Immobilization of Iodate and Iodide using Iron Oxides through Sorption and Co-precipitation at Hanford Site

NASA Astrophysics Data System (ADS)

Wang, G.; Qafoku, N. P.; Truex, M. J.; Strickland, C. E.; Freedman, V. L.

2017-12-01

Isotopes of iodine were generated during plutonium production at the U.S. Department of Energy (DOE) Hanford Site. The long half-life 129I generated during reactor operations has been released into the subsurface, resulting in several large plumes at the Hanford subsurface. We studied the interaction of iodate (IO3-) and iodide (I-) with Fe oxides. A series of batch experiments were conducted to investigate adsorption and co-precipitation of iodine species in the presence of a variety of Fe oxides, such as ferrihydrite, goethite, hematite and magnetite. In the sorption experiments, each Fe oxide was added to an artificial groundwater containing either iodate or iodide, and reacted at room temperature. The sorption batch experiments for each mineral were conducted at varied initial iodate or iodide concentrations under 3 different pH conditions (pH 5, 7, and 9). In the co-precipitation batch experiments, the initial Fe-mineral-forming solutions were prepared in artificial groundwater containing iodate or iodide. Our results indicate that both sorption and co-precipitation are viable mechanisms of the attenuation of the liquid phase iodine. Species Fe oxides could serve as hosts of iodate and iodide that are present at the Hanford subsurface.

Determination of iodide, iodate and organo-iodine in waters with a new total organic iodine measurement approach.

PubMed

Gong, Tingting; Zhang, Xiangru

2013-11-01

The dissolved iodine species that dominate aquatic systems are iodide, iodate and organo-iodine. These species may undergo transformation to one another and thus affect the formation of iodinated disinfection byproducts during disinfection of drinking waters or wastewater effluents. In this study, a fast, sensitive and accurate method for determining these iodine species in waters was developed by derivatizing iodide and iodate to organic iodine and measuring organic iodine with a total organic iodine (TOI) measurement approach. Within this method, organo-iodine was determined directly by TOI measurement; iodide was oxidized by monochloramine to hypoiodous acid and then hypoiodous acid reacted with phenol to form organic iodine, which was determined by TOI measurement; iodate was reduced by ascorbic acid to iodide and then determined as iodide. The quantitation limit of organo-iodine or sum of organo-iodine and iodide or sum of organo-iodine, iodide and iodate was 5 μg/L as I for a 40 mL water sample (or 2.5 μg/L as I for an 80 mL water sample, or 1.25 μg/L as I for a 160 mL water sample). This method was successfully applied to the determination of iodide, iodate and organo-iodine in a variety of water samples, including tap water, seawater, urine and wastewater. The recoveries of iodide, iodate and organo-iodine were 91-109%, 90-108% and 91-108%, respectively. The concentrations and distributions of iodine species in different water samples were obtained and compared. Copyright © 2013 Elsevier Ltd. All rights reserved.

Iodine uptake by spinach (Spinacia oleracea L.) plants grown in solution culture: effects of iodine species and solution concentrations.

PubMed

Zhu, Y-G; Huang, Y-Z; Hu, Y; Liu, Y-X

2003-04-01

A hydroponic experiment was carried out to investigate the effects of iodine species and solution concentrations on iodine uptake by spinach (Spinacia oleracea L.). Five iodine concentrations (0, 1, 10, 50 and 100 microM) for iodate (IO(3)(-)) and iodide (I(-)) were used. Results show that higher concentrations of I(-) (> or =10 microM) had some detrimental effect on plant growth, while IO(3)(-) had little effect on the biomass production of spinach plants. Increases in iodine concentration in the growth solution significantly enhanced I concentrations in plant tissues. The detrimental effect of I(-) on plant growth was probably due to the excessively high accumulation of I in plant tissues. The solution-to-spinach leaf transfer factors (TF(leaf), fresh weight basis) for plants treated with iodide were between 14.2 and 20.7 at different solution concentrations of iodide; TF(leaf) for plants treated with iodate decreased gradually from 23.7 to 2.2 with increasing solution concentrations of iodate. The distribution coefficients (DCs) of I between leaves and roots were constantly higher for plants treated with iodate than those treated with iodide. DCs for plants treated with iodide increased with increasing solution concentrations of iodide, while DCs for plants treated with iodate (around 5.5) were similar across the range of solution concentrations of iodate used in this experiment. The implications of iodine accumulation in leafy vegetables in human iodine nutrition are also discussed. Copyright 2002 Elsevier Science Ltd.

Iodine speciation in coastal and inland bathing waters and seaweeds extracts using a sequential injection standard addition flow-batch method.

PubMed

Santos, Inês C; Mesquita, Raquel B R; Bordalo, Adriano A; Rangel, António O S S

2015-02-01

The present work describes the development of a sequential injection standard addition method for iodine speciation in bathing waters and seaweeds extracts without prior sample treatment. Iodine speciation was obtained by assessing the iodide and iodate content, the two inorganic forms of iodine in waters. For the determination of iodide, an iodide ion selective electrode (ISE) was used. The indirect determination of iodate was based on the spectrophotometric determination of nitrite (Griess reaction). For the iodate measurement, a mixing chamber was employed (flow batch approach) to explore the inherent efficient mixing, essential for the indirect determination of iodate. The application of the standard addition method enabled detection limits of 0.14 µM for iodide and 0.02 µM for iodate, together with the direct introduction of the target water samples, coastal and inland bathing waters. The results obtained were in agreement with those obtained by ICP-MS and a colorimetric reference procedure. Recovery tests also confirmed the accuracy of the developed method which was effectively applied to bathing waters and seaweed extracts. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of Iodate in Food, Environmental, and Biological Samples after Solid-Phase Extraction with Ni-Al-Zr Ternary Layered Double Hydroxide as a Nanosorbent

PubMed Central

Abdolmohammad-Zadeh, Hossein; Tavarid, Keyvan; Talleb, Zeynab

2012-01-01

Nanostructured nickel-aluminum-zirconium ternary layered double hydroxide was successfully applied as a solid-phase extraction sorbent for the separation and pre-concentration of trace levels of iodate in food, environmental and biological samples. An indirect method was used for monitoring of the extracted iodate ions. The method is based on the reaction of the iodate with iodide in acidic solution to produce iodine, which can be spectrophotometrically monitored at 352 nm. The absorbance is directly proportional to the concentration of iodate in the sample. The effect of several parameters such as pH, sample flow rate, amount of nanosorbent, elution conditions, sample volume, and coexisting ions on the recovery was investigated. In the optimum experimental conditions, the limit of detection (3s) and enrichment factor were 0.12 μg mL−1 and 20, respectively. The calibration graph using the preconcentration system was linear in the range of 0.2–2.8 μg mL−1 with a correlation coefficient of 0.998. In order to validate the presented method, a certified reference material, NIST SRM 1549, was also analyzed. PMID:22619590

Effect of Co-Contaminants Uranium and Nitrate on Iodine Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Lee, Brady D.; Lawter, Amanda R.

The objective of this study is to evaluate the significance of co-contaminants on the migration and transformation of iodine species in the Hanford subsurface environment. These impacts are relevant because remedies that target individual contaminants like iodine, may not only impact the fate and transport of other contaminants in the subsurface, but also inhibit the effectiveness of a targeted remedy. For example, iodine (as iodate) co-precipitates with calcite, and has been identified as a potential remedy because it immobilizes iodine. Since uranium also co-precipitates with calcite in field sediments, the presence of uranium may also inhibit iodine co-precipitation. Another potentiallymore » significant impact from co-existing contaminants is iodine and nitrate. The presence of nitrate has been shown to promote biogeochemical reduction of iodate to iodide, thereby increasing iodine species subsurface mobility (as iodide exhibits less sorption). Hence, this study reports on both laboratory batch and column experiments that investigated a) the change in iodate uptake mass and rate of uptake into precipitating calcite due to the presence of differing amounts of uranium, b) the amount of change of the iodate bio-reduction rate due to the presence of differing nitrate concentrations, and c) whether nitrite can reduce iodate in the presence of microbes and/or minerals acting as catalysts.« less

Lack of genotoxicity of potassium iodate in the alkaline comet assay and in the cytokinesis-block micronucleus test. Comparison to potassium bromate.

PubMed

Poul, J M; Huet, S; Godard, T; Sanders, P

2004-02-01

Iodine could be added to the diet of human population in the form of iodide or iodate but iodate had not been adequately tested for genotoxicity and carcinogenicity. In the present study, genotoxic effects of potassium iodate were evaluated in vitro using the alkaline comet assay and the cytokinesis-block micronucleus assay on CHO cells and compared to halogenate salt analogues potassium bromate and chlorate and also to their respective reduced forms (potassium iodide, bromide and chloride). The results showed that the comet assay failed to detect the presence of DNA damage after a treatment of cells by potassium iodate for concentrations up to 10 mM. This absence of primary DNA damage was confirmed in the cytokinesis-block micronucleus assay. In the same way, results showed that potassium chlorate as well as potassium iodide, bromide and chloride did not induced DNA damage in the alkaline comet assay for doses up to 10 mM. By contrast, potassium bromate exposure led to an increase in both DNA damage and frequency of micronucleated cells. The repair of bromate-induced DNA damage was incomplete 24 h after the end of treatment. These results seem to indicate that potassium bromate would induce DNA damage by several mechanisms besides oxidative stress.

Oxidation of iodide and iodine on birnessite (delta-MnO2) in the pH range 4-8.

PubMed

Allard, Sébastien; von Gunten, Urs; Sahli, Elisabeth; Nicolau, Rudy; Gallard, Hervé

2009-08-01

The oxidation of iodide by synthetic birnessite (delta-MnO(2)) was studied in perchlorate media in the pH range 4-8. Iodine (I(2)) was detected as an oxidation product that was subsequently further oxidized to iodate (IO(3)(-)). The third order rate constants, second order on iodide and first order on manganese oxide, determined by extraction of iodine in benzene decreased with increasing pH (6.3-7.5) from 1790 to 3.1M(-2) s(-1). Both iodine and iodate were found to adsorb significantly on birnessite with an adsorption capacity of 12.7 microM/g for iodate at pH 5.7. The rate of iodine oxidation by birnessite decreased with increasing ionic strength, which resulted in a lower rate of iodate formation. The production of iodine in iodide-containing waters in contact with manganese oxides may result in the formation of undesired iodinated organic compounds (taste and odor, toxicity) in natural and technical systems. The probability of the formation of such compounds is highest in the pH range 5-7.5. For pH <5 iodine is quickly oxidized to iodate, a non-toxic and stable sink for iodine. At pH >7.5, iodide is not oxidized to a significant extent.

Mercuric iodate precipitation from radioiodine-containing off-gas scrubber solution

DOEpatents

Partridge, Jerry A.; Bosuego, Gail P.

1982-01-01

Mercuric nitrate-nitric acid scrub solutions containing radioiodine may be reduced in volume without excessive loss of volatile iodine. The use of concentrated nitric acid during an evaporation process oxidizes the mercury-iodide complex to a less volatile mercuric iodate precipitate.

Technetium and iodine aqueous species immobilization and transformations in the presence of strong reductants and calcite-forming solutions: Remedial action implications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawter, Amanda R.; Garcia, Whitney L.; Kukkadapu, Ravi K.

At the Hanford Site in southeastern Washington State, radionuclide (Tc-99/I-129) laden liquid wastes have been discharged to ground, resulting in vadose zone contamination, which provides a continuous source of these contaminants to groundwater. The presence of multiple contaminants increases the complexity of finding viable remediation technologies to sequester vadose zone contaminants in situ and protect groundwater. Although previous studies have shown the efficiency of zero valent iron (ZVI) and sulfur modified iron (SMI) in reducing mobile Tc(VII) to immobile Tc(IV) and iodate incorporation into calcite, the coupled effects from simultaneously using these remedial technologies have not been previously studied. Inmore » this first-of-a-kind laboratory study, we used two efficient reductants (i.e., ZVI and SMI) and calcite-forming solutions to simultaneously remove aqueous Tc(VII) and iodate via reduction and incorporation, respectively. The results confirmed that Tc(VII) was rapidly removed from the aqueous phase via reduction to Tc(IV). ZVI removed Tc(VII) faster than SMI, although both had removed the same amount by the end of the experiments. Most of the aqueous iodate was rapidly transformed to iodide, and therefore was not incorporated into calcite, but instead remained in the aqueous phase. The iodate reduction to iodide was much faster than iodate incorporation into calcite, suggesting that this remedial pathway is not efficient in removing aqueous iodate when strong reductants are present. Other experiments suggested that iodate removal via calcite precipitation should occur first and then reductants should be added for Tc(VII) removal. Although ZVI can negatively impact microbial populations and thereby inhibit natural attenuation mechanisms, only changes in the makeup of the microbial community were observed. However, these changes in the microbial community may have an impact on remediation efforts in the long term that could not be seen in a short-term study. The results underscore the importance of identifying interactions between natural attenuation pathways and remediation technologies that only target individual contaminants.« less

A micro-flow-batch analyzer with solenoid micro-pumps for the photometric determination of iodate in table salt.

PubMed

Lima, Marcelo B; Barreto, Inakã S; Andrade, Stéfani Iury E; Almeida, Luciano F; Araújo, Mário C U

2012-10-15

In this study, a micro-flow-batch analyzer (μFBA) with solenoid micro-pumps for the photometric determination of iodate in table salt is described. The method is based on the reaction of iodate with iodide to form molecular iodine followed by the reaction with N,N-diethyl-p-phenylenediamine (DPD). The analytical signal was measured at 520 nm using a green LED integrated into the μFBA built in the urethane-acrylate resin. The analytical curve for iodate was linear in the range of 0.01-10.0 mg L(-1) with a correlation coefficient of 0.997. The limit of detection and relative standard deviation were estimated at 0.004 mg L(-1) and<1.5% (n=3), respectively. The accuracy was assessed through recovery test (97.6-103.5%) and independent analysis by a conventional titrimetric method. Comparing this technique with the conventional method, no statistically significant differences were observed when applying the paired t-test at a 95% confidence level. The proposed microsystem using solenoid micro-pumps presented satisfactory robustness and high sampling rate (170 h(-1)), with a low reagents consumption and a low cost to build the device. The proposed microsystem is a new alternative for automatic determination of iodate in table salt, comparing satisfactory to the recently flow system. Copyright © 2012 Elsevier B.V. All rights reserved.

URANOUS IODATE AS A CARRIER FOR PLUTONIUM

DOEpatents

Miller, D.R.; Seaborg, G.T.; Thompson, S.G.

1959-12-15

A process is described for precipitating plutonium on a uranous iodate carrier from an aqueous acid solution conA plutonium solution more concentrated than the original solution can then be obtained by oxidizing the uranium to the hexavalent state and dissolving the precipitate, after separating the latter from the original solution, by means of warm nitric acid.

Chemical transformation of iodate(IO3-) and nitrite(NO2-) in frozen solution and its environmental implications.

NASA Astrophysics Data System (ADS)

Kim, Kitae

2017-04-01

Ice is ubiquitous on earth and involved in various chemical reactions in the environment. Most chemical reactions are slowed down when temperature decreases according to Arrhenius equation. However, several chemical processes can be enhanced in frozen state. Reactive halogen species play important roles in the global environment. In particular, the presence of gaseous halogens in the polar and marine boundary layers is of great interest because these highly reactive species can affect ozone and mercury depletion events, oxidizing capacity, and DMS(dimethylsulfide) oxidation to form cloud-condensation nuclei. Among halogen compounds, the sources and emission mechanisms of inorganic iodine species in the polar region remain unclear. Iodide(I-) and iodate(IO3-) are the most dominant iodine species in nature and their chemical transformation or I-/IO3- ratio in frozen state remains poorly understood. Recent study shows that the production of active iodine compounds from frozen iodate salts during photochemical reaction. In previous study, nitrite(NO2-) oxidation to nitrate(NO3-), which is very slow reaction in aqueous solution, was significantly (105 times) accelerated in frozen state. The enhanced proton and oxygen concentration within ice grain boundaries are suspected that the enhanced oxidation of nitrite by freezing. Here we investigate chemical transformation of iodate/nitrite mixture in ice. The results show that the chemical reaction between iodate and nitrite in ice can potentially provide a new pathway for the source of reactive iodine species to the polar atmosphere. The detailed experimental conditions and mechanism will be discussed in the presentation.

Iodine stability and sensory quality of fermented fish and fish sauce produced with the use of iodated salt.

PubMed

Chanthilath, Boualapha; Chavasit, Visith; Chareonkiatkul, Somsri; Judprasong, Kunchit

2009-06-01

Universal salt iodization promotes the use of iodated salt for producing industrial food products, although it might affect product quality and iodine stability. To assess iodine loss during fermentation of fermented fish and fish sauces produced by using iodated salt and the effect on product sensory quality. Fermented fish and fish sauces were produced with iodated rock and grain sea salts (approximately 30 ppm iodine). Fermented fish was prepared from freshwater fish mixed with salt and rice bran and fermented for 6 months at room temperature. Fish sauces were prepared by mixing anchovy with salt and fermenting either exposed to sunlight or in the shade for 12 months. Residual iodine was determined with a spectrophotometer at day 0 and months 1, 3, and 6 for fermented fish and day 0 and months 3, 6, and 12 for fish sauces. After fermentation, the products were tested for sensory acceptability by Laotian and Thai panelists (approximately 50 in each panel) after they were cooked and served in the traditional manner. After fermentation, the level of residual iodine was 7.61 ppm (16% loss) infermented fish, 5.57 ppm (55% loss) in fish sauce prepared with exposure to sunlight, and 9.52 ppm (13% loss) in fish sauce prepared in the shade. Sensory qualities of the products that were produced from fortified and unfortified salts as well as dishes prepared from these products were not significantly different (p > 0.05). It is feasible to produce fermented fish and fish sauces with iodated salt and maintain acceptable iodine levels.

