Observations of I2 at a remote marine site

Inorganic iodine plays a significant role in the photochemistry of the marine boundary layer, but the sources and cycling of iodine are not well understood. We report the first I2 observations in marine air that is not impacted by coastal macroalgal emissions or sea ice chemistry. The data clearly demonstrate that the very high I2 levels previously reported for coastal air are not representative of open ocean conditions. In this study, gas phase I2 was measured at the Cape Verde Atmospheric Observatory, a semi-remote site in the eastern tropical Atlantic, using atmospheric pressure chemical ionization tandem mass spectrometry. Atmospheric I2 levels typically increased beginning at sunset, leveled off after midnight, and then rapidly decreased at sunrise. There was also a smaller midday maximum in I 2 that was probably caused by a measurement artifact. Ambient I 2 mixing ratios ranged from <0.02-0.6 pmol mol-1 in May 2007 and <0.03-1.67 pmol mol-1 in May 2009. The sea-air flux implied by the nighttime buildup of I2 is too small to explain the observed daytime IO levels at this site. Iodocarbon measurements made in this region previously are also insufficient to explain the observed 1-2 pmol mol-1 of daytime IO. The observations imply the existence of an unknown daytime source of gas phase inorganic iodine. Carpenter et al. (2013) recently proposed that sea surface emissions of HOI are several times larger than the flux of I2. Such a flux could account for both the nighttime I2 and the daytime IO observations

Nighttime atmospheric chemistry of iodine

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I₂ during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I₂ could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO₃+ HOI  →  IO + HNO₃ is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T)  =  2.7  ×  10¯¹² (300 K/T)²·⁶⁶ cm³ molecule¯¹ s¯¹. This reaction is included in two atmospheric models, along with the known reaction between I₂ and NO₃, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I₂, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI +I₂ and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO₃ radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation

Enhanced production of oxidised mercury over the tropical Pacific Ocean: A key missing oxidation pathway

Mercury is a contaminant of global concern. It is transported in the atmosphere primarily as gaseous elemental mercury, but its reactivity and deposition to the surface environment, through which it enters the aquatic food chain, is greatly enhanced following oxidation. Measurements and modelling studies of oxidised mercury in the polar to sub-tropical marine boundary layer (MBL) have suggested that photolytically produced bromine atoms are the primary oxidant of mercury. We report year-round measurements of elemental and oxidised mercury, along with ozone, halogen oxides (IO and BrO) and nitrogen oxides (NO2), in the MBL over the Galápagos Islands in the equatorial Pacific. Elemental mercury concentration remained low throughout the year, while higher than expected levels of oxidised mercury occurred around midday. Our results show that the production of oxidised mercury in the tropical MBL cannot be accounted for by bromine oxidation only, or by the inclusion of ozone and hydroxyl. As a two-step oxidation mechanism, where the HgBr intermediate is further oxidised to Hg(II), depends critically on the stability of HgBr, an additional oxidant is needed to react with HgBr to explain more than 50% of the observed oxidised mercury. Based on best available thermodynamic data, we show that atomic iodine, NO2, or HO2 could all play the potential role of the missing oxidant, though their relative importance cannot be determined explicitly at this time due to the uncertainties associated with mercury oxidation kinetics. We conclude that the key pathway that significantly enhances atmospheric mercury oxidation and deposition to the tropical oceans is missing from the current understanding of atmospheric mercury oxidation

Latitudinal distribution of reactive iodine in the Eastern Pacific and its link to open ocean sources

Ship-based Multi-Axis Differential Optical Absorption Spectroscopy measurements of iodine monoxide (IO) and atmospheric and seawater Gas Chromatography-Mass Spectrometer observations of methyl iodide (CH3I) were made in the Eastern Pacific marine boundary layer during April 2010 as a part of the HaloCarbon Air Sea Transect-Pacific (HaloCAST-P) scientific cruise. The presence of IO in the open ocean environment was confirmed, with a maximum differential slant column density of 5 × 1013 molecules cm−2 along the 1° elevation angle (corresponding to approximately 1 pptv) measured in the oligotrophic region of the Southeastern Pacific. Such low IO mixing ratios and their observed geographical distribution are inconsistent with satellite estimates and with previous understanding of oceanic sources of iodine. A strong correlation was observed between reactive iodine (defined as IO + I) and CH3I, suggesting common sources

Iodine chemistry after dark

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I₂ during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I₂ could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO₃ + HOI → IO + HNO₃ is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260 - 300 K and at a pressure of 1000 hPa to be k(T) = 2.7 x 10-¹² (300 K / T ) ².⁶⁶ cm³ molecule-¹ s-¹ . This reaction is included in two atmospheric models, along with the known reaction between I₂ and NO₃, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I₂, which results in the enhancement of more than 25% of nighttime ocean emissions of HOI + I₂ and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO₃ radical levels in the MBL and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation

Third revision of the global surface seawater dimethyl sulfide climatology (DMS-Rev3)

