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"Sulphur"
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Biosynthesis of Sulfur-Containing Small Biomolecules in Plants
by
Nakai, Yumi
,
Maruyama-Nakashita, Akiko
in
Biosynthesis
,
Biosynthetic Pathways - genetics
,
Carbon-Sulfur Lyases - biosynthesis
2020
Sulfur is an essential element required for plant growth. It can be found as a thiol group of proteins or non-protein molecules, and as various sulfur-containing small biomolecules, including iron-sulfur (Fe/S) clusters, molybdenum cofactor (Moco), and sulfur-modified nucleotides. Thiol-mediated redox regulation has been well investigated, whereas biosynthesis pathways of the sulfur-containing small biomolecules have not yet been clearly described. In order to understand overall sulfur transfer processes in plant cells, it is important to elucidate the relationships among various sulfur delivery pathways as well as to investigate their interactions. In this review, we summarize the information from recent studies on the biosynthesis pathways of several sulfur-containing small biomolecules and the proteins participating in these processes. In addition, we show characteristic features of gene expression in Arabidopsis at the early stage of sulfate depletion from the medium, and we provide insights into sulfur transfer processes in plant cells.
Journal Article
DMS oxidation and sulfur aerosol formation in the marine troposphere: a focus on reactive halogen and multiphase chemistry
2018
The oxidation of dimethyl sulfide (DMS) in the troposphere and subsequent chemical conversion into sulfur dioxide (SO2) and methane sulfonic acid (MSA) are key processes for the formation and growth of sulfur-containing aerosol and cloud condensation nuclei (CCN), but are highly simplified in large-scale models of the atmosphere. In this study, we implement a series of gas-phase and multiphase sulfur oxidation mechanisms into the Goddard Earth Observing System-Chemistry (GEOS-Chem) global chemical transport model – including two important intermediates, dimethyl sulfoxide (DMSO) and methane sulphinic acid (MSIA) – to investigate the sulfur cycle in the global marine troposphere. We found that DMS is mainly oxidized in the gas phase by OH (66 %), NO3 (16 %) and BrO (12 %) globally. DMS + BrO is important for the model's ability to reproduce the observed seasonality of surface DMS mixing ratio in the Southern Hemisphere. MSA is mainly produced from multiphase oxidation of MSIA by OH(aq) (66 %) and O3(aq) (30 %) in cloud droplets and aerosols. Aqueous-phase reaction with OH accounts for only 12 % of MSA removal globally, and a higher MSA removal rate is needed to reproduce observations of the MSA ∕ nssSO42- ratio. The modeled conversion yield of DMS into SO2 and MSA is 75 % and 15 %, respectively, compared to 91 % and 9 % in the standard model run that includes only gas-phase oxidation of DMS by OH and NO3. The remaining 10 % of DMS is lost via deposition of intermediates DMSO and MSIA. The largest uncertainties for modeling sulfur chemistry in the marine boundary layer (MBL) are unknown concentrations of reactive halogens (BrO and Cl) and OH(aq) concentrations in cloud droplets and aerosols. To reduce uncertainties in MBL sulfur chemistry, we should prioritize observations of reactive halogens and OH(aq).
Journal Article
Sulfur in nature and its impact on spiders
2023
This article provides information on the sulfur-containing LSD (decoction of sulfuric lime) and externally active substance (EAS) used against cotton spider mites. It has been established that when using these preparations, the Bukhara-6 variety received an additional yield of 4.2-4.4 c/ha with good commercial indicators.
