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1. Correlative chemical and elemental nano-imaging of morphology and disorder at the nacre-prismatic region interface in Pinctada margaritifera

   https://doi.org/10.1038/s41598-023-47446-5  

   O’Callahan, Brian T. ; Larsen, Amy ; Leichty, Sarah ; Cliff, John ; Gagnon, Alex C. ; Raschke, Markus B. ( December 2023 , Scientific Reports)

   Understanding biomineralization relies on imaging chemically heterogeneous organic–inorganic interfaces across a hierarchy of spatial scales. Further, organic minority phases are often responsible for emergent inorganic structures from the atomic arrangement of different polymorphs, to nano- and micrometer crystal dimensions, up to meter size mollusk shells. The desired simultaneous chemical and elemental imaging to identify sparse organic moieties across a large field-of-view with nanometer spatial resolution has not yet been achieved. Here, we combine nanoscale secondary ion mass spectroscopy (NanoSIMS) with spectroscopic IRs-SNOM imaging for simultaneous chemical, molecular, and elemental nanoimaging. At the example ofPinctada margaritiferamollusk shells we identify and resolve ~ 50 nm interlamellar protein sheets periodically arranged in regular ~ 600 nm intervals. The striations typically appear ~ 15 µm from the nacre-prism boundary at the interface between disordered neonacre to mature nacre. Using the polymorph distinctive IR-vibrational carbonate resonance, the nacre and prismatic regions are consistently identified as aragonite ($${\overline{\nu }}_{a}=860$$${\overline{\nu }}_a=860$cm⁻¹) and calcite ($${\overline{\nu }}_{c}=880$$${\overline{\nu }}_c=880$cm⁻¹), respectively. We observe previously unreported morphological features including aragonite subdomains encapsulated in extensions of the prism-covering organic membrane and regions of irregular nacre tablet formation coincident with dispersed organics. We also identify a ~ 200 nm region in the incipient nacre region with less well-defined crystal structure and integrated organics. These results show with the identification of the interlamellar protein layer how correlative nano-IR chemical and NanoSIMS elemental imaging can help distinguish different models proposed for shell growth in particular, and how organic function may relate to inorganic structure in other biomineralized systems in general.

    

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2. Florida mangrove saltmarsh reference surface soils

   https://doi.org/10.6073/pasta/0e08cbe07c84488cb7b9dd16669946d0  

   Lewis, David Bruce ( January 2021 , Environmental Data Initiative)