Uptake mechanism for iodine species to black carbon.

PubMed

Choung, Sungwook; Um, Wooyong; Kim, Minkyung; Kim, Min-Gyu

2013-09-17

Natural organic matter (NOM) plays an important role in determining the fate and transport of iodine species such as iodide (I(-)) and iodate (IO3(-)) in groundwater system. Although NOM exists as diverse forms in environments, prior iodine studies have mainly focused on uptake processes of iodide and iodate to humic materials. This study was conducted to determine the iodide and iodate uptake potential for a particulate NOM (i.e., black carbon [BC]). A laboratory-produced BC and commercial humic acid were used for batch experiments to compare their iodine uptake properties. The BC exhibited >100 times greater uptake capability for iodide than iodate at low pH of ~3, while iodide uptake was negligible for the humic acid. The uptake properties of both solids strongly depend on the initial iodine aqueous concentrations. After uptake reaction of iodide to the BC, X-ray absorption fine structure spectroscopy results indicated that the iodide was converted to electrophilic species, and iodine was covalently bound to carbon atom in polycyclic aromatic hydrocarbons present in the BC. The computed distribution coefficients (i.e., Kd values) suggest that the BC materials retard significantly the transport of iodide at low pH in environmental systems containing even a small amount of BC.

Separation of iodine from mercury containing scrubbing solutions

DOEpatents

Burger, Leland L.; Scheele, Randall D.

1979-01-01

Radioactive iodines can be recovered from a nitric acid scrub solution containing mercuric nitrate by passing a current through the scrub solution to react the iodine with the mercuric nitrate to form mercuric iodate which precipitates out. The mercuric iodate can then be reacted to recover the radioiodine for further processing into a form suitable for long-term storage and to recover the mercury for recycling.

The biogeochemical effect of seaweeds upon close-to natural concentrations of dissolved iodate and iodide in seawater Preliminary study with Laminaria digitata and Fucus serratus

NASA Astrophysics Data System (ADS)

Truesdale, Victor W.

2008-06-01

Toward assessing the biogeochemical significance of seaweeds in relation to dissolved iodine in seawater, the effect of whole seaweeds ( Laminaria digitata and Fucus serratus) upon iodide and iodate, at essentially natural concentrations, has been studied. The weeds were carefully removed from the sub-littoral zone of the Menai Straits and exposed to iodide and iodate at their natural temperature (6 °C), but under continuous illumination. Laminaria digitata was found to decrease the concentration of iodate with an exponential rate constant of 0.008-0.24 h -1. This is a newly discovered process which, if substantiated, will require an entirely new mechanism. Generally, apparent iodide concentration increased except in a run with seawater augmented with iodide, where it first decreased. The rate constant for loss of iodide was 0.014-0.16 h -1. Meanwhile, F. serratus was found not to decrease iodate concentrations, as did L. digitata. Indeed, after ˜30 h iodate concentrations increased, suggesting that the weed may take in iodide before oxidising and releasing it. If substantiated, this finding may offer a way into one of the most elusive of processes within the iodine cycle - iodide oxidation. With both seaweeds sustained long-term increases of apparent iodide concentration are most easily explained as a secretion by the weeds of organic matter which is capable of reducing the Ce(IV) reagent used in determination of total iodine. Modelling of the catalytic method used is provided to support this contention. The possibility of developing this to measure the strain that seaweeds endure in this kind of biogeochemical flux experiment is discussed. A Chemical Oxygen Demand type of approach is applied using Ce(IV) as oxidant. The results of the iodine experiments are contrasted with the several investigations of 131I interaction with seaweeds, which have routinely used discs of weed cut from the frond. It is argued that experiments conducted with stable iodine may measure a different variable to that measured in radio-iodine experiments.

Tanzania national survey on iodine deficiency: impact after twelve years of salt iodation.

PubMed

Assey, Vincent D; Peterson, Stefan; Kimboka, Sabas; Ngemera, Daniel; Mgoba, Celestin; Ruhiye, Deusdedit M; Ndossi, Godwin D; Greiner, Ted; Tylleskär, Thorkild

2009-09-03

In many low-income countries, children are at high risk of iodine deficiency disorders, including brain damage. In the early 1990s, Tanzania, a country that previously suffered from moderate to severe iodine deficiency, adopted universal salt iodation (USI) as an intervention strategy, but its impact remained unknown. We report on the first national survey in mainland Tanzania, conducted in 2004 to assess the extent to which iodated salt was used and its apparent impact on the total goitre prevalence (TGP) and urinary iodine concentrations (UIC) among the schoolchildren after USI was initiated. In 2004, a cross-sectional goitre survey was conducted; covering 140,758 schoolchildren aged 6 - 18 years were graded for goitre according to new WHO goitre classification system. Comparisons were made with district surveys conducted throughout most of the country during the 1980s and 90s. 131,941 salt samples from households were tested for iodine using rapid field test kits. UIC was determined spectrophotometrically using the ammonium persulfate digestion method in 4523 sub-sampled children. 83.6% (95% CI: 83.4 - 83.8) of salt samples tested positive for iodine. Whereas the TGP was about 25% on average in the earlier surveys, it was 6.9% (95%CI: 6.8-7.0) in 2004. The TGP for the younger children, 6-9 years old, was 4.2% (95%CI: 4.0-4.4), n = 41,965. In the 27 goitre-endemic districts, TGP decreased from 61% (1980s) to 12.3% (2004). The median UIC was 204 (95% CF: 192-215) microg/L. Only 25% of children had UIC <100 microg/L and 35% were > or = 300 microg/L, indicating low and excess iodine intake, respectively. Our study demonstrates a marked improvement in iodine nutrition in Tanzania, twelve years after the initiation of salt iodation programme. The challenge in sustaining IDD elimination in Tanzania is now two-fold: to better reach the areas with low coverage of iodated salt, and to reduce iodine intake in areas where it is excessive. Particular attention is needed in improving quality control at production level and perhaps the national salt iodation regulations may need to be reviewed.

Spectrophotometric study of the reaction mechanism between DDQ as π-acceptor and potassium iodate and flucloxacillin and dicloxacillin drugs and their determination in pure and in dosage forms

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; Nour El-Dien, F. A.; Farag, Eman U.

2006-09-01

Two simple and accurate spectrophotometric methods are presented for the determination of β-lactam drugs, flucloxacillin (Fluclox) and dicloxacillin (Diclox), in pure and in different pharmaceutical preparations. The charge transfer (CT) reactions between Fluclox and Diclox as electron donors and 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ) π-acceptor and potassium iodate via oxidation reduction reaction where the highly coloured complex species or the liberated iodine have been spectrophotometrically studied. The optimum experimental conditions have been studied carefully. Beer's law is obeyed over the concentration range of 2-450 μg ml -1 for Fluclox and 10-450 μg ml -1 for Diclox using DDQ reagent and at 50-550 μg ml -1 for Fluclox and 50-560 μg ml -1 for Diclox using iodate method, respectively. For more accurate results, Ringbom optimum concentration range is calculated and found to be 6-450 and 15-450 μg ml -1 for Fluclox and Diclox using DDQ, respectively, and 65-550 and 63-560 μg ml -1 for Fluclox and Diclox using iodine, respectively. The Sandell sensitivity is found to be 0.018 and 0.011 μg cm -2 for DDQ method and 0.013 and 0.011 μg cm -2 for iodate method for Fluclox and Diclox, respectively, which indicates the high sensitivity of both methods. Standard deviation (S.D. = 0.01-0.80 and 0.07-0.98) and relative standard deviation (R.S.D. = 0.13-0.44 and 0.11-0.82%) ( n = 5) for DDQ and iodate methods, respectively, refer to the high accuracy and precision of the proposed methods. These results are also confirmed by between-day precision of percent recovery of 99.87-100.2 and 99.90-100% for Fluclox and Diclox by DDQ method and 99.88-100.1 and 99.30-100.2% for Fluclox and Diclox by iodate method, respectively. These data are comparable to those obtained by British and American pharmacopoeias assay for the determination of Fluclox and Diclox in raw materials and in pharmaceutical preparations.

Spectrophotometric study of the reaction mechanism between DDQ as pi-acceptor and potassium iodate and flucloxacillin and dicloxacillin drugs and their determination in pure and in dosage forms.

PubMed

Mohamed, Gehad G; Nour El-Dien, F A; Farag, Eman U

2006-09-01

Two simple and accurate spectrophotometric methods are presented for the determination of beta-lactam drugs, flucloxacillin (Fluclox) and dicloxacillin (Diclox), in pure and in different pharmaceutical preparations. The charge transfer (CT) reactions between Fluclox and Diclox as electron donors and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) pi-acceptor and potassium iodate via oxidation reduction reaction where the highly coloured complex species or the liberated iodine have been spectrophotometrically studied. The optimum experimental conditions have been studied carefully. Beer's law is obeyed over the concentration range of 2-450 microg ml(-1) for Fluclox and 10-450 microg ml(-1) for Diclox using DDQ reagent and at 50-550 microg ml(-1) for Fluclox and 50-560 microg ml(-1) for Diclox using iodate method, respectively. For more accurate results, Ringbom optimum concentration range is calculated and found to be 6-450 and 15-450 microg ml(-1) for Fluclox and Diclox using DDQ, respectively, and 65-550 and 63-560 microg ml(-1) for Fluclox and Diclox using iodine, respectively. The Sandell sensitivity is found to be 0.018 and 0.011 microg cm(-2) for DDQ method and 0.013 and 0.011 microg cm(-2) for iodate method for Fluclox and Diclox, respectively, which indicates the high sensitivity of both methods. Standard deviation (S.D.=0.01-0.80 and 0.07-0.98) and relative standard deviation (R.S.D.=0.13-0.44 and 0.11-0.82%) (n=5) for DDQ and iodate methods, respectively, refer to the high accuracy and precision of the proposed methods. These results are also confirmed by between-day precision of percent recovery of 99.87-100.2 and 99.90-100% for Fluclox and Diclox by DDQ method and 99.88-100.1 and 99.30-100.2% for Fluclox and Diclox by iodate method, respectively. These data are comparable to those obtained by British and American pharmacopoeias assay for the determination of Fluclox and Diclox in raw materials and in pharmaceutical preparations.

Technetium and iodine aqueous species immobilization and transformations in the presence of strong reductants and calcite-forming solutions: Remedial action implications.

PubMed

Lawter, Amanda R; Garcia, Whitney L; Kukkadapu, Ravi K; Qafoku, Odeta; Bowden, Mark E; Saslow, Sarah A; Qafoku, Nikolla P

2018-04-30

At the Hanford Site in southeastern Washington, discharge of radionuclide laden liquid wastes resulted in vadose zone contamination, providing a continuous source of these contaminants to groundwater. The presence of multiple contaminants (i.e., 99 Tc and 129 I) increases the complexity of finding viable remediation technologies to sequester contaminants in situ and protect groundwater. Although previous studies have shown the efficiency of zero valent iron (ZVI) and sulfur modified iron (SMI) in reducing mobile Tc(VII) to immobile Tc(IV) and iodate incorporation into calcite, the coupled effects from simultaneously using these remedial technologies have not been previously studied. In this first-of-a-kind laboratory study, we used reductants (ZVI or SMI) and calcite-forming solutions to simultaneously remove aqueous Tc(VII) and iodate via reduction and incorporation, respectively. The results confirmed that Tc(VII) was rapidly removed from the aqueous phase via reduction to Tc(IV). Most of the aqueous iodate was transformed to iodide faster than incorporation into calcite occurred, and therefore the I remained in the aqueous phase. These results suggested that this remedial pathway is not efficient in immobilizing iodate when reductants are present. Other experiments suggested that iodate removal via calcite precipitation should occur prior to adding reductants for Tc(VII) removal. When microbes were included in the tests, there was no negative impact on the microbial population but changes in the makeup of the microbial community were observed. These microbial community changes may have an impact on remediation efforts in the long-term that could not be seen in a short-term study. The results underscore the importance of identifying interactions between natural attenuation pathways and remediation technologies that only target individual contaminants. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis, crystal structure and optical properties of two new layered cadmium iodates: Cd(IO{sub 3})X (X=Cl, OH)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Bing-Ping, E-mail: ybp@fjirsm.ac.cn; Mao, Jiang-Gao

Systematic explorations of new compounds in the cadmium iodate system by hydrothermal reactions led to two layered iodates, namely, Cd(IO{sub 3})X (X=Cl, OH). Cd(IO{sub 3})Cl crystallizes in the orthorhombic space group Cmca (No. 64) whereas Cd(IO{sub 3})(OH) crystallizes in the orthorhombic space group Pnma (No. 62). Cd(IO{sub 3})Cl displays a unique double layered structure composed of {sup 1}{sub ∞}[Cd−O{sub 3}Cl]{sub n} chains. Cadmium octahedrons form a 1D chain along the a-axis through edge sharing, and such chains are further interconnected via IO{sub 3} groups to form a special double layer on (020) plane. Cd(IO{sub 3})(OH) also exhibits a layered structuremore » that is composed of cadmium cations, IO{sub 3} groups and hydroxyl ions. Within a layer, chains of CdO{sub 6} edge-shared octahedra are observed along the b-axis. And these chains are connected by IO{sub 3} groups into a layer parallel to the bc plane. Spectroscopic characterizations, elemental analysis, and thermogravimetric analysis for the reported two compounds are also presented. - Graphical abstract: Two new layered cadmium iodates Cd(IO{sub 3})X (X=Cl, OH) are reported. Cd(IO{sub 3})Cl features a unique double layered structure whereas Cd(IO{sub 3})(OH) displays an ordinary layered structure. - Highlights: • Two new layered cadmium iodates Cd(IO{sub 3})X (X=Cl, OH) are reported. • Cd(IO{sub 3})Cl features a unique double layered structure. • Cd(IO{sub 3})(OH) displays an ordinary layered structure. • The spectroscopic and thermal properties have been studied in detail.« less

Two Barium Gold Iodates: Syntheses, Structures, and Properties of Polar BaAu(IO3)5 and Nonpolar HBa4Au(IO3)12 Materials.

PubMed

Yang, Bing-Ping; Hu, Chun-Li; Mao, Fei-Fei; Xu, Xiang; Mao, Jiang-Gao

2017-06-19

Two new barium gold iodates, namely, BaAu(IO 3 ) 5 and HBa 4 Au(IO 3 ) 12 , have been prepared. BaAu(IO 3 ) 5 crystallizes in the polar space group Pca2 1 , whereas HBa 4 Au(IO 3 ) 12 crystallizes in the centrosymmetric space group P2 1 /c. BaAu(IO 3 ) 5 consists of unique polar [Au(IO 3 ) 4 ] - anions whose four iodate groups are located at both sides of the AuO 4 plane and the polarity points in the [001̅] direction. BaAu(IO 3 ) 5 displays strong second-harmonic-generation (SHG) effects about 0.6KTiOPO 4 (KTP) and is phase-matchable. Thermal properties, optical spectra analyses, and theoretical calculations are also reported.

Iodine-129 and iodine-127 speciation in groundwater at the Hanford site, US: iodate incorporation into calcite.

PubMed

Zhang, Saijin; Xu, Chen; Creeley, Danielle; Ho, Yi-Fang; Li, Hsiu-Ping; Grandbois, Russell; Schwehr, Kathleen A; Kaplan, Daniel I; Yeager, Chris M; Wellman, Dawn; Santschi, Peter H

2013-09-03

The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounted for up to 84% of the total iodine present. The alkaline pH (pH ∼ 8) and predominantly oxidizing environment may have prevented reduction of the iodate. In addition, groundwater samples were found to have large amounts of calcite precipitate which were likely formed as a result of CO2 degassing during removal from the deep subsurface (>70m depth). Further analyses indicated that between 7 and 40% of the dissolved (127)I and (129)I that was originally in the groundwater had coprecipitated in the calcite. Iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevating the pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of (129)I. Furthermore, the common sampling artifact resulting in the precipitation of calcite by degassing CO2, had the unintended consequence of providing insight into a potential solution for the in situ remediation of groundwater (129)I.