Journal Article
A shift in sulfur-cycle manipulation from atmospheric emissions to agricultural additions
by
Crawford, John T
,
Fakhraei Habibollah
,
Hinckley, Eve-Lyn S
in
Acid rain
,
Agricultural land
,
Anthropogenic factors
2020
Burning fossil fuels has resulted in a prominent yet unintended manipulation of the global sulfur cycle. Emissions of sulfur dioxide and reactive sulfur to the atmosphere have caused widespread health and environmental impacts and have led, ultimately, to calls to decrease sulfur emissions. However, anthropogenic modification of the sulfur cycle is far from over. Using four contrasting case studies from across the United States, we show how high levels of sulfur are added to croplands as fertilizers and pesticides and constitute a major yet under-studied environmental perturbation. Long-term sulfur additions to crops probably cause similar consequences for the health of soil and downstream aquatic ecosystems as those observed in regions historically impacted by acid rain, yet the cascade of effects has not been broadly explored. A new wave of research on the sulfur cycle will require studies that examine the integrated roles of climate, hydrology and other element cycles in modifying sulfur processes and flows within and downgradient of agricultural source areas. Such research must include not only scientists, but also farmers, regulating authorities and land managers who are engaged in developing approaches to monitor and mitigate environmental and human health impacts.Deliberate application of sulfur onto croplands as fertilizer and pesticide probably causes environmental damage similar to historical acid rain events, according to a literature review and four case studies from the United States.
Journal Article
Structure of the human frataxin-bound iron-sulfur cluster assembly complex provides insight into its activation mechanism
2019
The core machinery for de novo biosynthesis of iron-sulfur clusters (ISC), located in the mitochondria matrix, is a five-protein complex containing the cysteine desulfurase NFS1 that is activated by frataxin (FXN), scaffold protein ISCU, accessory protein ISD11, and acyl-carrier protein ACP. Deficiency in FXN leads to the loss-of-function neurodegenerative disorder Friedreich’s ataxia (FRDA). Here the 3.2 Å resolution cryo-electron microscopy structure of the FXN-bound active human complex, containing two copies of the NFS1-ISD11-ACP-ISCU-FXN hetero-pentamer, delineates the interactions of FXN with other component proteins of the complex. FXN binds at the interface of two NFS1 and one ISCU subunits, modifying the local environment of a bound zinc ion that would otherwise inhibit NFS1 activity in complexes without FXN. Our structure reveals how FXN facilitates ISC production through stabilizing key loop conformations of NFS1 and ISCU at the protein–protein interfaces, and suggests how FRDA clinical mutations affect complex formation and FXN activation.
The iron-sulfur cluster (ISC) assembly complex is activated by frataxin (FXN) and Friedreich’s ataxia is caused by FXN deficiency. Here the authors present the 3.2 Å resolution cryo-EM structure of the human frataxin bound ISC complex and discuss how FXN activates enzymatic activity.
Journal Article
Effects of global ship emissions on European air pollution levels
by
Schulz, Michael
,
Fagerli, Hilde
,
Jalkanen, Jukka-Pekka
in
Acidification
,
Air pollution
,
Air pollution control
2020
Ship emissions constitute a large, and so far poorly regulated, source of air pollution. Emissions are mainly clustered along major ship routes both in open seas and close to densely populated shorelines. Major air pollutants emitted include sulfur dioxide, NOx, and primary particles. Sulfur and NOx are both major contributors to the formation of secondary fine particles (PM2.5) and to acidification and eutrophication. In addition, NOx is a major precursor for ground-level ozone. In this paper, we quantify the contributions from international shipping to European air pollution levels and depositions. This study is based on global and regional model calculations. The model runs are made with meteorology and emission data representative of the year 2017 after the tightening of the SECA (sulfur emission control area) regulations in 2015 but before the global sulfur cap that came into force in 2020. The ship emissions have been derived using ship positioning data. We have also made model runs reducing sulfur emissions by 80 % corresponding to the 2020 requirements. This study is based on model sensitivity studies perturbing emissions from different sea areas: the northern European SECA in the North Sea and the Baltic Sea, the Mediterranean Sea and the Black Sea, the Atlantic Ocean close to Europe, shipping in the rest of the world, and finally all global ship emissions together. Sensitivity studies have also been made setting lower bounds on the effects of ship plumes on ozone formation. Both global- and regional-scale calculations show that for PM2.5 and depositions of oxidised nitrogen and sulfur, the effects of ship emissions are much larger when emissions occur close to the shore than at open seas. In many coastal countries, calculations show that shipping is responsible for 10 % or more of the controllable PM2.5 concentrations and depositions of oxidised nitrogen and sulfur. With few exceptions, the results from the global and regional calculations are similar. Our calculations show that substantial reductions in the contributions from ship emissions to PM2.5 concentrations and to depositions of sulfur can be expected in European coastal regions as a result of the implementation of a 0.5 % worldwide limit of the sulfur content in marine fuels from 2020. For countries bordering the North Sea and Baltic Sea SECA, low sulfur emissions have already resulted in marked reductions in PM2.5 from shipping before 2020. For ozone, the lifetime in the atmosphere is much longer than for PM2.5, and the potential for ozone formation is much larger in otherwise pristine environments. We calculate considerable contributions from open sea shipping. As a result, we find that the largest contributions to ozone in several regions and countries in Europe are from sea areas well outside European waters.
