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We investigated the effects of biochar (BC) at 0 and 20 t ha-1, combined with two organic fertilizers (municipal solid waste compost, MC, and sewage sludge, SS), on soil organic matter (SOM) in a 9-year field experiment. To capture the protection by soil minerals and iron (Fe) against microbial decomposition, we fractionated SOM into particulate (POM) and mineral-associated organic matter (MAOM), and analyzed the fractions by iron (Fe) K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.BC and the two organic amendments increased soil organic carbon (OC) content, but only the organic fertilizers significantly increased total nitrogen (N) content. BC increased particulate OC and total N contents, while the organic fertilizers only increased particulate total N content. BC significantly increased mineral-associated OC content, while the organic fertilizers increased both mineral-associated OC and total N contents. We found no interaction between BC and organic fertilizers on mineral-associated OC and total N contents. The Fe EXAFS data fitting showed that the Fe(III)-SOM content of the Fe phases in POM and MAOM in unamended soils were noticeably different. Hematite represented the main Fe oxide phase in the POM fractions from all the amended soils, and Fe(III)-SOM averaged around 15%. In the amended soils, besides hematite (also present in the unamended soil), ferrihydrite occurred in all MAOM fractions, although at a different proportion.

Future long-term space missions beyond Low Earth Orbit (e.g., to Mars) depend on the development of bioregenerative life support systems able to produce food crops based on in situ resource utilization. Mars regolith potentially contains most of the essential nutrients for plant growth, except for organic matter (OM). Several strategies and treatments can be applied to improve nutrient deficiency of simulants and enhance their performance as plant growth substrates. Although Mars regolith simulants have been characterized by mineralogical, physico-chemical and hydraulic properties, no data are available to date in the scientific literature about the stabilization of exogeneous OM by minerals, including iron (Fe) oxides, over time.This study aims at understanding the mineral transformation and OM turnover in the early stages of terraforming. The Mojave Mars Simulant MMS-1, alone (R100) and with a commercial compost 70:30 v:v (R70C30), was compared to a fluvial sand, alone and with compost (S100 and S70C30). Potato was grown on these substrates for 99 days in greenhouse. Samples were fractionated, obtaining particulate OM (POM) and mineral associated OM (MAOM), andcharacterized for total nitrogen and organic carbon (OC), total element concentration (ICP-OES) and by Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS).In the whole medium, OC increased in S70C30 (10×) and R70C30 (25×). As expected, most of the OC accumulated in the POM fraction of both growing media (10× in S70C30 and 20× in R70C30), while OC in the MAOM was 3-times higher in R70C30 than in S70C30. Chlorite, smectite and goethite were the main Fe species in S100, according to XANES, while Fe(III)-OM was found in both fractions of S70C30. Moreover, according to EXAFS, hematite occurred in POM, whereas goethite in MAOM. XANES revealed the occurrence of smectite, maghemite and ferrihydrite in R100, and of nontronite and hematite in the MAOM and POM, respectively.Revealing Fe species involved in the formation of organo-mineral interactions will help to identify the main critical aspects and future challenges related to sustainable space farming improving the in-situ use of Martian resources.

This study aims to investigate the mechanisms of soil organic carbon (SOC) sequestration with depth as a function of time and climate. Two chronosequences located along a climate gradient were investigated. The first chronosequence (ADI) consisted of fluvial terraces, whereas the second (LED) of fluvio-glacial terraces. Four sites (Q2, Q3, Q4 and Q5) located in 3 terraces (T1, T2, and T3), with age ranging from about 125,000 to 2,000 yr, were investigated for ADI, while 3 sites (Q1, Q2, and Q3) in 3 terraces (T1, T2, and T3, respectively), with age range from about 16,000 to 10,000 yr, were selected for LED. All sites were grasslands. Soil samples were collected (1 profile and 2 cores per site) by horizon, and each horizon sub-sampled by depth (each 5 cm). The sub-samples were characterized for pH, EC, total organic C, total N, texture, mineralogy, total and extractable elements, and for soil respiration. Particulate organic matter (POM) and mineral-associated organic matter (MAOM) were isolated and characterized by elemental and thermal analyses.In ADI, the oldest site (ADIQ2) stocks 2 times more C in the topsoil (15 cm) than the youngest site (ADIQ5) (60 and 27 MgC/ha, respectively). Furthermore, in ADIQ3, 38% of the total SOC accumulated between 30 and 80 cm (48 MgC/ha). In LED, the youngest site (LEDQ3) shows the highest SOC stock to both 15 and 30 cm (86 and 138 MgC/ha, respectively). In LEDQ1, 46% of the total SOC accumulated between 30 and 90 cm (94 MgC/ha). Among sites having same age but different climate, LEDQ3 (the wettest and coldest site) stocks ~2 times more carbon than ADIQ3 (the driest and warmest site) to the first 30 cm of depth.In LED, the ratio between the organic C in MAOM/POM in the topsoil ranges between 0.6 and 1.8, while in ADI between 1.1 and 3.9. Thermal indices (e.g., WL400-550/200-300, TG-T50) show that the stability of bulk SOM and pools generally increased with depth in ADI sites, whereas remained constant in LED. ADI soils had similar cumulative respiration (RHCUM), whereas LEDQ3 exhibited the highest RHCUM along the first 30 cm. Indeed, LEDQ3 had a 3× higher RHCUM than ADIQ3 in topsoil.Our data show that significant amounts of organic C were accumulated in deeper soils (>30cm). Moreover, soil organic matter (SOM) stability, and especially that of MAOM, in ADI increased with depth. The relative contribution of POM to C storage was more important in LED than in ADI, especially in the topsoil. Overall, our data suggest that climate has a greater influence on the size of SOC stocks than age, which in turn exerts a major influence on the stability of SOM.

