Iodine Species Research Articles

Impact of iodide ions on the speciation of radiolytic transients in molten LiCl-KCl eutectic salt mixtures.

The fate of fission-product iodine is critical for the deployment of next generation molten salt reactor technologies, owing to its volatility and biological impacts if it were to be released into the environment. To date, little is known on how ionizing radiation fields influence the redox chemistry, speciation, and transport of iodine in high temperature molten salts. Here we employ picosecond electron pulse irradiation techniques to elucidate for the first time the impact of iodide ions (I-) on the speciation and chemical kinetics of the primary radiation-induced transient radicals generated in molten chloride salt mixtures (eS- and Cl2˙-) as a function of temperature (400-700 °C). In the presence of I- ions (≥ 1 wt% KI in LiCl-KCl eutectic), we find that the transient spectrum following the electron pulse is composed of at least three overlapping species: the eS- and the Cl2˙- and ICl˙- radical anions, for which a deconvoluted spectrum of the latter is reported here for the first time in molten salts. This new transient spectrum was consistent with gas phase density functional theory calculations. The lifetime of the eS- was unaffected by the addition of I- ions. The newly observed interhalogen radical anion, ICl˙-, exhibited a lifetime on the order of microseconds over the investigated temperature range. The associated chemical kinetics indicate that the predominate mechanism of ICl˙- decay is via reaction with the Cl2˙- radical anion. The iodine containing product of this reaction is expected to be ICl2-, which will have implications for the transport of fission-product iodine in MSR technologies.

Chemical species of cesium and iodine in condensed vaporized microparticles formed by melting nuclear fuel components with concrete materials.

In this study, we report chemical species of Cs and I in condensed vaporized particles (CVPs) produced by melting experiments using nuclear fuel components containing CsI with concrete. Analyses of CVPs by SEM with EDX showed the formation of many round particles containing Cs and I of diameters less than ∼20 μm. X-ray absorption near-edge-structure and SEM-EDX analyses showed two kinds of particles: one containing large amounts of Cs and I, suggesting the presence of CsI, and the other containing small amounts of Cs and I with large Si content. When CVSs were placed in contact with deionized water, most of the CsI from both particles was dissolved. In contrast, some fractions of Cs remained from the latter particles and possessed different chemical species from CsI. In addition, the remaining Cs was concomitantly present with Si, resembling chemical components in the highly radioactive cesium-rich microparticles (CsMPs) released by nuclear plant accidents into the surrounding environments. These results strongly suggest that Cs was incorporated in CVSs along with Si by melting nuclear fuel components to form sparingly-soluble CVMPs.

Iodide uptake by forest soils is principally related to the activity of extracellular oxidases.

129I is a nuclear fission decay product of concern because of its long half-life (16Ma) and propensity to bioaccumulate. Microorganisms impact iodine mobility in soil systems by promoting iodination (covalent binding) of soil organic matter through processes that are not fully understood. Here, we examined iodide uptake by soils collected at two depths (0-10 and 10-20cm) from 5 deciduous and coniferous forests in Japan and the United States. Autoclaved soils, and soils amended with an enzyme inhibitor (sodium azide) or an antibacterial agent (bronopol), bound significantly less 125I tracer (93%, 81%, 61% decrease, respectively) than the untreated control soils, confirming a microbial role in soil iodide uptake. Correlation analyses identified the strongest significant correlation between 125I uptake and three explanatory variables, actinobacteria soil biomass (p = 6.04E-04, 1.35E-02 for Kendall-Tau and regression analysis, respectively), soil nitrogen content (p = 4.86E-04, 4.24E-03), and soil oxidase enzyme activity at pH 7.0 using the substrate L-DOPA (p = 2.83E-03, 4.33E-04) and at pH 5.5 using the ABTS (p = 5.09E-03, 3.14E-03). Together, the results suggest that extracellular oxidases, primarily of bacterial origin, are the primary catalyst for soil iodination in aerobic, surface soils of deciduous and coniferous forests, and that soil N content may be indicative of the availability of binding sites for reactive iodine species.