Tanzania national survey on iodine deficiency: impact after twelve years of salt iodation

PubMed Central

Assey, Vincent D; Peterson, Stefan; Kimboka, Sabas; Ngemera, Daniel; Mgoba, Celestin; Ruhiye, Deusdedit M; Ndossi, Godwin D; Greiner, Ted; Tylleskär, Thorkild

2009-01-01

Background In many low-income countries, children are at high risk of iodine deficiency disorders, including brain damage. In the early 1990s, Tanzania, a country that previously suffered from moderate to severe iodine deficiency, adopted universal salt iodation (USI) as an intervention strategy, but its impact remained unknown. Methods We report on the first national survey in mainland Tanzania, conducted in 2004 to assess the extent to which iodated salt was used and its apparent impact on the total goitre prevalence (TGP) and urinary iodine concentrations (UIC) among the schoolchildren after USI was initiated. In 2004, a cross-sectional goitre survey was conducted; covering 140,758 schoolchildren aged 6 - 18 years were graded for goitre according to new WHO goitre classification system. Comparisons were made with district surveys conducted throughout most of the country during the 1980s and 90s. 131,941 salt samples from households were tested for iodine using rapid field test kits. UIC was determined spectrophotometrically using the ammonium persulfate digestion method in 4523 sub-sampled children. Results 83.6% (95% CI: 83.4 - 83.8) of salt samples tested positive for iodine. Whereas the TGP was about 25% on average in the earlier surveys, it was 6.9% (95%CI: 6.8-7.0) in 2004. The TGP for the younger children, 6-9 years old, was 4.2% (95%CI: 4.0-4.4), n = 41,965. In the 27 goitre-endemic districts, TGP decreased from 61% (1980s) to 12.3% (2004). The median UIC was 204 (95% CF: 192-215) μg/L. Only 25% of children had UIC <100 μg/L and 35% were ≥ 300 μg/L, indicating low and excess iodine intake, respectively. Conclusion Our study demonstrates a marked improvement in iodine nutrition in Tanzania, twelve years after the initiation of salt iodation programme. The challenge in sustaining IDD elimination in Tanzania is now two-fold: to better reach the areas with low coverage of iodated salt, and to reduce iodine intake in areas where it is excessive. Particular attention is needed in improving quality control at production level and perhaps the national salt iodation regulations may need to be reviewed. PMID:19728863

Application of 129I/127I Ratios in Groundwater Studies Conducted at Los Alamos National Laboratory, New Mexico

NASA Astrophysics Data System (ADS)

Longmire, P.; Dale, M.; Granzow, K.; Yanicak, S. M.

2014-12-01

Los Alamos National Laboratory (LANL) is an operating nuclear site that has released treated effluents from three plutonium-processing facilities since the mid 1940s. The radioisotope 129I (T1/2 = 15.7 Myrs) derived from235U and 239Pu processing at LANL is locally detected in groundwater above background concentrations. This isotope provides a unique tracer for groundwater investigations conducted at LANL that helps to identify source releases linked to groundwater-flow paths in aquifers subject to binary and ternary mixing of natural- and industrial-derived waters containing chromate and other chemicals. Bromide, chlorate, chloride, nitrate, perchlorate, sulfate, and tritium were associated with multiple outfalls at LANL and, therefore, do not provide unique chemical signatures identifying a specific point of release or source. Natural and anthropogenic ratios of 129I/127I measured in groundwater samples collected at LANL were quantified using accelerator mass spectrometry at Purdue Rare Isotope Measurement Laboratory, Purdue University. Anthropogenic ratios of 129I/127I range from 1,531 X 10-15 to 10,323 X 10-15 within perched-intermediate groundwater present in volcanoclastic and basalt aquifers (210 - 216 m depth). Anthropogenic ratios of 129I/127I range from 359 X 10-15 to 4,350 X 10-15 within the regional aquifer (280 m depth) consisting of volcanoclastic sediments of variable hydraulic properties. Local background ratios of 129I/127I have a narrow range of 171 X 10-15 to 378 X 10-15 in the regional aquifer. Dissolved iodide measured in groundwater at LANL is stable dominantly as iodate. Background concentrations of dissolved iodate (0.1 to 33.2 nM) are less variable compared to anthropogenic iodate (8.0 to 246 nM) in groundwater at the site. Variability in concentrations of anthropogenic iodate is controlled by heterogeneous source releases of iodate over time and non-uniform mixing of groundwater in the different aquifers.

Gel electrophoresis coupled to inductively coupled plasma-mass spectrometry using species-specific isotope dilution for iodide and iodate determination in aerosols.

PubMed

Brüchert, Wolfram; Helfrich, Andreas; Zinn, Nico; Klimach, Thomas; Breckheimer, Markus; Chen, Hongwei; Lai, Senchao; Hoffmann, Thorsten; Bettmer, Jörg

2007-02-15

In this paper, we present an online coupling of gel electrophoresis (GE) and inductively coupled plasma-mass spectrometry (ICP-MS) for the determination of iodine species (iodide and iodate) in liquid (seawater) and aerosol samples. For the first time, this approach is applied to the analysis of small molecules, and initial systematic investigations revealed that the migration behavior as well as the detection sensitivity strongly depends on the matrix (e.g., high concentrations of chloride). These effects could consequently affect the accuracy of analytical results, so that they need to be considered for the analysis of real samples. The technique used for quantification is species-specific isotope dilution analysis (ssIDA), which is a matrix-independent calibration method under certain conditions. We demonstrate that the use of 129I-enriched iodide and iodate allows the correction of the impact of the matrix on both, the electrophoretic migration and the detection sensitivity of the ICP-MS. After optimization, this coupling offers a novel and alternative method in the analysis of iodine compounds in various matrices. Here, we demonstrate the analytical capability of the technique for the chemical characterization of marine aerosols. The results show the presence of iodide and iodate at the ng m(-3) and sub-ng m(-3) level in the investigated aerosol samples, which were taken at the coastal research station in Mace Head, Ireland. These results are in good agreement with other recent studies, which demonstrated that the iodine chemistry in the marine atmosphere is only poorly understood. In addition to iodide and iodate, another iodine compound could be separated and detected in certain samples with high total iodine concentrations and was identified as elemental iodine, probably in form of triiodide, by peak matching. However, it may arise from an artifact during sample preparation.

Spectrophotometric determination of norepinephrine with sodium iodate and determination of its acidity constants

NASA Astrophysics Data System (ADS)

Hashem, E. Y.; Youssef, A. K.

2013-05-01

A spectrophotometric method is proposed for the determination of norepinephrine (NE) and its bitartrate salts. The method was based on the development of a red color (λmax = 495 nm) with sodium iodate in aqueous alcoholic medium at pH 5. The color was stable for at least 4 hrs. The molar reacting ratio of NE to sodium iodate was 1:4. A linear relationship was obtained between the absorption intensity and NE concentration in the range of 3.384-37.224 μg/ml with detection limit of 0.067 μg/ml and correlation coefficient of 0.9972. The present work facilitated the determination of the three acidity constants, 7.564 ± 0.02, 9.036 ± 0.034, and 10.761 ± 0.023. The reaction mechanism was also described. The proposed method was successfully applied for the determination of NE in pharmaceutical formulations. Results for analysis of bulk drugs and injections agree with those of official methods.

Physical properties of iodate solutions and the deliquescence of crystalline I2O5 and HIO3

NASA Astrophysics Data System (ADS)

Kumar, R.; Saunders, R. W.; Mahajan, A. S.; Plane, J. M. C.; Murray, B. J.

2010-12-01

Secondary aerosol produced from marine biogenic sources in algal-rich coastal locations will initially be composed of iodine oxide species, most likely I2O5, or its hydrated form HIO3, formed as a result of iodine gas-phase chemistry. At present, there is no quantitative hygroscopic data for these compounds and very little data available for iodate solutions (HIO3 and I2O5 share a common aqueous phase). With increased interest in the role of such aerosol in the marine atmosphere, we have conducted studies of (i) the deliquescence behaviour of crystalline HIO3 and I2O5 at 273-303 K, (ii) the efflorescence behaviour of aqueous iodate solution droplets, and (iii) properties (water activity, density, and viscosity) of subsaturated and saturated iodate solutions. The deliquescence of I2O5 crystals at 293 K was observed to occur at a relative humidity (DRH) of 80.8±1.0%, whereas for HIO3, a DRH of 85.0±1.0% was measured. These values are consistent with measured water activity values for saturated I2O5 and HIO3 solutions at 293 K of 0.80±0.01 and 0.84±0.01 respectively. At all temperatures, DRH values for HIO3 crystals were observed to be higher than for those of I2O5. The temperature-dependent DRH data, along with solubility and water activity data were used to evaluate the enthalpy of solution (ΔHsol) for HIO3 and I2O5. A ΔHsol value of 8.3±0.7 kJ mol-1 was determined for HIO3 which is consistent with a literature value of 8.8 kJ mol-1. For I2O5, we report for the first time its solubility at various temperatures and ΔHsol = 12.4±0.6 kJ mol-1. The measured water activity values confirm that aqueous iodate solutions are strongly non-ideal, consistent with previous reports of complex ion formation and molecular aggregation.

Physical properties of iodate solutions and the deliquescence of crystalline I2O5 and HIO3

NASA Astrophysics Data System (ADS)

Kumar, R.; Saunders, R. W.; Mahajan, A. S.; Plane, J. M. C.; Murray, B. J.

2010-09-01

Secondary aerosol produced from marine biogenic sources in algal-rich coastal locations will initially be composed of iodine oxide species, most likely I2O5, or its hydrated form HIO3, formed as a result of iodine gas-phase chemistry. At present, there is no quantitative hygroscopic data for these compounds and very little data available for iodate solutions (HIO3 and I2O5 share a common aqueous phase). With increased interest in the role of such aerosol in the marine atmosphere, we have conducted studies of (i) the deliquescence behaviour of crystalline HIO3 and I2O5 at 273-303 K, (ii) the efflorescence behaviour of aqueous iodate solution droplets, and (iii) properties (water activity, density, and viscosity) of subsaturated and saturated iodate solutions. The deliquescence of I2O5 crystals at 293 K was observed to occur at a relative humidity (DRH) of 80.8±1.0%, whereas for HIO3, a DRH of 85.0±1.0% was measured. These values are consistent with measured water activity values for saturated I2O5 and HIO3 solutions at 293 K of 0.80±0.01 and 0.84±0.01 respectively. At all temperatures, DRH values for HIO3 crystals were observed to be higher than for those of I2O5. The temperature-dependent DRH data, along with solubility and water activity data were used to evaluate the enthalpy of solution (ΔHsol) for HIO3 and I2O5. A (ΔHsol value of 8.3±0.7 kJ mol-1 was determined for HIO3 which is consistent with a literature value of 8.8 kJ mol-1. For I2O5, we report for the first time its solubility at various temperatures and (ΔHsol=12.4±.6 kJ mol-1. The measured water activity values confirm that aqueous iodate solutions are strongly non-ideal, consistent with previous reports of complex ion formation and molecular aggregation.

The distribution of iodine in the Croatian marine lake, Mir - The missing iodate

NASA Astrophysics Data System (ADS)

Žic, Vesna; Truesdale, Victor W.; Garnier, Cédric; Cukrov, Neven

2012-12-01

The marine chemistry of iodine has been studied in the marine lake, Mir, regarded as a natural reactor situated in the karstificated carbonate rocks of the Croatian Adriatic coast. The investigation covered the major variables: salinity, temperature, dissolved oxygen, pH and alkalinity, some nutrients, organic carbon, and iodide, iodate and organic-I. Lake Mir was found to be meso-trophic, with dynamic nutrient cycling of a magnitude usually associated with the temperate zone but within a Mediterranean clime. An essentially U-shaped pattern exists in the plot of nutrient concentration versus time for the June-November period studied. Together, the major variables and the nutrient chemistry confirm that Lake Mir is essentially isolated from the nearby (90 m) Adriatic seawater, and this also may explain the meso-trophic nature of the lake, with dry and wet deposition as the source of the extra nutrient. It is of note that iodate was essentially absent from Mir during the sampling period. This appears to be consistent with iodine's behaviour in the oceans in general, where iodate is reduced generally as a result of the presence of the biota. The chemistry of iodine in Lake Mir is consequently dominated by changes in iodide and organic-I concentrations, with the latter at higher concentrations than those found in seawater. Even so, the total iodine concentration in Mir is only about one-quarter of that in the adjacent Adriatic seawater, and again it is argued that this is probably a function of Lake Mir's isolation.

A Highly Sensitive and Selective Method for the Determination of an Iodate in Table-salt Samples Using Malachite Green-based Spectrophotometry.

PubMed

Konkayan, Mongkol; Limchoowong, Nunticha; Sricharoen, Phitchan; Chanthai, Saksit

2016-01-01

A simple, rapid, and sensitive malachite green-based spectrophotometric method for the selective trace determination of an iodate has been developed and presented for the first time. The reaction mixture was specifically involved in the liberation of iodine in the presence of an excess of iodide in an acidic condition following an instantaneous reaction between the liberated iodine and malachite green dye. The optimum condition was obtained with a buffer solution pH of 5.2 in the presence of 40 mg L -1 potassium iodide and 1.5 × 10 -5 M malachite green for a 5-min incubation time. The iodate contents in some table-salt samples were in the range of 26 to 45 mg kg -1 , while those of drinking water, tap water, canal water, and seawater samples were not detectable (< 96 ng mL -1 of limits of detection, LOQ) with their satisfied method of recoveries of between 93 and 108%. The results agreed with those obtained using ICP-OES for comparison.

Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid with Permanganate: Oxidation and Disproportionation.

PubMed

Zhao, Xiaodan; Salhi, Elisabeth; Liu, Huiling; Ma, Jun; von Gunten, Urs

2016-04-19

Oxidation kinetics of iodide and HOI/OI(-) by permanganate were studied in the pH range of 5.0-10.0. Iodide oxidation and iodate formation were faster at lower pH. The apparent second-order rate constants (k(obs)) for iodide oxidation by permanganate decrease with increasing pH from 29 M(-1) s(-1) at pH 5.0 and 6.9 M(-1) s(-1) at pH 7.0 to 2.7 M(-1) s(-1) at pH 10.0. k(obs) for HOI abatement are 56 M(-1) s(-1) at pH 5.0, 2.5 M(-1) s(-1) at pH 7.0, and 173 M(-1) s(-1) at pH 10.0. Iodate yields over HOI abatement decrease from 98% at pH 6.0 to 33% for pH ≥ 9.5, demonstrating that HOI disproportionation dominates HOI transformation by permanganate at pH ≥ 8.0. MnO2 formed as a product from permanganate reduction, oxidizes HOI to iodate for pH < 8.0, and promotes HOI disproportionation for pH ≥ 8.0. The rate of HOI oxidation or disproportionation induced by MnO2 is much lower than for permanganate. During treatment of iodide-containing waters, the potential for iodinated disinfection byproducts (I-DBPs) formation is highest at pH 7.0-8.0 due to the long lifetime of HOI. For pH < 6.0, HOI/I2 is quickly oxidized by permanganate to iodate, whereas for pH ≥ 8.0, HOI/OI(-) undergoes a fast permanganate-mediated disproportionation.

Iodine chemistry in the water column of the Chesapeake Bay: Evidence for organic iodine forms

NASA Astrophysics Data System (ADS)

Luther, George W.; Ferdelman, Timothy; Culberson, Charles H.; Kostka, Joel; Wu, Jingfeng

1991-03-01

During the summer of 1987, we collected and analysed Chesapeake Bay water samples for the inorganic iodine species: iodide (by cathodic-stripping squarewave voltammetry) and iodate (by differential pulse polarography); and total iodine (by hypochlorite oxidation of the seawater sample to iodate). The difference between the sum of the inorganic iodine species and the total iodine was significant for about one-third of the samples collected from the Bay. Thus, in these samples, a third (or more) 'new' form(s) of iodine was present. These samples were primarily from oxygen-saturated surface waters of high biological activity (primary productivity and bacterial processes). This 'new' form can make up as much as 70% of the total iodine. Waters containing low oxygen concentrations showed less of this 'new' form of iodine whereas anoxic and sulphidic bottom waters contained only iodide. This 'new' form of iodine is organic in nature and probably non-volatile. It may reside in the peptide and humic fractions. Only reduced iodine (iodide and organic iodine) was detected in waters from the northern section of the Bay, whereas only iodide and iodate were detected in the southern section of the Bay. In only two samples were iodide, iodate and the 'new' form of iodine found to coexist. Iodide and organic iodine are probably cycled in the surface waters of the northern section of the Bay via a combination of biogeochemical and photochemical processes which produce the reactive intermediates, molecular iodine and hypoiodous acid. These react quickly with reduced inorganic and organic compounds to maintain the reduced forms of iodine in the water column. Only total iodine is conservative throughout the estuary. The inorganic iodine forms can be used as geochemical tracers.

Mn0.95I0.02[PO3(OH)] · 2H2O phosphate-iodate, an inorganic analogue of phosphonates

NASA Astrophysics Data System (ADS)

Belokoneva, E. L.; Dimitrova, O. V.; Volkov, A. S.

2015-09-01

The new Mn0.95I0.02[PO3(OH)] · 2H2O phosphate-iodate (space group Pnam = Pnma, D {2/h 16}) is obtained under hydrothermal conditions. The crystal structure is determined without preliminary knowledge of the chemical formula. The structure consists of layers of MnО6 octahedra connected with PO4 tetrahedra. Water molecules are located between the layers. [IO3]- groups having a typical umbrella-like coordination are statistically implanted in layers of MnО6 octahedra at a distance of 1.2 Å from Mn atoms. Their content in the crystal is minor. The structures of the phosphate-iodate coincides with the structures of phosphonates with consideration for the replacement of one (OH) vertex of the РО4 tetrahedron by the organic methyl radical СН3. In the structures of phosphonates and earlier studied phosphates, identical layers are distinguished and the cause of the existence of two MDO varieties is established based on the analysis within the OD theory. Possible hybrid structures derived from the prototypes under consideration are predicted.

Iodine-Rich Imidazolium Iodate and Periodate Salts: En Route to Single-Based Biocidal Agents.

