Explore the vast range of titles available.

In natural coastal wetlands, high supplies of marine sulfate suppress methanogenesis. Coastal wetlands are, however, often subject to disturbance by diking and drainage for agricultural use and can turn to potent methane sources when rewetted for remediation. This suggests that preceding land use measures can suspend the sulfate-related methane suppressing mechanisms. Here, we unravel the hydrological relocation and biogeochemical S and C transformation processes that induced high methane emissions in a disturbed and rewetted peatland despite former brackish impact. The underlying processes were investigated along a transect of increasing distance to the coastline using a combination of concentration patterns, stable isotope partitioning, and analysis of the microbial community structure. We found that diking and freshwater rewetting caused a distinct freshening and an efficient depletion of the brackish sulfate reservoir by dissimilatory sulfate reduction (DSR). Despite some legacy effects of brackish impact expressed as high amounts of sedimentary S and elevated electrical conductivities, contemporary metabolic processes operated mainly under sulfate-limited conditions. This opened up favorable conditions for the establishment of a prospering methanogenic community in the top 30–40 cm of peat, the structure and physiology of which resemble those of terrestrial organic-rich environments. Locally, high amounts of sulfate persisted in deeper peat layers through the inhibition of DSR, probably by competitive electron acceptors of terrestrial origin, for example Fe(III). However, as sulfate occurred only in peat layers below 30–40 cm, it did not interfere with high methane emissions on an ecosystem scale. Our results indicate that the climate effect of disturbed and remediated coastal wetlands cannot simply be derived by analogy with their natural counterparts. From a greenhouse gas perspective, the re-exposure of diked wetlands to natural coastal dynamics would literally open up the floodgates for a replenishment of the marine sulfate pool and therefore constitute an efficient measure to reduce methane emissions.

Trichodesmium is an important dinitrogen (N 2 )-fixing cyanobacterium in marine ecosystems. Recent nucleic acid analyses indicate that Trichodesmium colonies with their diverse epibionts support various nitrogen (N) transformations beyond N 2 fixation. However, rates of these transformations and concentration gradients of N compounds in Trichodesmium colonies remain largely unresolved. We combined isotope-tracer incubations, micro-profiling and numeric modelling to explore carbon fixation, N cycling processes as well as oxygen, ammonium and nitrate concentration gradients in individual field-sampled Trichodesmium colonies. Colonies were net-autotrophic, with carbon and N 2 fixation occurring mostly during the day. Ten percent of the fixed N was released as ammonium after 12-h incubations. Nitrification was not detectable but nitrate consumption was high when nitrate was added. The consumed nitrate was partly reduced to ammonium, while denitrification was insignificant. Thus, the potential N transformation network was characterised by fixed N gain and recycling processes rather than denitrification. Oxygen concentrations within colonies were ~60–200% air-saturation. Moreover, our modelling predicted steep concentration gradients, with up to 6-fold higher ammonium concentrations, and nitrate depletion in the colony centre compared to the ambient seawater. These gradients created a chemically heterogeneous microenvironment, presumably facilitating diverse microbial metabolisms in millimetre-sized Trichodesmium colonies.

To gain insight into the bacterial communities involved in iron-(Fe) cycling under marine conditions, we analysed sediments with Fe-contents (0.5–1.5 wt %) from the suboxic zone at a marine site in the Skagerrak (SK) and a brackish site in the Bothnian Bay (BB) using 16S rRNA gene pyrosequencing. Several bacterial families, including Desulfobulbaceae, Desulfuromonadaceae and Pelobacteraceae and genera, including Desulfobacter and Geobacter, known to reduce Fe were detected and showed highest abundance near the Fe(III)/Fe(II) redox boundary. Additional genera with microorganisms capable of coupling fermentation to Fe-reduction, including Clostridium and Bacillus, were observed. Also, the Fe-oxidizing families Mariprofundaceae and Gallionellaceae occurred at the SK and BB sites, respectively, supporting Fe-cycling. In contrast, the sulphate (SO4 2−) reducing bacteria Desulfococcus and Desulfobacterium were more abundant at greater depths concurring with a decrease in Fe-reducing activity. The communities revealed by pyrosequencing, thus, match the redox stratification indicated by the geochemistry, with the known Fe-reducers coinciding with the zone of Fe-reduction. Not the intensely studied model organisms, such as Geobacter spp., but rather versatile microorganisms, including sulphate reducers and possibly unknown groups appear to be important for Fe-reduction in these marine suboxic sediments. This study gives insight into the bacterial community composition related to iron-cycling in suboxic marine sediments based on 16S rRNA gene pyrosequencing. Graphical Abstract Figure. This study gives insight into the bacterial community composition related to iron-cycling in suboxic marine sediments based on 16S rRNA gene pyrosequencing.