Biogeochemical cycling of Cd, Mn, and Ce in the Eastern Tropical North Pacific oxygen‐deficient zone

AbstractOxygen‐deficient zones (ODZs) play an important role in the distribution and cycling of trace metals in the ocean, as important sources of metals including Fe and Mn, and also as possible sinks of chalcophile elements such as Cd. The Eastern Tropical North Pacific (ETNP) ODZ is one of the three largest ODZs worldwide. Here, we present results from two sectional surveys through the ETNP ODZ conducted in 2018, providing high‐resolution concentrations of several metals, along with complimentary measurements of nutrients and iodine speciation. We show that samples obtained from the ship's regular rosette are clean for Cd, Mn, Ni, and light rare earth elements, while uncontaminated Fe, Zn, Cu, and Pb samples cannot be obtained without a special trace‐metal clean sampling system. Our results did not show evidence of Cd sulfide precipitation, even within the most oxygen‐depleted water mass. High Mn and Ce concentrations and high Ce anomalies were observed in low‐oxygen seawater. These maxima were most pronounced in the upper water column below the oxycline, coincident with the secondary nitrite maxima and the lowest oxygen concentrations, in what is generally considered the most microbially active part of the water column. High Mn and Ce features were also coincident with maxima in excess iodine, a tracer of shelf sediment sources. Mn and Ce maxima were most prominent within the 13°C water mass, spanning a density horizon that enhances isopycnal transport from the shelf sediments, resulting in transport of Mn and Ce at least 2500 km offshore.

Sequential combination of pre-chlorination and powdered activated carbon adsorption on iodine removal and I-THMs control in drinking water

Combining pre-oxidation with activated carbon adsorption was explored as an ideal approach for removing iodine from water source to eliminate the formation of Iodinated trihalomethanes (I-THMs). Compared with permanganate and monochloramine, chlorine is more suitable as pre-oxidant to obtain higher active iodine species (HOI/I2). Active iodine species adsorption using both powdered activated carbon (PAC) and granular activated carbon (GAC) can be well fitted the pseudo-second-order kinetic model indicating that chemical adsorption was the dominant mechanism for HOI/I2 adsorption. The average pore size of activated carbons was the most strongly correlated with the adsorption capacity (R2 > 0.98), followed by methylene blue (R2 > 0.76), pore volume (R2 > 0.70) and iodine number (R2 > 0.67). Moreover, three models, including intraparticle diffusion, Byod kinetic, and diffusion-chemisorption were used to illustrate the mechanisms of HOI/I2 adsorption. Chemical adsorption was the dominant mechanism for HOI/I2 adsorption. In summary, at the molar ratio of [NaClO] and [I−] as 1.2, pre-chloriantion time of 5 min, subsequently dosage of 15 mg/L of PAC E with 20 min adsorption can remove 79.8% iodine. In addition, the combined process can eliminate 61%–87.2% of I-THMs in the subsequent chlor(am)ination. The results indicate that pre-chlorination combined with PAC can effectively removed HOI/I2 and attenuate I-THMs formation in the subsequent disinfection process.

Chemical characterization of organic compounds involved in iodine-initiated new particle formation from coastal macroalgal emission

Abstract. Iodine-initiated new particle formation (I-NPF) has long been recognized in coastal hotspot regions. However, no prior work has studied the exact chemical composition of organic compounds and their role in coastal I-NPF. Here we present an important complementary study to the ongoing laboratory and field research on iodine nucleation in the coastal atmosphere. Oxidation and NPF experiments with vapor emissions from real-world coastal macroalgae were simulated in a bag reactor. On the basis of comprehensive mass spectrometry measurements, we reported for the first time a variety of volatile precursors and their oxidation products in gas and particle phases in such a highly complex system. Organic compounds overwhelmingly dominated over iodine in the new particle growth initiated by iodine species. The identity and transformation mechanisms of organic compounds were proposed in this study to provide a more complete story of coastal NPF from low-tide macroalgal emission.

