and occur as rhodochrosite (MnCO3). In order to constrain the age of Mn ores, here we report Re-Os isochron age of the ore-bearing black shale from the Member I of the Datangpo Formation. The Re-Os isochron age of the Member I black shale is 660.6±7.5 Ma, consistent with the zircon U-Pb age of the tuff layer from the base of the Datangpo Formation and other Re-Os isochron ages from other localities (such as Canada, Australia, Scotland, and Mongolia). Furthermore, the initial value of 187Os/188Os from the Re-Os isochron age is 0.781, suggesting predominantly terrestrial input. Based on previous research, it is shown that during the Sturtian glaciation, under the influence of sea ice cover barrier and atmospheric material exchange, the hypoxic water led to the formation of iron and sulfide rich environments on the seafloor near hydrothermal vents, giving rise to a large number of rift basins rich in Mn2+. After the glaciation and water and atmospheric exchange of material recovery, the glacier meltwater carries the terrigenous material into the rift basin containing Mn2+, accompanied by the melting of the land glacier and the rapid increase of the atmospheric oxygen content. The surface water body of the rift basin is rapidly oxidized, and the oxidation degree is higher than the ocean area. Mn2+ are also oxidized to MnO2 and precipitate back into the environment, where they buried with organic matter, undergo diagenesis, and eventually form rhodochrosite.

FluxnetLSM R package (v1.0): a community tool for processing FLUXNET data for use in land surface modelling

Abstract. Flux towers measure ecosystem-scale surface–atmosphere exchanges of energy, carbon dioxide and water vapour. The network of flux towers now encompasses ∼ 900 sites, spread across every continent. Consequently, these data have become an essential benchmarking tool for land surface models (LSMs). However, these data as released are not immediately usable for driving, evaluating and benchmarking LSMs. Flux tower data must first be transformed into a LSM-readable file format, a process which involves changing units, screening missing data and varying degrees of additional gap-filling. All of this often leads to an under-utilisation of these data in model benchmarking. To resolve some of these issues, and to help make flux tower measurements more widely used, we present a reproducible, open-source R package that transforms the FLUXNET2015 and La Thuile data releases into community standard NetCDF files that are directly usable by LSMs. We note that these data would also be useful for any other user or community seeking to independently quality control, gap-fill or use the FLUXNET data.

Responses of surface ozone air quality to anthropogenic nitrogen deposition in the Northern Hemisphere

Abstract. Human activities have substantially increased atmospheric deposition of reactive nitrogen to the Earth's surface, inducing unintentional effects on ecosystems with complex environmental and climate consequences. One consequence remaining unexplored is how surface air quality might respond to the enhanced nitrogen deposition through surface–atmosphere exchange. Here we combine a chemical transport model (GEOS-Chem) and a global land model (Community Land Model, CLM) to address this issue with a focus on ozone pollution in the Northern Hemisphere. We consider three processes that are important for surface ozone and can be perturbed by the addition of atmospheric deposited nitrogen – namely, emissions of biogenic volatile organic compounds (VOCs), ozone dry deposition, and soil nitrogen oxide (NOx) emissions. We find that present-day anthropogenic nitrogen deposition (65 Tg N a−1 to the land), through enhancing plant growth (represented as increases in vegetation leaf area index, LAI, in the model), could increase surface ozone from increased biogenic VOC emissions (e.g., a 6.6 Tg increase in isoprene emission), but it could also decrease ozone due to higher ozone dry deposition velocities (up to 0.02–0.04 cm s−1 increases). Meanwhile, deposited anthropogenic nitrogen to soil enhances soil NOx emissions. The overall effect on summer mean surface ozone concentrations shows general increases over the globe (up to 1.5–2.3 ppbv over the western US and South Asia), except for some regions with high anthropogenic NOx emissions (0.5–1.0 ppbv decreases over the eastern US, western Europe, and North China). We compare the surface ozone changes with those driven by the past 20-year climate and historical land use changes. We find that the impacts from anthropogenic nitrogen deposition can be comparable to the climate- and land-use-driven surface ozone changes at regional scales and partly offset the surface ozone reductions due to land use changes reported in previous studies. Our study emphasizes the complexity of biosphere–atmosphere interactions, which can have important implications for future air quality prediction.

