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1. 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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2. Particle size determines the accumulation of platinum nanoparticles in the estuarine amphipod, Leptocheirus plumulosus

   https://doi.org/10.1039/d1en00713k  

   Sikder, Mithun ; Eudy, Emily ; Cai, Bo ; Chandler, G. Thomas ; Baalousha, Mohammed ( February 2022 , Environmental Science: Nano)

   Nanoparticles (NPs) typically display a wide distribution of different sizes in aquatic environments, yet little information is available on the impact of particle size dispersity on organismal uptake and elimination. This study investigated uptake and elimination of polyvinylpyrrolidone-coated platinum nanoparticles (PVP-PtNPs) of different sizes ( e.g. , 20.0 ± 4.8 nm, 40.5 ± 4.1 nm, and 70.8 ± 4.2 nm) by the estuarine amphipod Leptocheirus plumulosus . Accumulation and elimination were determined by measuring total Pt body burden in amphipods exposed to PtNPs using inductively coupled plasma-mass spectroscopy, as well as the mass and number PtNP body burden using single particle-ICP-MS (sp-ICP-MS). L. plumulosus accumulated Pt from PtNP suspensions of different sizes from water exposure, mostly ( e.g. , >90%) as PtNPs rather than as dissolved Pt. Mass- and number-based uptake increased with decreases in PtNP size whereas mass- and number-based elimination increased with increasing PtNP size. The residual whole-animal body burden of PtNPs after 48 h elimination increased with decreases in PtNP size, with residual body burdens approximately two-fold higher for amphipods exposed to 20 nm PtNPs than amphipods exposed to 70 nm PtNPs. PtNP influx rate ( k uw ) increased with decreasing NP size, with k uw s of 1.07 ± 0.31, 0.82 ± 0.22, and 0.67 ± 0.10 μg g −1 d −1 for 20 nm, 40 nm, and 70 nm PtNPs, respectively. PtNP efflux rate ( k e ) increased with increasing PtNP size, with k e s of 0.31 ± 0.08, 0.66 ± 0.04, and 0.83 ± 0.07 d −1 for 20 nm, 40 nm, and 70 nm PtNP, respectively. When exposed to mixtures of 40 and 70 nm PtNPs with equal masses, surface areas, or number concentrations of 40 nm and 70 nm PtNPs, L. plumulosus accumulated higher numbers of the 40 nm PtNPs than 70 nm PtNPs from all mixtures. The increased exposure concentration of 70 nm PtNPs in the mixture did not affect the uptake of 40 nm PtNPs, suggesting that in a polydispersed NP suspension the uptake of a given size fraction is independent of other size fractions in the mixture. 

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3. Silver Nanoparticles Stable to Oxidation and Silver Ion Release Show Size-Dependent Toxicity In Vivo

   https://doi.org/10.3390/nano11061516  

   Cunningham, Brittany ; Engstrom, Arek M. ; Harper, Bryan J. ; Harper, Stacey L. ; Mackiewicz, Marilyn R. ( June 2021 , Nanomaterials)

   null (Ed.)

   Silver nanoparticles (AgNPs) are widely used in commerce, however, the effect of their physicochemical properties on toxicity remains debatable because of the confounding presence of Ag+ ions. Thus, we designed a series of AgNPs that are stable to surface oxidation and Ag+ ion release. AgNPs were coated with a hybrid lipid membrane comprised of L-phosphatidylcholine (PC), sodium oleate (SOA), and a stoichiometric amount of hexanethiol (HT) to produce oxidant-resistant AgNPs, Ag–SOA–PC–HT. The stability of 7-month aged, 20–100 nm Ag–SOA–PC–HT NPs were assessed using UV–Vis, dynamic light scattering (DLS), and inductively coupled plasma mass spectrometry (ICP-MS), while the toxicity of the nanomaterials was assessed using a well-established, 5-day embryonic zebrafish assay at concentrations ranging from 0–12 mg/L. There was no change in the size of the AgNPs from freshly made samples or 7-month aged samples and minimal Ag+ ion release (<0.2%) in fishwater (FW) up to seven days. Toxicity studies revealed AgNP size- and concentration-dependent effects. Increased mortality and sublethal morphological abnormalities were observed at higher concentrations with smaller nanoparticle sizes. This study, for the first time, determined the effect of AgNP size on toxicity in the absence of Ag+ ions as a confounding variable. 