Environmental iodine speciation quantification in seawater and snow using ion exchange chromatography and UV spectrophotometric detection

The behaviour and distribution of iodine in the environment are of significant interest in a range of scientific disciplines, from health, as iodine is an essential element for humans and animals, to climate and air quality, to geochemistry. Aquatic environments are the reservoir for iodine, where it exists in low concentrations as iodide, iodate and dissolved organic iodine and in which it undergoes redox reactions. The current measurement techniques for iodine species are typically time-consuming, subject to relatively poor precision and require specialist instrumentation including those that require mercury as an electrode. We present a new method for measuring iodine species, that is tailored towards lower dissolved organic carbon waters, such as seawater, rainwater and snow, using ion exchange chromatography (IC) with direct ultra-violet spectrophotometric detection of iodide and without the need for sample pre-concentration. Simple chemical amendments to the sample allow for the quantification of both iodate and dissolved organic iodine in addition to iodide. The developed IC method, which takes 16 min, was applied to contrasting samples that encompass a wide range of aqueous environments, from Arctic sea-ice snow (low concentrations) to coastal seawater (complex sample matrix). Linear calibrations are demonstrated for all matrices, using gravimetrically prepared potassium iodide standards. The detection limit for the iodide ion is 0.12 nM based on the standard deviation of the blank, while sample reproducibility is typically <2% at >8 nM and ∼4% at <8 nM. Since there is no environmental certified reference material for iodine species, the measurements made on seawater samples using this IC method were compared to those obtained using established analytical techniques; iodide voltammetry and iodate spectrophotometry. We calculated recoveries of 102 ± 16% (n = 107) for iodide and 116 ± 9% (n = 103) for iodate, the latter difference may be due to an underestimation of iodate by the spectrophotometric method. We further compared a chemical oxidation and reduction of the sample to an ultra-violet digestion to establish the total dissolved iodine content, the average recovery following chemical amendments was 98 ± 4% (n = 92). The new method represents a simple, efficient, green, precise and sensitive method for measuring dissolved speciated iodine in complex matrices.

Degradation of iopamidol in the permanganate/sulfite process: Evolution of iodine species and effect on the subsequent formation of disinfection by-products

Permanganate/sulfite (Mn(VII)/S(IV)) process is a promising pre-oxidation technology for sequestering the emerging organic contaminants in drinking water treatment plant. Iopamidol (IPM), a representative of iodinated X-ray contrast media, has been widely detected in water sources and has the risk of forming iodinated disinfection byproducts (I-DBPs) in water treatment system. In this study, we investigated the evolution of iodine species during the IPM degradation by the Mn(VII)/S(IV) process and its effect on the subsequent formation of I-DBPs during chlorination at pH 7.0 and 8.0. IPM could be effectively degraded in the Mn(VII)/S(IV) process at environmentally relevant pH (pH 7.0 and 8.0). The results of quenching and competitive oxidation kinetic experiments revealed that SO4·– was the major reactive oxidizing species contributing to the degradation of IPM whereas the contributions of HO· and reactive manganese species were negligible in the Mn(VII)/S(IV) process. I– and IO3– were generated while no HOI was detected during the degradation of IPM in the Mn(VII)/S(IV) process. The effects of IPM oxidation by Mn(VII)/S(IV) on the subsequent formation of chlorinated disinfection by-products (Cl-DBPs) during chlorination were related to the category of Cl-DBPs. The pre-oxidation of IPM by Mn(VII)/S(IV) resulted in the generation of I-DBPs during the disinfection process although no I-DBPs were detected if no pre-oxidation was applied. The finding of this study suggested that attention should be paid to the toxicity of DBPs when water containing iodinated organic contaminants is treated by Mn(VII)/S(IV) process or other pre-oxidation technologies.

