Tracing sources of dissolved organic matter along the terrestrial-aquatic continuum in the Ore Mountains, Germany.

There is growing concern about the rising levels of dissolved organic matter (DOM) in surface waters across the Northern hemisphere. However, only limited research has been conducted to unveil its precise origin. Compositional changes along terrestrial-aquatic pathways can help determine the terrestrial sources of DOM in streams. Stream water, soil water and soil horizons were sampled at four sites representing typical settings within a forested catchment in the Ore Mountains (Erzgebirge, Germany) from winter 2020 to spring 2022. The samples were analyzed using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The resulting data were successfully subjected to semi-automatic processing of the molecular composition of DOM, reaching a percentage of identified peaks up to 98 %. Principal component analysis (PCA) and cluster analyses were carried out to identify distinct differences between DOM from the potential sources and in the streams. According to the PCA, organic soil horizons, soil water, and stream water samples could be clearly distinguished. Cluster analysis revealed that soil water DOM at all depths of Peats and deeper horizons of the Peaty Gleysols contributed the most to DOM in the stream section dominated by organic soils. In areas dominated by mineral soils, stream DOM resembled the DOM from the deeper mineral horizons of Cambisols and Podzols. Overall, our results suggested that most of the DOM exported from the catchment was derived from deeper mineral soil horizons, with little contribution of DOM derived from organic soils. Therefore, DOM fingerprint analysis of in-situ soil water proved to be a promising approach for tracing back the main sources of stream water DOM.

The glacial-terrestrial-fluvial pathway: A multiparametrical analysis of spatiotemporal dissolved organic matter variation in three catchments of Lake Nam Co, Tibetan Plateau.

The Tibetan Plateau (TP) is a sensitive alpine environment of global importance, being Asia's water tower, featuring vast ice masses and comprising the world's largest alpine grasslands. Intensified land-use and pronounced global climate change have put pressure on the environment of the TP. We studied the tempo-spatial variability of dissolved organic matter (DOM) to better understand the fluxes of nutrients and energy from terrestrial to aquatic ecosystems in the TP. We used a multiparametrical approach, based on inorganic water chemistry, dissolved organic carbon (DOC) concentration, dissolved organic matter (DOM) characteristics (chromophoric DOM, fluorescence DOM and δ13C of DOM) in stream samples of three catchments of the Nam Co watershed and the lake itself. Satellite based plant cover estimates were used to link biogeochemical data to the structure and degradation of vegetation zones in the catchments. Catchment streams showed site-specific DOM signatures inherited from glaciers, wetlands, groundwater, and Kobresia pygmaea pastures. By comparing stream and lake samples, we found DOM processing and unification by loss of chromophoric DOM signatures and a change towards an autochthonous source of lake DOM. DOM diversity was largest in the headwaters of the catchments and heavily modified in terminal aquatic systems. Seasonality was characterized by a minor influence of freshet and by a very strong impact of the Indian summer monsoon on DOM composition, with more microbial DOM sources. The DOM of Lake Nam Co differed chemically from stream water samples, indicating the lake to be a quasi-marine environment in regards to the degree of chemical modification and sources of DOM. DOM proved to be a powerful marker to elucidate consequences of land use and climatic change on biogeochemical processes in High Asian alpine ecosystems.

Iron oxides and aluminous clays selectively control soil carbon storage and stability in the humid tropics.