Northern peatlands store globally-important amounts of carbon in the form of partly decomposed plant detritus. Drying associated with climate and land-use change may lead to increased fire frequency and severity in peatlands and the rapid loss of carbon to the atmosphere. However, our understanding of the patterns and drivers of peatland burning on an appropriate decadal to millennial timescale relies heavily on individual site-based reconstructions. For the first time, we synthesise peatland macrocharcoal re-cords from across North America, Europe, and Patagonia to reveal regional variation in peatland burning during the Holocene. We used an existing database of proximal sedimentary charcoal to represent regional burning trends in the wider landscape for each region. Long-term trends in peatland burning appear to be largely climate driven, with human activities likely having an increasing influence in the late Holocene. Warmer conditions during the Holocene Thermal Maximum (similar to 9e6 cal. ka BP) were associated with greater peatland burning in North America's Atlantic coast, southern Scandinavia and the Baltics, and Patagonia. Since the Little Ice Age, peatland burning has declined across North America and in some areas of Europe. This decline is mirrored by a decrease in wider landscape burning in some, but not all sub-regions, linked to fire-suppression policies, and landscape fragmentation caused by agricultural expansion. Peatlands demonstrate lower susceptibility to burning than the wider landscape in several instances, probably because of autogenic processes that maintain high levels of near-surface wetness even during drought. Nonetheless, widespread drying and degradation of peatlands, particularly in Europe, has likely increased their vulnerability to burning in recent centuries. Consequently, peatland restoration efforts are important to mitigate the risk of peatland fire under a changing climate. Finally, we make recommendations for future research to improve our understanding of the controls on peatland fires.(c) 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Monitoring crop physiological responses to drought is crucial to understand progressive impacts on food production and identify resilient and sustainable irrigation practices. Although many climate research experiments provide valuable data, long-term measurements of soil properties and plant characteristics at the field scale are not always affordable. We combined drone-based multispectral remote sensing with measurements of soil properties over multiple pilot farms, where soil sampling was performed for each plot during the drone survey. Our goal was to determine if drone-based indices capture drought stress responses of different crops (maize and sugar beet) and whether responses are affected by soil physical and chemical characteristics (e.g., texture, density, porosity, moisture, pH, electrical conductivity, organic carbon and total nitrogen contents, availability of micro and macro nutrients). Significant relationships were found between vegetation indices and soil features for different crop types. Differences found at the field scale were related mostly to organic carbon content and resulted in heterogeneous responses to irrigation practices. Our spatial variability analysis pointed out an overall homogeneous response for areas submitted to severe and moderate drought having similar soil properties, independently of the crop type. More investigation is needed to address the possible effect of local practices (e.g., fertilization, amendment, tillage) at the field scale. The feasibility of carrying out systematic drone flights coincidentally or close to-ground campaigns will reveal the consistency of the observed spatial patterns in the long run.

We report the first example of very efficient NIR Circularly Polarized Luminescence (CPL) (around 970 nm) in water, obtained thanks to the combined use of a chiral Yb complex and of poly lactic-co-glycolic acid (PLGA) nanoparticles. [YbL(tta)

The aim of this work is to investigate the mechanisms of soil organic carbon (SOC) sequestration as a function of time and depth. A chronosequence, consisting of two orders (T2 and T1) of the Adige river terraces (Veneto region, North of Italy) and 3 sites (Q2, Q3, and Q4), has been investigated. The highest and oldest terrace (T1) is located in Montalto di Gaium, 125 m above the current Adige riverbed level. This terrace was probably formed during the last interglacial (ca. 125,000 years BP) and was characterized by Paleudalf soils. Conversely, T2 represents the youngest order of terraces (probably formed during the early Holocene) and is situated 15 m above the current riverbed level. The Q2 site was located in T1 whereas Q3 and Q4 in T2; all sites have a common vegetation. From each site, soil samples have been collected (1 profile and 2 cores per site) by soil horizon, and each horizon sub-sampled by depth (each 5 cm). Five-cm thick sub-samples have been characterized for pH, electrical conductivity, total organic C (Corg), total N (NTOT), texture, and micro and macro nutrients. Particulate organic matter (POM) and mineral-associated organic matter (MAOM) have been isolated using a physical fractionation method and characterized by elemental (CHNS) and thermal analysis (TGA-DSC).The average Corg content in the topsoil (20 cm) is quite constant in the three sites (27.4 mg/g), whereas the average NTOT concentration ranges between 2.7 and 3.1 mg/g. In all sites, the Corg concentration along the profile is positively correlated with NTOT (porg and clay (porg sequestration. SOC stock in topsoil is 47% higher in Q2 (T1) (72±3 MgC/ha) than in Q4 (T2) (49±5 MgC/ha), but such a difference decreases at 35 cm (96±2 and 76±7 MgC/ha, respectively). Furthermore, in the site showing the deepest soil profile (Q3), the SOC accumulated between 35 and 80 cm (42 MgC/ha) represents the 33% of the total. The average content of the MAOM pool is constant along the T2 (Q3 and Q4) profiles (52%), while increases with depth in T1 (up to 62% in deeper layers).Thermal indices (e.g., WL400-550/200-300, TG-T50, DSC-T50) suggest that the stability of bulk SOM generally increases with depth in the three sites. Moreover, a general increase in the thermal stability of both MAOM and POM is observed with depth in all sites, with Q2 (i.e., the site in the oldest terrace) showing a larger increase of MAOM thermal stability in deeper soil compared to Q3 and Q4 (located on the youngest terrace).While most of the studies on SOC sequestration and stabilization focuses on topsoils, our preliminary data show that a significant stock of more recalcitrant organic C accumulates in deeper soils. Future data will help to better understand the effect of time on SOC distribution among different pools and as a function of depth.