Carbon and chlorine isotope effects for biotransformation of chloroform by different microbes show significant variability. Reductive dehalogenases (RDase) enzymes contain different cobamides, affecting substrate preferences, growth yields, and dechlorination rates and extent. We investigate the role of cobamide type on carbon and chlorine isotopic signals observed during reductive dechlorination of chloroform by the RDase CfrA. Microcosm experiments with two subcultures of a Dehalobacter‐containing culture expressing CfrA—one with exogenous cobamide (Vitamin B12, B12+) and one without (to drive native cobamide production)—resulted in a markedly smaller carbon isotope enrichment factor (εC, bulk) for B12− (−22.1 ± 1.9‰) compared to B12+ (−26.8 ± 3.2‰). Both cultures exhibited significant chlorine isotope fractionation, and although a lower εCl, bulk was observed for B12− (−6.17 ± 0.72‰) compared to B12+ (−6.86 ± 0.77‰) cultures, these values are not statistically different. Importantly, dual‐isotope plots produced identical slopes of ΛCl/C (ΛCl/C, B12+ = 3.41 ± 0.15, ΛCl/C, B12− = 3.39 ± 0.15), suggesting the same reaction mechanism is involved in both experiments, independent of the lower cobamide bases. A nonisotopically fractionating masking effect may explain the smaller fractionations observed for the B12− containing culture. The presence of vitamin B12 has a significant effect on carbon isotope effects, consistent with an isotope masking effect. We interpret this in the context of predicted enzyme structures.

The role of hydromorphological degradation and temporal variation for food webs in human-modified rivers is still not fully evaluated. We tested the hypothesis that man-made engineering structures alter macroinvertebrate resource use in the Elbe River (Germany) in relation to seasonal variation. Stable isotopes (δ13C, δ15N) and mixing models revealed that dietary contributions of benthic organic matter (BOM) and phytoplankton were driven by engineering structure. Contributions of biofilm were driven by season, while contributions of terrestrial particulate organic matter (t-POM) were driven by both engineering structure and season. Contributions of t-POM were larger than those of phytoplankton in spring and summer, but not in autumn, which adds to the debate about the sources of organic matter fuelling riverine benthic food webs. Resource availability was not systematically related to resource use, indicating that factors other than resource limitation were responsible for the observed results. By demonstrating that human alterations determine consumer resource use independently from resource availability, our study links hydromorphological modifications to fluxes of matter in riverine food webs. Future studies should quantify organic matter fluxes from various autochthonous and allochthonous pathways in human-modified and natural rivers to allow for a robust synthesis of how hydromorphological modifications alter benthic food webs.

Abstract Reductive dehalogenases (RDases) are corrinoid-dependent enzymes that reductively dehalogenate organohalides in respiratory processes. By comparing isotope effects in biotically catalyzed reactions to reference experiments with abiotic corrinoid catalysts, compound-specific isotope analysis (CSIA) has been shown to yield valuable insights into enzyme mechanisms and kinetics, including RDases. Here, we report isotopic fractionation (ε) during biotransformation of chloroform (CF) for carbon (εC = -1.52 ± 0.34‰) and chlorine (εCl = -1.84 ± 0.19‰), corresponding to a ΛC/Cl value of 1.13 ± 0.35. These results are highly suppressed compared to isotope effects observed both during CF biotransformation by another organism with a highly similar RDase (>95% sequence identity) at the amino acid level, and to those observed during abiotic dehalogenation of CF. Amino acid differences occur at four locations within the two different RDases’ active sites, and this study examines whether these differences potentially affect the observed εC, εCl, and ΛC/Cl. Structural protein models approximating the locations of the residues elucidate possible controls on reaction mechanisms and/or substrate binding efficiency. These four locations are not conserved among other chloroalkane reducing RDases with high amino acid similarity (>90%), suggesting that these locations may be important in determining isotope fractionation within this homologous group of RDases. This study investigates the relationship between active site amino acid sequences with carbon and chlorine isotope fractionation for chlorinated alkane biotransformation by reductive dehalogenases..

Carbon and chlorine isotope effects for biotransformation of chloroform by different microbes show significant variability. Reductive dehalogenases (RDase) enzymes contain different cobamides, affecting substrate preferences, growth yields, and dechlorination rates and extent. We investigate the role of cobamide type on carbon and chlorine isotopic signals observed during reductive dechlorination of chloroform by the RDase CfrA. Microcosm experiments with two subcultures of a Dehalobacter ‐containing culture expressing CfrA—one with exogenous cobamide (Vitamin B 12 , B12 + ) and one without (to drive native cobamide production)—resulted in a markedly smaller carbon isotope enrichment factor ( ε C, bulk ) for B12 − (−22.1 ± 1.9‰) compared to B12 + (−26.8 ± 3.2‰). Both cultures exhibited significant chlorine isotope fractionation, and although a lower ε Cl, bulk was observed for B12 − (−6.17 ± 0.72‰) compared to B12 + (−6.86 ± 0.77‰) cultures, these values are not statistically different. Importantly, dual‐isotope plots produced identical slopes of Λ Cl/C ( Λ Cl/C, B12+  = 3.41 ± 0.15, Λ Cl/C, B12 − = 3.39 ± 0.15), suggesting the same reaction mechanism is involved in both experiments, independent of the lower cobamide bases. A nonisotopically fractionating masking effect may explain the smaller fractionations observed for the B12 − containing culture.

