As the interface between plants and soil, the organic horizon is the foundation of forest ecosystems. Two potential predictors of O-horizon properties, vegetation and mineral soil type, are difficult to separate because they typically covary. We conducted a factorial study involving four canopy tree species and two soil types with different hydrology and topographic position to parse patterns in chemistry and microbiota of the O-horizon in a north-temperate deciduous forest. There were frequent strong effects of tree species. Organic horizon properties under white ash frequently differed from the other trees: e.g., lower cation exchange capacity and exchangeable acidity, thinner Oi horizon, lower

Mercury is a soil pollutant of widespread concern, usually derived from airborne deposition. A long–term forest soil monitoring program began in 2002 at five sites (elevation 590–1140 m) in Vermont, USA. Total mercury (THg) and soil organic carbon (SOC) were assessed in the uppermost humified soil layer, either an Oa or A horizon. Sampling occurred every 5 years from ten subplots at each site. Tree species ranged from deciduous, mixed deciduous/conifer, to all conifer. After five samplings, the site means for THg ranged from 167 to 447 µg kg–1 and increased linearly with elevation (R2 = 0.78). One site had a significant temporal increase in THg of 3.9 µg kg–1 yr–1 (p = 0.02). Overall SOC site means ranged from 133 to 434 g kg–1. One site showed a significant temporal increase in SOC (p = 0.01). The mean ratio of THg:SOC was similar at four of the sites (1318–1518 µg kg–1) but much lower (648 µg kg–1) at the site with the highest SOC and the temporal increase in THg. Within individual subplots, THg increased up to a maximum SOC concentration of 320 g kg–1 and usually decreased above that threshold. Although both wet and dry mercury deposition in the northeast USA have declined, no evidence of declining soil THg concentration was found, likely due to strong retention by SOC. Continued monitoring is essential considering ongoing changes in deposition and future changes in the source–sink balance of mercury.

Hydrologic behavior and soil properties across forested landscapes with complex topography exhibit high variability. The interaction of groundwater with spatially distinct soils produces and transports solutes across catchments, however, the spatiotemporal relationships between groundwater dynamics and soil solute fluxes are difficult to directly evaluate. While whole-catchment export of solutes by shallow subsurface flow represents an integration of soil environments and conditions but many studies compartmentalize soil solute fluxes as hillslope vs. riparian, deep vs. shallow, or as individual soil horizon contributions. This potentially obscures and underestimates the hillslope variation and magnitude of solute fluxes and soil development across the landscape. This study determined the spatial variation and of shallow soil base cation fluxes associated with weathering reactions (Ca, Mg, and Na), soil elemental depletion, and soil saturation dynamics in upland soils within a small, forested watershed at the Hubbard Brook Experimental Forest, NH. Base cation fluxes were calculated using a combination of ion-exchange resins placed in shallow groundwater wells (0.3 - 1 m depth) located across hillslope transects (ridges to lower backslopes) and measurements of groundwater levels. Groundwater levels were also used to create metrics of annual soil saturation. Base cation fluxes were positively correlated with soil saturation frequency and were greatest in soil profiles where primary minerals were most depleted of base cations (i.e., highly weathered). Spatial differences in soil saturation across the catchment were strongly related to topographic properties of the upslope drainage area and are interpreted to result from spatial variations in transient groundwater dynamics. Results from this work suggest that the structure of a catchment defines the spatial architecture of base cation fluxes, likely reflecting the mediation of subsurface stormflow dynamics on soil development. Furthermore, this work highlights the importance of further compartmentalizing solute fluxes along hillslopes, where certain areas may disproportionately contribute solutes to the whole catchment. Refining catchment controls on base cation generation and transport could be an important tool for opening the black box of catchment elemental cycling.