   Site description. This data package consists of data obtained from sampling surface soil (the 0-7.6 cm depth profile) in black mangrove (Avicennia germinans) dominated forest and black needlerush (Juncus roemerianus) saltmarsh along the Gulf of Mexico coastline in peninsular west-central Florida, USA. This location has a subtropical climate with mean daily temperatures ranging from 15.4 °C in January to 27.8 °C in August, and annual precipitation of 1336 mm. Precipitation falls as rain primarily between June and September. Tides are semi-diurnal, with 0.57 m median amplitudes during the year preceding sampling (U.S. NOAA National Ocean Service, Clearwater Beach, Florida, station 8726724). Sea-level rise is 4.0 ± 0.6 mm per year (1973-2020 trend, mean ± 95 % confidence interval, NOAA NOS Clearwater Beach station). The A. germinans mangrove zone is either adjacent to water or fringed on the seaward side by a narrow band of red mangrove (Rhizophora mangle). A near-monoculture of J. roemerianus is often adjacent to and immediately landward of the A. germinans zone. The transition from the mangrove to the J. roemerianus zone is variable in our study area. An abrupt edge between closed-canopy mangrove and J. roemerianus monoculture may extend for up to several hundred meters in some locations, while other stretches of ecotone present a gradual transition where smaller, widely spaced trees are interspersed into the herbaceous marsh. Juncus roemerianus then extends landward to a high marsh patchwork of succulent halophytes (including Salicornia bigellovi, Sesuvium sp., and Batis maritima), scattered dwarf mangrove, and salt pans, followed in turn by upland vegetation that includes Pinus sp. and Serenoa repens. Field design and sample collection. We established three study sites spaced at approximately 5 km intervals along the western coastline of the central Florida peninsula. The sites consisted of the Salt Springs (28.3298°, -82.7274°), Energy Marine Center (28.2903°, -82.7278°), and Green Key (28.2530°, -82.7496°) sites on the Gulf of Mexico coastline in Pasco County, Florida, USA. At each site, we established three plot pairs, each consisting of one saltmarsh plot and one mangrove plot. Plots were 50 m^2 in size. Plots pairs within a site were separated by 230-1070 m, and the mangrove and saltmarsh plots composing a pair were 70-170 m apart. All plot pairs consisted of directly adjacent patches of mangrove forest and J. roemerianus saltmarsh, with the mangrove forests exhibiting a closed canopy and a tree architecture (height 4-6 m, crown width 1.5-3 m). Mangrove plots were located at approximately the midpoint between the seaward edge (water-mangrove interface) and landward edge (mangrove-marsh interface) of the mangrove zone. Saltmarsh plots were located 20-25 m away from any mangrove trees and into the J. roemerianus zone (i.e., landward from the mangrove-marsh interface). Plot pairs were coarsely similar in geomorphic setting, as all were located on the Gulf of Mexico coastline, rather than within major sheltering formations like Tampa Bay, and all plot pairs fit the tide-dominated domain of the Woodroffe classification (Woodroffe, 2002, "Coasts: Form, Process and Evolution", Cambridge University Press), given their conspicuous semi-diurnal tides. There was nevertheless some geomorphic variation, as some plot pairs were directly open to the Gulf of Mexico while others sat behind keys and spits or along small tidal creeks. Our use of a plot-pair approach is intended to control for this geomorphic variation. Plot center elevations (cm above mean sea level, NAVD 88) were estimated by overlaying the plot locations determined with a global positioning system (Garmin GPS 60, Olathe, KS, USA) on a LiDAR-derived bare-earth digital elevation model (Dewberry, Inc., 2019). The digital elevation model had a vertical accuracy of ± 10 cm (95 % CI) and a horizontal accuracy of ± 116 cm (95 % CI). Soil samples were collected via coring at low tide in June 2011. From each plot, we collected a composite soil sample consisting of three discrete 5.1 cm diameter soil cores taken at equidistant points to 7.6 cm depth. Cores were taken by tapping a sleeve into the soil until its top was flush with the soil surface, sliding a hand under the core, and lifting it up. Cores were then capped and transferred on ice to our laboratory at the University of South Florida (Tampa, Florida, USA), where they were combined in plastic zipper bags, and homogenized by hand into plot-level composite samples on the day they were collected. A damp soil subsample was immediately taken from each composite sample to initiate 1 y incubations for determination of active C and N (see below). The remainder of each composite sample was then placed in a drying oven (60 °C) for 1 week with frequent mixing of the soil to prevent aggregation and liberate water. Organic wetland soils are sometimes dried at 70 °C, however high drying temperatures can volatilize non-water liquids and oxidize and decompose organic matter, so 50 °C is also a common drying temperature for organic soils (Gardner 1986, "Methods of Soil Analysis: Part 1", Soil Science Society of America); we accordingly chose 60 °C as a compromise between sufficient water removal and avoidance of non-water mass loss. Bulk density was determined as soil dry mass per core volume (adding back the dry mass equivalent of the damp subsample removed prior to drying). Dried subsamples were obtained for determination of soil organic matter (SOM), mineral texture composition, and extractable and total carbon (C) and nitrogen (N) within the following week. Sample analyses. A dried subsample was apportioned from each composite sample to determine SOM as mass loss on ignition at 550 °C for 4 h. After organic matter was removed from soil via ignition, mineral particle size composition was determined using a combination of wet sieving and density separation in 49 mM (3 %) sodium hexametaphosphate ((NaPO_3)_6) following procedures in Kettler et al. (2001, Soil Science Society of America Journal 65, 849-852). The percentage of dry soil mass composed of silt and clay particles (hereafter, fines) was calculated as the mass lost from dispersed mineral soil after sieving (0.053 mm mesh sieve). Fines could have been slightly underestimated if any clay particles were burned off during the preceding ignition of soil. An additional subsample was taken from each composite sample to determine extractable N and organic C concentrations via 0.5 M potassium sulfate (K_2SO_4) extractions. We combined soil and extractant (ratio of 1 g dry soil:5 mL extractant) in plastic bottles, reciprocally shook the slurry for 1 h at 120 rpm, and then gravity filtered it through Fisher G6 (1.6 μm pore size) glass fiber filters, followed by colorimetric detection of nitrite (NO_2^-) + nitrate (NO_3^-) and ammonium (NH_4^+) in the filtrate (Hood Nowotny et al., 2010,Soil Science Society of America Journal 74, 1018-1027) using a microplate spectrophotometer (Biotek Epoch, Winooski, VT, USA). Filtrate was also analyzed for dissolved organic C (referred to hereafter as extractable organic C) and total dissolved N via combustion and oxidation followed by detection of the evolved CO_2 and N oxide gases on a Formacs HT TOC/TN analyzer (Skalar, Breda, The Netherlands). Extractable organic N was then computed as total dissolved N in filtrate minus extractable mineral N (itself the sum of extractable NH_4-N and NO_2-N + NO_3-N). We determined soil total C and N from dried, milled subsamples subjected to elemental analysis (ECS 4010, Costech, Inc., Valencia, CA, USA) at the University of South Florida Stable Isotope Laboratory. Median concentration of inorganic C in unvegetated surface soil at our sites is 0.5 % of soil mass (Anderson, 2019, Univ. of South Florida M.S. thesis via methods in Wang et al., 2011, Environmental Monitoring and Assessment 174, 241-257). Inorganic C concentrations are likely even lower in our samples from under vegetation, where organic matter would dilute the contribution of inorganic C to soil mass. Nevertheless, the presence of a small inorganic C pool in our soils may be counted in the total C values we report. Extractable organic C is necessarily of organic C origin given the method (sparging with HCl) used in detection. Active C and N represent the fractions of organic C and N that are mineralizable by soil microorganisms under aerobic conditions in long-term soil incubations. To quantify active C and N, 60 g of field-moist soil were apportioned from each composite sample, placed in a filtration apparatus, and incubated in the dark at 25 °C and field capacity moisture for 365 d (as in Lewis et al., 2014, Ecosphere 5, art59). Moisture levels were maintained by frequently weighing incubated soil and wetting them up to target mass. Daily CO_2 flux was quantified on 29 occasions at 0.5-3 week intervals during the incubation period (with shorter intervals earlier in the incubation), and these per day flux rates were integrated over the 365 d period to compute an estimate of active C. Observations of per day flux were made by sealing samples overnight in airtight chambers fitted with septa and quantifying headspace CO_2 accumulation by injecting headspace samples (obtained through the septa via needle and syringe) into an infrared gas analyzer (PP Systems EGM 4, Amesbury, MA, USA). To estimate active N, each incubated sample was leached with a C and N free, 35 psu solution containing micronutrients (Nadelhoffer, 1990, Soil Science Society of America Journal 54, 411-415) on 19 occasions at increasing 1-6 week intervals during the 365 d incubation, and then extracted in 0.5 M K_2SO_4 at the end of the incubation in order to remove any residual mineral N. Active N was then quantified as the total mass of mineral N leached and extracted. Mineral N in leached and extracted solutions was detected as NH_4-N and NO_2-N + NO_3-N via colorimetry as above. This incubation technique precludes new C and N inputs and persistently leaches mineral N, forcing microorganisms to meet demand by mineralizing existing pools, and thereby directly assays the potential activity of soil organic C and N pools present at the time of soil sampling. Because this analysis commences with disrupting soil physical structure, it is biased toward higher estimates of active fractions. Calculations. Non-mobile C and N fractions were computed as total C and N concentrations minus the extractable and active fractions of each element. This data package reports surface-soil constituents (moisture, fines, SOM, and C and N pools and fractions) in both gravimetric units (mass constituent / mass soil) and areal units (mass constituent / soil surface area integrated through 7.6 cm soil depth, the depth of sampling). Areal concentrations were computed as X × D × 7.6, where X is the gravimetric concentration of a soil constituent, D is soil bulk density (g dry soil / cm^3), and 7.6 is the sampling depth in cm. 