The knowledge of the viscosity of magmas as a function of melt composition and temperature is central in the numerical modeling of the magmatic dynamics and eruptive scenarios. Recent studies suggest that the measure of the viscosity of volcanic melts is affected by the occurrence of nano-scale modification (i.e., crystallization) of the melt structure during the measurement. This challenges the possibility of being able to quantify the crystal-free melt phase contribution to the measured viscosity. Herein we provide a new strategy that allows an accurate estimation of the melt viscosity at eruptive conditions starting from the Brillouin and Raman scattering of parental glasses. Our results show that the ratio between bulk and shear moduli and the boson peak position of glass embed the melt fragility. However, at the moment there are no known reasons why some of these quantities are linked together in such multicomponent systems. At this effort, we also provided a mean to evaluate whether the local structure of glasses may justify this correlation by testing the well-known prototypical binary system Na2O-SiO2. Concluding, our strategy allows the estimation of the melt viscosity as a function of temperature avoiding its direct measurement, ridding also the measurement from unwished crystallization.

A 3-m thick sediment was found in a limestone mine located in the Apulia region (south of Italy), at a depth of 25-30 m from the current ground level. Samples from 5 layers were investigated by X-ray Absorption Near Edge Spectroscopy (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) at the iron (Fe) K-edge, paired with Raman spectroscopy (RS) and thermal analysis.The pedosediment record under investigation represents a peculiar stratigraphic series showing complex features related to the Fe dynamic.From a technical point of view, the challenges of phase identification in Fe oxides are many, but the application of multiple techniques provides sufficient evidence for the identification and discrimination of Fe phases. The combination of Fe XANES and EXAFS allowed to get information on the Fe speciation and its local structure. In detail, ferrihydrite is the most abundant Fe species, followed by goethite and minor amounts of hematite. Ferrihydrite content decreases with depth, where goethite and hematite occur. The presence of ferrihydrite, only detected by Linear Combination Fitting (LCF) on the first-derivative XANES spectra and on the EXAFS spectra, suggests that redox cycling of Fe occurred in these sediments. In addition, higher contents in Fe(III) complexed by organic matter is found in the top and deepest layer.Generally speaking, RS and thermal analysis might present a promising tool to unravel some mineralogical components such as calcite, goethite and some Mn-oxides. Unlike for the identification of some Fe-bearing minerals like ferrihydrite, RS seems to be not well suited and this aspect require further investigations.Definitely, this study confirms that each layer has preserved the distinct features that relate to its time of deposition. We underline how a multidisciplinary approach is strongly required to obtain reliable records when peculiar environments like karst pedosequences are investigated.

Northern peatlands sequester carbon (C) and nitrogen (N) over millennia, at variable rates that depend on climate, environmental variables and anthropogenic activity. The ombrotrophic peatlands of central and northern Alberta (Canada) have developed under variable climate conditions during the last hundreds to thousands of years, while in the course of the twentieth century, some regions were also likely subjected to anthropogenic disturbance. We aimed to quantify peat C and N accumulation rates for the last millennium from seven peatlands to estimate the relative influence of climate and anthropogenic disturbance on C accumulation dynamics. Peatlands have accumulated C at an average rate of 25.3 g C m−2 year−1 over the last millennium. Overall, climate was likely a major factor as, on average, highest apparent rates of C accumulation were found around 1100 CE, during the warmer Medieval Climate Anomaly, with lowest rates during the Little Ice Age, around 1750 CE. Local factors, such as disturbance, played a role in C sequestration at the site scale. The average N accumulation rate was 0.55 g N m−2 year−1, with high inter- and intra-site variability. In general, N accumulation mirrored patterns in C sequestration for peat deposited pre-1850 CE. However, higher N accumulation rates observed after 1850 CE, averaging 0.94 g N m−2 year−1, were not correlated with C accumulation. Moreover, some of the historically strongly accumulating sites may have become less efficient in sequestering C, and vice versa. All seven sites showed a marked decrease in δ15N when comparing pre- and post-1850 timeframes, consistent with increasing post-1850 N additions from an atmospheric source, likely biological N fixation. Overall, N was not a driving factor for C accumulation.