Journal Article
Biodegradation and bioavailability of low-molecular-weight dissolved organic sulphur in soil and its role in plant-microbial S cycling
2024
Background
Plant sulphur (S) deficiency occurs worldwide; however, in comparison to other macronutrients (e.g., N, P), limited attention has been paid to the content, composition, bioavailability, and cycling of S in soil. An increased knowledge of S biogeochemical cycling, however, can aid soil S management and plant S nutrition.
Scope
This review discusses current knowledge on the bioavailability and decomposition of soil-soluble organic S, focusing mainly on proteins and two S-containing amino acids (methionine (Met) and cysteine (Cys)).
Conclusions
Proteins represent the major S input into soil with most held within insoluble organic matter and a lesser proportion present as dissolved organic S (DOS). The size of the DOS pool is typically much lower than that of the inorganic SO
4
2−
pool, however, this reflects the rapid turnover and replenishment of this pool, which is orders of magnitude faster than the inorganic S pool, reflecting the importance of soil organic S cycling. Soluble proteins can be decomposed to SO
4
2−
within minutes, and S-containing amino acids can be mineralised within seconds to hours. Microorganisms utilise S-containing amino acids in three steps: uptake into the microbial biomass within seconds; release of CO
2
, NH
4
+
, and SO
4
2−
within minutes to hours; and the re-utilisation of released inorganic S and nitrogen (N) by microorganisms and plants. Current evidence suggests that Met and Cys play limited roles in plant N nutrition due to intense competition from soil microbes and the supply of inorganic N in fertilisers, however, these amino acids can account for ca. 10% of total plant S uptake (intact form and the inorganic S derived from them). We conclude that direct uptake of S-containing amino acids by microbes, and to a lesser extent plants, is an effective and energy efficient way to bypass the SO
4
2−
pool and that the production and consumption of DOS cycling represents the key central cog in soil S cycling.
Journal Article
Crystallographic snapshots of sulfur insertion by lipoyl synthase
by
Goldman, Peter J.
,
McLaughlin, Martin I.
,
Lee, Kyung-Hoon
in
Amino Acid Motifs
,
Bacterial Proteins - chemistry
,
Bacterial Proteins - genetics
2016
Lipoyl synthase (LipA) catalyzes the insertion of two sulfur atoms at the unactivated C6 and C8 positions of a protein-bound octanoyl chain to produce the lipoyl cofactor. To activate its substrate for sulfur insertion, LipA uses a [4Fe-4S] cluster and S-adenosylmethionine (AdoMet) radical chemistry; the remainder of the reaction mechanism, especially the source of the sulfur, has been less clear. One controversial proposal involves the removal of sulfur from a second (auxiliary) [4Fe-4S] cluster on the enzyme, resulting in destruction of the cluster during each round of catalysis. Here, we present two high-resolution crystal structures of LipA from Mycobacterium tuberculosis: one in its resting state and one at an intermediate state during turnover. In the resting state, an auxiliary [4Fe-4S] cluster has an unusual serine ligation to one of the irons. After reaction with an octanoyllysine-containing 8-mer peptide substrate and 1 eq AdoMet, conditions that allow for the first sulfur insertion but not the second insertion, the serine ligand dissociates from the cluster, the iron ion is lost, and a sulfur atom that is still part of the cluster becomes covalently attached to C6 of the octanoyl substrate. This intermediate structure provides a clear picture of iron–sulfur cluster destruction in action, supporting the role of the auxiliary cluster as the sulfur source in the LipA reaction and describing a radical strategy for sulfur incorporation into completely unactivated substrates.
Journal Article