PubMed

He, Chunlin; Hooper, Joseph P; Shreeve, Jean'ne M

2016-12-19

Two classes of iodine-rich salts that consist of iodine-rich cations and iodate (IO 3 - ) or periodate (IO 4 - ) anions were synthesized. The synthesis of analogous I 3 O 8 - salts was more difficult because of poor solubility and hydrolytic instability. All iodine-rich salts were fully characterized by infrared, 1 H nuclear magnetic resonance, and 13 C nuclear magnetic resonance spectroscopy as well as elemental analyses. The molecular structures of compounds 15 and 24 were elucidated by X-ray single-crystal diffraction. Additionally, the heats of formation were calculated with Gaussian 03. The detonation properties and biocidal efficiency were calculated and evaluated using CHEETAH 7.

The potential role of kelp forests on iodine speciation in coastal seawater

PubMed Central

Gonzales, Jennifer; Tymon, Teresa; Küpper, Frithjof C.; Edwards, Matthew S.

2017-01-01

Kelps have a major role in marine and atmospheric iodine cycling in the coastal zone of temperate regions, with potential wide-ranging impacts on ozone destruction in the coastal marine boundary layer. However, little is known about the impact of kelp forests on iodine speciation in coastal sea water. To address this, we examined iodide and iodate concentrations in seawater in and around a giant kelp forest near San Diego, CA, USA, and a nearby site that was not influenced by kelp biology. Our data shows that while both iodide and iodate concentrations remained unchanged during the year at the nearby site, these concentrations changed significantly in and around the kelp forest, and were strongly related to changes in kelp canopy biomass. In particular, iodide reached its highest concentration and iodate reached its lowest concentration during the summer when the kelp canopies were near their maximum, while the opposite pattern was observed during the winter and spring when the kelp canopies were near their minimum. Further, comparisons of these changes with corresponding changes in seawater temperature and wind speed indicated that these relationships were relatively small compared to those with changes in kelp biomass. Together, our data show a strong relationship between kelp biomass and iodine metabolism. PMID:28800586

Mn{sub 0.95}I{sub 0.02}[PO{sub 3}(OH)] · 2H{sub 2}O phosphate–iodate, an inorganic analogue of phosphonates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belokoneva, E. L., E-mail: elbel@geol.msu.ru; Dimitrova, O. V.; Volkov, A. S.

2015-09-15

The new Mn{sub 0.95}I{sub 0.02}[PO{sub 3}(OH)] · 2H{sub 2}O phosphate–iodate (space group Pnam = Pnma, D{sub 2h}{sup 16}) is obtained under hydrothermal conditions. The crystal structure is determined without preliminary knowledge of the chemical formula. The structure consists of layers of MnO{sub 6} octahedra connected with PO{sub 4} tetrahedra. Water molecules are located between the layers. [IO3]{sup –} groups having a typical umbrella-like coordination are statistically implanted in layers of MnO{sub 6} octahedra at a distance of 1.2 Å from Mn atoms. Their content in the crystal is minor. The structures of the phosphate–iodate coincides with the structures of phosphonatesmore » with consideration for the replacement of one (OH) vertex of the PO{sub 4} tetrahedron by the organic methyl radical CH{sub 3}. In the structures of phosphonates and earlier studied phosphates, identical layers are distinguished and the cause of the existence of two MDO varieties is established based on the analysis within the OD theory. Possible hybrid structures derived from the prototypes under consideration are predicted.« less

The potential role of kelp forests on iodine speciation in coastal seawater.

PubMed

Gonzales, Jennifer; Tymon, Teresa; Küpper, Frithjof C; Edwards, Matthew S; Carrano, Carl J

2017-01-01

Kelps have a major role in marine and atmospheric iodine cycling in the coastal zone of temperate regions, with potential wide-ranging impacts on ozone destruction in the coastal marine boundary layer. However, little is known about the impact of kelp forests on iodine speciation in coastal sea water. To address this, we examined iodide and iodate concentrations in seawater in and around a giant kelp forest near San Diego, CA, USA, and a nearby site that was not influenced by kelp biology. Our data shows that while both iodide and iodate concentrations remained unchanged during the year at the nearby site, these concentrations changed significantly in and around the kelp forest, and were strongly related to changes in kelp canopy biomass. In particular, iodide reached its highest concentration and iodate reached its lowest concentration during the summer when the kelp canopies were near their maximum, while the opposite pattern was observed during the winter and spring when the kelp canopies were near their minimum. Further, comparisons of these changes with corresponding changes in seawater temperature and wind speed indicated that these relationships were relatively small compared to those with changes in kelp biomass. Together, our data show a strong relationship between kelp biomass and iodine metabolism.

Mixed-metal uranium(VI) iodates: hydrothermal syntheses, structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K, Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)].

PubMed

Sykora, Richard E; McDaniel, Steven M; Wells, Daniel M; Albrecht-Schmitt, Thomas E

2002-10-07

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.

Intermittent Chaos in the Bray-Liebhafsky Oscillator. Dependence of Dynamic States on the Iodate Concentration

NASA Astrophysics Data System (ADS)

Bubanja, I. N.; Ivanović-Šašić, A.; Čupić, Ž.; Anić, S.; Kolar-Anić, Lj.

2017-12-01

Chaotic dynamic states with intermittent oscillations were generated in a Bray-Liebhafsky (BL) oscillatory reaction in an isothermal open reactor i.e., in the continuously-fed well-stirred tank reactor (CSTR) when the inflow concentration of potassium iodate was the control parameter. They are found between periodic oscillations obtained when [KIO3]0 < 3.00 × 10-2 M and stable steady states when [KIO3]0 > 4.10 × 10-2 M. It was shown that the most chaotic states obtained experimentally somewhere in the middle of this region are in high correlation with results obtained by means of largest Lyapunov exponents and phenomenological analysis based on the quantitative characteristics of intermittent oscillations.

Selective Precipitation of Thorium lodate from a Tartaric Acid-Hydrogen Peroxide Medium Application to Rapid Spectrophotometric Determination of Thorium in Silicate Rocks and in Ores

USGS Publications Warehouse

Grimaldi, F.S.

1957-01-01

This paper presents a selective iodate separation of thorium from nitric acid medium containing d-tartaric acid and hydrogen peroxide. The catalytic decomposition of hydrogen peroxide is prevented by the use of 8quinolinol. A few micrograms of thorium are separated sufficiently clean from 30 mg. of such oxides as cerium, zirconium, titanium, niobium, tantalum, scandium, or iron with one iodate precipitation to allow an accurate determination of thorium with the thoronmesotartaric acid spectrophotometric method. The method is successful for the determination of 0.001% or more of thorium dioxide in silicate rocks and for 0.01% or more in black sand, monazite, thorite, thorianite, eschynite, euxenite, and zircon.

Formation of iodinated trihalomethanes during UV/chloramination with iodate as the iodine source.

PubMed

Zhang, Tian-Yang; Lin, Yi-Li; Wang, An-Qi; Tian, Fu-Xiang; Xu, Bin; Xia, Sheng-Ji; Gao, Nai-Yun

2016-07-01

Iodinated trihalomethanes (I-THMs) are a group of emerging disinfection by-products with high toxicity, and iodide (I(-)) as well as iodinated organic compounds are expected to be their iodine sources. Nevertheless, in this study, iodate (IO3(-)) was proven to be a new iodine source of I-THM formation during UV/chloramination. In the iodate-containing waters (without any other iodine sources), I-THM formation increased with the increase of UV dose, IO3(-) and NH2Cl concentrations. With the increase of Br(-)/IO3(-) molar ratio, I-THM formation (especially for the brominated species) increased. Besides, NOM species could affect I-THM formation from IO3(-) during UV/chloramination. Fulvic acid could promote IO3(-) phototransformation to I(-) but humic acid impeded the production of I(-) during UV irradiation. Under realistic drinking water treatment conditions (DOC = 5.0 mg-C/L, IO3(-) = 12.7 μg-I/L, UV dose = 50 mJ/cm(2), NH2Cl = 5 mg-Cl2/L), CHCl2I was detected as 0.17 μg/L using solid-phase microextraction method, and the production rate of I-THMs from IO3(-) was about 7% of that from I(-). Copyright © 2016 Elsevier Ltd. All rights reserved.

Radioiodine sorption/desorption and speciation transformation by subsurface sediments from the Hanford Site.

PubMed

Xu, Chen; Kaplan, Daniel I; Zhang, Saijin; Athon, Matthew; Ho, Yi-Fang; Li, Hsiu-Ping; Yeager, Chris M; Schwehr, Kathleen A; Grandbois, Russell; Wellman, Dawn; Santschi, Peter H

2015-01-01

During the last few decades, considerable research efforts have been extended to identify more effective remediation treatment technologies to lower the (129)I concentrations to below federal drinking water standards at the Hanford Site (Richland, USA). Few studies have taken iodate into consideration, though recently iodate, instead of iodide, was identified as the major species in the groundwater of 200-West Area within the Hanford Site. The objective of this study was thus to quantify and understand aqueous radioiodine species transformations and uptake by three sediments collected from the semi-arid, carbonate-rich environment of the Hanford subsurface. All three sediments reduced iodate (IO3(-)) to iodide (I(-)), but the loamy-sand sediment reduced more IO3(-) (100% reduced within 7 days) than the two sand-textured sediments (∼20% reduced after 28 days). No dissolved organo-iodine species were observed in any of these studies. Iodate uptake Kd values ([Isolid]/[Iaq]; 0.8-7.6 L/kg) were consistently and appreciably greater than iodide Kd values (0-5.6 L/kg). Furthermore, desorption Kd values (11.9-29.8 L/kg) for both iodate and iodide were consistently and appreciably greater than uptake Kd values (0-7.6 L/kg). Major fractions of iodine associated with the sediments were unexpectedly strongly bound, such that only 0.4-6.6 % of the total sedimentary iodine could be exchanged from the surface with KCl solution, and 0-1.2% was associated with Fe or Mn oxides (weak NH2HCl/HNO3 extractable fraction). Iodine incorporated into calcite accounted for 2.9-39.4% of the total sedimentary iodine, whereas organic carbon (OC) is likely responsible for the residual iodine (57.1-90.6%) in sediments. The OC, even at low concentrations, appeared to be controlling iodine binding to the sediments, as it was found that the greater the OC concentrations in the sediments, the greater the values of uptake Kd, desorption Kd, and the greater residual iodine concentrations (non-exchangeable, non-calcite-incorporated and non-Mn, Fe-oxide associated). This finding is of particular interest because it suggests that even very low OC concentrations, <0.2%, may have an impact on iodine geochemistry. The findings that these sediments can readily reduce IO3(-), and that IO3(-) sorbs to a greater extent than I(-), sheds light into earlier unexplained Hanford field data that demonstrated increases in groundwater (127)I(-)/(127)IO3(-) ratios and a decrease groundwater (129)IO3(-) concentrations along a transect away from the point sources, where iodine was primarily introduced as IO3(-). While a majority of the radioiodine does not bind to these alkaline sediments, there is likely a second smaller iodine fraction in the Hanford subsurface that is strongly bound, presumably to the sediment OC (and carbonate) phases. This second fraction may have an impact on establishing remediation goals and performance assessment calculations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Spatial variation of a short-lived intermediate chemical species in a Couette reactor

NASA Astrophysics Data System (ADS)

Vigil, R. Dennis; Ouyang, Q.; Swinney, Harry L.

1992-04-01

We have conducted experiments and simulations of the spatial variation of a short-lived intermediate species (triiodide) in the autocatalytic oxidation of arsenite by iodate in a reactor that is essentially one dimensional—the Couette reactor. (This reactor consists of two concentric cylinders with the inner one rotating and the outer one at rest; reagents are continuously fed and removed at each end in such a way that there is no net axial flux and there are opposing arsenite and iodate gradients.) The predictions of a one-dimensional reaction-diffusion model, which has no adjustable parameters, are in good qualitative (and, in some cases, quantitative) agreement with experiments. Thus, the Couette reactor, which is used to deliberately create spatial inhomogeneities, can be exploited to enhance the recovery of short-lived intermediate species relative to that which can be obtained with either a batch or continuous-flow stirred-tank reactor.

Sorption and transport of iodine species in sediments from the Savannah River and Hanford Sites.

PubMed

Hu, Qinhong; Zhao, Pihong; Moran, Jean E; Seaman, John C

2005-07-01

Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at the Savannah River and Hanford Sites, where anthropogenic (129)I from prior nuclear fuel processing activities poses an environmental risk. We conducted integrated column and batch experiments to investigate the interconversion, sorption and transport of iodine species, and the sediments we examined exhibit a wide range in organic matter, clay mineralogy, soil pH, and texture. The results of our experiments illustrate complex behavior with various processes occurring, including iodate reduction, irreversible retention or mass loss of iodide, and rate-limited and nonlinear sorption. There was an appreciable iodate reduction to iodide, presumably mediated by the structural Fe(II) in some clay minerals; therefore, careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. The different iodine species exhibited dramatically different sorption and transport behavior in three sediment samples, possessing different physico-chemical properties, collected from different depths at the Savannah River Site. Our study yielded additional insight into processes and mechanisms affecting the geochemical cycling of iodine in the environment, and provided quantitative estimates of key parameters (e.g., extent and rate of sorption) for risk assessment at these sites.

Evaporation of iodine-containing off-gas scrubber solution

DOEpatents

Partridge, J.A.; Bosuego, G.P.

1980-07-14

Mercuric nitrate-nitric acid scrub solutions containing radioiodine may be reduced in volume without excessive loss of volatile iodine. The use of concentrated nitric acid during an evaporation process oxidizes the mercury-iodide complex to a less volatile mercuric iodate precipitate.

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

Iodide and iodate effects on the growth and fruit quality of strawberry.

PubMed

Li, Rui; Liu, Hui-Ping; Hong, Chun-Lai; Dai, Zi-Xi; Liu, Jia-Wei; Zhou, Jun; Hu, Chun-Qing; Weng, Huan-Xin

2017-01-01

Iodine deficiency is an environmental health problem affecting one-third of the global population. An iodine biofortification hydroponic experiment was conducted to explore the iodide and iodate uptake characteristics of strawberry plants, to measure the dosage effects of iodine on plant growth and to evaluate the influence of I - or IO 3 - application on fruit quality. After biofortification, the iodine contents of the fresh strawberry fruits were 600-4000 µg kg -1 , covering the WHO dietary iodine allowance of 150 µg · day -1 for adults. The iodine uptake of the strawberry plants increased with increasing I - or IO 3 - concentration of the culture solution. At the same iodine concentration, the iodate uptakes of various plant organs under I - treatments were apparently more than those under IO 3 - treatments. Low-level exogenous iodine (I - ≤ 0.25 mg L -1 or IO 3 - ≤ 0.50 mg L -1 ) not only promoted plant growth and increased biomass per plant, but also improved fruit quality by enhancing the vitamin C and soluble sugar contents of the strawberry fruits. Nevertheless, excessive exogenous iodine inhibited plant growth and reduced biomass per plant. IO 3 - uptake apparently increased the total acidity and nitrate content of the fruits, reducing the quality of the strawberry fruits. Conversely, I - uptake obviously decreased the total acidity and nitrate content of the strawberry fruits, improving the fruit quality. The strawberry can be used as a target crop for iodine biofortification. Furthermore, applying an appropriate dose of KI can improve the fruit quality of the strawberry plants. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Pattern formation in the iodate-sulfite-thiosulfate reaction-diffusion system.

PubMed

Liu, Haimiao; Pojman, John A; Zhao, Yuemin; Pan, Changwei; Zheng, Juhua; Yuan, Ling; Horváth, Attila K; Gao, Qingyu

2012-01-07

Sodium polyacrylate-induced pH pattern formation and starch-induced iodine pattern formation were investigated in the iodate-sulfite-thiosulfate (IST) reaction in a one-side fed disc gel reactor (OSFR). As binding agents of the autocatalyst of hydrogen ions or iodide ions, different content of sodium polyacrylate or starch has induced various types of pattern formation. We observed pH pulses, striped patterns, mixed spots and stripes, and hexagonal spots upon increasing the content of sodium polyacrylate and observed iodine pulses, branched patterns, and labyrinthine patterns upon increasing the starch content in the system. Coexistence of a pH front and an iodine front was also studied in a batch IST reaction-diffusion system. Both pH and iodine front instabilities were observed in the presence of sodium polyacrylate, i.e., cellular fronts and transient Turing structures resulting from the decrease in diffusion coefficients of activators. The mechanism of multiple feedback may explain the different patterns in the IST reaction-diffusion system.

Sodium Iodate Selectively Injuries the Posterior Pole of the Retina in a Dose-Dependent Manner: Morphological and Electrophysiological Study

PubMed Central

Machalińska, Anna; Lubiński, Wojciech; Kłos, Patrycja; Kawa, Miłosz; Baumert, Bartłomiej; Penkala, Krzysztof; Grzegrzółka, Ryszard; Karczewicz, Danuta; Wiszniewska, Barbara

2010-01-01

Sequential morphological and functional features of retinal damage in mice exposed to different doses (40 vs. 20 mg/kg) of sodium iodate (NaIO3) were analyzed. Retinal morphology, apoptosis (TUNEL assay), and function (electroretinography; ERG) were examined at several time points after NaIO3 administration. The higher dose of NaIO3 caused progressive degeneration of the whole retinal area and total suppression of scotopic and photopic ERG. In contrast, the lower dose induced much less severe degeneration in peripheral part of retina along with a moderate decline of b- and a-wave amplitudes in ERG, corroborating the presence of regions within retina that retain their function. The peak of photoreceptor apoptosis was found on the 3rd day, but the lower dose induced more intense reaction within the central retina than in its peripheral region. In conclusion, these results indicate that peripheral area of the retina reveals better resistance to NaIO3 injury than its central part. PMID:20725778

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, B.C.; Musich, M.A.