Purpose: The craniometrics of head circumference (HC) and ventricular size are part of the clinical assessment of infants with hydrocephalus and are often utilized in conjunction with other clinical and radiological parameters to determine the success of treatment. We aimed to assess the effect of endoscopic third ventriculostomy (ETV) and shunting on craniometric measurements during the follow-up of a cohort of infants with symptomatic triventricular hydrocephalus secondary to aqueductal stenosis. Methods: We performed a post hoc analysis of data from the International Infant Hydrocephalus Study (IIHS)-a prospective, multicenter study of infants (< 24 months old) with hydrocephalus from aqueductal stenosis who were treated with either an ETV or shunt. During various stages of a 5-year follow-up period, the following craniometrics were measured: HC, HC centile, HC z-score, and frontal-occipital horn ratio (FOR). Data were compared in an analysis of covariance, adjusting for baseline variables including age at surgery and sex. Results: Of 158 enrolled patients, 115 underwent an ETV, while 43 received a shunt. Both procedures led to improvements in the mean HC centile position and z-score, a trend which continued until the 5-year assessment point. A similar trend was noted for FOR which was measured at 12 months and 3 years following initial treatment. Although the values were consistently higher for ETV compared with shunt, the differences in HC value, centile, and z-score were not significant. ETV was associated with a significantly higher FOR compared with shunting at 12 months (0.52 vs 0.44; p = 0.002) and 3 years (0.46 vs 0.38; p = 0.03) of follow-up. Conclusion: ETV and shunting led to improvements in HC centile, z-score, and FOR measurements during long-term follow-up of infants with hydrocephalus secondary to aqueductal stenosis. Head size did not significantly differ between the treatment groups during follow-up, however ventricle size was greater in those undergoing ETV when measured at 1 and 3 years following treatment.

Peatlands are a major carbon (C) sink and represent important habitats for nature conservation because of the occurrence of specifically adapted organisms. Peatlands are typically nutrient-poor environments, and thus extremely sensitive to nitrogen (N) depositions. In fact, increasing N inputs can cause a shift from a Sphagnum moss- to a vascular plant-dominated vegetation as well as an alteration of the mire geochemistry which, in turn, affects the litter composition and decomposition rate. Peatland is an extremely fragile ecosystem: at the European level, >60% of this habitat type has been lost just in the last decades. In Alpine peatlands, in particular, overgrazing has been identified as a main problem for habitat integrity and biodiversity.In the present study, six Belarus (50-cm deep) cores were collected from several peatlands located in the Adamello-Brenta Nature Park (Trentino, Italy) mirroring a grazing-induced disturbance gradient. All cores were cut frozen into 3-cm sections, and analysed for dry density, water content, pH, EC, and elemental (CHNS) composition. Diatom taphocoenoses were also determined. In particular, diatom frustules were prepared using hot hydrogen peroxide and finally mounted in the Naphrax© resin to produce permanent mounts for identifications and counts. 400 valves were counted and identified to the species level in each slide using a light microscope at x1000 magnification. The whole procedure was kept quantitative to allow the calculation of absolute abundances (n-valves/g-peat-dw).Physical, chemical and biological parameters generally underlined how the grazing influence was clear mainly in the top 20 cm, and resulted in an increasing of density (up to 2×) and N concentration (up to 3×) as well as in a lower gravimetric water content (up to 50%). No significant differences were observed below 30 cm of depth. More than 100 diatom species were identified throughout the 6 cores investigated, and several of them are included in threat categories of the Red List for central Europe (e.g., Cymbopleura valaiseana, Eunotia hexaglyphis, E. triodon). Since diatoms can reflect major regional environmental gradients, they can be used as indicators of ecological conditions in peatlands. In fact, some species that are trivial (= frequent and often abundant) in mire environments in spite of being relatively rare at the overall level of European inland waters (e.g., Aulacoseira alpigena, Encyonema perpusillum, Kobayasiella micropunctata) were found in the cores from highly-grazed areas whilst several rare and sensitive species were detected only (or were clearly more frequent) in cores from mildly-grazed areas.This research can provide useful indications on the harmful effects of grazing in terms of both biogeochemical cycles and nature/habitats conservation.

A 3-m thick sediment sequence, found in a limestone mine located in the south of Italy at a depth of ca. 25–30 m from the current ground level, was investigated. Samples from 5 layers were analysed by X-ray diffraction, elemental analysis, Inductively Coupled Plasma Mass Spectrometry and micromorphology. Microbial DNA was analysed by 16S rRNA gene metabarcoding. The main mineral compounds found in the 5 layers were calcite (70–80%) and clay minerals in layers #1 and #5, goethite (75%) and hematite in layer #2, manganese (66%) and iron oxides in layer #3, and almost exclusively goethite in layer #4. Micromorphology data allowed to shed light in understanding whether these sediments formed by subsequent weathering of carbonates and silicates or by migration of soil sediments from the surface, or also by the accumulation of shallow marine sediments occurring between the middle Pliocene and the lower Pleistocene, when the extreme western sector of this area underwent strong subsidence. From the microbiological point of view, upon the 16S rRNA gene analysis, these 5 layers appear to cluster in three groups. Overall, such a distribution suggests that, both in the top (#1) and in bottom layers (#4 and #5), different communities would have undergone in situ reproduction and colonization exploiting metabolically the substrate, whereas the two mid layers would have received bacterial convection by passive transport of percolating waters. At the same time, micromorphological data show that each layer preserved its distinct features to be related to the environmental condition at the time of deposition. The chemical, mineralogical and micromorphological features of the layers and the known physiology of the microbial taxa thereby encountered highlight the possible role of the latter in elucidating the occurrence of certain mineral species as well as the biogeochemistry of elements like Mn and Fe in sediment layers.