Mineral weathering is an important soil-forming process driven by the interplay of water, organisms, solution chemistry, and mineralogy. The influence of hillslope-scale patterns of water flux on mineral weathering in soils is still not well understood, particularly in humid postglacial soils, which commonly harbor abundant weatherable primary minerals. Previous work in these settings showed the importance of lateral hydrologic patterns to hillslope-scale pedogenesis. In this study, we hypothesized that there is a corresponding relationship between hydrologically driven pedogenesis and chemical weathering in podzols in the White Mountains of New Hampshire, USA. We tested this hypothesis by quantifying the depletion of plagioclase in the fine fraction (≤2 mm) of closely spaced, similar-age podzols along a gradient in topography and depth to bedrock that controls lateral water flow. Along this gradient, laterally developed podzols formed through frequent, episodic flushing by upslope groundwater, and vertically developed podzols formed through characteristic vertical infiltration. We estimated the depletion of plagioclase-bound elements within the upper mineral horizons of podzols using mass transfer coefficients (τ) and quantified plagioclase losses directly through electron microscopy and microprobe analysis. Elemental depletion was significantly more pronounced in the upslope lateral eluvial (E horizon-dominant) podzols relative to lateral illuvial (B horizon-dominant) and vertical (containing both E and B horizons) podzols downslope, with median Na losses of ∼74 %, ∼56 %, and ∼40 %, respectively. When comparing genetic E horizons, Na and Al were significantly more depleted in laterally developed podzols relative to vertically developed podzols. Microprobe analysis revealed that ∼74 % of the plagioclase was weathered from the mineral pool of lateral eluvial podzols, compared to ∼39 % and ∼23 % for lateral illuvial podzols and vertically developed podzols, respectively. Despite this intense weathering, plagioclase remains the second most abundant mineral in soil thin sections. These findings confirm that the concept of soil development as occurring vertically does not accurately characterize soils in topographically complex regions. Our work improves the current understanding of pedogenesis by identifying distinct, short-scale gradients in mineral weathering shaped by local patterns of hydrology and topography.

Sequestration and storage of organic carbon (C) in soil is an essential component of climate change mitigation and fundamental in promoting the health and climate resilience of soils. Sources of available soil C data are increasing, which complicates efforts to consolidate the data in forms that can be readily used by stakeholders. Spatial and temporal gaps in data availability also limit the quantification of changes in soil C through space and time. Improved coordination among producers and users of soil C data would provide data compatibility at the spatial and temporal resolution required for C monitoring, accounting, and verification of policy implementation. These challenges can be addressed by forming regional-scale networks to coordinate the collection and use of soil C data by promoting consistency in methods, collecting new data to fill critical gaps, integrating existing data from multiple sources, and providing data interpretation to stakeholders in readily usable forms. Forming networks in regions such as the Northeastern United States would require close coordination with existing programs that are involved in collecting or aggregating soil C within that region. Network formation could be accomplished by (1) producing a planning document, (2) designing a network structure tailored to the region, and (3) acquiring the institutional support to establish and operate the network. Increasing the availability and usage of soil C data through regional networks would support the development of climate change solutions and increased ecosystem services through land management efforts that increase soil C storage.

In headwater catchments, surface groundwater discharge areas have unique soil biogeochemistry and can be hot spots for solute contribution to streams. Across the northeastern United States, headwater hillslopes with surface groundwater discharge were enriched in soil Mn, including Watershed 3 of Hubbard Brook Experimental Forest, New Hampshire. Soils of this site were investigated along a grid to determine extent of Mn-rich zone(s) and relationships to explanatory variables using ordinary kriging. The O and B horizons were analyzed for total secondary Mn and Fe, Cr oxidation potential, total organic C, moisture content, wetness ratio, and pH. Two Mn hot spots were found: a poorly drained, flowing spring (Location A); and a moderately well-drained swale (Location B). Both had similar to 6,000-9,000 mg Mn kg(-1) soil. However, Location A had high Cr oxidation potential (a measure of Mn reactivity), whereas Location B did not. Location C, a poorly drained seep with slow-moving water, had lower Mn content and Cr oxidation potential. Manganese-rich soil particles were analyzed using X-ray absorption near-edge structure and micro-X-ray diffraction; the dominant oxidation state was Mn(IV), and the dominant Mn oxide species was a layer-type Mn oxide (L-MnO2). We propose input of Mn(II) with groundwater, which is oxidized by soil microbes. Studies of catchment structure and response could benefit from identifying hot spots of trace metals, sourced mainly from parent material but which accumulate according to hydropedologic conditions. Small-scale variation in Mn enrichment due to groundwater and microtopography appears to be more important than regional-scale variation due to air pollution.