Net ecosystem exchange and energy fluxes measured with the eddy covariance technique in a western Siberian bog

Abstract. Very few studies of ecosystem–atmosphere exchange involving eddy covariance data have been conducted in Siberia, with none in the western Siberian middle taiga. This work provides the first estimates of carbon dioxide (CO2) and energy budgets in a typical bog of the western Siberian middle taiga based on May–August measurements in 2015. The footprint of measured fluxes consisted of a homogeneous mixture of tree-covered ridges and hollows with the vegetation represented by typical sedges and shrubs. Generally, the surface exchange rates resembled those of pine-covered bogs elsewhere. The surface energy balance closure approached 100 %. Net CO2 uptake was comparatively high, summing up to 202 gC m−2 for the four measurement months, while the Bowen ratio was seasonally stable at 28 %. The ecosystem turned into a net CO2 source during several front passage events in June and July. The periods of heavy rain helped keep the water table at a sustainably high level, preventing a usual drawdown in summer. However, because of the cloudy and rainy weather, the observed fluxes might rather represent the special weather conditions of 2015 than their typical magnitudes.

Carbon budget of a shallow, lagoonal estuary: Transformations and source‐sink dynamics along the river‐estuary‐ocean continuum

AbstractA comprehensive carbon budget was constructed to quantify carbon flows through the freshwater‐marine continuum of a temperate, microtidal estuary. We performed coordinated measurements of dissolved inorganic carbon and total organic carbon fluxes to resolve spatial variability between and along the channel and shoals and diel variability across the entire estuary for 2 yr. Net ecosystem metabolism (NEM) was the most significant control on carbon flow within estuary regions. However, metabolic rates were spatially coupled such that counteracting fluxes across the channel‐shoal gradient or along the river‐ocean gradient resulted in system‐wide NEM that was closely in balance (–3.0 ± 3.3 to 1.1 ± 4.4 molC m−2 yr−1). Similarly, large diel and seasonal variability in air–water CO2 fluxes were observed during 72 spatial surveys, but these short‐term variations generally cancelled out when aggregated to annual budget terms. Although atmospheric exchanges were small (–0.2 ± 0.1 to 2.0 ± 0.4 molC m−2 yr−1), they were subject to large errors (± 4 molC m−2 yr−1) if diel variability was neglected. Internal mechanisms that maintained balanced carbon flows were strongly impacted by river discharge and were only apparent by separately quantifying channel and shoal fluxes. Notably, metabolic responses of the shoal to river forcing outweighed the responses of the channel, and the net impact was contrary to prior relationships derived from synthesis of lower‐resolution carbon budgets. Our budget demonstrates that resolution of carbon fluxes at appropriate scales, including channel‐shoal and diel variability, is critical to characterizing ecosystem function and the fate of carbon within the river‐ocean continuum.

Sensitivity of global greenhouse gas budgets to tropospheric ozone pollution mediated by the biosphere

Tropospheric ozone (O3), a harmful secondary air pollutant, can affect the climate via direct radiative forcing and by modifying the radiative forcing of aerosols through its role as an atmospheric oxidant. Moreover, O3 exerts a strong oxidative pressure on the biosphere and indirectly influences the climate by altering the materials and energy exchange between terrestrial ecosystems and the atmosphere. However, the magnitude by which O3 affects the global budgets of greenhouse gases (GHGs: CO2, CH4, and N2O) through altering the land–atmosphere exchange is largely unknown. Here we assess the sensitivity of these budgets to tropospheric O3 pollution based on a meta-analysis of experimental studies on the effects of elevated O3 on GHG exchange between terrestrial ecosystems and the atmosphere. We show that across ecosystems, elevated O3 suppresses N2O emissions and both CH4 emissions and uptake, and has little impact on stimulation of soil CO2 emissions except at relatively high concentrations. Therefore, the soil system would be transformed from a sink into a source of GHGs with O3 levels increasing. The global atmospheric budget of GHGs is sensitive to O3 pollution largely because of the carbon dioxide accumulation resulting from suppressed vegetation carbon uptake; the negative contributions from suppressed CH4 and N2O emissions can offset only ∼10% of CO2 emissions from the soil–vegetation system. Based on empirical data, this work, though with uncertainties, provides the first assessment of sensitivity of global budgets of GHGs to O3 pollution, representing a necessary step towards fully understanding and evaluating O3–climate feedbacks mediated by the biosphere.