Clay minerals and pedogenic metal (oxyhydr)oxides are the most reactive soil mineral constituents controlling the long-term persistence of organic carbon (OC) in terrestrial ecosystems. However, their co-occurrence in most soils complicates direct assessment of their individual contribution to OC persistence. Making use of unique mineralogical combinations in soils located in the East Usambara Mountains of Tanzania, we disentangled the contribution of clay-sized aluminous minerals (kaolinite, gibbsite) and pedogenic Fe (oxyhydr)oxides (predominant goethite and hematite) on OC storage and stabilization under natural forests and croplands. Topsoil samples, varying in contents but not types of aluminous clays and pedogenic Fe (oxyhydr)oxides, were identified by selective extractions, X-ray diffraction, and Mössbauer spectroscopy. Associated abundance of particulate and mineral-associated organic matter (OM) was quantified by density fractionation and their changes during land-use conversion were determined as a measure of OC persistence. Additionally, we assessed the resistance of OC to chemical oxidation as well as microbial decomposition in a 50-day laboratory incubation. We found that the ratio of pedogenic Fe to aluminous clay is more consequential for OC storage and stabilization than their individual contents, despite the fact that Fe (oxyhydr)oxides generally exert a stronger impact on OC than aluminous clays. Conjunction of large amounts of Fe (oxyhydr)oxides with low aluminous clay contents caused the strongest accumulation of mineral-associated OC, a low soil respiration, high OC stability against chemical oxidation, and high OC persistence during land-use change. Our study suggests that certain mineralogical combinations in the humid tropics alleviate OM losses during land conversion because of the strong and selective mineral control on OC stabilization, particular if the weight ratio of pedogenic Fe to aluminous clay exceeds the threshold range of 0.44‒0.56.

Global CO2 fertilization of Sphagnum peat mosses via suppression of photorespiration during the twentieth century.

Natural peatlands contribute significantly to global carbon sequestration and storage of biomass, most of which derives from Sphagnum peat mosses. Atmospheric CO2 levels have increased dramatically during the twentieth century, from 280 to > 400 ppm, which has affected plant carbon dynamics. Net carbon assimilation is strongly reduced by photorespiration, a process that depends on the CO2 to O2 ratio. Here we investigate the response of the photorespiration to photosynthesis ratio in Sphagnum mosses to recent CO2 increases by comparing deuterium isotopomers of historical and contemporary Sphagnum tissues collected from 36 peat cores from five continents. Rising CO2 levels generally suppressed photorespiration relative to photosynthesis but the magnitude of suppression depended on the current water table depth. By estimating the changes in water table depth, temperature, and precipitation during the twentieth century, we excluded potential effects of these climate parameters on the observed isotopomer responses. Further, we showed that the photorespiration to photosynthesis ratio varied between Sphagnum subgenera, indicating differences in their photosynthetic capacity. The global suppression of photorespiration in Sphagnum suggests an increased net primary production potential in response to the ongoing rise in atmospheric CO2, in particular for mire structures with intermediate water table depths.

Baltic Sea sediments record anthropogenic loads of Cd, Pb, and Zn.

The unsustainable settlement and high industrialization around the catchment of the Baltic Sea has left records of anthropogenic heavy metal contamination in Baltic Sea sediments. Here, we show that sediments record post-industrial and anthropogenic loads of Cd, Zn, and Pb over a large spatial scale in the Baltic Sea. We also demonstrate that there is a control on the accumulation of these metals in relation to oxic/anoxic conditions of bottom waters. The total concentrations of Cd, Zn, and Pb were obtained with the near-total digestion method in thirteen cores collected from the Bothnian Bay, the Bothnian Sea, and the west and central Baltic Proper. The lowest average concentrations of Cd, Zn, and Pb were observed in Bothnian Bay (0.4, 125, 40.2 mg kg-1 DW, respectively). In contrast, the highest concentrations were observed in the west Baltic Proper (5.5, 435, and 56.6 mg kg-1 DW, respectively). The results indicate an increasing trend for Cd, Zn, and Pb from the early nineteenth century until the 1970s, followed by a decrease until 2000-2008. However, surface sediments still have concentrations above the pre-industrial values suggested by the Swedish EPA (Cd is 0.2, Zn is 85, and Pb is 31 mg kg-1 DW). The results also show that the pre-industrial Cd, Zn, and Pb concentrations obtained from 3 cores with ages < 1500 B.C. were 1.8, 1.7, and 1.2 times higher, respectively, than the pre-industrial values suggested by the Swedish EPA. To conclude, accumulations of metals in the Baltic Sea are governed by anthropogenic load and the redox conditions of the environment. The significance of correct environmental governance (measures) can be illustrated with the reduction in the pollution of Pb, Zn, and Cd within the Baltic Sea since the 1980s.

Persistent Activities of Extracellular Enzymes Adsorbed to Soil Minerals.