This is the final version. Available on open access from Copernicus Publications via the DOI in this recordCode and data availability: ​​​​​​​The data used for creating the climatology, along with the algorithm, can be found in the online repository: https://doi.org/10.17632/hyn62spny2.1 (Mahajan, 2021).This paper presents an updated estimation of the bottom-up global surface seawater dimethyl sulfide (DMS) climatology. This update, called DMS-Rev3, is the third of its kind and includes five significant changes from the last climatology, L11 (Lana et al., 2011), that was released about a decade ago. The first change is the inclusion of new observations that have become available over the last decade, creating a database of 873 539 observations leading to an ∼18-fold increase in raw data as compared to the last estimation. The second is significant improvements in data handling, processing, and filtering, to avoid biases due to different observation frequencies which result from different measurement techniques. Thirdly, we incorporate the dynamic seasonal changes observed in the geographic boundaries of the ocean biogeochemical provinces. The fourth change involves the refinement of the interpolation algorithm used to fill in the missing data. Lastly, an upgraded smoothing algorithm based on observed DMS variability length scales (VLS) helps to reproduce a more realistic distribution of the DMS concentration data. The results show that DMS-Rev3 estimates the global annual mean DMS concentration to be ∼2.26 nM (2.39 nM without a sea-ice mask), i.e., about 4 % lower than the previous bottom-up L11 climatology. However, significant regional differences of more than 100 % as compared to L11 are observed. The global sea-to-air flux of DMS is estimated at ∼27.1 TgS yr-1, which is about 4 % lower than L11, although, like the DMS distribution, large regional differences were observed. The largest changes are observed in high concentration regions such as the polar oceans, although oceanic regions that were under-sampled in the past also show large differences between revisions of the climatology. Finally, DMS-Rev3 reduces the previously observed patchiness in high productivity regions. Copyright

Protection from Experimental Cerebral Malaria with a Single Dose of Radiation-Attenuated, Blood-Stage Plasmodium berghei Parasites

BACKGROUND: Whole malaria parasites are highly effective in inducing immunity against malaria. Due to the limited success of subunit based vaccines in clinical studies, there has been a renewed interest in whole parasite-based malaria vaccines. Apart from attenuated sporozoites, there have also been efforts to use live asexual stage parasites as vaccine immunogens. METHODOLOGY AND RESULTS: We used radiation exposure to attenuate the highly virulent asexual blood stages of the murine malaria parasite P. berghei to a non-replicable, avirulent form. We tested the ability of the attenuated blood stage parasites to induce immunity to parasitemia and the symptoms of severe malaria disease. Depending on the mouse genetic background, a single high dose immunization without adjuvant protected mice from parasitemia and severe disease (CD1 mice) or from experimental cerebral malaria (ECM) (C57BL/6 mice). A low dose immunization did not protect against parasitemia or severe disease in either model after one or two immunizations. The protection from ECM was associated with a parasite specific antibody response and also with a lower level of splenic parasite-specific IFN-γ production, which is a mediator of ECM pathology in C57BL/6 mice. Surprisingly, there was no difference in the sequestration of CD8+ T cells and CD45+ CD11b+ macrophages in the brains of immunized, ECM-protected mice. CONCLUSIONS: This report further demonstrates the effectiveness of a whole parasite blood-stage vaccine in inducing immunity to malaria and explicitly demonstrates its effectiveness against ECM, the most pathogenic consequence of malaria infection. This experimental model will be important to explore the formulation of whole parasite blood-stage vaccines against malaria and to investigate the immune mechanisms that mediate protection against parasitemia and cerebral malaria

Induction of endogenous γ-globin gene expression with decoy oligonucleotide targeting Oct-1 transcription factor consensus sequence

Human β-globin disorders are relatively common genetic diseases cause by mutations in the β-globin gene. Increasing the expression of the γ-globin gene has great benefits in reducing complications associated with these diseases. The Oct-1 transcription factor is involved in the transcriptional regulation of the γ-globin gene. The human γ-globin genes (both Aγ and Gγ-globin genes) carry three Oct-1 transcription factor consensus sequences within their promoter regions. We have studied the possibility of inducing γ-globin gene expression using decoy oligonucleotides that target the Oct-1 transcription factor consensus sequence. A double-stranded 22 bp decoy oligonucleotide containing the Oct-1 consensus sequence was synthesized. The results obtained from our in vitro binding assay revealed a strong competitive binding of the decoy oligonucleotide for the Oct-1 transcription factor. When K562 human erythroleukemia cells were treated with the Oct-1 decoy oligonucleotide, significant increases in the level of the γ-globin mRNA were observed. The results of our western blots further demonstrated significant increases of the fetal hemoglobin (HbF, α2γ2) in the Oct-1 decoy oligonucleotide-treated K562 cells. The results of our immunoprecipitation (IP) studies revealed that the treatment of K562 cells with the Oct-1 decoy oligonucleotide significantly reduced the level of the endogenous γ-globin gene promoter region DNA co-precipitated with the Oct-1 transcription factor. These results suggest that the decoy oligonucleotide designed for the Oct-1 transcription factor consensus sequence could induce expression of the endogenous γ-globin gene through competitive binding of the Oct-1 transcription factor, resulting in activation of the γ-globin genes. Therefore, disrupting the bindings of the Oct-1 transcriptional factors with the decoy oligonucleotide provides a novel approach for inducing expression of the γ-globin genes. It also provides an innovative strategy for the treatment of many disease conditions, including sickle cell anemia and β-thalassemia

A Metasystem of Framework Model Organisms to Study Emergence of New Host-Microbe Adaptations

An unintended consequence of global industrialization and associated societal rearrangements is new interactions of microbes and potential hosts (especially mammals and plants), providing an opportunity for the rapid emergence of host-microbe adaptation and eventual establishment of new microbe-related diseases. We describe a new model system comprising the model plant Arabidopsis thaliana and several microbes, each representing different modes of interaction, to study such “maladaptations”. The model microbes include human and agricultural pathogens and microbes that are commonly considered innocuous. The system has a large knowledge base corresponding to each component organism and is amenable to high-throughput automation assisted perturbation screens for identifying components that modulate host-pathogen interactions. This would aid in the study of emergence and progression of host-microbe maladaptations in a controlled environment