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Parameterisation of the air-sea gas transfer velocity of CO2 and other trace gases under open-ocean conditions has been a focus of air-sea interaction research and is required for accurately determining ocean carbon uptake. Ships are the most widely used platform for air-sea flux measurements but the quality of the data can be compromised by airflow distortion and sensor cross-sensitivity effects. Recent improvements in the understanding of these effects have led to enhanced corrections to the shipboard eddy covariance (EC) measurements. Here, we present a revised analysis of eddy covariance measurements of air-sea CO2 and momentum fluxes from the Southern Ocean Surface Ocean Aerosol Production (SOAP) study. We show that it is possible to significantly reduce the scatter in the EC data and achieve consistency between measurements taken on station and with the ship underway. The gas transfer velocities from the EC measurements correlate better with the EC friction velocity (u∗) than with mean wind speeds derived from shipboard measurements corrected with an airflow distortion model. For the observed range of wind speeds (u10N =3-23 ms-1), the transfer velocities can be parameterised with a linear fit to u∗. The SOAP data are compared to previous gas transfer parameterisations using u10N computed from the EC friction velocity with the drag coefficient from the Coupled Ocean-Atmosphere Response Experiment (COARE) model version 3.5. The SOAP results are consistent with previous gas transfer studies, but at high wind speeds they do not support the sharp increase in gas transfer associated with bubble-mediated transfer predicted by physically based models.

Simultaneous air-sea fluxes and concentration differences of dimethylsulfide (DMS) and carbon dioxide (CO2) were measured during a summertime North Atlantic cruise in 2011. This data set reveals significant differences between the gas transfer velocities of these two gases (Î"kw) over a range of wind speeds up to 21ĝ€mĝ€sĝ'1. These differences occur at and above the approximate wind speed threshold when waves begin breaking. Whitecap fraction (a proxy for bubbles) was also measured and has a positive relationship with Î"kw, consistent with enhanced bubble-mediated transfer of the less soluble CO2 relative to that of the more soluble DMS. However, the correlation of Î"kw with whitecap fraction is no stronger than with wind speed. Models used to estimate bubble-mediated transfer from in situ whitecap fraction underpredict the observations, particularly at intermediate wind speeds. Examining the differences between gas transfer velocities of gases with different solubilities is a useful way to detect the impact of bubble-mediated exchange. More simultaneous gas transfer measurements of different solubility gases across a wide range of oceanic conditions are needed to understand the factors controlling the magnitude and scaling of bubble-mediated gas exchange.

The air-sea gas transfer velocity k is frequently estimated as an empirical function of wind speed. However, it is widely recognized that k depends on processes other than wind speed alone. The small-eddy model, which describes periodic events of small eddies disturbing the sea surface with water from below, suggests a direct relation between k and the dissipation rate of turbulent kinetic energy ϵ at the air-sea interface. This relation has been proven both in laboratories and in the field in various freshwater and coastal environments, but to date has not been verified in open ocean conditions. Here, concurrent North Atlantic field observations of ϵ and eddy covariance measurements of DMS and CO2 air-sea gas flux are presented. Using ϵ measurements, we compare the small-eddy model at various depths to previously published observations. Extrapolating the measured ϵ profiles to the thickness of the viscous sublayer allows us to formulate a function of k that depends solely on the water side friction velocity u*w, which can be inferred from direct eddy covariance measurements of the air-side friction velocity u*a. These field observations are generally consistent with the theoretical small-eddy model. Utilizing a variable Schmidt number exponent in the model, rather than a constant value of 1/2 yields improved agreement between model and observations.