Adsorption of extracellular enzymes to soil minerals is assumed to protect them against degradation, while modifying their activities at the same time. However, the persistence of the activity of adsorbed enzymes remains poorly understood. Therefore, we studied the persistence of cellulase and α-amylase activities after adsorption to soil amended with various amounts (+1, +5, and +10 wt.%) of three typical soil minerals, montmorillonite, kaolinite, and goethite. Soil without mineral addition (pure soil), pure minerals, and pure dissolved enzymes were used as references. Soil mineral-enzyme complexes were prepared and then incubated for 100 days; temporal changes in enzyme activities were analyzed after 0, 0.1, 1, 10, and 100 days. The specific enzyme activities (activities normalized to protein content) and their persistence (activities relative to activities at day 0) were compared to enzyme activities in solution and after sorption to the control soil. Amylase adsorption to pure minerals increased in the following order: montmorillonite > kaolinite > goethite. That of cellulase increased in the following order: goethite > montmorillonite > kaolinite. Adsorption of enzymes to soils did not increase in the same order of magnitude as the addition of reactive binding sites. Based on inverse relationships between the amount of enzyme adsorbed and the specific enzyme activity and their persistency, we showed that a limited availability of sorption sites is important for high specific activity and persistence of the enzymes. This is probably the consequence of less and weaker bonds, as compared to a high availability of sorption sites, resulting in a smaller impact on the active sites of the enzyme. Hence, we suppose that the soil mineral phase supports microorganisms in less-sorptive environments by saving energy on enzyme production, since small enzyme release could already result in sufficient activities to degrade respective target carbon substrates.

An examination of the role of biochar and biochar water-extractable substances on the sorption of ionizable herbicides in rice paddy soils.

The application of biochar as a soil amendment can increase concentrations of soil organic matter, especially water-extractable organic substances. Due to their mobility and reactivity, more studies are needed to address the potential impact of biochar water-extractable substances (BWES) on the sorption of herbicides in agricultural soils that are periodically flooded. Two paddy soils (100 and 700 years of paddy soil development), unamended or amended with raw (BC) or washed biochar (BCW), were used to test the influence of BWES on the sorption behavior of the herbicides azimsulfuron (AZ) and penoxsulam (PE). The adsorption of AZ to biochar was much stronger than that to the soils, and it was adsorbed to a much larger extent to BC than to BCW. The depletion of polar groups in the BWES from the washed biochar reduced AZ adsorption but had no effect on PE adsorption. The adsorption of AZ increased when the younger soil (P100) was amended with BC and decreased when it was amended with BCW. In P700, which has lower dissolved organic carbon (DOC) content than P100, the adsorption of AZ increased regardless of whether biochar was raw or washed. The adsorption of PE slightly decreased when P100 was amended with BC or BCW and slightly increased when P700 was amended with BC or BCW. In order to evaluate compositional differences in the biochar and BWES before and after the washing treatment, we performed solid-state 13C NMR spectroscopy of BC and BCW, and high resolution mass spectrometry of BWES. Our observations stress the importance of proper consideration of soil and biochar properties before their incorporation into paddy soils, since biochar may reduce or increase the mobility of AZ and PE depending on soil properties and time of application.

Nitrogen turnover and N2O/N2 ratio of three contrasting tropical soils amended with biochar.