A 3D microfluidic paper-based analytical device with smartphone-assisted colorimetric detection for iodine speciation in seaweed samples

The present work reports on the development of a 3D origami microfluidic paper-based analytical device (3D µPAD) for the determination of iodide and iodate in edible seaweeds by smartphone-based colorimetric detection. In addition, a methacrylate holder was designed and fabricated to enhance interlayer contact in 3D µPADs, obtaining excellent sensitivity and precision, also allowing real-time monitoring in a straightforward and expeditious way. The reported assay, based on the formation of a blue colored triiodide-starch complex at the detection areas of the 3D µPAD, represents an affordable, fast and greener alternative for the simultaneous determination of inorganic iodine species. Under optimal conditions, the proposed method showed limits of detection and quantification of 9.8 and 32.7 µM for I- and 0.6 and 1.8 µM for IO3-, respectively. The repeatability, expressed as relative standard deviation, was 1.7% and 3.3% for I- and IO3-, respectively. The proposed 3D µPAD was applied to the determination of iodine species in extracts of edible seaweeds and related food additives, showing satisfactory recoveries (90–109%).

Surface iodine modification inducing robust CEI enables ultra-stable Li-Se batteries

Lithium-selenium batteries (LSeBs) have attracted increasing attention due to their excellent electronic conductivity and high theoretical specific capacity. However, there are still difficult problems such as low utilization rate and fast capacity decay in the actual application process. Herein, a surface iodine modified three-dimensional (3D) nano hollow carbon fiber (I-NHCF) network is designed and synthesized as Se host (Se@I-NHCF) for highly stable LSeBs. The surface iodine species induce the formation of robust cathode electrolyte interface (CEI), thus preventing the transformation of amorphous selenium to low-activity crystalline selenium and enabling stable electrochemical performance. Moreover, the surface iodine species promote rapid charge transfer, enhancing the chemical reaction kinetics and improving the utilization of the active Se species. As a result, the Se@I-NHCF cathode exhibits superior specific capacity of 581.8 mAh g−1 with a high stability (0.0054% capacity decay per cycle) after 500 cycles at 1C, and an excellent rate performance of 567.6 mAh g−1 at 2C. This work addresses the problem of rapid capacity decay by the formation of uniform and robust CEI to conserve highly reactive amorphous Se species, improve Se utilization, and achieve ultra-stable Li-Se batteries with high energy and long cycle life.

Deficiency and excess of groundwater iodine and their health associations

More than two billion people worldwide have suffered thyroid disorders from either iodine deficiency or excess. By creating the national map of groundwater iodine throughout China, we reveal the spatial responses of diverse health risks to iodine in continental groundwater. Greater non-carcinogenic risks relevant to lower iodine more likely occur in the areas of higher altitude, while those associated with high groundwater iodine are concentrated in the areas suffered from transgressions enhanced by land over-use and intensive anthropogenic overexploitation. The potential roles of groundwater iodine species are also explored: iodide might be associated with subclinical hypothyroidism particularly in higher iodine regions, whereas iodate impacts on thyroid risks in presence of universal salt iodization exhibit high uncertainties in lower iodine regions. This implies that accurate iodine supply depending on spatial heterogeneity and dietary iodine structure optimization are highly needed to mitigate thyroid risks in iodine-deficient and -excess areas globally.

A Crosslinked Ionic Organic Framework for Efficient Iodine and Iodide Remediation in Water.

Iodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (≈5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer-directed synthesis of a single-crystalline ionic hydrogen-bonded crosslinked organic framework (HC OF-7). HC OF-7 removes iodine and iodide species in water efficiently through halogen bonding and anion exchange, reducing the total iodine concentration to 0.22 ppm at room temperature. Packed HC OF-7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L g-1 ). The high iodine/iodide removal benchmarks recorded under practical conditions make HC OF-7 a promising adsorbent for water treatment.