Rainfall induces a vertical salinity gradient directly below the ocean surface, the strength and lifetime of which depend on the size of the rain event, the availability of mixing, and the air‐sea heat fluxes. The presence of rain in turn influences the near‐surface turbulent mixing and air‐sea exchange processes. During a campaign in the midlatitude North Atlantic, the Air‐Sea Interaction Profiler (ASIP) was used to investigate changes in the vertical distribution of salinity (S), temperature (T), and turbulent kinetic energy dissipation rate (ϵ) caused by four rain events. During one of the rain events a strong shallow stratification was formed. The buoyancy effect of this freshwater lens changes the dominant wind‐driven turbulent mixing. The surface momentum flux was limited to a shallow layer, and below it ϵ is reduced by 2 orders of magnitude. For a different rain event of higher‐peak rain rate, the salinity anomaly is smaller and is dispersed deeper into the water column. The difference in ocean response shows that the upper ocean is sensitive to changes in the atmospheric forcing associated with the rain events. The observed salinity anomalies as a function of rain rate and wind speed are compared to relationships from studies with the 1‐D turbulence model GOTM and satellite validation. The observations suggest that the vertical salinity anomaly is best described as a function of total rain. A higher‐resolution prognostic model for sea surface salinity and temperature is shown to perform well in predicting the observed S and T anomalies. Key Points: The evolution of rain‐induced shallow stratification in a midlatitude open‐ocean region is highly sensitive to atmospheric forcingEmpirical models do not well represent the observed salinity anomaliesA recent prognostic model for sea surface salinity and temperature accurately simulates rain‐induced salinity and temperature anomalies [ABSTRACT FROM AUTHOR]

Eddy covariance measurements of air-sea CO2 fluxes can be affected by cross-sensitivities of the CO2 measurement to water vapour, resulting in order-of-magnitude biases. Well-established causes for these biases are (i) cross-sensitivity of the broadband non-dispersive infrared sensors due to band-broadening and spectral overlap (commercial sensors typically correct for this) and (ii) the effect of air density fluctuations (removed by determining the dry air CO2 mixing ratio). Another bias related to water vapour fluctuations has recently been observed with open-path sensors, attributed to sea salt build-up and water films on sensor optics. Two very different approaches have been used to deal with these water vapour-related biases. Miller et al. (2010) employed a membrane drier to physically eliminate 97% of the water vapour fluctuations in the sample air before it entered a closed-path gas analyser. Prytherch et al. (2010a) employed the empirical (Peter K. Taylor, PKT) post-processing correction to correct open-path sensor data. In this paper, we test these methods side by side using data from the Surface Ocean Aerosol Production (SOAP) experiment in the Southern Ocean. The air-sea CO2 flux was directly measured with four closed-path analysers, two of which were positioned down-stream of a membrane dryer. The CO2 fluxes from the two dried gas analysers matched each other and were in general agreement with common parameterisations. The flux estimates from the un-dried sensors agreed with the dried sensors only during periods with low latent heat flux (≤7 W m-2). When latent heat flux was higher, CO2 flux estimates from the un-dried sensors exhibited large scatter and an order-of-magnitude bias. Applying the PKT correction to the flux data from the un-dried analysers did not remove the bias when compared to the data from the dried gas analyser. The results of this study demonstrate the validity of measuring CO2 fluxes using a pre-dried air stream and show that the PKT correction is not valid for the correction of CO2 fluxes. [ABSTRACT FROM AUTHOR]