The longevity of a single 22.4 Mg·ha −1 application of dolomitic limestone at four northern hardwood stands was evaluated over 30 years (1986–2016) to determine whether changes in soils, foliage, and tree growth were sustained on the unglaciated Allegheny Plateau in northern Pennsylvania, USA. In limed plots, soils, sampled to 45–55 cm depth, and sugar maple (Acer saccharum Marsh.) and black cherry (Prunus serotina Ehrh.) foliage had significantly (P ≤ 0.05) greater concentrations of calcium (Ca) and magnesium (Mg) through 2016 compared with samples from unlimed plots. Ca and Mg capitals (g·m −2 ) in the Oi through A horizons combined were greater on limed plots than unlimed plots, largely due to increases in the thickness and nutrient concentration in the A horizon. Over 30 years, sugar maple basal area increment (cm 2 ·year −1 BAINC) was greater in limed plots (30.6 cm 2 ·year −1 vs unlimed 13.3), American beech (Fagus grandifolia Ehrh.) BAINC was unaffected by lime application, and black cherry BAINC was reduced in limed plots compared with unlimed plots. The sustained effect of this one-time lime treatment shows the strong role of efficient nutrient cycling in forests and suggests that the benefits over a substantial portion of a stand rotation may increase the feasibility of operational liming.

Catchment‐scale assessments of nitrogen retention and loss rarely account for soil and landscape heterogeneity and are, thus, unable to account for the suite of nitrogen cycling processes that ultimately affect the export of nitrate via stream water. Long‐term study at the Hubbard Brook Experimental Forest, NH has generated a unique data set that facilitates spatially explicit examination of interactions among hydrology, soil development, and nitrogen cycling processes. Using high‐frequency streamwater chemistry data with intensive subsurface hydrology and solute monitoring, we tracked areas of the catchment that are hydrologically active under different flow conditions to identify the source area of streamwater nitrate. We hypothesize that as the drainage network expands, increasing hydrologic connection to bedrock outcrop‐associated soils, streamwater nitrate concentration, and flux at the catchment outlet increase. Most nitrate export (>80%) occurred during high flows when high nitrate, bedrock‐controlled areas of the catchment were most connected hydrologically to the drainage network (∼15% of the time). End‐member mixing analysis demonstrated that the bedrock‐controlled upper part of the catchment influences nitrate concentration at the outlet and contributes most to catchment nitrate export compared to the near‐stream soil units and seeps. Most of the time, nitrate at the catchment outlet comes from seeps and the near‐stream zone; under high flow conditions, bedrock‐controlled hotspots for nitrate production contribute more to export of nitrate. This analysis demonstrates how the source area of streamwater nitrate varies under different flow conditions, suggesting that long‐term nitrate dynamics may be driven primarily by a relatively small part of the catchment.

Managing tree health in urban environments is complicated due to the disconnect that exists between novel environmental conditions created by urbanization and those under which tree species evolved. Soils influence tree health and growth, but optimal nutrient and pH recommendations are often informed by agricultural and horticultural norms which do not typically include norms for forest tree species. At the Arnold Arboretum in Boston, Massachusetts, USA, we investigated the relationships between tree health, foliar chemistry, and soil chemistry for three native forest tree species (Acer saccharum, Quercus alba, and Tsuga canadensis) located throughout the arboretum. We compared these ranges and relationships to data collected from trees of the same species growing in forested areas throughout the northeastern United States. For all species, the distributions of most foliar nutrient concentrations were similar in the arboretum and across the region. However, foliar potassium (K) concentrations were lower at the arboretum than in reference datasets. Soil pH was higher at the arboretum than most forest soils in the region, potentially a result of liming and irrigation with city water. Concentrations of soil and foliar magnesium were also high at the arboretum. Potassium deficiency could result from the blocking of K uptake by magnesium or limited K availability due to forest floor loss. In addition, there is some evidence that manganese is at low to deficient levels. These results show the value of comparing chemical conditions between urban tree populations with trees in natural forests in nearby rural settings to identify potential areas of concern and inform soil management strategies.