Wind farm density and harvested power in very large wind farms: A low-order model

In this work we create new understanding of wind turbine wakes recovery process as a function of wind farm density using large-eddy simulations of an atmospheric boundary layer diurnal cycle. Simulations are forced with a constant geostrophic wind and a time varying surface temperature extracted from a selected period of the Cooperative Atmospheric Surface Exchange Study field experiment. Wind turbines are represented using the actuator disk model with rotation and yaw alignment. A control volume analysis around each turbine has been used to evaluate wind turbine wake recovery and corresponding harvested power. Results confirm the existence of two dominant recovery mechanisms, advection and flux of mean kinetic energy, which are modulated by the background thermal stratification. For the low-density arrangements advection dominates, while for the highly loaded wind farms the mean kinetic energy recovers through fluxes of mean kinetic energy. For those cases in between, a smooth balance of bothmechanisms exists. From the results, a low-order model for the wind farms' harvested power as a function of thermal stratification and wind farm density has been developed, which has the potential to be used as an order-of-magnitude assessment tool.

Climate and basin drivers of seasonal river water temperature dynamics

Abstract. Stream water temperature is a key control of many river processes (e.g. ecology, biogeochemistry, hydraulics) and services (e.g. power plant cooling, recreational use). Consequently, the effect of climate change and variability on stream temperature is a major scientific and practical concern. This paper aims (1) to improve the understanding of large-scale spatial and temporal variability in climate–water temperature associations, and (2) to assess explicitly the influence of basin properties as modifiers of these relationships. A dataset was assembled including six distinct modelled climatic variables (air temperature, downward short-wave and long-wave radiation, wind speed, specific humidity, and precipitation) and observed stream temperatures for the period 1984–2007 at 35 sites located on 21 rivers within 16 basins (Great Britain geographical extent); the study focuses on broad spatio-temporal patterns, and hence was based on 3-month-averaged data (i.e. seasonal). A wide range of basin properties was derived. Five models were fitted (all seasons, winter, spring, summer, and autumn). Both site and national spatial scales were investigated at once by using multi-level modelling with linear multiple regressions. Model selection used multi-model inference, which provides more robust models, based on sets of good models, rather than a single best model. Broad climate–water temperature associations common to all sites were obtained from the analysis of the fixed coefficients, while site-specific responses, i.e. random coefficients, were assessed against basin properties with analysis of variance (ANOVA). All six climate predictors investigated play a role as a control of water temperature. Air temperature and short-wave radiation are important for all models/seasons, while the other predictors are important for some models/seasons only. The form and strength of the climate–stream temperature association vary depending on season and on water temperature. The dominating climate drivers and physical processes may change across seasons and across the stream temperature range. The role of basin permeability, size, and elevation as modifiers of the climate–water temperature associations was confirmed; permeability has the primary influence, followed by size and elevation. Smaller, upland, and/or impermeable basins are the most influenced by atmospheric heat exchanges, while larger, lowland and permeable basins are the least influenced. The study showed the importance of accounting properly for the spatial and temporal variability of climate–stream temperature associations and their modification by basin properties.

Demonstration of Passive Tritium Oxidation Using a Hydrophobic Catalytic Recombiner for Detritiation System

Technical reliability of tritium confinement shall be elevated taking hypothetic extraordinary situations occurred in a nuclear fusion facility such as events of fire and loss of electric power fully into consideration in order to enhance public acceptance of a nuclear fusion reactor. Considerable attention has been paid to the research of passive tritium conversion in the research field of detritiation system. Demonstration of detritiation to grasp the dynamic behavior is practically important to enhance the tritium confinement. In this study, passive detritiation of a 12 [m3] container was demonstrated with hydrophobic catalyst packed in a catalytic reactor. Initial tritium concentration in the container was 1.0 [GBq/m3]. The volume of hydrophobic catalyst packed in the passive catalytic reactor was 1000 [cm3]. The flow rate was set to 2.4 [Nm3/h] which is equivalent to atmosphere exchange rate of 5 times per day. The tritium concentration in the container successfully decreased two order magnitude after 23 hours processing. The conversion rate of tritium by passive catalytic reactor was initially 99.1 [%] and it decreased gradually with an increase in processing time. The rate fell to 70.7 [%] after 23 hours processing due mainly to the effect of hydrogen concentration on conversion efficiency. Unreacted amount of tritium passed through the passive catalytic reactor was less than 4.8 [%] of initial tritium amount. We have confirmed that the passive tritium oxidation is feasible with the hydrophobic platinum catalyst even in the presence of moisture.

Role of gas ebullition in the methane budget of a deep subtropical lake: What can we learn from process‐based modeling?