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3. Permafrost soil complexity evaluated by laboratory imaging Vis ‐ NIR spectroscopy

   https://doi.org/10.1111/ejss.12927  

   Mueller, Carsten W. ; Steffens, Markus ; Buddenbaum, Henning ( January 2020 , European Journal of Soil Science)

   The biogeochemical functioning of soils (e.g., soil carbon stabilization and nutrient cycling) is determined at the interfaces of specific soil structures (e.g., aggregates, particulate organic matter (POM) and organo‐mineral associations). With the growing accessibility of spectromicroscopic techniques, there is an increase in nano‐ to microscale analyses of biogeochemical interfaces at the process scale, reaching from the distribution of elements and isotopes to the localization of microorganisms. A widely used approach to study intact soil structures is the fixation and embedding of intact soil samples in resin and the subsequent analyses of soil cross‐sections using spectromicroscopic techniques. However, it is still challenging to link such microscale approaches to larger scales at which normally bulk soil analyses are conducted. Here we report on the use of laboratory imaging Vis–NIR spectroscopy on resin embedded soil sections and a procedure for supervised image classification to determine the microscale soil structure arrangement, including the quantification of soil organic matter fractions. This approach will help to upscale from microscale spectromicroscopic techniques to the centimetre and possibly pedon scale. Thus, we demonstrate a new approach to integrate microscale soil analyses into pedon‐scale conceptual and experimental approaches.