A fixed-bed reactor system with continuous Hg{sup 0} analysis capabilities was used to evaluate commercial carbon sorbents for the removal of elemental mercury from simulated flue gas. The objectives of the program were to compare the sorbent effectiveness under identical test conditions and to identify the effects of various flue gas components on elemental mercury sorption. Sorbents tested included steam-activated lignite, chemical-activated hardwood and bituminous coal, iodated steam-activated coconut shell, and sulfur-impregnated steam-activated bituminous coal. The iodated carbon was the most effective carbon, showing over 99% mercury removal according to EPA Method 101A. Data indicate that O{sub 2} (4 vol%)more » and SO{sub 2} (500 ppm) improved the mercury removal of the other carbons for tests at 150{degrees}C using 100 {mu}g/m{sup 3} Hg{sup 0}. Further, the presence of HCl (at 50 ppm) produced a magnitude increase in mercury removal for the steam-activated and sulfur-impregnated bituminous coal-based carbons.« less

The Vitamin C Clock Reaction.

ERIC Educational Resources Information Center

Wright, Stephen W.

2002-01-01

Describes an iodine clock reaction that produces an effect similar to the Landolt clock reaction. This reaction uses supermarket chemicals and avoids iodate, bisulfite, and mercury compounds. Ascorbic acid and tincture of iodine are the main reactants with alternate procedures provided for vitamin C tablets and orange juice. (DDR)

21 CFR 184.1206 - Calcium iodate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... may be obtained from the National Academy Press, 2101 Constitution Ave. NW., Washington, DC 20418, or... availability of this material at NARA, call 202-741-6030, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html. (c) The ingredient is used as a dough strengthener as...

Improving the Explosive Performance of Aluminum Nanoparticles with Aluminum Iodate Hexahydrate (AIH).

PubMed

Gottfried, Jennifer L; Smith, Dylan K; Wu, Chi-Chin; Pantoya, Michelle L

2018-05-23

A new synthesis approach for aluminum particles enables an aluminum core to be passivated by an oxidizing salt: aluminum iodate hexahydrate (AIH). Transmission electron microscopy (TEM) images show that AIH replaces the Al 2 O 3 passivation layer on Al particles that limits Al oxidation. The new core-shell particle reactivity was characterized using laser-induced air shock from energetic materials (LASEM) and results for two different Al-AIH core-shell samples that vary in the AIH concentration demonstrate their potential use for explosive enhancement on both fast (detonation velocity) and slow (blast effects) timescales. Estimates of the detonation velocity for TNT-AIH composites suggest an enhancement of up to 30% may be achievable over pure TNT detonation velocities. Replacement of Al 2 O 3 with AIH allows Al to react on similar timescales as detonation waves. The AIH mixtures tested here have relatively low concentrations of AIH (15 wt. % and 6 wt. %) compared to previously reported samples (57.8 wt. %) and still increase TNT performance by up to 30%. Further optimization of AIH synthesis could result in additional increases in explosive performance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, B.C.; Musich, M.A.

A fixed-bed reactor system with continuous Hg{sup 0} analysis capabilities was used to evaluate commercial carbon sorbents for the removal of elemental mercury from simulated flue gas. The objectives of the program were to compare the sorbent effectiveness under identical test conditions and to identify the effects of various flue gas components on elemental mercury sorption. Sorbents tested included steam-activated lignite, chemically activated hardwood, chemically activated bituminous coal, iodated steam-activated coconut shell, and sulfur-impregnated steam-activated bituminous coal. The iodated carbon was the most effective sorbent, showing over 99% mercury removal according to U.S. Environmental Protection Agency (EPA) Method 101A. Datamore » indicate that adding O{sub 2} at 4 vol% reduced the effectiveness of the steam-activated lignite, chemically activated hardwood, and sulfur- impregnated steam-activated bituminous coal. Adding SO{sub 2} at 500 ppm improved the mercury removal of the sulfur-impregnated carbon. Further, the presence of HCl gas (at 50 ppm) produced an order of magnitude increase in mercury removal with the chemically activated and sulfur-impregnated bituminous coal-based carbons.« less

Simultaneous quantification of iodine and high valent metals via ICP-MS under acidic conditions in complex matrices.

PubMed

Brix, Kristina; Hein, Christina; Sander, Jonas Michael; Kautenburger, Ralf

2017-05-15

The determination of iodine as a main fission product (especially the isotopes I-129 and I-131) of stored HLW in a disposal beside its distribution as a natural ingredient of many different products like milk, food and seawater is a matter of particular interest. The simultaneous ICP-MS determination of iodine as iodide together with other elements (especially higher valent metal ions) relevant for HLW is analytically very problematic. A reliable ICP-MS quantification of iodide must be performed at neutral or alkaline conditions in contrast to the analysis of metal ions which are determined in acidic pH ranges. Herein, we present a method to solve this problem by changing the iodine speciation resulting in an ICP-MS determination of iodide as iodate. The oxidation from iodide to iodate with sodium hypochlorite at room temperature is a fast and convenient method with flexible reaction time, from one hour up to three days, thus eliminating the disadvantages of quantifying iodine species via ICP-MS. In the analysed concentration range of iodine (0.1-100µgL -1 ) we obtain likely quantitative recovery rates for iodine between 91% and 102% as well as relatively low RSD values (0.3-4.0%). As an additional result, it is possible to measure different other element species in parallel together with the generated iodate, even high valent metals (europium and uranium beside caesium) at recovery rates in the same order of magnitude (93-104%). In addition, the oxidation process operates above pH 7 thus offering a wide pH range for sample preparation. Even analytes in complex matrices, like 5M saline (NaCl) solution or artificial cement pore water (ACW) can be quantified with this robust sample preparation method. Copyright © 2017 Elsevier B.V. All rights reserved.

Excision of uranium oxide chains and ribbons in the novel one-dimensional uranyl iodates K(2)[(UO(2))3(IO(3))(4)O(2)] and Ba[(UO(2)2(IO(3))(2)O(2)](H(2)O).

PubMed

Bean, A C; Ruf, M; Albrecht-Schmitt, T E

2001-07-30

The alkali metal and alkaline-earth metal uranyl iodates K(2)[(UO(2))(3)(IO(3))(4)O(2)] and Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) have been prepared from the hydrothermal reactions of KCl or BaCl(2) with UO(3) and I(2)O(5) at 425 and 180 degrees C, respectively. While K(2)[(UO(2))(3)(IO(3))(4)O(2)] can be synthesized under both mild and supercritical conditions, the yield increases from <5% to 73% as the temperature is raised from 180 to 425 degrees C. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), however, has only been isolated from reactions performed in the mild temperature regime. Thermal measurements (DSC) indicate that K(2)[(UO(2))(3)(IO(3))(4)O(2)] is more stable than Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) and that both compounds decompose through thermal disproportionation at 579 and 575 degrees C, respectively. The difference in the thermal behavior of these compounds provides a basis for the divergence of their preparation temperatures. The structure of K(2)[(UO(2))(3)(IO(3))(4)O(2)] is composed of [(UO(2))(3)(IO(3))(4)O(2)](2)(-) chains built from the edge-sharing UO(7) pentagonal bipyramids and UO(6) octahedra. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) consists of one-dimensional [(UO(2))(2)(IO(3))(2)O(2)](2)(-) ribbons formed from the edge sharing of distorted UO(7) pentagonal bipyramids. In both compounds the iodate groups occur in both bridging and monodentate binding modes and further serve to terminate the edges of the uranium oxide chains. The K(+) or Ba(2+) cations separate the chains or ribbons in these compounds forming bonds with terminal oxygen atoms from the iodate ligands. Crystallographic data: K(2)[(UO(2))(3)(IO(3))(4)O(2)], triclinic, space group P_1, a = 7.0372(5) A, b = 7.7727(5) A, c = 8.9851(6) A, alpha = 93.386(1) degrees, beta = 105.668(1) degrees, gamma = 91.339(1) degrees, Z = 1; Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), monoclinic, space group P2(1)/c, a = 8.062(4) A, b = 6.940(3) A, c = 21.67(1), beta= 98.05(1) degrees, Z = 4.

Improved cell metabolism prolongs photoreceptor survival upon retinal-pigmented epithelium loss in the sodium iodate induced model of geographic atrophy

PubMed Central

Zieger, Marina; Punzo, Claudio

2016-01-01

Age-related macular degeneration (AMD) is characterized by malfunction and loss of retinal-pigmented epithelium (RPE) cells. Because the RPE transfers nutrients from the choriocapillaris to photoreceptor (PR), PRs are affected as well. Geographic atrophy (GA) is an advanced form of AMD characterized by severe vision impairment due to RPE loss over large areas. Currently there is no treatment to delay the degeneration of nutrient deprived PRs once RPE cells die. Here we show that cell-autonomous activation of the key regulator of cell metabolism, the kinase mammalian target of rapamycin complex 1 (mTORC1), delays PR death in the sodium iodate induced model of RPE atrophy. Consistent with this finding loss of mTORC1 in cones accelerates cone death as cones fail to balance demand with supply. Interestingly, promoting rod survival does not promote cone survival in this model of RPE atrophy as both, rods and cones suffer from a sick and dying RPE. The findings suggest that activation of metabolic genes downstream of mTORC1 can serve as a strategy to prolong PR survival when RPE cells malfunction or die. PMID:26883199

JPRS Report, Science & Technology, USSR: Chemistry.

DTIC Science & Technology

1987-12-11

UDC 536.75:541.128.7 BIFURCATIONAL ANALYSIS OF AUTO-OSCILLATING MODEL OF SYSTEM POTASSIUM IODATE - HYDROGEN PEROXIDE - CYSTE1NE - SULFURIC ACID Kiev...the explosive drilling team of the first ore administration of the Ural Potassium Association headed by Hero of Socialist Labor N. P. Savchuk, because...Republic Socialist Republic of Rumania USSR CSSR Mineral fertilizers Nitrogen Phosphate Potassium Mineral fertilizers play a significant role in

Iodine

USGS Publications Warehouse

Krukowski, S.T.

2006-01-01

In descending order, Chile, Japan and the United States have the largest iodine reserves. Chile produces iodine from iodate minerals while Japan and the United States produce it from sodium iodide solutions found in underground iodide solutions. Iodine is also produced from subterranean brines in Azerbaijan, Russia, Turkmenista, Indonesia and Uzbekistan. In 2005, iodine prices increased sharply to US$19 to US$23 then leveled off at US$23 to US$25.

Technical Evaluation of Biogeochemical Transformation of Iodine at 200-UP-1, Hanford, WA

NASA Astrophysics Data System (ADS)

Lee, M. H.; Cordova, E.; Brooks, S.; Moser, E.; Wells, J.; Lee, B.

2015-12-01

From the 1940s through the early 1990s, liquid wastes from materials used and produced at the Hanford Site were disposed to the ground through cribs, ditches, ponds, and trenches. Primary groundwater and vadose zone contaminants include carbon tetrachloride, uranium, nitrate, chromium, 129I, 99Tc, and tritium. Iodine-129 is of environmental concern due to its long half-life, mobility, and hazardous potential to humans through bioaccumulation, and is one of the primary risk drivers for the Hanford site. The 200 West area of the Hanford Site contains two separate plumes covering 1,500 acres where 129I concentrations are ~3.5 pCi/L in Hanford groundwater. Speciation analysis shows that iodate comprises 70.6% of the iodine present, and organo-iodide and iodide comprise 25.8% and 3.6% respectively. While hydraulic containment is the currently selected remedy for 129I in the groundwater, there is currently no remedy selected for controlling migration of 129I from the vadose zone to the groundwater. Research is currently underway to develop a site conceptual model for understanding the biogeochemical drivers for iodine speciation and determine the processes that drive the fate and transport of 129I through the vadose zone and into groundwater. These data will provide the information to decrease the uncertainty related to the inventory, distribution, and transport properties which will lead to appropriate treatment strategies for the 129I plume(s). Understanding the mechanisms and contributors to iodine speciation is important in order to develop bioremediation strategies for contaminated areas. The effect that microbial communities and humic acid have on iodine speciation and sorption was explored using Ringold sediment from the 200 West Area exposed to varying levels of 129I contamination in conjunction with varying growth media constituents. Several isolates obtained from these batch studies have been shown to reduce over 80% of iodate present in growth media when nitrate was present. No iodate reduction was observed in the absence of nitrate. Additionally, several isolates have been identified that can oxidize iodide. Currently, analytical techniques are underway to quantify the effect of microbial interaction on iodine speciation along with characterization of these diverse microbial isolates.

I/Ca records of local redox history for contrasting depositional environments during Cenomanian-Turonian OAE2

NASA Astrophysics Data System (ADS)

Lu, Z.; Zhou, X.; Junium, C. K.; Sageman, B. B.; Jenkyns, H.

2012-12-01

Periods of catastrophic marine oxygen-depletion are known as Oceanic Anoxic Events (OAEs). The most severe OAE intervals in the geological record can be recognized by both positive and negative δ13C excursions, indicating major changes in the global carbon cycle. However, such geochemical expressions only mark the most significant periods of the OAE, characterized by massive carbon burial and/or injection of isotopically light carbon into the ocean-atmosphere system, effects that typically developed after the initial build-up of anoxic/euxinic conditions in many different basins worldwide. Iodide (I-) and iodate (IO3-) are the thermodynamically stable inorganic forms of iodine in seawater. Iodate is almost completely reduced to iodide in all investigated anoxic basins and OMZs. In a pilot study (Lu et al., 2010, Geology), I/Ca in synthetic calcite recorded iodate concentrations in the medium. This established the potential for I/Ca as a novel redox proxy and it was applied in two carbonate-rich sections recording the early Toarcian OAE (shallow-water carbonate platform site) and the Cenomanian-Turonian OAE 2 (pelagic chalk, Eastbourne, UK). Here we report preliminary I/Ca data from three more Cretaceous OAE 2 sections: Raia del Pedale (Italy), South Ferriby (UK), and Denver (USA) representing the Western Interior Seaway. Raia del Pedale is a shallow-water carbonate platform site. It has lower I/Ca values compared to those of the pelagic sites and the reducing condition lasted relatively longer. I/Ca data from the South Ferriby section have baseline values similar to those at Eastbourne (both are in chalk facies), while positive spikes on the profile may record upwelling episodes. The Western Interior Seaway site shows unique trends in redox conditions during the OAE, consistent with changes in TOC content. These preliminary data indicate that the development of reducing conditions was not synchronous on a global scale and that local environmental factors modified the global OAE imprint. The findings highlight the potential sensitivity of I/Ca as a proxy for reconstruction of redox histories.

Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

NASA Astrophysics Data System (ADS)

Stein, David

This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented. In this mechanism, the colloid reacts with the chemistry of the slurry to produce active sites. These active sites become inactive by removing tungsten from the film. The process repeats when then inactive sites are reconverted to active sites. It is shown that the empirical form of the heuristic mechanism fits all of the data obtained. The mechanism also agrees with the limiting cases that were investigated.

Modern and ancient geochemical constraints on Proterozoic atmosphere-ocean redox evolution

NASA Astrophysics Data System (ADS)

Hardisty, D. S.; Horner, T. J.; Wankel, S. D.; Lu, Z.; Lyons, T.; Nielsen, S.

2017-12-01

A detailed understanding of the spatiotemporal oxygenation of Earth's atmosphere-ocean system through the Precambrian has important implications for the environments capable of sustaining early eukaryotic life and the evolving oxidant budget of subducted sediments. Proxy records suggest an anoxic Fe-rich deep ocean through much of the Precambrian and atmospheric and surface-ocean oxygenation that started in earnest at the Paleoproterozoic Great Oxidation Event (GOE). The marine photic zone represented the initial site of oxygen production and accumulation via cyanobacteria, yet our understanding of surface-ocean oxygen contents and the extent and timing of oxygen propagation and exchange between the atmosphere and deeper ocean are limited. Here, we present an updated perspective of the constraints on atmospheric, surface-ocean, and deep-ocean oxygen contents starting at the GOE. Our research uses the iodine content of Proterozoic carbonates as a tracer of dissolved iodate in the shallow ocean, a redox-sensitive species quantitatively reduced in modern oxygen minimum zones. We supplement our understanding of the ancient record with novel experiments examining the rates of iodate production from oxygenated marine environments based on seawater incubations. Combining new data from iodine with published shallow marine (Ce anomaly, N isotopes) and atmospheric redox proxies, we provide an integrated view of the vertical redox structure of the atmosphere and ocean across the Proterozoic.

Two-photon fluorescence and fluorescence imaging of two styryl heterocyclic dyes combined with DNA

NASA Astrophysics Data System (ADS)

Gao, Chao; Liu, Shu-yao; Zhang, Xian; Liu, Ying-kai; Qiao, Cong-de; Liu, Zhao-e.