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4. Applying the core-satellite species concept: Characteristics of rare and common riverine dissolved organic matter

   https://doi.org/10.3389/frwa.2023.1156042  

   Stadler, Masumi ; Barnard, Malcolm A. ; Bice, Kadir ; de Melo, Michaela L. ; Dwivedi, Dipankar ; Freeman, Erika C. ; Garayburu-Caruso, Vanessa A. ; Linkhorst, Annika ; Mateus-Barros, Erick ; Shi, Cheng ; et al ( March 2023 , Frontiers in Water)

   Dissolved organic matter (DOM) composition varies over space and time, with a multitude of factors driving the presence or absence of each compound found in the complex DOM mixture. Compounds ubiquitously present across a wide range of river systems (hereafter termed core compounds) may differ in chemical composition and reactivity from compounds present in only a few settings (hereafter termed satellite compounds). Here, we investigated the spatial patterns in DOM molecular formulae presence (occupancy) in surface water and sediments across 97 river corridors at a continental scale using the “Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems—WHONDRS” research consortium.

   We used a novel data-driven approach to identify core and satellite compounds and compared their molecular properties identified with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS).

   We found that core compounds clustered around intermediate hydrogen/carbon and oxygen/carbon ratios across both sediment and surface water samples, whereas the satellite compounds varied widely in their elemental composition. Within surface water samples, core compounds were dominated by lignin-like formulae, whereas protein-like formulae dominated the core pool in sediment samples. In contrast, satellite molecular formulae were more evenly distributed between compound classes in both sediment and water molecules. Core compounds found in both sediment and water exhibited lower molecular mass, lower oxidation state, and a higher degree of aromaticity, and were inferred to be more persistent than global satellite compounds. Higher putative biochemical transformations were found in core than satellite compounds, suggesting that the core pool was more processed.

   The observed differences in chemical properties of core and satellite compounds point to potential differences in their sources and contribution to DOM processing in river corridors. Overall, our work points to the potential of data-driven approaches separating rare and common compounds to reduce some of the complexity inherent in studying riverine DOM.

    

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5. Fundamental drivers of dissolved organic matter composition across an Arctic effective precipitation gradient

   https://doi.org/10.1002/lno.11385  

   Kellerman, Anne M. ; Arellano, Ana ; Podgorski, David C. ; Martin, Ellen E. ; Martin, Jonathan B. ; Deuerling, Kelly M. ; Bianchi, Thomas S. ; Spencer, Robert G. M. ( December 2019 , Limnology and Oceanography)

   The standard model for aquatic ecosystems is to link hydrologic connectivity to dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition and, ultimately, reactivity. Studies across effective precipitation gradients have been suggested as models for predicting how carbon cycling will change in Arctic aquatic ecosystems with projected drying (i.e., reduced hydrologic connectivity). To evaluate links between DOM dynamics and hydrologic connectivity, 41 stream samples from Greenland were analyzed across an effective precipitation gradient for DOM optical properties and elemental composition using ultrahigh‐resolution mass spectrometry. Sites with negative effective precipitation and decreased hydrologic connectivity exhibited elevated specific conductivity (SpC) and DOC concentrations as well as DOM composition indicative of decreased hydrologic connectivity, for example, lower aromaticity, assessed using carbon‐specific UV absorbance at 254 nm, decreased relative abundances of polyphenolic and condensed aromatic compounds, and increased relative abundances of highly unsaturated and phenolic compounds. Allochthonous inputs decreased as the summer progressed as exhibited by decreases in aromatic compounds. A decrease in molecular richness and N‐containing compounds coincided with the decrease in allochthonous inputs. DOC concentrations increased over the summer but more slowly than SpC, suggesting degradation processes outweighed combined evapoconcentration and production. The patterns in DOM composition suggest evapoconcentration and photodegradation are dominant controls. However, when hydrologic connectivity was high, regardless of effective precipitation, DOM reflected allochthonous sources such as snowmelt‐fed wetlands. These results highlight the challenges of modeling carbon cycling in aquatic ecosystems across effective precipitation gradients, particularly those with strong seasonality and regional variability in hydrologic inputs.

    

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