Reductions in exchangeable calcium and magnesium and increase in exchangeable aluminum concentrations have been shown in soils impacted by acid deposition, including at four sites on the Allegheny Plateau, PA, USA, sampled in 1967 and 1997 during a period of peak deposition. We repeated sampling at these sites in 2017 to evaluate changes in soils during the more recent period when there has been a strong decline in acid deposition. The uppermost horizons, including the Oa and A horizons where humified organic matter transitions to mineral soil, were thicker, had higher concentrations of organic carbon and exchangeable calcium and magnesium, and lower concentrations of exchangeable aluminum in 2017 compared to 1997, approximating values measured in 1967. Below the Oa/A horizons, 2017 soil chemistry was more similar to the 1997 results, with some reduction of Ca in the recent measurements. These results suggest recovery of base cation–aluminum balance in surface horizons and may indicate a reduction of aluminum mobilization and increased efficiency of vegetation recycling of nutrients with decreased acid anion concentrations. These changes are consistent with a partial recovery from acid deposition. However, the increase in humified soil organic matter may also be affected by coincident increases in temperature and soil moisture.

Small catchments have served as sentinels of forest ecosystem responses to changes in air quality and climate. The Hubbard Brook Experimental Forest in New Hampshire has been tracking catchment water budgets and their controls - meteorology and vegetation - since 1956. Water budgets in four reference catchments indicated an approximately 30% increase in the evapotranspiration (ET) as estimated by the difference between precipitation (P) and runoff (RO) starting in 2010 and continuing through 2019. We analyzed the annual water budgets, cumulative deviations of the daily P, RO and water budget residual (WBR = P - RO), potential ET (PET) and indicators of subsurface storage to gain greater insight into this shift in the water budgets. The PET and the subsurface storage indicators suggest that this change in WBR was primarily due to increasing ET. While multiple long-term hydrological and micrometeorological data sets were used to detect and investigate this change in ET, additional measurements of groundwater storage and soil moisture would enable better estimation of ET within the catchment water balance. Increasing the breadth of long-term measurements across small gauged catchments allows them to serve as more effective sentinels of substantial hydrologic changes like the ET increase that we observed.

Reductions in acidic deposition rates through legislative actions in North America and Europe have stemmed further environmental degradation and shifted the focus to potential recovery [...]

Long-term monitoring of forest soils is necessary to understand the effects of continued environmental change, including climate change, atmospheric deposition of metals, and, in many regions, recovery from acidic precipitation. A monitoring program was initiated in 2002 at five protected forest sites, primarily Spodosol soils, in Vermont, northeastern USA. Every 5 years, ten soil pits were sampled from random subplots in a 50 × 50-m plot at each site. Samples were taken by genetic horizon and, to reduce variability and improve comparability, from four specific layers: the combined Oi/Oe layer, the combined Oa/A layer, the top 10 cm of the B horizon, and 60–70 cm below the soil surface (usually the C horizon). The samples were archived and a subset analyzed for carbon, nitrogen, and exchangeable cations. After four sampling campaigns, the average coefficients of variation (CVs) at each site had a broad range, 10.7% for carbon in the Oa/A horizon to 84.3% for exchangeable Ca2+ in the B horizon. An investigation of variability within the upper 10 cm of the B horizon across a 90-cm soil pit face showed similar CVs to the entire site, emphasizing the need for consistent and careful sampling. After 15 years, temporal trends were significant in the Oa/A and B horizons at two of the five sites, with one site showing an increase in carbon concentration in both layers along with increases in both exchangeable Ca2+ and Al3+ in the B horizon, perhaps linked to recovery from acidification. The monitoring program plans to continue at 5-year intervals for the next century.