A Crosslinked Ionic Organic Framework for Efficient Iodine and Iodide Remediation in Water

AbstractIodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (≈5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer‐directed synthesis of a single‐crystalline ionic hydrogen‐bonded crosslinked organic framework (HCOF‐7). HCOF‐7 removes iodine and iodide species in water efficiently through halogen bonding and anion exchange, reducing the total iodine concentration to 0.22 ppm at room temperature. Packed HCOF‐7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L g−1). The high iodine/iodide removal benchmarks recorded under practical conditions make HCOF‐7 a promising adsorbent for water treatment.

Physicochemical Confinement Effect Enables High-Performing Zinc-Iodine Batteries.

Zinc-iodine batteries are promising energy storage devices with the unique features of aqueous electrolytes and safer zinc. However, their performances are still limited by the polyiodide shuttle and the unclear redox mechanism of iodine species. Herein, a single iron atom was embedded in porous carbon with the atomic bridging structure of metal-nitrogen-carbon to not only enhance the confinement effect but also invoke the electrocatalytic redox conversion of iodine, thereby enabling the large capacity and good cycling stability of the zinc-iodine battery. In addition to the physical trapping effect of porous carbon with good electronic conductivity, the in situ experimental characterization and theoretical calculation reveal that the metal-nitrogen-carbon bridging structure modulates the electronic properties of carbon and adjusts the intrinsic activity for the reversible conversion of iodine via the thermodynamically favorable pathway. This work demonstrates that the physicochemical confinement effect can be invoked by the rational anchoring of a single metal atom with nitrogen in a porous carbon matrix to enhance the electrocatalytic redox conversion of iodine, which is crucial to fabricating high-performing zinc-iodine batteries and beyond by applying the fundamental principles.

Emerging Concepts in Iodine Transfer Polymerization

AbstractControlled radical polymerization corresponds to variety of synthetic strategies that aim the generation of precise macromolecular architectures. Iodine transfer polymerization (ITP) is one of the oldest methods to conduct controlled radical polymerization; however, it seems to have lost visibility compared to other popular techniques. It relies on utilization of iodine species in reversible deactivation kinetics, and it has some significant advantages compared to other methods. Its simplicity, minimized toxicity, metal‐free nature, no coloring on final product, and ease of purification provide widespread applicability, even in industry. In this perspective, the basics of ITP are re‐introduced, and emerging technologies (heterophase polymerization, photoinitiation, and sustainability) in ITP are discussed.

Electrochemically Induced Synthesis of Imidazoles from Vinyl Azides and Benzyl Amines.

An electrochemically induced synthesis of imidazoles from vinyl azides and benzyl amines was developed. A wide range of imidazoles were obtained, with yields of 30 to 64%. The discovered transformation is a multistep process whose main steps include the generation of electrophilic iodine species, 2H-azirine formation from the vinyl azide, followed by its reactions with benzyl amine and with imine generated from benzyl amine. The cyclization and aromatization of the obtained intermediate lead to the target imidazole. The synthesis proceeds under constant current conditions in an undivided cell. Despite possible cathodic reduction of various unsaturated intermediates with C=N bonds, the efficient electrochemically induced synthesis of imidazoles was carried out.

Electrocatalytic Synthesis of Substituted Pyrazoles via Hypervalent Iodine Mediated Intramolecular C−N Coupling

AbstractThe electrochemical intramolecular cross‐dehydrogenative C(sp2)−H/N−H coupling of α,β‐unsaturated hydrazones resulting in substituted pyrazoles has been discovered. The process is catalyzed by hypervalent iodine species generated in situ through anodic oxidation of aryl iodide in fluorinated alcohol media. The formation of hypervalent iodine compound and its key role in the construction of a new C−N bond was confirmed with CV and NMR experiments. A wide range of substituted pyrazoles were obtained in yields ranging from 46% to 88%.magnified image

Iodine and Carbonate Species Monitoring in Molten NaOH-KOH Eutectic Scrubber via Dual-Phase In Situ Raman Spectroscopy.