Biochar has been reported to reduce emission of nitrous oxide (N2O) from soils, but the mechanisms responsible remain fragmentary. For example, it is unclear how biochar effects on N2O emissions are mediated through biochar effects on soil gross N turnover rates. Hence, we conducted an incubation study with three contrasting agricultural soils from Kenya (an Acrisol cultivated for 10-years (Acrisol10); an Acrisol cultivated for over 100-years (Acrisol100); a Ferralsol cultivated for over 100 years (Ferralsol)). The soils were amended with biochar at either 2% or 4% w/w. The 15N pool dilution technique was used to quantify gross N mineralization and nitrification and microbial consumption of extractable N over a 20-day incubation period at 25 °C and 70% water holding capacity of the soil, accompanied by N2O emissions measurements. Direct measurements of N2 emissions were conducted using the helium gas flow soil core method. N2O emissions varied across soils with higher emissions in Acrisols than in Ferralsols. Addition of 2% biochar reduced N2O emissions in all soils by 53 to 78% with no significant further reduction induced by addition at 4%. Biochar effects on soil nitrate concentrations were highly variable across soils, ranging from a reduction, no effect and an increase. Biochar addition stimulated gross N mineralization in Acrisol-10 and Acrisol-100 soils at both addition rates with no effect observed for the Ferralsol. In contrast, gross nitrification was stimulated in only one soil but only at a 4% application rate. Also, biochar effects on increased NH4 + immobilization and NO3 -consumption strongly varied across the three investigated soils. The variable and bidirectional biochar effects on gross N turnover in conjunction with the unambiguous and consistent reduction of N2O emissions suggested that the inhibiting effect of biochar on soil N2O emission seemed to be decoupled from gross microbial N turnover processes. With biochar application, N2 emissions were about an order of magnitude higher for Acrisol-10 soils compared to Acrisol-100 and Ferralsol-100 soils. Our N2O and N2 flux data thus support an explanation of direct promotion of gross N2O reduction by biochar rather than effects on soil extractable N dynamics. Effects of biochar on soil extractable N and gross N turnover, however, might be highly variable across different soils as found here for three typical agricultural soils of Kenya.

Split-root labelling to investigate 15N rhizodeposition by Pinus sylvestris and Picea abies.

We investigated the transfer of 15N into the soil via 15N uptake and release by tree roots, which involves the principles of the split-root technique. One half of the root system received an injection of (15NH4)2SO4 and the other half equivalent amounts of (NH4)2SO4 at 15N natural abundance level. 15N was transferred from one side of the root system (15N side) to the other side (14N side) and released into the soil. The method was conducted with Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies [L.] Karst). Two concentration levels of (NH4)2SO4 were used, corresponding with annual N deposition in the Netherlands (30 kg N ha-1) and a twelfth of that (2.5 kg N ha-1). Samples were taken 3 and 6 weeks after labelling and divided into needles + stem, roots, rhizosphere and bulk soil. Already 3 weeks after labelling, Scots pine took up 23.7 % of the low and 9.1 % of the high amounts of 15N, while Norway spruce took up 21.5 and 32.1 %, respectively. Both species transported proportions of 15N to the rhizosphere (0.1-0.2 %) and bulk soil (0.3-0.9 %). The method is a useful tool to investigate the fate of root-derived N in soils, for example, for the formation of stable forms of soil organic matter.

Emissions intensity and carbon stocks of a tropical Ultisol after amendment with Tithonia green manure, urea and biochar.

Biochar has been shown to reduce soil emissions of CO2, CH4 and N2O in short-term incubation and greenhouse experiments. Such controlled experiments failed to represent variable field conditions, and rarely included crop growth feedback. The objective of this study was to assess the effect of biochar, in comparison to green manure and mineral nitrogen, on greenhouse gas Emissions Intensity (EI = emissions in CO2 equivalents per ton of grain yield) in a low-fertility tropical Ultisol. Using a field trial in western Kenya, biochar (0 and 2.5 t ha-1; made from Eucalyptus wood) was integrated with urea (0 and 120 kg N ha-1) and green manure (Tithonia diversifolia; 0, 2.5 and 5 t ha-1) in a factorial design for four consecutive seasons from October 2012 to August 2014. Compared to the control, biochar increased soil CO2 emissions (9-33%), reduced soil CH4 uptake (7-59%) and reduced soil N2O emissions (1-42%) in each season, with no seasonal differences. N2O emissions increased following amendment with T. diversifolia (6%) and urea (13%) compared to the control. Generally, N2O emissions decreased where only biochar was applied. The greatest decrease in N2O (42%) occurred where all three amendments were applied compared to when they were added separately. EI in response to any of the amendments was lower than the control, ranging from 9 to 65% (33.0 ± 3.2 = mean ± SE). The amendments increased SOC stocks by 0.1-1.2 t ha-1 year-1 (mean ± SE of 0.8 ± 0.09 t ha-1 year-1). The results suggest decreased net EI with biochar in low fertility soils mainly through greater net primary productivity (89% of the decrease).

Incubation of solid state C60 fullerene under UV irradiation mimicking environmentally relevant conditions.