AbstractWe analyzed the processes affecting the methane (CH4) budget in Lake Kinneret, a deep subtropical lake, using a suite of three models: (1) a bubble model to determine the fate of CH4 bubbles released from the sediment; (2) the one‐dimensional physical lake model Simstrat to calculate the mixing dynamics; and (3) a biogeochemical model implemented in Aquasim to quantify the CH4 sources and sinks. The key pathways modeled include diffusive and bubble release of CH4 from the sediment, aerobic CH4 oxidation, and atmospheric gas exchange. The temporal and spatial dynamics of dissolved CH4 concentrations observed in the lake during 3 years could be well represented by the combined models. Remarkably, the relative contributions of ebullition and diffusive transport to the accumulation of CH4 in the hypolimnion during the stratified period could not be accurately constrained based only on the observed evolution of CH4 concentrations in the water column. Importantly, however, our analysis showed that most (∼99%) of the CH4 supplied to the water column by bubble dissolution and diffusive transport from the sediment is aerobically oxidized, whereas a substantial fraction (∼60%) of the sediment‐released bubble CH4 is directly transported to the atmosphere. Ebullition is thus responsible for the bulk of the emissions from Lake Kinneret to the atmosphere. Therefore, as in all freshwaters, ebullition quantification is crucial for accurately assessing CH4 emissions to the atmosphere. This task remains challenging due to high spatio‐temporal variability, but combining in situ measurements with a process‐based modeling can help to better constrain flux estimates.

C and N stocks are not impacted by land use change from Brazilian Savanna (Cerrado) to agriculture despite changes in soil fertility and microbial abundances

AbstractCentral Brazil is the region with the most dynamic agriculture expansion worldwide, where tropical forests and Cerrado (Brazilian savanna) are converted to pastures and crop fields. Following deforestation, agricultural practices, such as fertilization, tillage and crop rotations, alter soil parameters and affect microbial abundances and the C and N cycles. The objective of this study was to compare changes in soil fertility, stocks of soil C and N, microbial biomass, and abundance of bacteria, fungi and archaea in Cerrado soils following land use change to crops (soybean/corn/cotton) and pasture (the perennial forage grass Brachiaria brizantha A. Rich.). Agriculture increased soil fertility and conserved soil C and N since their absolute concentration values were highest in agriculture soils and the C and N stocks adjusted by soil density were similar to the native vegetation soils. At the same time, agriculture changed the microbial abundances (decrease of microbial biomass C and N, increase of archaea, and reduction of bacteria and fungi at the crop sites), and N dynamics (increase of soil ammonium and nitrate concentrations). Even if these changes can be beneficial for food and agricultural commodities production, all these soil alterations should be further investigated due to their possible unknown effects on biosphere–hydrosphere–atmosphere exchange processes such as greenhouse gases emissions and nitrate leaching.

Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds.

Herein we report the observation of atmospheric pressure in-source hydrogen-deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. Graphical Abstract ᅟ.

Filling the gap in Ca input-output budgets in base-poor forest ecosystems: The contribution of non-crystalline phases evidenced by stable isotopic dilution

In terrestrial ecosystems, plant-available pools of magnesium and calcium are assumed to be stored in the soil as exchangeable cations adsorbed on the surface of mineral and/or organic particles. The pools of exchangeable magnesium and calcium are measured by ion-exchange soil extractions. These pools are sustained in the long term by the weathering of primary minerals in the soil and atmospheric inputs. This conceptual model is the base of input-output budgets from which soil acidification and the sustainability of soil chemical fertility is inferred. However, this model has been questioned by data from long-term forest ecosystem monitoring sites, particularly for calcium. Quantifying the contribution of atmospheric inputs, ion exchange and weathering of both primary, secondary and non-crystalline phases to tree nutrition in the short term is challenging.In this study, we developed and applied a novel isotopic dilution technique using the stable isotopes of magnesium and calcium to study the contribution of the different soil phases to soil solution chemistry in a very acidic soil. The labile pools of Mg and Ca in the soil (pools in equilibrium with the soil solution) were isotopically labeled by spraying a solution enriched in 26Mg and 44Ca on the soil. Labeled soil columns were then percolated with a dilute acid solution during a 3-month period and the isotopic dilution of the tracers was monitored in the leaching solution, in the exchangeable (2 sequential 1molL−1 ammonium acetate extractions) and non-crystalline (2 sequential soil digestions: oxalic acid followed by nitric acid) phases.Significant amounts of Mg and Ca isotope tracer were recovered in the non-crystalline soil phases. These phases represented from 5% to 25% and from 24% to 50%, respectively, of the Mg and Ca labile pools during the experiment. Our results show that non-crystalline phases act as both a source and a sink of calcium and magnesium in the soil, and contribute directly to soil solution chemistry on very short-term time scales. These phases are very abundant in acid soils and, in the present study, represent a substantial calcium pool (equivalent in size to the Ca exchangeable pool). The gradual isotopic dilution of Mg and Ca isotope ratios in the leaching solution during the experiment evidenced an input flux of Mg and Ca originating from a pool other than the labile pool. While the Mg input flux originated primarily from the weathering of primary minerals and secondarily from the non-crystalline phases, the Ca input flux originated primarily from the non-crystalline phases. Our results also show that the net calcium release flux from these phases may represent a significant source of calcium in forest ecosystems and actively contribute to compensating the depletion of Ca exchangeable pools in the soil. Non-crystalline phases therefore should be taken into account when computing input-output nutrient budgets and soil acid neutralizing capacity.