Eddy covariance measurements of air--sea CO2 fluxes can be affected by crosssensitivities of the CO2 measurement to water vapour, resulting in order-of-magnitude biases. Well established causes for these biases are (i) cross-sensitivity of the broadband non-dispersive infrared sensors due to band-broadening and spectral over lap (commercial sensors typically correct for this) and (ii) the effect of air density fluctuations (removed by determining the CO2 mixing ratio respective to dry air). However, another bias related to water vapour fluctuations has recently been observed with openpath sensors, and was attributed to sea salt build-up and water films on sensor optics. Two very different approaches have been used to deal with these water vapour-related biases. Miller et al. (2010) employed a membrane drier to physically eliminate 97% of the water vapour fluctuations in the sample air before it enters the gas analyser. Prytherch et al. (2010a), on the other hand, employed the empirical (Peter K. Taylor, PKT) post-processing correction to correct open-path sensor data. In this paper, we test these methods side by side using data from the Surface Ocean Aerosol Production (SOAP) experiment in the Southern Ocean. The air--sea CO2 flux was directly measured with four closed-path analysers, two of which were positioned down-stream of a membrane dryer. The CO2 fluxes from the two dried gas analysers matched each other and were in general agreement with common parametrisations. The flux estimates from the un-dried sensors agreed with the dried sensors only during periods with low latent heat flux (≤ 7Wm-²). When latent heat flux was higher, CO2 flux estimates from the un-dried sensors exhibited large scatter and an order-of magnitude bias. We applied the PKT correction to the flux data from the un-dried analysers and found that it did not remove the bias when compared to the data from the dried gas analyser. Our detailed analysis of the correction algorithm reveals that this method is not valid for the correction of CO2 fluxes. [ABSTRACT FROM AUTHOR]

Abstract: The combined action of endo-polygalacturonase (endo-PGII), pectin lyase (PL), pectin methyl esterase (fungal PME) and RG-I degrading enzymes enabled the extended degradation of methylesterified and acetylated sugar beet pectins (SBPs). The released oligomers were separated, identified and quantified using hydrophilic interaction liquid chromatography (HILIC) with online electrospray ionization ion trap mass spectrometry (ESI-IT-MS n ) and evaporative light scattering detection (ELSD). By MS n , the structures of galacturonic acid (GalA) oligomers having an acetyl group in the O-2 and/or O-3 positions eluting from the HILIC column were elucidated. The presence of methylesterified and/or acetylated galacturonic acid units within an oligomer reduced the interaction with the HILIC column significantly compared to the unsubstituted GalA oligomers. The HILIC column enables a good separation of most oligomers present in the digest. The use of ELSD to quantify oligogalacturonides was validated using pure GalA standards and the signal was found to be independent of the chemical structure of the oligomer being detected. The combination of chromatographic and enzymatic strategies enables to distinguish SBPs having different methylesters and acetyl group distribution. [Copyright &y& Elsevier]

Chitin polymers are an essential structural component of fungal cell walls, but host chitinases can weaken them, contributing to disease resistance in fungal pathogens. Chitin oligomers thus produced are immunogenic signal molecules eliciting additional disease resistance mechanisms. Fungi may counteract these, e.g. by partial deacetylation of chitin, converting it into chitosans, protecting the cell walls against chitinase attack, and inactivating elicitor active oligomers. This molecular stealth hypothesis for fungal pathogenicity has repeatedly been tested by mutating single or multiple chitin deacetylase genes, supporting the hypothesis but simultaneously suggesting additional roles for chitin deacetylation in virulence, such as surface attachment and sensing, host tissue penetration and colonization, as well as spore formation, stabilization, and germination. Interestingly, recent evidence suggests that host plants have evolved counter strategies by inhibiting fungal chitin deacetylases, lending further credibility to the suggested action of these enzymes as pathogenicity/virulence factors, and possibly offering leads toward novel functional fungicides., Competing Interests: Declaration of competing interest The authors declare no financial interests/personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Effector secretion is crucial for root endophytes to establish and protect their ecological niche. We used time-resolved transcriptomics to monitor effector gene expression dynamics in two closely related Sebacinales, Serendipita indica and Serendipita vermifera, during symbiosis with three plant species, competition with the phytopathogenic fungus Bipolaris sorokiniana, and cooperation with root-associated bacteria. We observed increased effector gene expression in response to biotic interactions, particularly with plants, indicating their importance in host colonization. Some effectors responded to both plants and microbes, suggesting dual roles in intermicrobial competition and plant-microbe interactions. A subset of putative antimicrobial effectors, including a GH18-CBM5 chitinase, was induced exclusively by microbes. Functional analyses of this chitinase revealed its antimicrobial and plant-protective properties. We conclude that dynamic effector gene expression underpins the ability of Sebacinales to thrive in diverse ecological niches with a single fungal chitinase contributing substantially to niche defense., (© 2024 The Author(s). New Phytologist © 2024 New Phytologist Foundation.)