Dissolved organic matter (DOM) can serve as an indicator of watershed carbon cycling, and links terrestrial to aquatic ecosystems. The extent DOM is microbially processed before it enters aquatic ecosystems is expected to change with soil depth and landscape position, and as some research suggests, in response to recovery from chronic acidification. Here we examined DOM within freely flowing soil pore water and stream water collected from reference and calcium silicate‐treated watersheds at the Hubbard Brook Experimental Forest, New Hampshire, USA. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations as well as, absorption and fluorescence properties were analyzed to assess patterns in DOM quantity and quality. Parallel factor analysis was used to identify three predominant fluorescing DOM components (C1‐3). All three components were terrestrial in origin, however C3 exhibited spectral properties previously linked to the microbial processing of humic material. Distinct horizonal patterns emerged between genetic soil horizons. DOC quantity decreased with soil depth, so too did, the plant derived lignin‐like fraction (C2), while the C3 fraction increased. High‐elevation coniferous zones with shallow bedrock contributed to higher DOC concentrations in soil and stream water, while high and low‐elevation mineral soils exhibited greater C3 fractions and fluorescence indicators of microbially processed DOM. This pattern suggests these mineral soils are important organic carbon sinks, due to greater rates of microbial DOM processing. DOC in forest floor solutions, C3 fractions, and indicators of smaller molecular size (E 2 :E 3 ) were all higher in the calcium silicate‐treated watershed, suggesting greater microbial processing of DOM.

Specific electrical conductivity (SC) is a basic, effective indicator of water quality.The recent increase in SC data collected with high-frequency sensors has created a strong need for algorithms that can aid interpretation of these data.This study presents an algorithm that finds and quantifies SC temporal patterns and applies that algorithm to a data set from a forested catchment.During and after rain events, we show three patterns that emerge in SC time series: a solute flush, resulting in an initial increase in SC, followed by a dilution, followed by the SC's recovery toward pre-rain conditions.We compared these SC patterns to precipitation amount and intensity, antecedent wetness, and seasonality.Our results indicate that the magnitude of the flush was driven primarily by precipitation intensity and total rainfall during a storm, and secondarily by antecedent moisture conditions.The magnitude of the dilution was driven mainly by precipitation amount.The rate of SC recovery was driven by precipitation amount and was correlated with the dilution.Overall, the algorithm successfully extracted event-driven characteristics in the SC time series, allowing the development of functional relationships with hydrologic drivers.Applying similar methodologies to more catchments in the future will help identify functional relationships at more sites and use these relationships to identify catchments most sensitive to future precipitation changes.

Stream solute monitoring has produced many insights into ecosystem and Earth system functions. Although new sensors have provided novel information about the fine-scale temporal variation of some stream water solutes, we lack adequate sensor technology to gain the same insights for many other solutes. We used two machine learning algorithms - Support Vector Machine and Random Forest - to predict concentrations at 15-min resolution for 10 solutes, of which eight lack specific sensors. The algorithms were trained with data from intensive stream sensing and manual stream sampling (weekly) for four full years in a hydrologic reference stream within the Hubbard Brook Experimental Forest in New Hampshire, USA. The Random Forest algorithm was slightly better at predicting solute concentrations than the Support Vector Machine algorithm (Nash-Sutcliffe efficiencies ranged from 0.35 to 0.78 for Random Forest compared to 0.29 to 0.79 for Support Vector Machine). Solute predictions were most sensitive to the removal of fluorescent dissolved organic matter, pH and specific conductance as independent variables for both algorithms, and least sensitive to dissolved oxygen and turbidity. The predicted concentrations of calcium and monomeric aluminium were used to estimate catchment solute yield, which changed most dramatically for aluminium because it concentrates with stream discharge. These results show great promise for using a combined approach of stream sensing and intensive stream discrete sampling to build information about the high-frequency variation of solutes for which an appropriate sensor or proxy is not available.