The HD(CP)<sup>2</sup> Observational Prototype Experiment (HOPE) – an overview

Abstract. The HD(CP)2 Observational Prototype Experiment (HOPE) was performed as a major 2-month field experiment in Jülich, Germany, in April and May 2013, followed by a smaller campaign in Melpitz, Germany, in September 2013. HOPE has been designed to provide an observational dataset for a critical evaluation of the new German community atmospheric icosahedral non-hydrostatic (ICON) model at the scale of the model simulations and further to provide information on land-surface–atmospheric boundary layer exchange, cloud and precipitation processes, as well as sub-grid variability and microphysical properties that are subject to parameterizations. HOPE focuses on the onset of clouds and precipitation in the convective atmospheric boundary layer. This paper summarizes the instrument set-ups, the intensive observation periods, and example results from both campaigns. HOPE-Jülich instrumentation included a radio sounding station, 4 Doppler lidars, 4 Raman lidars (3 of them provide temperature, 3 of them water vapour, and all of them particle backscatter data), 1 water vapour differential absorption lidar, 3 cloud radars, 5 microwave radiometers, 3 rain radars, 6 sky imagers, 99 pyranometers, and 5 sun photometers operated at different sites, some of them in synergy. The HOPE-Melpitz campaign combined ground-based remote sensing of aerosols and clouds with helicopter- and balloon-based in situ observations in the atmospheric column and at the surface. HOPE provided an unprecedented collection of atmospheric dynamical, thermodynamical, and micro- and macrophysical properties of aerosols, clouds, and precipitation with high spatial and temporal resolution within a cube of approximately 10 × 10 × 10 km3. HOPE data will significantly contribute to our understanding of boundary layer dynamics and the formation of clouds and precipitation. The datasets have been made available through a dedicated data portal. First applications of HOPE data for model evaluation have shown a general agreement between observed and modelled boundary layer height, turbulence characteristics, and cloud coverage, but they also point to significant differences that deserve further investigations from both the observational and the modelling perspective.

Ecosystem variability along the estuarine salinity gradient: Examples from long‐term study of San Francisco Bay

AbstractThe salinity gradient of estuaries plays a unique and fundamental role in structuring spatial patterns of physical properties, biota, and biogeochemical processes. We use variability along the salinity gradient of San Francisco Bay to illustrate some lessons about the diversity of spatial structures in estuaries and their variability over time. Spatial patterns of dissolved constituents (e.g., silicate) can be linear or nonlinear, depending on the relative importance of river‐ocean mixing and internal sinks (diatom uptake). Particles have different spatial patterns because they accumulate in estuarine turbidity maxima formed by the combination of sinking and estuarine circulation. Some constituents have weak or no mean spatial structure along the salinity gradient, reflecting spatially distributed sources along the estuary (nitrate) or atmospheric exchanges that buffer spatial variability of ecosystem metabolism (dissolved oxygen). The density difference between freshwater and seawater establishes stratification in estuaries stronger than the thermal stratification of lakes and oceans. Stratification is strongest around the center of the salinity gradient and when river discharge is high. Spatial distributions of motile organisms are shaped by species‐specific adaptations to different salinity ranges (shrimp) and by behavioral responses to environmental variability (northern anchovy). Estuarine spatial patterns change over time scales of events (intrusions of upwelled ocean water), seasons (river inflow), years (annual weather anomalies), and between eras separated by ecosystem disturbances (a species introduction). Each of these lessons is a piece in the puzzle of how estuarine ecosystems are structured and how they differ from the river and ocean ecosystems they bridge.