Thauera is one of the main genera involved in polyhydroxyalkanoate (PHA) production in microbial mixed cultures (MMCs) from volatile fatty acids (VFAs). However, no Thauera strains involved in PHA accumulation have been obtained in pure culture so far. This study is the first report of the isolation and characterization of a Thauera sp. strain, namely Sel9, obtained from a sequencing batch reactor (S-SBR) set up for the selection of PHA storing biomass. The 16S rRNA gene evidenced a high sequence similarity with T. butanivorans species. Genome sequencing identified all genes involved in PHA synthesis, regulation and degradation. The strain Sel9 was able to grow with an optimum of chemical oxygen demand-to-nitrogen (COD:N) ratio ranging from 4.7 to 18.9. Acetate, propionate, butyrate and valerate were used as sole carbon and energy sources: a lag phase of 72 h was observed in presence of propionate. Final production of PHAs, achieved with a COD:N ratio of 75.5, was 60.12 ± 2.60 %, 49.31 ± 0.7 %, 37.31 ± 0.43 % and 18.06 ± 3.81 % (w/w) by using butyrate, acetate, valerate and propionate as substrates, respectively. Also, the 3-hydroxybutyrate/3-hydroxyvalerate ratio reflected the type of carbon sources used: 12.30 ± 0.82 for butyrate, 3.56 ± 0.02 for acetate, 0.93 ± 0.03 for valerate and 0.76 ± 0.02 for propionate. The results allow a better elucidation of the role of Thauera in MMCs and strongly suggest a possible exploitation of Thauera sp. Sel9 for a cost-effective and environmentally friendly synthesis of PHAs using VFAs as substrate.

Drought and surface water ponding (DSP) are one of the major natural hazards affecting crop production, especially in low-land irrigated areas.This work focus on an irrigated area in north-eastern Italy, a territory of about 400k ha, part of the central Veneto, where water demands is met through a mechanical and well-regulated widespread distribution of water resources. For this complex landscape, reliance on weather data alone is not sufficient to monitor areas of DSP, particularly when these data can be i) untimely, sparse, and incomplete, and ii) water inflows are mechanically controlled, with varying flow exchanges, not necessarily reflecting climatic fluctuations.Augmenting climatic data with satellite images to identify the location and severity of DSP phenomena, therefore, is a must for complete, up-to-date, and comprehensive coverage of current crop conditions.The objective of this research is to apply and standardize open source data to augment DSP-monitoring techniques. The study was conducted with 5 years (2015-2021) of Sentinel2-10m satellite images. Z-scores of the NDVI distribution are used to estimate the probability of occurrence of the present vegetation condition at a given location relative to the possible range of vegetative vigor, historically. This information is coupled with soil data, topographic information, and accurate information on the system water fluxes, to identify and target locations more susceptible to DSP. Findings indicate that the framework, along with other monitoring tools, is useful for assessing the extent and severity of DSP at a spatial resolution of 10m. The framework is capable of providing a near-real-time indicator of vegetation conditions within irrigated regions, and, more specifically, areas of varying water management conditions.The present study is founded by the Consorzio LEB, Cologna Veneta, Italy

Physical fractionation methods used in soil organic matter (SOM) research commonly include density-based procedures with heavy liquids to separate SOM pools with varying turnover rates and functions. Once separated, the heavy SOM pools are often thoroughly rinsed with water to wash off any residues of the heavy liquids. Using four soils with contrasting properties, we investigated the effects of using either sodium polytungstate (SPT) or sodium iodide (NaI), two of the most commonly used heavy liquids, on the distribution of organic carbon (C) and total nitrogen (N) in free light, intra-aggregate light, and mineral-associated heavy SOM pools isolated by a common fractionation scheme. We also determined the effects of washing the mineral-associated heavy SOM fractions on the recovery of organic C and total N after separation. Because of its smaller viscosity compared to that of NaI, SPT consistently yielded greater intra-aggregate and smaller mineral-associated soil organic C contents. We also confirm that some commercial SPT products, such as the one used here, can contaminate organo-mineral heavy pools with N during density-based fractionation procedures. We do not recommend the repeated washing of heavy fractions separated with Na-based heavy liquids, as this can mobilize SOM.

The application of biochar is presumed to be a climate change mitigation strategy in agriculture. However, we still need to better understand the effects of biochar application on soil properties, particularly on soil microbial activity. This is because soil microorganisms play a key role in ecosystems functioning, as they have a central role in soil metabolic activity given that they are responsible for soil organic matter decomposition and nutrient cycling. Conversely, little is known about how climate change will affect the soil microbial activity.In a rainfed field experiment, we studied the effect of forecasted warming and rainfall reduction on soil respiration and soil enzymatic activities after 3 years of consecutive application of biochar at a rate of 20 t/ha on a barley-camelina-fallow rotation in a semiarid region in Central Spain. Soil respiration was not affected by the application of biochar or/and warming and rainfall reduction treatments in comparison to the control treatment (no amendment). However, biochar amended soils had lower temperature sensitivity of soil C mineralization in the first two years when soils were cultivated but higher temperature sensitivity of soil C mineralization in the third year during fallow treatment. Enzymes involved in the C and N cycles (dehydrogenase, β-glucosidase and urease) significantly increased their activity under warming and rainfall reduction treatments, albeit biochar application tended to decrease the enzymatic activity under those treatments.Acknowledgments: to the Spanish MICINN (MINECO, AEI, FEDER, EU) for supporting the research projects AGL2016-75762-R and CGL2015-65162-R.