Carbon-based nanomaterials, such as C60 fullerenes, are expected to accumulate in soil due to direct release and deposition from the atmosphere. However, little is known about the environmental fate of these nanoparticles which may be susceptible to photochemical and microbial degradation. In the present work, C60 was incubated for a period of 28 days and irradiated with UVA light. Three experiments were carried out where the fullerenes were either spiked onto a glass surface or added to quartz sand or sandy soil samples. At specific time intervals the samples were extracted and analysed by liquid chromatography coupled to UV or high resolution mass spectrometric (HRMS) detection. The fullerenes were degraded in all the treatments and the decay followed a pseudo-first-order rate law. In absence of a solid matrix, the half-life (t1/2) of the C60 was 13.1 days, with an overall degradation of 45.1% that was accompanied by the formation of functionalized C60-like structures. Furthermore, mass spectrometric analysis highlighted the presence of a large number of transformation products that were not directly related to the irradiation and presented opened cage and oxidized structures. When C60 was spiked into solid matrices the degradation occurred at a faster rate (t1/2 of 4.5 and 0.8 days for quartz sand and sandy soil, respectively). Minor but consistent losses were found in the non-irradiated samples, presumably due to biotic or chemical processes occurring in these samples. The results of this study suggest that light-mediated transformation of the fullerenes will occur in the environment.

Molecular Features of Humic Acids and Fulvic Acids from Contrasting Environments.

Insight in the molecular structure of humic acid (HA) and fulvic acid (FA) can contribute to identify relationships between their molecular properties, and further our quantitative abilities to model important organic matter functions such as metal complexation and association with mineral surfaces. Pyrolysis gas chromatography/mass spectrometry (Py-GC-MS) is used to compare the molecular composition of HA and FA. A systematic comparison was obtained by using samples from different environmental sources, including solid and aqueous samples from both natural and waste sources. The chemical signature of the pyrolysates was highly variable and no significant difference between HA and FA was found for major chemical groups, that is, carbohydrates, phenols, benzenes, and lignin phenols, together accounting for 62-96% of all quantified pyrolysis products. However, factor analysis showed that within each sample, FAs consistently differed from corresponding HAs in a larger contribution from mono- and polyaromatic hydrocarbons and heterocyclic hydrocarbons, together accounting for 3.9-44.5% of the quantified pyrolysis products. This consistent difference between FAs and corresponding HAs, suggests that their binding properties may, in addition to the carboxyl and phenolic groups, be influenced by the molecular architecture. Py-GC-MS may thus contribute to identify relationships between HA and FA binding- and molecular-properties.

Aggregate size distribution in a biochar-amended tropical Ultisol under conventional hand-hoe tillage.

Biochar (or pyrogenic organic matter) is increasingly proposed as a soil amendment for improving fertility, carbon sequestration and reduction of greenhouse gas emissions. However, little is known about its effects on aggregation, an important indicator of soil quality and functioning. The aim of this study was to assess the effect of Eucalyptus wood biochar (B, pyrolyzed at 550 °C, at 0 or 2.5 t ha-1), green manure (T, from Tithonia diversifolia at 0, 2.5 or 5.0 t ha-1) and mineral nitrogen (U, urea, at 0, or 120 kg N ha-1) on soil respiration, aggregate size distribution and SOC in these aggregate size fractions in a 2-year field experiment on a low-fertility Ultisol in western Kenya under conventional hand-hoe tillage. Air-dry 2-mm sieved soils were divided into four fractions by wet sieving: Large Macro-aggregates (LM; >1000 µm); Small Macro-aggregates (SM, 250-1000 µm); Micro-aggregates (M, 250-53 µm) and Silt + Clay (S + C, < 53 µm). We found that biochar alone did not affect a mean weight diameter (MWD) but combined application with either T. diversifolia (BT) or urea (BU) increased MWD by 34 ± 5.2 µm (8%) and 55 ± 5.4 µm (13%), respectively, compared to the control (P = 0.023; n = 36). The B + T + U combination increased the proportion of the LM and SM by 7.0 ± 0.8%, but reduced the S + C fraction by 5.2 ± 0.23%. SOC was 30%, 25% and 23% in S + C, M and LM/SM fractions, and increased by 9.6 ± 1.0, 5.7 ± 0.8, 6.3 ± 1.1 and 4.2 ± 0.9 g kg-1 for LM, SM, M and S + C, respectively. MWD was not related to either soil respiration or soil moisture but decreased with higher SOC (R2  = 0.37, P = 0.014, n = 26) and increased with greater biomass production (R2  = 0.11, P = 0.045, n = 33). Our data suggest that within the timeframe of the study, biochar is stored predominantly as free particulate OC in the silt and clay fraction and promoted a movement of native SOC from larger-size aggregates to the smaller-sized fraction in the short-term (2 years).