The Hubbard Brook Experimental Forest (HBEF) was established in 1955 by the U.S. Department of Agriculture, Forest Service out of concerns about the effects of logging increasing flooding and erosion. To address this issue, within the HBEF hydrological and micrometeorological monitoring was initiated in small watersheds designated for harvesting experiments. The Hubbard Brook Ecosystem Study (HBES) originated in 1963, with the idea of using the small watershed approach to study element fluxes and cycling and the response of forest ecosystems to disturbances, such as forest management practices and air pollution. Early evidence of acid rain was documented at the HBEF and research by scientists at the site helped shape acid rain mitigation policies. New lines of investigation at the HBEF have built on the long legacy of watershed research resulting in a shift from comparing inputs and outputs and quantifying pools and fluxes to a more mechanistic understanding of ecosystem processes within watersheds. For example, hydropedological studies have shed light on linkages between hydrologic flow paths and soil development that provide valuable perspective for managing forests and understanding stream water quality. New high frequency in situ stream chemistry sensors are providing insights about extreme events and diurnal patterns that were indiscernible with traditional weekly sampling. Additionally, tools are being developed for visual and auditory data exploration and discovery by a broad audience. Given the unprecedented environmental change that is occurring, data from the small watersheds at the HBEF are more relevant now than ever and will continue to serve as a basis for sound environmental decision‐making.

The response of mineral-stabilized soil organic carbon (SOC) to environmental change is a source of uncertainty in the understanding of SOC cycling. Fluctuating wet-dry cycles and associated redox changes in otherwise well-drained soils may drive mineral dissolution, organic carbon (OC) mobilization, and subsequent OC mineralization. However, the extent to which rapid fluctuations between water-saturated and unsaturated conditions (i.e., flashy conditions) result in long-term changes in mineral composition and organo-mineral interactions is not well understood. In this study, the effect of variable saturation frequency on soil mineral composition, mineral-associated OC, and OC mineralizability was tested using selective dissolution, bulk spectroscopy, microscale imaging, and aerobic-anaerobic incubation experiments. Previous water table fluctuation measurements and diagnostic profile characteristics at Hubbard Brook Experimental Forest (NH) were used to identify soils with high, medium, and low saturation frequency regimes (defined by historical water table cycling frequency; i.e., water table presence and recession in the upper B horizon). We found the amount of OC released during extractions targeting non-crystalline minerals was of similar magnitude as extracted iron (Fe) in lower saturation frequency soils. However, the magnitude of extracted OC was 2.5 times greater than Fe but more similar to extractable aluminum (Al) in higher saturation frequency soils. Bulk soil Fe was spatially more strongly correlated to soil organic matter (SOM) in lower saturation frequency soils (Spearman Rank r(s) = 0.62, p < 0.005), whereas strong correlations between Al and SOM were observed in higher saturation frequency soils (r(s) = 0.88, p < 0.005) using nanoscale secondary ion mass spectrometry (NanoSIMS) imaging. Characterization of bulk soil Fe with X-ray absorption spectroscopy showed 1.2-fold greater Fe(II) and 1-fold lower contribution of Fe-organic bonding in soils with high saturation frequency. Fe(III) interactions with carboxylic and aromatic C were identified with C-13 nuclear magnetic resonance (NMR) spectroscopy Fe(III) interference experiments. Additionally, carboxylic acid enrichment in high saturation frequency soils quantified by C K-edge X-ray absorption spectroscopy point towards the role of carboxylic functional groups in Al-organic in addition to Fe-organic interactions. In our incubation experiments, a doubling in short-term CO2 evolution (per unit total soil C) was detected for high relative to low saturation frequency soils. Further, an order of magnitude increase in CO2 evolution (per unit water-extractable OC) following anaerobic incubation was only detected in high saturation frequency soils. The observed shift towards Al-dominated SOC interactions and higher OC mineralizability highlights the need to describe C stabilization in soils with flashy wet-dry cycling separately from soils with low saturation frequency or persistent saturation.