Background Legacy data are unique occasions for estimating soil organic carbon (SOC) concentration changes and spatial variability, but their use can pose limitations due to the sampling schemes adopted and improvements may be needed in the analysis methodologies. When SOC changes is estimated with legacy data, the use of soil samples collected in different plots (i.e., non-aligned data) may lead to biased results. In the present work, N=302 georeferenced soil samples were selected from a regional (Sicily, south of Italy) soil database. An operational sampling approach was developed to spot SOC concentration changes from 1994 to 2017 in the same plots at the 0-30 cm soil depth and tested. Results The measurements were conducted after computing the minimum number of samples needed to have a reliable estimate of SOC variation after 23 years. By applying an effect size based methodology, 30 out of 302 sites were resampled in 2017 to achieve a power of 80%, and an a=0.05. A Wilcoxon test applied to the variation of SOC from 1994 to 2017 suggested that there was not a statistical difference in SOC concentration after 23 years (Z = -0.556; 2-tailed asymptotic significance = 0.578). In particular, only 40% of resampled sites showed a higher SOC concentration than in 2017. Conclusions This finding contrasts with a previous SOC concentration increase that was found in 2008 (75.8% increase when estimated as differences of 2 models built with non-aligned data), when compared to 1994 observed data (Z = -9.119; 2-tailed asymptotic significance < 0.001). Such a result implies that the use of legacy data to estimate SOC concentration dynamics requires soil resampling in the same locations to overcome the stochastic model errors. Further experiment is needed to identify the percentage of the sites to resample in order to align two legacy datasets in the same area.

A 3-m thick sediment was found in a limestone mine located in the southern part of the Gargano Promontory, Apulia region (south of Italy), at a depth of ca. 25-30 m from the current ground level.Samples from 5 layers were analysed by X-ray diffraction (XRD), elementar analysis (CHNS), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Microbial DNA was also extracted and bacterial diversity analysed by PCR amplification and Illumina High-Throughput Sequencing (HTS) of the V3-V4 hypervariable regions of 16S rRNA.Preliminary data showed that these sediments formed by subsequent weathering of carbonates and silicates, either by in situ oxidation or by dissolution followed by migration and reprecipitation, rather than during the accumulation of shallow marine sediments occurring between the middle Pliocene and the lower Pleistocene, when the extreme western sectors of the Apulian foreland underwent strong subsidence.The main mineral compounds occurring in the 5 layers, from the top to the bottom, were the following: calcite (80%) and clay minerals in sample #1, goethite (75%) and hematite in sample #2, manganese (66%) and iron oxides in sample #3, almost exclusively goethite in sample #4, and calcite (71%) and clay minerals in sample #5.From the microbiological point of view, drawn from a 16S metabarcoding amplicons sequencing analysis, these 5 layers appear to cluster in three groups: a) the uppermost layer (sample #1), dominated by a single and abundant taxon of Arthrobacter sp., which includes species known for the capability of calcite precipitation; b) a middle layer (including samples #2 and #3), without prevailing abundances and less consistent occurrences across replicates, which featured members of the Oxalobacteraceae family and of the Methylophilus genus. Their closest matches in Genbank subjects included isolates from habitats such as calcium carbonate (moonmilk) muds in percolating waters within caves, mine tailings and other groundwater microcosms; c) a bottom layer (samples #4 and #5), showing an oligarchic situation and high abundances of bacteria but different from the ones that prevailed in the top layer and including members of the Nocardioidacaeae family. Also for these sequence queries, the closest GenBank subjects include cases with calcium carbonate-precipitating capabilities isolated from cave and groundwater sediments or former mining sites in studies on iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations.Overall, such a distribution suggests that, both in the top and bottom layer, different communities would have undergone in situ-reproduction and colonization exploiting metabolically the substrate, whereas the mid layers would have received bacterial convection by passive transport of percolating waters.

Peatland is a major carbon (C) sink, sequestering more atmospheric carbon dioxide (CO2) than any other terrestrial ecosystem. Peatlands, and especially bogs, are typically nutrient-poor environments, extremely sensitive to increases in nitrogen (N) deposition. In fact, increasing N content often causes a shift from a moss- to a vascular-plant-dominated vegetation resulting in lower C sequestration rates and/or mobilization of N and C stored in peat by promoting microbial activity. Peatlands are also very selective environments (sub-oxic to anoxic conditions, acidic pH, low N), and thus important habitats for nature conservation because of the occurrence of specifically adapted organisms. Peatlands cover ca. 3% of the world’s land surface but Europe lost >60% of this habitat type in the last decades. Moreover, in Italy they are in a marginal position from the phytogeographical standpoint.Cattle grazing and trampling is a cause of peatland degradation resulting in peat compaction, shift in plant and microbial community composition, and N inputs in form of excreta. In Alpine peatlands overgrazing has been identified as a main problem for habitat integrity and biodiversity.In the present work, 50-cm deep Belarus cores were collected from the Canton di Ritorto peatland (Adamello-Brenta Nature Park, Trentino, Italy) along a grazing-induced disturbance gradient. The study site has a bog-like vegetation; common species are Pinus mugo, Carex pauciflora, C. echinata, Eriophorum vaginatum, Vaccinium uliginosum, and many Sphagnum species including S. capillifolium, S. medium, S. subfulvum, S. subnites. Peat thickness ranges between 40-160 cm, while electrical conductivity and pH at the surface range between 10-31 µS/cm and 4.0-5.2, respectively.Cores were cut frozen into 3-cm sections, and analysed for bulk density, water and ash content, and elemental composition (C, N and S). Moreover, diatom taphocoenoses were studied in two peat cores (i.e., the most affected by grazing and the control), investigating alternate slices (i.e., at 6-cm resolution). Diatoms were prepared using hot hydrogen peroxide and/or muffling, and finally embedded in the Naphrax© resin to produce permanent mounts for identifications and counts. The whole procedure was kept quantitative to allow not only the assessment of the per cent composition of taphocoenoses, but also the calculation of absolute abundances (N-valves/g-peat-dw).Preliminary data show that small-scale grazing significantly lowered water content (by 5-10%) and gravimetric water content (by 30-50%), and increased bulk density (1.5-2.2x) compared to the control. Moreover, N concentration was 2-to-3 times higher in grazing-affected sites. Differences between cores affected by grazing and the control were evident in the top 20 cm, whereas no significant differences were observed below 30 cm of depth. More than 80 diatom species were identified throughout the two cores. Several of these are included in threat categories of the Red List for central Europe, and we could also identify a putative species new to science, which is being characterized and described. Some species that tolerate moderate nutrient enrichment were found in the core at the "grazed" extreme of the gradient, whilst several species sensitive to organic pollution were detected only (or were clearly more frequent) in the control.