Chitosans are versatile biopolymers with antimicrobial and plant-strengthening properties relevant to agriculture. However, a limited understanding of molecular structure-function relationships and cellular modes of action of chitosans hampers the development of effective chitosan-based agro-biologics. We partially hydrolyzed a chitosan polymer (degree of polymerization DP 800, fraction of acetylation F A 0.2) using acetic acid, a GH18 chitinase, or a GH8 chitosanase. All hydrolysates contained mixtures of chitosan oligomers and small polymers, but their composition in terms of DP, F A , and pattern of acetylation (PA) differed greatly. Importantly, chitinase products had mostly deacetylated residues at their ends, flanking mostly deacetylated residues, and vice versa for chitosanase products, while the products of acid hydrolysis had random PA. Acid hydrolysis did not significantly change antifungal and antibacterial activities. In contrast, chitinase hydrolysis slightly increased antibacterial, and chitosanase almost abolished antifungal activity. Elicitor and priming activities in the plant Arabidopsis were unchanged by acid, destroyed by chitinase, and increased by chitosanase hydrolysis. Transcriptomic analysis revealed that the chitosan polymer strongly induced genes involved in photosynthesis, while the chitosanase hydrolysate strongly induced genes involved in disease resistance. Clearly, different bioactivities require different chitosans, and enzymatic modification can fine-tune these activities as required for different agricultural products., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Bruno M. Moerschbacher, Stefan Cord-Landwehr and Carolin Richter have a patent pending to the University of Münster. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Chitosans are promising biopolymers for diverse applications, with material properties and bioactivities depending i.a. on their pattern of acetylation (PA). Commercial chitosans are typically produced by heterogeneous deacetylation of chitin, but whether this process yields chitosans with a random or block-wise PA has been debated for decades. Using a combination of recently developed in vitro assays and in silico modeling surprisingly revealed that both hypotheses are wrong; instead, we found a more regular PA in heterogeneously deacetylated chitosans, with acetylated units overrepresented at every third position in the polymer chain. Compared to random-PA chitosans produced by homogeneous deacetylation of chitin or chemical N-acetylation of polyglucosamine, this regular PA increases the elicitation activity in plants, and generates different product profiles and distributions after enzymatic and chemical cleavage. A regular PA may be beneficial for some applications but detrimental for others, stressing the relevance of the production process for product development., (© 2024. The Author(s).)

The thorough characterization of chitosan-cleaving enzymes is crucial to unveil structure-function relationships of this promising class of biomolecules for both, enzymatic fingerprinting analyses and to use the enzymes as biotechnological tools to produce tailor-made chitosans for diverse applications. Analyzing polymeric substrates as well as oligomeric products has been established as an effective way to understand the actions of enzymes, but it currently requires separate, rather laborious methods to obtain the full picture. Here, we present ultra high performance size exclusion chromatography coupled to refractive index and mass spectrometry detection (UHPSEC-RI-MS) as a straightforward method for the semi-quantitative analysis of chitosan oligomers of up to ten monomers in length. Additionally, the method allows to determine the average molecular weight of the remaining polymers and its distribution. By sampling live from an ongoing enzymatic reaction, UHPSEC-RI-MS offers the unique opportunity to analyze polymers and oligomers simultaneously-i.e., to monitor the molecular weight reduction of the polymeric substrate over the course of the digestion, while at the same time analyzing the emerging oligomeric products in a semi-quantitative manner. In this way, a single simple analysis yields detailed insights into an enzyme's action on a given substrate., (© 2024. The Author(s).)