2016-03-01

Two new styryl heterocyclic two-photon (TP) materials, 4-[4-(N-methyl)styrene]-imidazo [4,5-f][1,10] phenanthroline-benzene iodated salt (probe-1) and 4,4- [4-(N-methyl)styrene] -benzene iodated salt (probe-2) were successfully synthesized and studied as potential fluorescent probes of DNA detection. The linear and nonlinear photophysical properties of two compounds in different solvents were investigated. The absorption, one- and two-photon fluorescent spectra of the free dye and dye-DNA complex were also examined to evaluate their photophysical properties. The binding constants of dye-DNA were obtained according to Scatchard equation with good values. The results showed that two probes could be used as fluorescent DNA probes by two-photon excitation, and TP fluorescent properties of probe-1 are superior to that of probe-2. The fluorescent method date indicated that the mechanisms of dye-DNA complex interaction may be groove binding for probe-1 and electrostatic interaction for probe-2, respectively. The MTT assay experiments showed two probes are low toxicity. Moreover, the TP fluorescence imaging of DNA detection in living cells at 800 nm indicated that the ability to locate in cell nuclei of probe-1 is better than that of probe-2.

Two-photon fluorescence and fluorescence imaging of two styryl heterocyclic dyes combined with DNA.

PubMed

Gao, Chao; Liu, Shu-yao; Zhang, Xian; Liu, Ying-kai; Qiao, Cong-de; Liu, Zhao-e

2016-03-05

Two new styryl heterocyclic two-photon (TP) materials, 4-[4-(N-methyl)styrene]-imidazo [4,5-f][1,10] phenanthroline-benzene iodated salt (probe-1) and 4,4-[4-(N-methyl)styrene]-benzene iodated salt (probe-2) were successfully synthesized and studied as potential fluorescent probes of DNA detection. The linear and nonlinear photophysical properties of two compounds in different solvents were investigated. The absorption, one- and two-photon fluorescent spectra of the free dye and dye-DNA complex were also examined to evaluate their photophysical properties. The binding constants of dye-DNA were obtained according to Scatchard equation with good values. The results showed that two probes could be used as fluorescent DNA probes by two-photon excitation, and TP fluorescent properties of probe-1 are superior to that of probe-2. The fluorescent method date indicated that the mechanisms of dye-DNA complex interaction may be groove binding for probe-1 and electrostatic interaction for probe-2, respectively. The MTT assay experiments showed two probes are low toxicity. Moreover, the TP fluorescence imaging of DNA detection in living cells at 800 nm indicated that the ability to locate in cell nuclei of probe-1 is better than that of probe-2. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, Crystal Structure, and Topology-Symmetry Analysis of a New Modification of NaIn[IO3]4

NASA Astrophysics Data System (ADS)

Belokoneva, E. L.; Karamysheva, A. S.; Dimitrova, O. V.; Volkov, A. S.

2018-01-01

Crystals of new iodate NaIn[IO3]4 were prepared by the hydrothermal synthesis. The unit cell parameters are a = 7.2672(2) Å, b = 15.2572(6) Å, c = 15.0208(6) Å, β = 101.517(3)°, sp. gr. P21/ c. The formula was determined during the structure determination and refinement of a twinned crystal based on a set of reflections from the atomic planes of the major individual. The refinement with anisotropic displacement parameters was performed for both twin components to the final R factor of 0.050. The In and Na atoms are in octahedral coordination formed by oxygen atoms. The oxygen octahedra are arranged into columns by sharing edges, and the columns are connected by isolated umbrella-like [IO3]- groups to form layers. The new structure is most similar to the isoformular iodate NaIn[IO3]4, which crystallizes in the same sp. gr. P21/ c and is structurally similar, but has a twice smaller unit cell and is characterized by another direction of the monoclinic axis. The structural similarity and difference between the two phases were studied by topologysymmetry analysis. The formation of these phases is related to different combinations of identical one-dimensional infinite chains of octahedra.

Impact of potassium bromate and potassium iodate in a pound cake system.

PubMed

Wilderjans, Edith; Lagrain, Bert; Brijs, Kristof; Delcour, Jan A

2010-05-26

This study investigates the impact of the oxidants potassium bromate and potassium iodate (8, 16, 32, 64, and 128 micromol/g dry matter of egg white protein) on pound cake making. The impact of the oxidants on egg white characteristics was studied in a model system. Differential scanning calorimetry showed that the oxidants caused egg white to denature later. During heating in a rapid visco analyzer, the oxidants caused the free sulfhydryl (SH) group levels to decrease more intensively and over a smaller temperature range. The oxidants made the proteins more resistant to decreases in protein extractability in sodium dodecyl sulfate containing buffer during cake recipe mixing and less resistant to such decreases during cake baking. We assume that, during baking, the degree to which SH/disulfide exchange and SH oxidation can occur depends on the properties of the protein at the onset of the process. In our view, the prevention of extractability loss during mixing increased the availability of SH groups and caused more such loss during baking. During cooling, all cakes baked with added oxidants showed less collapse. On the basis of the presented data, we put forward that only those protein reactions that occur during baking contribute to the formation of a network that supports final cake structure and prevents collapse.

Assessment of the Performance of Iodine-Treated Biocidal Filters and Characterization of Virus Aerosols

DTIC Science & Technology

2009-07-01

a decrease of germicidal activity due to increased iodine decomposition (Wyss and Strandskov 1945 ). Generally, iodine inactivation is effective in...wet dissemination because dehydration is an inevitable condition (Cox 1989). Songer (1967) studied the effects of RH and temperature on various... hydrolysis to form hypoiodous acid (HOI) as shown in Eq. (1-1). Hypoiodous acid then disproportionates to iodate (IO3-) as depicted in Eq. (1-2

Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO 3) 3 and Ln(IO 3) 3(H 2O) ( Lndbnd Yb, Lu)

NASA Astrophysics Data System (ADS)

Assefa, Zerihun; Ling, Jie; Haire, Richard G.; Albrecht-Schmitt, Thomas E.; Sykora, Richard E.

2006-12-01

The reaction of Lu 3+ or Yb 3+ and H 5IO 6 in aqueous media at 180 °C leads to the formation of Yb(IO 3) 3(H 2O) or Lu(IO 3) 3(H 2O), respectively, while the reaction of Yb metal with H 5IO 6 under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO 3) 3. Under supercritical conditions Lu 3+ reacts with HIO 3 and KIO 4 to yield the isostructural Lu(IO 3) 3. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (Mo Kα, λ=0.71073 Å): Yb(IO 3) 3, monoclinic, space group P2 1/ n, a=8.6664(9) Å, b=5.9904(6) Å, c=14.8826(15) Å, β=96.931(2)°, V=766.99(13), Z=4, R( F)=4.23% for 114 parameters with 1880 reflections with I>2 σ( I); Lu(IO 3) 3, monoclinic, space group P2 1/ n, a=8.6410(9), b=5.9961(6), c=14.8782(16) Å, β=97.028(2)°, V=765.08(14), Z=4, R( F)=2.65% for 119 parameters with 1756 reflections with I>2 σ( I); Yb(IO 3) 3(H 2O), monoclinic, space group C2/ c, a=27.2476(15), b=5.6296(3), c=12.0157(7) Å, β=98.636(1)°, V=1822.2(2), Z=8, R( F)=1.51% for 128 parameters with 2250 reflections with I>2 σ( I); Lu(IO 3) 3(H 2O), monoclinic, space group C2/ c, a=27.258(4), b=5.6251(7), c=12.0006(16) Å, β=98.704(2)°, V=1818.8(4), Z=8, R( F)=1.98% for 128 parameters with 2242 reflections with I>2 σ( I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO 3) 3(H 2O) and Yb(IO 3) 3(H 2O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.

Disposal of radioactive iodine in space

NASA Technical Reports Server (NTRS)

Burns, R. E.; Defield, J. G.

1978-01-01

The possibility of space disposal of iodine waste from nuclear power reactors is investigated. The space transportation system utilized relies upon the space shuttle, a liquid hydrogen/liquid oxygen orbit transfer vehicle, and a solid propellant final stage. The iodine is assumed to be in the form of either an iodide or an iodate, and calculations assume that the final destination is either solar orbit or solar system escape. It is concluded that space disposal of iodine is feasible.

[Determination of americium-241 in urine].

PubMed

Shvydko, N S; Mikhaĭlova, O A; Popov, D K

1988-01-01

A technique has been developed for the determination of americium 241 in urine by a radiochemical purification of the nuclide from uranium (upon co-precipitation of americium 241 with calcium and lanthanum), plutonium, thorium, and polonium 210 (upon co-precipitation of these radionuclides with zirconium iodate). alpha-Radioactivity was measured either in a thick layer of the americium 241 precipitate with a nonisotope carrier or in thin-layer preparations after electrolytic precipitation of americium 241 on a cathode.

Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

2017-02-01

Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

Microfluidic Analysis with Front-Face Fluorometric Detection for the Determination of Total Inorganic Iodine in Drinking Water.

PubMed

Inpota, Prawpan; Strzelak, Kamil; Koncki, Robert; Sripumkhai, Wisaroot; Jeamsaksiri, Wutthinan; Ratanawimarnwong, Nuanlaor; Wilairat, Prapin; Choengchan, Nathawut; Chantiwas, Rattikan; Nacapricha, Duangjai

2018-01-01

A microfluidic method with front-face fluorometric detection was developed for the determination of total inorganic iodine in drinking water. A polydimethylsiloxane (PDMS) microfluidic device was employed in conjunction with the Sandell-Kolthoff reaction, in which iodide catalyzed the redox reaction between Ce(IV) and As(III). Direct alignment of an optical fiber attached to a spectrofluorometer was used as a convenient detector for remote front-face fluorometric detection. Trace inorganic iodine (IO 3 - and I - ) present naturally in drinking water was measured by on-line conversion of iodate to iodide for determination of total inorganic iodine. On-line conversion efficiency of iodate to iodide using the microfluidic device was investigated. Excellent conversion efficiency of 93 - 103% (%RSD = 1.6 - 11%) was obtained. Inorganic iodine concentrations in drinking water samples were measured, and the results obtained were in good agreement with those obtained by an ICP-MS method. Spiked sample recoveries were in the range of 86%(±5) - 128%(±8) (n = 12). Interference of various anions and cations were investigated with tolerance limit concentrations ranging from 10 -6 to 2.5 M depending on the type of ions. The developed method is simple and convenient, and it is a green method for iodine analysis, as it greatly reduces the amount of toxic reagent consumed with reagent volumes in the microfluidic scale.

Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO{sub 3}){sub 3} and Ln(IO{sub 3}){sub 3}(H{sub 2}O) (Ln =Yb, Lu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Assefa, Zerihun; Ling Jie; Haire, Richard G.

2006-12-15

The reaction of Lu{sup 3+} or Yb{sup 3+} and H{sub 5}IO{sub 6} in aqueous media at 180 {sup o}C leads to the formation of Yb(IO{sub 3}){sub 3}(H{sub 2}O) or Lu(IO{sub 3}){sub 3}(H{sub 2}O), respectively, while the reaction of Yb metal with H{sub 5}IO{sub 6} under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO{sub 3}){sub 3}. Under supercritical conditions Lu{sup 3+} reacts with HIO{sub 3} and KIO{sub 4} to yield the isostructural Lu(IO{sub 3}){sub 3}. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoK{alpha}, {lambda}=0.71073 A): Yb(IO{sub 3}){sub 3}, monoclinic, space group P2{sub 1}/n, a=8.6664(9)more » A, b=5.9904(6) A, c=14.8826(15) A, {beta}=96.931(2){sup o}, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2{sigma}(I); Lu(IO{sub 3}){sub 3}, monoclinic, space group P2{sub 1}/n, a=8.6410(9), b=5.9961(6), c=14.8782(16) A, {beta}=97.028(2){sup o}, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2{sigma}(I); Yb(IO{sub 3}){sub 3}(H{sub 2}O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) A, {beta}=98.636(1){sup o}, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2{sigma}(I); Lu(IO{sub 3}){sub 3}(H{sub 2}O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) A, {beta}=98.704(2){sup o}, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2{sigma}(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO{sub 3}){sub 3}(H and Yb(IO{sub 3}){sub 3}(H{sub 2}O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds. - Graphical abstract: Four new metal iodates, Yb(IO{sub 3}){sub 3}, Lu(IO{sub 3}){sub 3}, Yb(IO{sub 3}){sub 3}(H{sub 2}O), and Lu(IO{sub 3}){sub 3}(H{sub 2}O), have all been isolated as single crystals through the use of hydrothermal reactions. Structural determinations using single-crystal X-ray diffraction have shown that the materials are all alike in that they contain two-dimensional structures. Vibrational profiles for all of the materials have been collected, using Raman spectroscopy, and analyzed.« less

Engineering and Development Support of General Decon Technology for the DARCOM Installation Restoration Program. Task 4. General Technology Literature Searches (II) Solidification Techniques for Lagoon Waters

DTIC Science & Technology

1980-12-01

40.8 Sodium 70.1 Zinc 0.01 37 The process includes the following steps (Pichat et al., 1979): - neutralization precipitation (silicates, borates...Compressive Strength of Polyester - Encapsulated Sodium Sulfate Waste Composite ....... .............. 64 9. Deep Chemical Mixer Mounted on a Barge...zinc, copper, lead, manganese and tin; sodium salts of arsenate, borate, phosphate, iodate, and sulfide; and sulfate salts. Sulfate salts form calcium

Oxidation of thymidylate synthase by inorganic compounds.

PubMed

Aull, J L; Ivery, T C; Daron, H H

1984-10-01

Thymidylate synthase from methotrexate-resistant Lactobacillus casei was rapidly and completely inactivated by low concentrations of permanganate, periodate, or potassium triiodide at 0 degree C. The enzyme was not inactivated to any appreciable extent by iodate, iodide, ferricyanate, iodosobenzoate, or hydrogen peroxide. The inactivation by permanganate was retarded by the substrate 2'-deoxyuridylate and, to a lesser extent, by phosphate. Titration of enzyme activity with permanganate showed that two moles of permanganate were required to completely inactivate one mole of thymidylate synthase.

Evaluation of the Performance of Iodine-Treated Biocide Filters Challenged with Bacterial Spores and Viruses

DTIC Science & Technology

2006-11-01

water starts from hydrolysis to form hypoiodous acid (HOI) as 4 shown in Eq. (1). Hypoiodous acid then disproportionates to iodate (IO3-) and iodide...of iodine with Bacillus metiens spores showed that the decrease of germicidal activity is due to increased iodine decomposition [39]. Studies on the...the test filter was expected to be low. The agar plate was replaced with a fresh one every 20 mins for 2 hrs to avoid overloading and dehydration of

Iodine conceptual model at Hanford: Aqueous speciation and interactions with minerals

NASA Astrophysics Data System (ADS)

Qafoku, N. P.; Lawter, A.; McElroy, E.; Szecsody, J. E.; Lee, B.; Truex, M. J.; Smith, F.; Kerisit, S.; Freedman, V. L.

2017-12-01

Isotopes of iodine were generated during plutonium production at the U.S. Department of Energy Hanford Site. The fate and transport of 129I in the environment and potential remediation technologies are currently being studied as part of environmental remediation activities at the Hanford Site. A conceptual model describing the nature and extent of subsurface contamination, processes and reactions that control plume behavior, and factors relevant to potential remediation processes is needed to support environmental remedy decisions. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited. As part of the effort to develop a comprehensive conceptual model of iodine at the Hanford subsurface, we conducted a series of bench-scale experiments to determine the extent of iodine interactions with minerals, abiotic and biotic species transformation via electron transfer reactions, and mechanisms of iodine aqueous species attentuation (i.e., adsorption and co-precipitation). We will also present data collected from solid phase characterization efforts using SEM/EDS, SEM/FIB, TEM/SAED, XANES and NanoSIMS. Interactions of iodine species with natural organic matter are also important; we determined the identity of organic matter compounds at Hanford and their affinity for different aqueous iodine species (i.e., iodate and iodide) using FTICR-MS along with tandem mass spectrometry (MS/MS) to verify organo-iodide/iodate binding. Finally, we used a variety of molecular dymanic calculations to identify energetically competitive incorporation scenarios, and determine incorporation limits and charge compensation mechanisms.

Electronic Structure and Properties of Berkelium Iodates.