Legacy data are frequently unique sources of data for the estimation of past soil properties. With the rising concerns about greenhouse gases (GHG) emission and soil degradation due to intensive agriculture and climate change effects, soil organic carbon (SOC) concentration might change heavily over time.When SOC changes is estimated with legacy data, the use of soil samples collected in different plots (i.e., non-aligned data) may lead to biased results. The sampling schemes adopted to capture SOC variation usually involve the resampling of the original sample using a so called paired-site approach.In the present work, a regional (Sicily, south of Italy) soil database, consisting of N=302 georeferenced soil samples from arable land collected in 1993 [1], was used to select coinciding sites to test a former temporal variation (1993-2008) obtained by a comparison of models built with data sampled in non-coinciding locations [2]. A specific sampling strategy was developed to spot SOC concentration changes from 1994 to 2017 in the same plots at the 0-30 cm soil depth and tested.To spot SOC changes the minimum number of samples needed to have a reliable estimate of SOC variation after 23 years has been estimated. By applying an effect size based methodology, 30 out of 302 sites were resampled in 2017 to achieve a power of 80%, and an a=0.05.After the collection of the 30 samples, SOC concentration in the newly collected samples was determined in lab using the same methodA Wilcoxon test applied to the variation of SOC from 1994 to 2017 suggested that there was not a statistical difference in SOC concentration after 23 years (Z = -0.556; 2-tailed asymptotic significance = 0.578). In particular, only 40% of resampled sites showed a higher (not always significant) SOC concentration than in 2017.This finding contrasts with a previous SOC concentration increase that was found in 2008 (75.8% increase when estimated as differences of 2 models built with non-aligned data) [2], when compared to 1994 observed data (Z = -9.119; 2-tailed asymptotic significance < 0.001).Such a result implies that the use of legacy data to estimate SOC concentration changes need soil resampling in the same locations to overcome the stochastic model errors. Further experiment is needed to identify the percentage of the sites to resample in order to align two legacy datasets in the same area.Bibliography[1]Schillaci C, et al.,2019. A simple pipeline for the assessment of legacy soil datasets: An example and test with soil organic carbon from a highly variable area. CATENA.[2]Schillaci C, et al., 2017. Spatio-temporal topsoil organic carbon mapping of a semi-arid Mediterranean region: The role of land use, soil texture, topographic indices and the influence of remote sensing data to modelling. Sci Total Environ.

Background An insight into the molecular composition of ombrotrophic peats of different geographical origin and collected at different depths was achieved by the humeomics method. The humeomic fractionation allowed the separation of molecular components in either organic solvents or water on the basis of their progressive binding strength to the humic matrix. The solubilized matter in fractions was analyzed by gas chromatography–mass spectrometry (GC–MS) or by proton nuclear magnetic resonance (1H NMR) spectroscopy, while the residues depleted of the extracted material were observed by 13C cross-polarization magic-angle-spinning nuclear magnetic resonance (13C-CPMAS-NMR) spectroscopy. Results The analytical characterization of fractions and residues differentiated peats not only on the basis of the different classes of extracted molecules, but also on their binding strength to the complex peat matrix. Aromatic, lipidic, and sugar compounds were the most representative molecular classes extracted in the humeomic fractions and their abundance varied with depth. The distribution and abundance of extracted compounds provided an indication of the extent of organic matter accumulation in peat. The NMR spectra of solid residues supported the interpretation of the characteristics of the various extracts. Conclusions Our findings proved that the humeomic approach allows to provide important information on both the molecular composition of peats and its variation with depth.

Redox-driven changes in Fe crystallinity and speciation may affect soil organic matter (SOM) stabilization and carbon (C) turnover, with consequent influence on global terrestrial soil organic carbon (SOC) cycling. Under reducing conditions, increasing concentrations of Fe(II) released in solution from the reductive dissolution of Fe (hydr)oxides may accelerate ferrihydrite transformation, although our understanding of the influence of SOM on these transformations is still lacking. Here, we evaluated abiotic Fe(II)-catalyzed mineralogical changes in Fe (hydr)oxides in bulk soils and size-fractionated SOM pools (for comparison, fine silt plus clay, FSi+Cl, and fine sand, FSa) of an agricultural soil, unamended or amended with biochar, municipal solid waste compost, and a combination of both. FSa fractions showed the most significant Fe(II)-catalyzed ferrihydrite transformations with the consequent production of well-ordered Fe oxides irrespective of soil amendment, with the only exception being the compost-amended soils. In contrast, poorly crystalline ferrihydrite still constituted ca. 45% of the FSi+Cl fractions of amended soils, confirming the that the higher SOM content in this fraction inhibits atom exchange between aqueous Fe(II) and the solid phase. Building on our knowledge of Fe(II)-catalyzed mineralogical changes in simple systems, our results evidenced that the mechanisms of abiotic Fe mineral transformations in bulk soils depend on Fe mineralogy, organic C content and quality, and organo-mineral associations that exist across particle-size SOM pools. Our results underline that in the fine fractions the increase in SOM due to organic amendments can contribute to limiting abiotic Fe(II)-catalyzed ferrihydrite transformation, while coarser particle-size fractions represent an understudied pool of SOM subjected to Fe mineral transformations.