   Quantification of soil constituents using Vis‐NIR spectroscopy.

   New approach to use resin embedded soil core sections with intact structure.

   Reproducible quantification of soil constituents important for soil carbon storage.

   Vis‐NIR as promising tool for upscaling from microscale to pdeon scale.

    

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4. Nitrogen increases soil organic carbon accrual and alters its functionality

   https://doi.org/10.1111/gcb.16588  

   Tang, Bo ; Rocci, Katherine S. ; Lehmann, Anika ; Rillig, Matthias C. ( January 2023 , Global Change Biology)

   Nitrogen (N) availability has been considered as a critical factor for the cycling and storage of soil organic carbon (SOC), but effects of N enrichment on the SOC pool appear highly variable. Given the complex nature of the SOC pool, recent frameworks suggest that separating this pool into different functional components, for example, particulate organic carbon (POC) and mineral‐associated organic carbon (MAOC), is of great importance for understanding and predicting SOC dynamics. Importantly, little is known about how these N‐induced changes in SOC components (e.g., changes in the ratios among these fractions) would affect the functionality of the SOC pool, given the differences in nutrient density, resistance to disturbance, and turnover time between POC and MAOC pool. Here, we conducted a global meta‐analysis of 803 paired observations from 98 published studies to assess the effect of N addition on these SOC components, and the ratios among these fractions. We found that N addition, on average, significantly increased POC and MAOC pools by 16.4% and 3.7%, respectively. In contrast, both the ratios of MAOC to SOC and MAOC to POC were remarkably decreased by N enrichment (4.1% and 10.1%, respectively). Increases in the POC pool were positively correlated with changes in aboveground plant biomass and with hydrolytic enzymes. However, the positive responses of MAOC to N enrichment were correlated with increases in microbial biomass. Our results suggest that although reactive N deposition could facilitate soil C sequestration to some extent, it might decrease the nutrient density, turnover time, and resistance to disturbance of the SOC pool. Our study provides mechanistic insights into the effects of N enrichment on the SOC pool and its functionality at global scale, which is pivotal for understanding soil C dynamics especially in future scenarios with more frequent and severe perturbations.

    

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5. Competing Processes Drive the Resistance of Soil Carbon to Alterations in Organic Inputs

   https://doi.org/10.3389/fenvs.2021.527803  

   Pierson, Derek ; Peter-Contesse, Hayley ; Bowden, Richard D. ; Nadelhoffer, Knute ; Kayhani, Kamron ; Evans, Lucas ; Lajtha, Kate ( April 2021 , Frontiers in Environmental Science)

   null (Ed.)

   Protecting existing soil carbon (C) and harnessing the C sequestration potential of soils require an improved understanding of the processes through which soil organic matter accumulates in natural systems. Currently, competing hypotheses exist regarding the dominant mechanisms for soil C stabilization. Many long-standing hypotheses revolve around an assumed positive relationship between the quantity of organic inputs and soil C accumulation, while more recent hypotheses have shifted attention toward the complex controls of microbial processing and organo-mineral complexation. Here, we present the observed findings of soil response to 20 years of detrital manipulations in the wet, temperate forest of the H.J. Andrews Experimental Station. Annual additions of low-quality (high C:N content) wood litter to the soil surface led to a greater positive effect on observed mean soil C concentration relative to additions of higher-quality (low C:N content) needle litter over the 20-year study period. However, high variability in measurements of soil C led to a statistically non-significant difference in C concentration between the two treatments and the control soil. The observed soil C responses to these two addition treatments demonstrates the long timescale and potential magnitude of soil C responses to management or disturbance led changes in forest litter input composition. Detrital input reduction treatments, including cutting off live root activity and the aboveground removal of surface litter, led to relatively small, non-significant effects on soil C concentrations over the 20-year study period. Far greater negative effects on mean soil C concentrations were observed for the combined removal of both aboveground litter and belowground root activity, which led to an observed, yet also non-significant, 20% decline in soil C stocks. The substantial proportion of remaining soil C following these dramatic, long-term reductions in above- and belowground detrital inputs suggests that losses of C in these forest soils are not readily achieved over a few decades of reductions in detrital input and may require far greater periods of time or further perturbations to the environment. Further, the observed soil C responses to detrital manipulations support recent hypotheses regarding soil C stabilization, which emphasize litter quality and mineral stabilization as relevant controls over forest soil C. 

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