Succession of Bacterial Communities in a Seasonally Stratified Lake with an Anoxic and Sulfidic Hypolimnion.

Although bacteria play key roles in aquatic food webs and biogeochemical cycles, information on the seasonal succession of bacterial communities in lakes is still far from complete. Here, we report results of an integrative study on the successional trajectories of bacterial communities in a seasonally stratified lake with an anoxic hypolimnion. The bacterial community composition of epilimnion, metalimnion, and hypolimnion diverged during summer stratification and converged when the lake was mixed. In contrast, bacterial communities in the sediment remained relatively stable over the year. Phototrophic Cyanobacteria and heterotrophic Actinobacteria, Alphaproteobacteria and Planktomycetes were abundant in the aerobic epilimnion, Gammaproteobacteria (mainly Chromatiaceae) dominated in the metalimnion, and Chlorobi, Betaproteobacteria, Deltaproteobacteria, and Firmicutes were abundant in the anoxic sulfidic hypolimnion. Anoxic but nonsulfidic conditions expanded to the surface layer during fall turnover, when the epilimnion, metalimnion and upper hypolimnion mixed. During this period, phototrophic sulfur bacteria (Chromatiaceae and Chlorobi) disappeared, Polynucleobacter (Betaproteobacteria) and Methylobacter (Gammaproteobacteria) spread out from the former meta- and hypolimnion to the surface layer, and Epsilonproteobacteria dominated in the bottom water layer. Cyanobacteria and Planktomycetes regained dominance in early spring, after the oxygen concentration was restored by winter mixing. In total, these results show large spatio-temporal changes in bacterial community composition, especially during transitions from oxic to anoxic and from sulfidic to nonsulfidic conditions.

Effects of clay minerals, hydroxides, and timing of dissolved organic matter addition on the competitive sorption of copper, nickel, and zinc: A column experiment.

Infiltration of heavy metal (HM) polluted wastewater can seriously compromise soil and groundwater quality. Interactions between mineral soil components (e.g. clay minerals) and dissolved organic matter (DOM) play a crucial role in determining HM mobility in soils. In this study, the influence of the timing of addition of DOM, i.e. concurrent with or prior to HMs, on HM mobility was explored in a set of continuous flow column experiments using well defined natural soil samples amended with goethite, birnessite and/or smectite. The soils were subjected to concurrent and sequential additions of solutions of DOM, and Cu, Ni and Zn. The resulting breakthrough curves were fitted with a modified dose-response model to obtain the adsorption capacity (q0). Addition of DOM prior to HMs moderately enhanced q0 of Cu (8-25%) compared to a control without DOM, except for the goethite amended soil that exhibited a 10% reduction due to the blocking of binding sites. Meanwhile, for both Zn and Ni sequential addition of DOM reduced q0 by 1-36% for all tested soils due to preferential binding of Zn and Ni to mineral phases. In contrast, concurrent addition of DOM and HMs resulted in a strong increase of q0 for all tested metals and all tested soil compositions compared to the control: 141-299% for Cu, 29-102% for Zn and 32-144% for Ni. Our study shows that when assessing the impact of soil pollution through HM containing wastewater it is crucial to take into account the presence of DOM.

Analysis of fullerenes in soils samples collected in The Netherlands.