PubMed

Silver, Mark A; Cary, Samantha K; Garza, Alejandro J; Baumbach, Ryan E; Arico, Alexandra A; Galmin, Gregory A; Chen, Kuan-Wen; Johnson, Jason A; Wang, Jamie C; Clark, Ronald J; Chemey, Alexander; Eaton, Teresa M; Marsh, Matthew L; Seidler, Kevin; Galley, Shane S; van de Burgt, Lambertus; Gray, Ashley L; Hobart, David E; Hanson, Kenneth; Van Cleve, Shelley M; Gendron, Frédéric; Autschbach, Jochen; Scuseria, Gustavo E; Maron, Laurent; Speldrich, Manfred; Kögerler, Paul; Celis-Barros, Cristian; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro; Ruf, Michael; Albrecht-Schmitt, Thomas E

2017-09-27

The reaction of 249 Bk(OH) 4 with iodate under hydrothermal conditions results in the formation of Bk(IO 3 ) 3 as the major product with trace amounts of Bk(IO 3 ) 4 also crystallizing from the reaction mixture. The structure of Bk(IO 3 ) 3 consists of nine-coordinate Bk III cations that are bridged by iodate anions to yield layers that are isomorphous with those found for Am III , Cf III , and with lanthanides that possess similar ionic radii. Bk(IO 3 ) 4 was expected to adopt the same structure as M(IO 3 ) 4 (M = Ce, Np, Pu), but instead parallels the structural chemistry of the smaller Zr IV cation. Bk III -O and Bk IV -O bond lengths are shorter than anticipated and provide further support for a postcurium break in the actinide series. Photoluminescence and absorption spectra collected from single crystals of Bk(IO 3 ) 4 show evidence for doping with Bk III in these crystals. In addition to luminescence from Bk III in the Bk(IO 3 ) 4 crystals, a broad-band absorption feature is initially present that is similar to features observed in systems with intervalence charge transfer. However, the high-specific activity of 249 Bk (t 1/2 = 320 d) causes oxidation of Bk III and only Bk IV is present after a few days with concomitant loss of both the Bk III luminescence and the broadband feature. The electronic structure of Bk(IO 3 ) 3 and Bk(IO 3 ) 4 were examined using a range of computational methods that include density functional theory both on clusters and on periodic structures, relativistic ab initio wave function calculations that incorporate spin-orbit coupling (CASSCF), and by a full-model Hamiltonian with spin-orbit coupling and Slater-Condon parameters (CONDON). Some of these methods provide evidence for an asymmetric ground state present in Bk IV that does not strictly adhere to Russel-Saunders coupling and Hund's Rule even though it possesses a half-filled 5f 7 shell. Multiple factors contribute to the asymmetry that include 5f electrons being present in microstates that are not solely spin up, spin-orbit coupling induced mixing of low-lying excited states with the ground state, and covalency in the Bk IV -O bonds that distributes the 5f electrons onto the ligands. These factors are absent or diminished in other f 7 ions such as Gd III or Cm III .

Synthesis, Structures, and Vibrational Spectroscopy of the Two-Dimensional Iodates Ln(IO) 3 and Ln(IO 3) 3(H 2O) ( Ln-Yb,Lu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Assefa, Zerihun; Ling, Jie; Haire, Richard

2006-01-01

The reaction of Lu3+ or Yb3+ and H5IO6 in aqueous media at 180 C leads to the formation of Yb(IO3)3(H2O) or Lu(IO3)3(H2O), respectively, while the reaction of Yb metal with H5IO6 under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO3)3. Under supercritical conditions Lu3+ reacts with HIO3 and KIO4 to yield the isostructural Lu(IO3)3. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKa, {lambda}=0.71073 {angstrom}): Yb(IO3)3, monoclinic, space group P21/n, a=8.6664(9) {angstrom}, b=5.9904(6) {angstrom}, c=14.8826(15) {angstrom}, {beta}=96.931(2){sup o}, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2s(I); Lu(IO3)3, monoclinic, space group P21/n,more » a=8.6410(9), b=5.9961(6), c=14.8782(16) {angstrom}, {beta}=97.028(2){sup o}, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2s(I); Yb(IO3)3(H2O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) {angstrom}, {beta}=98.636(1){sup o}, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2s(I); Lu(IO3)3(H2O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) {angstrom}, {beta}=98.704(2){sup o}, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2s(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO3)3(H2O) and Yb(IO3)3(H2O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.« less

WET FLUORIDE SEPARATION METHOD

DOEpatents

Seaborg, G.T.; Gofman, J.W.; Stoughton, R.W.

1958-11-25

The separation of U/sup 233/ from thorium, protactinium, and fission products present in neutron-irradiated thorium is accomplished by dissolving the irradiated materials in aqueous nitric acid, adding either a soluble fluoride, iodate, phosphate, or oxalate to precipltate the thorium, separating the precipltate from the solution, and then precipitating uranlum and protactinium by alkalizing the solution. The uranium and protactinium precipitate is removcd from the solution and dissolved in nitric acid. The uranyl nitrate may then be extracted from the acid solution by means of ether, and the protactinium recovered from the aqueous phase.

Pylorogastric intussusception in a Chihuahua puppy. A case report

PubMed Central

Lideo, L.; Mutinelli, F.; Milan, R.

2010-01-01

A three-month-old Chihuahua dog was presented with acute abdominal pain, vomiting and cardiovascular shock. Abdominal ultrasound (US) and iodated contrast gastrogram revealed suspected pylorogastric intussusception. Because of the poor prognosis the dog was euthanatized. Diagnosis of pylorogastric intussusception was confirmed at necropsy. Parasitological, virological, serological and histological examinations were also performed. This report documents the sixth case of pylorogastric (i.e. duodenogastric, gastrogastric) intussusception in the veterinary medical literature and it is the first report on a puppy dog in which US and radiographic diagnosis were confirmed post mortem. PMID:23396815

CONCENTRATION AND DECONTAMINATION OF SOLUTIONS CONTAINING PLUTONIUM VALUES BY BISMUTH PHOSPHATE CARRIER PRECIPITATION METHODS

DOEpatents

Seaborg, G.T.; Thompson, S.G.

1960-08-23

A process is given for isolating plutonium present in the tetravalent state in an aqueous solution together with fission products. First, the plutonium and fission products are coprecipitated on a bismuth phosphate carrier. The precipitate obtained is dissolved, and the plutonium in the solution is oxidized to the hexavalent state (with ceric nitrate, potassium dichromate, Pb/ sub 3/O/sub 4/, sodium bismuthate and/or potassium dichromate). Thereafter a carrier for fission products is added (bismuth phosphate, lanthanum fluoride, ceric phosphate, bismuth oxalate, thorium iodate, or thorium oxalate), and the fission-product precipitation can be repeated with one other of these carriers. After removal of the fission-product-containing precipitate or precipitates. the plutonium in the supernatant is reduced to the tetravalent state (with sulfur dioxide, hydrogen peroxide. or sodium nitrate), and a carrier for tetravalent plutonium is added (lanthanum fluoride, lanthanum hydroxide, lanthanum phosphate, ceric phosphate, thorium iodate, thorium oxalate, bismuth oxalate, or niobium pentoxide). The plutonium-containing precipitate is then dissolved in a relatively small volume of liquid so as to obtain a concentrated solution. Prior to dissolution, the bismuth phosphate precipitates first formed can be metathesized with a mixture of sodium hydroxide and potassium carbonate and plutonium-containing lanthanum fluorides with alkali-metal hydroxide. In the solutions formed from a plutonium-containing lanthanum fluoride carrier the plutonium can be selectively precipitated with a peroxide after the pH was adjusted preferably to a value of between 1 and 2. Various combinations of second, third, and fourth carriers are discussed.

Retinal degeneration is delayed by tissue factor pathway inhibitor-2 in RCS rats and a sodium-iodate-induced model in rabbits.

PubMed

Obata, R; Yanagi, Y; Tamaki, Y; Hozumi, K; Mutoh, M; Tanaka, Y

2005-04-01

To investigate the in vivo effects of tissue factor pathway inhibitor 2 (TFPI-2), which stimulates proliferation of retinal pigment epithelial cells, but not the proliferation of fibroblast and vascular endothelial cells in vitro, on retinal degeneration using a sodium-iodate (SI)-induced model in rabbits and Royal Collage of Surgeons (RCS) rats. 79 microg of recombinant TFPI-2 (rTFPI-2) or vehicle alone was injected intravitreously to 18 eyes of 12 pigmented rabbits a day after 20 mg/kg of SI was intravenously administered. Retinal function was assessed 4, 7, 14, and 21 days after the injection by analysing amplitudes of the c-wave of a bright flash electroretinogram. Additionally, 10 microg of rTFPI-2 or vehicle alone was injected intravitreously to 11 eyes of RCS rats at both 3 and 4 weeks old, then the retina was examined histologically at 5 weeks old. The rTFPI-2-treated eyes in rabbits showed a significantly less decrease in the relative amplitude of the c-wave than control eyes on days 4 and 7. The thickness of the outer nuclear layer was significantly thicker and the vacuole in the photoreceptor layer was less frequently observed in the rTFPI-2-treated RCS rats than the controls. Intravitreal injection of TFPI-2 rescues SI-induced retinal degeneration in rabbits and naturally occurring retinal degeneration in RCS rats at least partly. These results may suggest that this compound can be utilized in the treatment of retinal degeneration.

Mineral systems and the thermodynamics of selenites and selenates in the oxidation zone of sulfide ores - a review

NASA Astrophysics Data System (ADS)

Charykova, Marina V.; Krivovichev, Vladimir G.

2017-02-01

Contemporary mineralogy and geochemistry are concerned with understanding and deciphering processes that occur near the surface of the Earth. These processes are especially important for resolving ecological challenges and developing principles of good environmental management. Selenium oxysalts, selenites and selenates, are relatively rare as minerals; there are presently only 34 known mineral species. Thirty-one "pure" selenites, which contain only selenite anionic groups, are known to occur naturally. The other three minerals each contain two anionic groups: selenate and selenite (schmiederite), selenate and sulphate (olsacherite), and selenate and iodate (carlosruizite).

Nitric oxide is involved in the hypothyroidism with significant morphology changes in female Wistar rats induced by chronic exposure to high water iodine from potassium iodate.

PubMed

Rong, Shengzhong; Gao, Yanhui; Yang, Yanmei; Shao, Hanwen; Okekunle, Akinkunmi Paul; Lv, Chunpeng; Du, Yang; Sun, Hongna; Jiang, Yuting; Darko, Gottfried M; Sun, Dianjun

2018-05-03

Epidemiological studies indicated that chronic exposure to high water iodine is associated with primary hypothyroidism (PH) and subclinical hypothyroidism (SCH). However, the mechanism is not well understood. In this study, we explored whether chronic exposure to high water iodine from potassium iodate (KIO 3 ) can induce hypothyroidism in addition to determining if nitric oxide (NO) is involved in the pathogenesis. 96 female Wistar rats were divided into six groups: control, I 1000μg/L , I 3000μg/L , I 6000μg/L , N-nitro-L-arginine methylester (L-NAME) and L-NAME+I 6000μg/L . After 3 months, urine iodine concentration, thyroid hormone, NO and nitric oxide synthase (NOS) serum levels were determined. Additionally, thyroid expression of inducible nitric oxide synthase (iNOS) was also investigated. Thyroid morphology was observed under light microscopy and transmission electron microscope. SCH as indicated by elevated serum thyrotropin (TSH) was induced among rats exposed to 3000 μg/L I - , while rats treated with 6000 μg/L I - presented PH characterized by elevated TSH and lowered total thyroxine in serum. Moreover, serum NO, NOS and iNOS expression in the thyroid were significantly increased in I 3000μg/L and I 6000μg/L groups. Changes in thyroid function and morphology in the L-NAME+I 6000μg/L group were extenuated compared to I 6000μg/L group. These findings suggested that chronic exposure to high water iodine from KIO 3 likely induces hypothyroidism with significant morphology changes in female Wistar rats and NO appears to be involved in the pathogenesis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Iodate Reduction by Shewanella oneidensis Does Not Involve Nitrate Reductase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mok, Jung Kee; Toporek, Yael J.; Shin, Hyun-Dong

Microbial iodate (IO 3 -) reduction is a major component of the iodine biogeochemical reaction network and is the basis of alternative strategies for remediation of iodine-contaminated environments. The molecular mechanism of microbial IO 3 - reduction, however, is not well understood. In microorganisms displaying IO 3 - and nitrate (NO 3 -) reduction activities, NO 3 - reductase is postulated to reduce IO 3 - as alternate electron acceptor. In the present study, whole genome analyses of 25 NO 3 --reducing Shewanella strains identified various combinations of genes encoding one assimilatory (cytoplasmic Nas) and three dissimilatory (membrane-associated Nar andmore » periplasmic Napα and Napβ) NO 3 - reductases. S. oneidensis was the only Shewanella strain whose genome encoded a single NO 3 - reductase (Napβ). Terminal electron acceptor competition experiments in S. oneidensis batch cultures amended with both NO 3 - and IO 3 - demonstrated that neither NO 3 - nor IO 3 - reduction activities were competitively inhibited by the presence of the competing electron acceptor. The lack of involvement of S. oneidensis Napβ in IO 3 - reduction was confirmed via phenotypic analysis of an in-frame gene deletion mutant lacking napβΑ (encoding the NO 3 --reducing NapβA catalytic subunit). S. oneidensis ΔnapβA was unable to reduce NO 3 -, yet reduced IO 3 - at rates higher than the wild-type strain. Thus, NapβA is required for dissimilatory NO 3 - reduction by S. oneidensis, while neither the assimilatory (Nas) nor dissimilatory (Napα, Napβ, and Nar) NO 3 - reductases are required for IO 3 - reduction. These findings oppose the traditional view that NO 3 - reductase reduces IO 3 - as alternate electron acceptor and indicate that S. oneidensis reduces IO 3 - via an as yet undiscovered enzymatic mechanism.« less

Application of inorganic oxidants to the spectrophotometric determination of ribavirin in bulk and capsules.

PubMed

Darwish, Ibrahim A; Khedr, Alaa S; Askal, Hassan F; Mohamed, Ramadan M

2006-01-01

Eight spectrophotometric methods for determination of ribavirin have been developed and validated. These methods were based on the oxidation of the drug by different inorganic oxidants: ceric ammonium sulfate, potassium permanganate, ammonium molybdate, ammonium metavanidate, chromium trioxide, potassium dichromate, potassium iodate, and potassium periodate. The oxidation reactions were performed in perchloric acid medium for ceric ammonium sulfate and in sulfuric acid medium for the other reagents. With ceric ammonium sulfate and potassium permanganate, the concentration of ribavirin in its samples was determined by measuring the decrease in the absorption intensity of the colored reagents at 315 and 525 nm, respectively. With the other reagents, the concentration of ribavirin was determined by measuring the intensity of the developed colored reaction products at the wavelengths of maximum absorbance: 675, 780, 595, 595, 475, and 475 nm for reactions with ammonium molybdate, ammonium metavanidate, chromium trioxide, potassium dichromate, potassium iodate, and potassium periodate, respectively. Different variables affecting the reaction conditions were carefully studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9984-0.9998) were found between the absorbance readings and the concentrations of ribavirin in the range of 4-1400 microg/mL. The molar absorptivities were correlated with the oxidation potential of the oxidants used. The precision of the methods were satisfactory; the values of relative standard deviation did not exceed 1.64%. The proposed methods were successfully applied to the analysis of ribavirin in pure drug material and capsules with good accuracy and precision; the recovery values were 99.2-101.2 +/- 0.48-1.30%. The results obtained using the proposed spectrophotometric methods were comparable with those obtained with the official method stated in the United States Pharmacopeia.

Computation of iodine species concentrations in water

NASA Technical Reports Server (NTRS)

Schultz, John R.; Mudgett, Paul D.; Flanagan, David T.; Sauer, Richard L.

1994-01-01

During an evaluation of the use of iodine as a water disinfectant and the development of methods for measuring various iodine species in water onboard Space Freedom, it became necessary to compute the concentration of the various species based on equilibrium principles alone. Of particular concern was the case when various amounts of iodine, iodide, strong acid, and strong base are added to water. Such solutions can be used to evaluate the performance of various monitoring methods being considered. The authors of this paper present an overview of aqueous iodine chemistry, a set of nonlinear equations which can be used to model the above case, and a computer program for solving this system of equations using the Newton-Raphson method. The program was validated by comparing results over a range of concentrations and pH values with those previously presented by Gottardi for a given pH. Use of this program indicated that there are multiple roots to many cases and selecting an appropriate initial guess is important. Comparison of program results with laboratory results for the case when only iodine is added to water indicates the program gives high pH values for the iodine concentrations normally used for water disinfection. Extending the model to include the effects of iodate formation results in the computer pH values being closer to those observed, but the model with iodate does not agree well for the case in which base is added in addition to iodine to raise the pH. Potential explanations include failure to obtain equilibrium conditions in the lab, inaccuracies in published values for the equilibrium constants, and inadequate model of iodine chemistry and/or the lack of adequate analytical methods for measuring the various iodine species in water.

Sodium Iodate Produces a Strain-Dependent Retinal Oxidative Stress Response Measured In Vivo Using QUEST MRI.

PubMed

Berkowitz, Bruce A; Podolsky, Robert H; Lenning, Jacob; Khetarpal, Nikita; Tran, Catherine; Wu, Johnny Y; Berri, Ali M; Dernay, Kristin; Shafie-Khorassani, Fatema; Roberts, Robin

2017-06-01

We identify noninvasive biomarkers that measure the severity of oxidative stress within retina layers in sodium iodate (SI)-atrophy vulnerable (C57BL/6 [B6]) and SI-atrophy resistant (129S6/SvEvTac [S6]) mice. At 24 hours after administering systemic SI to B6 and S6 mice we measured: (1) superoxide production in whole retina ex vivo, (2) excessive free radical production in vivo based on layer-specific 1/T1 values before and after α-lipoic acid (ALA) administration while the animal was inside the magnet (QUEnch-assiSTed MRI [QUEST MRI]), and (3) visual performance (optokinetic tracking) ± antioxidants; control mice were similarly assessed. Retinal layer spacing and thickness in vivo also were evaluated (optical coherence tomography, MRI). SI-treated B6 mice retina had a significantly higher superoxide production than SI-treated S6 mice. ALA-injected SI-treated B6 mice had reduced 1/T1 in more retinal layers in vivo than in SI-treated S6 mice. Uninjected and saline-injected SI-treated B6 mice had similar transretinal 1/T1 profiles. Notably, the inner segment layer 1/T1 of SI-treated B6 mice was responsive to ALA but was unresponsive in SI-treated S6 mice. In both SI-treated strains, antioxidants improved contrast sensitivity to similar extents; antioxidants did not change acuity in either group. Retinal thicknesses were normal in both SI-treated strains at 24 hours after treatment. QUEST MRI uniquely measured severity of excessive free radical production within retinal layers of the same subject. Identifying the mechanisms underlying genetic vulnerabilities to oxidative stress is expected to help in understanding the pathogenesis of retinal degeneration.