Molten hydroxide scrubbing of off-gas vapors is a potential process to improve safety during the operation of generation IV molten salt nuclear reactors (MSRs). MSRs produce off-gases that can be vented by the reactor core and treated via off-gas scrubbers. Molten hydroxide scrubbers focus on capturing volatile iodine radionuclides, and they can also be used to capture aerosols and particulates and to neutralize acidic species. The performance of these scrubbers depends on the chemical interactions of the scrubbing medium with the off-gas species. Knowledge of the concentration and speciation of scrubbed or target species, as well as process and environmental interferents, can enable advanced operation of MSR off-gas treatment systems. Optical online monitoring is an excellent technology to provide this information in real time, while limiting the need for operators to interact with radioactive samples through hands-on interrogation. Raman spectroscopy can provide crucial chemical information on the state of the molten eutectic during treatment in the molten phase, as well as the gas phase. In this work, Raman spectroscopy is used to detect iodine species, specifically iodate, in the molten phase of a NaOH-KOH eutectic and to construct a calibration curve of the Raman signal of those species. Additionally, a carbonate interferent is followed from the gas phase to the liquid phase as a basis for reaching a Raman-aided mass balance of the molten hydroxide eutectic scrubber system.

Microfabrics and organominerals as indicator of microbial dolomite in deep time: An example from the Mesoproterozoic of North China

Both laboratory experiment and modern environment studies show that primary dolomite can precipitate at low temperature (≤60 ℃) only when microbes were involved. Vast dolostones in mid-Proterozoic have long been suspected to be the results of microbial mediation, but direct evidence is rare. To reveal their origin, an integrated study was conducted on the Mesoproterozoic Wumishan Formation (∼1.48 Ga) of North China using multiple techniques. The results show that the Wumishan dolostone contains abundant multiscale organominerals that are closely associated with fossilized remnants of extracellular polymeric substances (EPS) and putative bacteria fossils. These microfabrics are strikingly similar to those in dolomite precipitates produced in laboratory culture and modern sabkha environment, suggesting microbial origin. Nanoglobules (60–200 nm) preferentially attach to fossilized EPS filaments, and tend to merge into polyhedrons (3–8 μm) that in turn coalesce into microspheres (20–50 μm). EDS analysis revealed a successive decrease in carbon from nanoglobules to microspheres with the increases of Mg and Ca contents, implying an increased mineralization. Nanoglobules may have derived from EPS degradation during nucleation, and served as seeds for subsequent growth of carbonate polyhedrons. Microsphere, as a basic building block in dolostone, can transform into rhombohedral crystal via neomorphogenesis during early diagenesis. Petrographic and XRD analyses show that the dolostone is dominated by ordered dolomite and was largely formed in peritidal environment with thriving microbial community. Geochemical analyses of iodine species, redox sensitive elements, Ce anomalies, and C–O isotopes in the Wumishan dolostone suggested an environment predominated by anoxic to suboxic conditions, with low P but high Si contents in seawater.Our study offered direct evidence of microbial origin for the Mesoproterozoic dolostone, providing new insights into the “Dolomite Problem”. The massive development of microbial dolostone in Mesoproterozoic points to a specific ocean chemistry, where low oxygen and active bacterial metabolisms may have played crucial roles in precipitating dolomite. The co-existence of abundant microbial components and multiscale organominerals may be taken as textural evidence for microbial dolomites and signatures of life-environment interactions in deep time.

Iodobenzene-catalyzed photochemical heteroarylation of alcohols by rupture of inert C–H and C–C bonds

A Minisci-type reaction catalyzed by iodobenzene is disclosed here for the first time. The heteroarylation of unprotected aliphatic alcohols proceeds via alkoxy radical-induced homolytic cleavage of C–H and C–C bonds under photochemical conditions. The use of m-CPBA as the oxidant allows the oxidation of iodobenzene to a hypervalent iodine species, driving the catalytic cycle. The method features mild reaction conditions, broad scope of heteroarenes and alcohols, and scaled up preparations. This approach provides a notable supplement to iodobenzene-catalyzed ionic reactions, and opens up a new avenue for its application in radical chemistry.