Fullerenes are carbon based nanoparticles that may enter the environment as a consequence of both natural processes and human activities. Although little is known about the presence of these chemicals in the environment, recent studies suggested that soil may act as a sink. The aim of the present work was to investigate the presence of fullerenes in soils collected in The Netherlands. Samples (n = 91) were taken from 6 locations and analyzed using a new developed LC-QTOF-MS method. The locations included highly trafficked and industrialized as well as urban and natural areas. In general, C60 was the most abundant fullerene found in the environment, detected in almost a half of the samples and at concentrations in the range of ng/kg. Other fullerenes such as C70 and an unknown structure containing a C60 cage were detected to a lower extent. The highest concentrations were found in the proximity of combustion sites such as a coal power plant and an incinerator, suggesting that the nanoparticles were unintentionally produced during combustions processes and reached the soil through atmospheric deposition. Consistent with other recent studies, these results show that fullerenes are widely present in the environment and that the main route for their entrance may be due to human activities. These data will be helpful in the understanding of the distribution of fullerenes in the environment and for the study of their behavior and fate in soil.

Robust analysis of underivatized free amino acids in soil by hydrophilic interaction liquid chromatography coupled with electrospray tandem mass spectrometry.

Amino acids are an important and highly dynamic fraction of organic N in soils and their determination in soil without derivatization is challenging due to the difficulties in separation and detection of trace amounts of these polar analytes. In the present work, we developed an analytical method to quantify 20 free amino acids in aqueous soil extracts without derivatization. The method employed hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) technique combined with a cation exchange solid phase extraction (SPE). Four stable isotope labelled amino acids were used as internal standards to improve the method performance. Good separation of 20 underivatized amino acids was achieved within 12min. The limit of detection (LODs) and limit of quantification (LOQs) were in the range of 13-384ngg(-1) and 43-1267ngg(-1) (dry soil basis), respectively. The results showed that overall recoveries with high precision were obtained for the extracted free amino acids from ten different soils. The overall recoveries of 18 amino acids were similar for the ten soils used, which differed substantially in organic C content and in other properties as soil texture and pH. For most of the amino acids, the average recoveries from soil extracts were between 74% and 117%, with the exception of Met (31%), Pro (52%) and Arg (68%). Variability was within acceptable limits (relative standard deviations were between 4% and 13%), with the exception of Met (relative standard deviation=90%) and Arg (relative standard deviation=53%). Thus the proposed method with high throughout and high analyte specificity shows great promise for consistent analysis of free amino acids extracted from soils and offers new horizons for the analysis of amino acids in terrestrial and aquatic ecosystem.

A method for the determination of fullerenes in soil and sediment matrices using ultra-high performance liquid chromatography coupled with heated electrospray quadrupole time of flight mass spectrometry.

The increasing production of fullerenes likely means a release of these chemicals in the environment. Since soils and sediments are expected to act as a sink, analytical tools are needed to assess the presence of fullerenes in these matrices. In the present work, a method was developed for the determination of fullerenes at environmental relevant levels employing Ultra High Performance Liquid Chromatograph coupled with High Resolution Mass Spectrometry (UHPLC-HRMS). Chromatographic separation was achieved with a core-shell biphenyl stationary phase that provided fast analysis with complete baseline separation. Ion Booster Electro Spray Ionization (IB-ESI) resulted in higher ionization efficiency and was much less susceptible to adduct formation in comparison with standard ESI, whereas Quadrupole Time of Flight (QTOF) MS granted high resolution mass spectra used for accurate identification. The Instrumental method limits of detection (ILoD) and quantification (ILoQ) were 6 and 20 fg, respectively, for C60 and 12 and 39 fg, respectively, for C70. Matrix effects related to co-extractants were systematically investigated in soil and sediments extracts through standard addition method (SAM) and monitoring the signal response during the chromatographic run of these samples. Consequently, minor chromatographic modifications were necessary for the analysis of matrices with high organic carbon content. The method limit of detection (MLoD)ranged from 84 pg/kg to 335 pg/kg, whereas limit of quantification (MLoQ) ranged from 279 pg/kg to 1.1 ng/kg. Furthermore, the method was successfully applied for the analysis of functionalized fullerenes (i.e. methanofullerenes). To the best of our knowledge, this is the first analytical method for the analysis of fullerenes in soils and sediments that employ core-shell biphenyl stationary phase as well as IB-ESI-QTOF MS hyphenated with UHPLC.