In a previous study (Zaccone et al., 2018. Appl. Soil Ecol. 130, 134-142), we evaluated the potential ecological partition of microbial and plant DNA across soil organic matter (SOM) fractions linked to conceptual stabilization mechanisms. We found that different microbial taxa (bacterial and fungal) seem to be specifically associated to SOM fractions. In the present work we investigated the short-term distribution of exogenous microbial population in SOM fractions following inoculation, in order to track the fate of bacterial DNA (in the form of spores) artificially spiked in bulk soils. The main hypothesis was that the colonization of external organisms proceeds from the unprotected fraction (FR) towards those protected physically and/or chemically by soil minerals from decomposition (i.e., into macro and micro-aggregates [MA, MI] or interacting with mineral surfaces [MIN]).Three different soils with different pH, SOM content and texture were used in the experiment. One aliquot of soil was spiked with approx. 8 Log cfu of spore of Bacillus clausii from a commercial preparation of 4 strains. DNA was extracted from soil and recovered from SOM pools isolated using a physical fractionation method [Plaza et al., 2012. CLEAN-Soil Air Water 40, 134-139] and quantified by fluorescence (Qubit).DNA recovered from spiked vs. non-spiked samples followed two different patterns of distribution, according to the SOM fractions. Total DNA in the bulk soils varied according to the soil types and the effect of spiking 8 cfu was negligible. In the SOM fractions, while MI and MIN showed different concentration according to the soil type (no apparent influence of spiking), total DNA in FR was clearly higher for spiked samples, while MA had a putative interaction between soil type and spiking. Even if very preliminary, our results point out a possible mechanism of short-term distribution of exogenous DNA (through spores and potential vegetative forms of B. clausii germinated during the incubation) from the free SOM to the macroaggregates, with no apparent influence on MI and MIN yet.Further analyses (e.g., PCR-ARISA and qPCR) will allow to disclose whether indigenous vs. exogenous bacterial DNA are differentially distributed in SOM, possibly enhancing the description of the mechanisms underlying the distribution of microbial communities in soil, according to the different organization of the SOM in soil aggregates.

The role and distribution of iron (Fe) species in physical soil fractions have received remarkably little attention in field-scale systems. Here, we identify and quantify the Fe phases into two fractions (fine sand, FSa, and fine silt and clay, FSi + Cl), isolated from an agricultural soil unamended and amended with different organic materials, by Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The linear combination fitting and wavelet transform of EXAFS data revealed noticeable differences between unamended FSa and FSi + Cl fractions. Specifically, the FSi + Cl fraction was mainly characterized by ferrihydrite (48%) and Fe(III)-soil organic matter (SOM) complexes (37%), whereas in the FSa fraction, ferrihydrite still represented a major phase (44%), with a lower contribution from Fe(III)-SOM (18%). In the FSa fraction, the addition of the organic amendments resulted in an increase of Fe-SOM complexes (31-35%) and a decrease of ferrihydrite (28-29%). By contrast, in the amended FSi + Cl fractions, the added organic matter led to negligible changes in percent ferrihydrite. Therefore, regardless of the amendment type, the addition of organic matter to soil increased the capability of the coarse fraction (FSa) to stabilize organic carbon, thus pointing out that the role of FSa in carbon sequestration in agricultural soils at a global scale may be overlooked.

International audience; A recent paper by Miszczak et al. (2020) examines metal contamination of mires in Poland and Norway. The authors conclude that lead (Pb) records in ombrotrophic peatlands cannot be used to reconstruct the chronological history of anthropogenic activities due to post-depositional mobility of the metal. We contest this general conclusion which stands in contrast with a significant body of literature demonstrating that Pb is largely immobile in the vast majority of ombrotrophic peatlands. Our aim is to reaffirm the crucial contribution that peat records have Science of the Total Environment xxx (xxxx) xxx ⁎ Corresponding author at: Instituto Franco-Argentino para el Estudio del Clima y sus Impactos (j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v made to our knowledge of atmospheric Pb contamination. In addition, we reiterate the necessity of following established protocols to produce reliable records of anthropogenic Pb contamination in environmental archives.

Biochar application is now considered to be one of the most promising agricultural practices to mitigate climate change. However, to fully assess the benefits of biochar, we still need to better understand its effects on soil properties, and particularly on native soil organic matter (SOM) dynamics.In this work, we investigated soil respiration and changes in SOM pools (mineral-free, intra-aggregate, and mineral-associated SOM) as affected by the application of 20 t / ha per year of biochar alone or combined with mineral fertilizer, municipal solid waste compost, or sewage sludge. The experiment was run for 7 years in a semiarid agricultural soil. We found that biochar had no effect on soil respiration with respect to mineral fertilization and no amendment (control), and tended to decrease CO2 emissions from soils amended with municipal solid waste compost and sewage sludge. Biochar accumulated mainly in the mineral-free SOM fraction and its addition, especially in combination with municipal solid waste compost, promoted the amount of SOM occluded with aggregates and associated to mineral surfaces.Acknowledgments: to the Spanish MICINN (MINECO, AEI, FEDER, EU) for supporting the research project AGL2016-75762-R.