Using bulk tissue and fatty acid ¹³C analysis we investigated major trophic pathways from soil microorganisms to microbial consumers to predators in conventional versus organic farming systems planted for the first time with maize. Organic farming led to an increase in microbial biomass in particular that of fungi as indicated by phospholipid fatty acids (PLFAs). Microbial PLFAs reflected the conversion from C₃ to C₄ plants by a shift in δ¹³C of 2[per thousand], whereas the isotopic signal in fatty acids (FAs) of Collembola was much more pronounced. In the euedaphic Protaphorura fimata the δ¹³C values in maize fields exceeded that in C₃ (soybean) fields by up to 10[per thousand], indicating a close relationship between diet and vegetation cover. In the epedaphic Orchesella villosaδ¹³C values shifted by 4[per thousand], suggesting a wider food spectrum including carbon of former C₃ crop residues. Differences in δ¹³C of corresponding FAs in consumers and resources were assessed to assign food web links. P. fimata was suggested as root and fungal feeder in soybean fields, fungal feeder in conventional and leaf consumer in organically managed maize fields. O. villosa likely fed on root and bacteria under soybean, and bacteria and fungi under maize. Comparison of δ¹³C values in FAs of the cursorial spider Pardosaagrestis and O. villosa implied the latter as important prey species in soybean fields. In contrast, the web-building spider Mangora acalypha showed no predator-prey relationship with Collembola. The determination of δ¹³C values in trophic biomarker FAs allowed detailed insight into the structure of the decomposer food web and identified diet-shifts in both consumers at the base of the food web and in top predators in organic versus conventional agricultural systems. The results indicate changes in major trophic links and therefore carbon flux through the food web by conversion of conventional into organic farming systems.

Eurytemora affinis (Copepoda) were fed 15 N‐labeled Rhodomonas salina (Cryptophyta) or 15 N‐labeled Nodularia spumigena (Cyanobacteria) in excess under controlled laboratory conditions. Zooplankton collected from the Baltic Sea were fed natural phytoplankton amended with 15 N‐labeled N. spumigena . We quantified the direct incorporation of 15 N tracer from N 2 ‐fixing N. spumigena (diazotroph nitrogen) and ammonium‐utilizing R. salina into the amino acid nitrogen (AA‐N) of zooplankton using complementary gas chromatography‐combustion‐isotope ratio mass spectrometry, gas chromatography‐mass spectrometry, and elemental analysis‐isotope ratio mass spectrometry approaches. Specific and mass‐specific TN and AA‐N incorporation rates of the 15 N tracers were calculated for zooplankton. Highest incorporation of 15 N was found in field zooplankton relying on N. spumigena and in E. affinis relying on R. salina . Lowest incorporation was found in E. affinis relying on N. spumigena . Decreasing specific and mass‐specific rates during field experiments possibly were due to food shortage, whereas decreasing rates in E. affinis grazing on R. salina were more likely due to satiation. Specific and mass‐specific rates were consistently low in E. affinis when exposed to N. spumigena , suggesting that these animals were reluctant to feed on N. spumigena . Essential isoleucine received most of the diazotroph nitrogen in field zooplankton, while nonessential amino acids received most 15 N tracer in E. affinis . N. spumigena was clearly an important amino acid nitrogen source for Baltic Sea zooplankton.

Eurytemora affinis (Copepoda) were fed 15N-labeled Rhodomonas salina (Cryptophyta) or 15N-labeled Nodularia spumigena (Cyanobacteria) in excess under controlled laboratory conditions. Zooplankton collected from the Baltic Sea were fed natural phytoplankton amended with 15N-labeled N. spumigena. We quantified the direct incorporation of 15N tracer from N₂-fixing N. spumigena (diazotroph nitrogen) and ammonium-utilizing R. salina into the amino acid nitrogen (AA-N) of zooplankton using complementary gas chromatography–combustion–isotope ratio mass spectrometry, gas chromatography–mass spectrometry, and elemental analysis–isotope ratio mass spectrometry approaches. Specific and mass-specific TN and AA-N incorporation rates of the 15N tracers were calculated for zooplankton. Highest incorporation of 15N was found in field zooplankton relying on N. spumigena and in E. affinis relying on R. salina. Lowest incorporation was found in E. affinis relying on N. spumigena. Decreasing specific and mass-specific rates during field experiments possibly were due to food shortage, whereas decreasing rates in E. affinis grazing on R. salina were more likely due to satiation. Specific and mass-specific rates were consistently low in E. affinis when exposed to N. spumigena, suggesting that these animals were reluctant to feed on N. spumigena. Essential isoleucine received most of the diazotroph nitrogen in field zooplankton, while nonessential amino acids received most 15N tracer in E. affinis. N. spumigena was clearly an important amino acid nitrogen source for Baltic Sea zooplankton.