Iodide Protects Heart Tissue from Reperfusion Injury

PubMed Central

Iwata, Akiko; Morrison, Michael L.; Roth, Mark B.

2014-01-01

Iodine is an elemental nutrient that is essential for mammals. Here we provide evidence for an acute therapeutic role for iodine in ischemia reperfusion injury. Infusion of the reduced form, iodide, but not the oxidized form iodate, reduces heart damage by as much as 75% when delivered intravenously following temporary loss of blood flow but prior to reperfusion of the heart in a mouse model of acute myocardial infarction. Normal thyroid function may be required because loss of thyroid activity abrogates the iodide benefit. Given the high degree of protection and the high degree of safety, iodide should be explored further as a therapy for reperfusion injury. PMID:25379708

Analysis of iodinated X-ray contrast agents in water samples by ion chromatography and inductively-coupled plasma mass spectrometry.

PubMed

Sacher, Frank; Raue, Brigitte; Brauch, Heinz-Jürgen

2005-08-26

In this paper, an analytical method for the determination of six iodinated X-ray contrast agents (amidotrizoic acid, iohexol, iomeprol, iopamidol, iopromide, and ioxitalamic acid), iodide, and iodate in water samples is presented. The method is based on a separation of the analytes by ion chromatography (IC) and a subsequent detection by inductively-coupled plasma mass spectrometry (ICP-MS). The method was optimised with respect to separation conditions (column type and eluent composition) and extensively validated. Without pre-concentration of the samples, limits of detection below 0.2 microg/l could be achieved whereby reproducibility was below 6% for all compounds under investigation.

Indirect spectrophotometric determination of traces of bromide in water

USGS Publications Warehouse

Fishman, M. J.; Skougstad, M.W.

1963-01-01

A rapid, accurate, and sensitive indirect spectrophotometric method for the determination of bromide in natural waters is based on the catalytic effect of bromide on the oxidation of iodine to iodate by potassium permanganate in sulfuric acid solution. The method is applicable to concentrations ranging from 1 to 100 ??g. of bromide per liter, but may be modified to extend the concentration range. Most ions commonly occurring in water do not interfere. The standard deviation is 2.9 at bromide concentrations of 100 ??g. per liter and less at lower concentrations. The determination of bromide in samples containing known added amounts gave values ranging from 99 to 105% of the concentration calculated to be present.

Method for immobilizing radioactive iodine

DOEpatents

Babad, Harry; Strachan, Denis M.

1980-01-01

Radioactive iodine, present as alkali metal iodides or iodates in an aqueous solution, is incorporated into an inert solid material for long-term storage by adding to the solution a stoichiometric amount with respect to the formation of a sodalite (3M.sub.2 O.3Al.sub.2 O.sub.3. 6SiO.sub.2.2MX, where M=alkali metal; X=I.sup.- or IO.sub.3.sup.-) of an alkali metal, alumina and silica, stirring the solution to form a homogeneous mixture, drying the mixture to form a powder, compacting and sintering the compacted powder at 1073 to 1373 K (800.degree. to 1100.degree. C.) for a time sufficient to form sodalite.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santschi, Peter H.; Xu, Chen; Schwehr, Kathleen A.

Iodine (I) occurs in multiple oxidation states in aquatic systems in the form of organic and inorganic species (iodide and iodate). This fact leads to complex biogeochemical cycling of Iodine and its long-lived isotope, 129I, a major by-product of nuclear fission. Results from our newly developed, sensitive and rapid method for speciated isotopic ratios ( 129I/ 127I) via GC-MS, which compare favorably with Accelerator Mass Spectroscopy, demonstrate that the mobility of 129I species greatly depends on the type of I species and its concentration, pH, and sediment redox state. At ambient concentrations (~10 7 M), I- and IO -3 aremore » significantly retarded by sorption to mineral surfaces and covalent binding to aromatic moieties in natural organic matter (NOM), even when NOM is present at low concentrations such as occur at Hanford. At concentrations traditionally examined in sorption studies (≥ 10 -4 M), I- travels along with the water. Iodate removal can also occur through incorporation into CaCO 3 crystal lattice, e.g., at the Hanford Site. Removal of iodine from the groundwater through interaction with NOM is complicated by the release of mobile organo-I species, as was observed at SRS and Hanford. A small fraction of NOM that is bound to iodine can behave as a mobile organo-I source, a process that we were able to numerically simulate. Field and laboratory studies evaluating the cause for steady increases in 129I concentrations (up to 1000 pCi L-1) emanating from radiological basins at SRS indicate that an increase of 0.7 pH units in groundwater over 17 years can account for the observed increased groundwater 129I concentrations. Bacteria from a 129I-contaminated aerobic aquifer at the F-area of SRS can accumulate I- at environmentally relevant concentrations (10 -7 M), and enzymatically oxidize I-, which together with microbially produced MnO 2 and superoxide or organic acids can significantly contribute to organo-iodine formation.« less

Reactions of hypoiodous acid with model compounds and the formation of iodoform in absence/presence of permanganate.

PubMed

Zhao, Xiaodan; Ma, Jun; von Gunten, Urs

2017-08-01

The kinetics for the reactions of hypoiodous acid (HOI) with various phenols (phenol, 4-nitrophenol, 4-hydroxybenzoic acid), 3-oxopentanedioic acid (3-OPA) and flavone were investigated in the pH range of 6.0-11.0. The apparent second order rate constants for the reactions of HOI with phenolic compounds, 3-OPA, flavone and citric acid at pH 8.0 are 10-10 7  M -1 s -1 , (4.0 ± 0.3) × 10 3  M -1 s -1 , (2.5 ± 0.2) × 10 3  M -1 s -1 and <1 M -1 s -1 , respectively. The effect of buffer type and concentration was investigated with acetate, phosphate and borate. All tested buffers promote the HOI reactions with phenols. The percentage of iodine incorporation for various (hydroxyl)phenolic compounds and two NOM extracts ranges from 5% to 98%, indicating that electrophilic aromatic substitution and/or electron transfer can occur. The extent of these reactions depends on the number and relative position of the hydroxyl moieties on the phenolic compounds. Iodoform formation rates increase with increasing pH and iodoform yields increase from 9% to 67% for pH 6.0-10.0 for the HOI/3-OPA reactions. In the permanganate/HOI/3-OPA and permanganate/iodide/3-OPA system at pH < 8.0, iodoform formation is elevated compared to the HOI/3-OPA system in absence of permanganate. For pH > 8.0, in presence of permanganate, iodoform formation is significantly inhibited and iodate formation enhanced, which is due to a faster permanganate-mediated HOI disproportionation to iodate compared to the iodination process. The production of reactive iodine in real waters containing iodide in contact with permanganate may lead to the formation of iodinated organic compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

saltPAD: A New Analytical Tool for Monitoring Salt Iodization in Low Resource Settings

PubMed Central

Myers, Nicholas M.; Strydom, Emmerentia Elza; Sweet, James; Sweet, Christopher; Spohrer, Rebecca; Dhansay, Muhammad Ali; Lieberman, Marya

2016-01-01

We created a paper test card that measures a common iodizing agent, iodate, in salt. To test the analytical metrics, usability, and robustness of the paper test card when it is used in low resource settings, the South African Medical Research Council and GroundWork performed independent validation studies of the device. The accuracy and precision metrics from both studies were comparable. In the SAMRC study, more than 90% of the test results (n=1704) were correctly classified as corresponding to adequately or inadequately iodized salt. The cards are suitable for market and household surveys to determine whether salt is adequately iodized. Further development of the cards will improve their utility for monitoring salt iodization during production. PMID:29942380

Industrial Water Treatment Primer

DTIC Science & Technology

1992-03-01

calculated as follows: Sulfite, ppm = (ml solution) x (factor). EXAMPLE: 2.3 ml of Potassium Iodide - Iodate Solution were required to change the color of ...8217. 4A"O aqd. nd coffOicTAq ofd𔃾ne I" c ot(¶O f any.~.o W’dcmclojdn fb’e’ ~~t ,~~ P4 uOqj of 1’i 40flc~nof "fo~s~rmU l. If i Igo4 t fo, ’edvong IN% bw to...4sal g V IOA af e So ýn o irv , aw lo w inton ra ton 0w rtovr4 • a i I v j holq w- F _ O.f ,stwa. tjieI*.AI: 9 b. 1U 2 02. snd to thw Of ~e 0 ,*ot

Determination of hydrolyzable tannins (gallotannins and ellagitannins) after reaction with potassium iodate.

PubMed

Hartzfeld, Paul W; Forkner, Rebecca; Hunter, Mark D; Hagerman, Ann E

2002-03-27

A widely used method for analyzing hydrolyzable tannins afer reaction with KIO(3) has been modified to include a methanolysis step followed by oxidation with KIO(3). In the new method, hydrolyzable tannins (gallotannins and ellagitannins) are reacted at 85 degrees C for 20 h in methanol/sulfuric acid to quantitatively release methyl gallate. Dried plant samples can be methanolyzed under the same conditions to convert hydrolyzable tannins to methyl gallate. Oxidation of the methyl gallate by KIO(3) at pH 5.5, 30 degrees C, forms a chromophore with lambda(max) 525 nm, which is determined spectrophotometrically. The detection limit of the method is 1.5 microg of methyl gallate, and with plant samples, relative standard deviations of less than 3% were obtained.

Determination of thiourea in fruit juice by a kinetic spectrophotometric method.

PubMed

Abbasi, Shahryar; Khani, Hossein; Hosseinzadeh, Laleh; Safari, Zhila

2010-02-15

A catalytic kinetic method is described for determination of trace levels of thiourea based on its catalytic effect on the oxidation of Janus green (JG) by potassium iodate in hydrochloric acid media. The reaction was monitored by measuring the decrease in absorbance of the dye at 610 nm after 25 min. The effect of some factors on the reaction speed was investigated. The developed method allowed the determination of thiourea in range of 0.01-12.00 mg L(-1) with good precision, accuracy and the detection limit was 0.008 mg L(-1). Most of foreign species do not interfere with the determination. The method was found to be sensitive, selective and was applied to the determination of thiourea in fruit juices and orange peel.

Singlet oxygen production by chloroperoxidase-hydrogen peroxide-halide systems.

PubMed

Kanofsky, J R

1984-05-10

Singlet oxygen production in the chloroperoxidase-hydrogen peroxide-halide system was studied using 1268 nm chemiluminescence. With chloride or bromide ions, singlet oxygen is produced by the mechanism (formula; see text) (formula; see text) where X- is chloride or bromide ion. Under conditions where there is high enzyme activity and when Reaction B is fast relative to Reaction A, singlet oxygen is produced in near stoichiometric amounts. In contrast, when Reaction A is fast relative to Reaction B, oxidized halogen species (chlorine and hypochlorous acid for chloride ion; bromide, tribromide ion, and hypobromous acid for bromide ion) are the principle reaction products. With iodide ion, no 1268 nm chemiluminescence was detected. Past studies have shown that iodine and iodate ion are the major end products of this system.

Evaluation of potential for mercury volatilization from natural and FGD gypsum products using flux-chamber tests.

PubMed

Shock, Scott S; Noggle, Jessica J; Bloom, Nicholas; Yost, Lisa J

2009-04-01

Synthetic gypsum produced by flue-gas desulfurization (FGD) in coal-fired power plants (FGD gypsum) is put to productive use in manufacturing wallboard. FGD gypsum wallboard is widely used, accounting for nearly 30% of wallboard sold in the United States. Mercury is captured in flue gas and thus is one of the trace metals present in FGD gypsum; raising questions about the potential for mercury exposure from wallboard. Mercury is also one of the trace metals present in "natural" mined gypsum used to make wall board. Data available in the literature were not adequate to assess whether mercury in wallboard from either FGD or natural gypsum could volatilize into indoor air. In this study, mercury volatilization was evaluated using small-scale (5 L) glass and Teflon flux chambers, with samples collected using both iodated carbon and gold-coated sand traps. Mercury flux measurements made using iodated carbon traps (n=6) were below the detection limit of 11.5 ng/m2-day for all natural and synthetic gypsum wallboard samples. Mercury flux measurements made using gold-coated sand traps (n=6) were 0.92 +/- 0.11 ng/m2-day for natural gypsum wallboard and 5.9 +/- 2.4 ng/m2-day for synthetic gypsum wallboard. Room air mercury concentrations between 0.028 and 0.28 ng/m3 and between 0.13 and 2.2 ng/m3 were estimated based on the flux-rate data for natural and synthetic gypsum wallboard samples, respectively, and were calculated assuming a 3 m x 4 m x 5 m room, and 10th and 90th percentile air exchange rates of 0.18/hour and 1.26/hour. The resulting concentration estimates are well below the U.S. Environmental Protection Agency (EPA) reference concentration for indoor air elemental mercury of 300 ng/m3 and the Agency for Toxic Substances and Disease Registry minimal risk level (MRL) of 200 ng/m3. Further, these estimates are below background mercury concentrations in indoor air and within or below the range of typical background mercury concentrations in outdoor air.

Chemical Dynamics of nano-Aluminum and Iodine Based Oxidizers

NASA Astrophysics Data System (ADS)

Little, Brian; Ridge, Claron; Overdeep, Kyle; Slizewski, Dylan; Lindsay, Michael

2017-06-01

As observed in previous studies of nanoenergetic powder composites, micro/nano-structural features such as particle morphology and/or reactant spatial distance are expected to strongly influence properties that govern the combustion behavior of energetic materials (EM). In this study, highly reactive composites containing crystalline iodine (V) oxide or iodate salts with nano-sized aluminum (nAl) were blended by two different processing techniques and then collected as a powder for characterization. Physiochemical techniques such as thermal gravimetric analysis, calorimetry, X-ray diffraction, electron microscopy, high speed photography, pressure profile analysis, temperature programmed reactions, and spectroscopy were employed to characterize these EM with emphasis on correlating the chemical reactivity with inherent structural features and variations in stoichiometry. This work is a continuation of efforts to probe the chemical dynamics of nAl-iodine based composites.

An experimental design method leading to chemical Turing patterns.

PubMed

Horváth, Judit; Szalai, István; De Kepper, Patrick

2009-05-08

Chemical reaction-diffusion patterns often serve as prototypes for pattern formation in living systems, but only two isothermal single-phase reaction systems have produced sustained stationary reaction-diffusion patterns so far. We designed an experimental method to search for additional systems on the basis of three steps: (i) generate spatial bistability by operating autoactivated reactions in open spatial reactors; (ii) use an independent negative-feedback species to produce spatiotemporal oscillations; and (iii) induce a space-scale separation of the activatory and inhibitory processes with a low-mobility complexing agent. We successfully applied this method to a hydrogen-ion autoactivated reaction, the thiourea-iodate-sulfite (TuIS) reaction, and noticeably produced stationary hexagonal arrays of spots and parallel stripes of pH patterns attributed to a Turing bifurcation. This method could be extended to biochemical reactions.

Influence of an electric field on the buoyancy-driven instabilities.

PubMed

Zadrazil, Ales; Sevcíková, Hana

2005-11-01

The influence of dc electric fields (EFs) on the development of buoyancy-driven instabilities of reaction fronts is investigated experimentally in a modified Hele-Shaw cell for the arsenous acid-iodate system. Assessment of effects of external EFs is made both visually and through dispersion curves. It is shown that density fingering, observed on ascending fronts, is suppressed by the EF if the front propagates towards the positive electrode and is enhanced when the front propagates towards the negative electrode. The stabilizing (destabilizing) effects include slower (faster) development of fingers and the decrease (increase) in their numbers. The descending front, stable under no EF conditions, remains stable when an EF is applied with the positive electrode facing the approaching front. When the descending front faces the negative electrode, the tiny fingerlike structure develops after quite a long time.

Evaluation of the normal range of values for uptake of radioactive iodine by the thyroid gland.

PubMed Central

Schober, B.; Hunt, J. A.

1976-01-01

Uptake of radioactive iodine by the thyroid gland after oral administration of 75 muCi was determined in 1971-72 in 60 euthyroid female volunteers from the North Shore of Vancouver. Values were as low as 3% at 4 hours and 7% at 24 hours in subjects otherwise proven to be euthyroid. The highest values found were 13 and 26% at 4 and 24 hours. The effective thyroxine ratios were all within the accepted normal range. However, more than half of the volunteers showed some enlargement of the thyroid gland. These results suggest an increased iodine pool in the subjects, the likley source being iodine in mild, dairy products and erythrosine, a colouring agent in foods and pharmaceutical products. Potassium iodate, used sometimes in bread baking, contributed little to this pool in our sample. Subjects were, on the average, 9 to 25% heavier than their peers 20 years ago. PMID:1277057

Characterization of oxidized coal surfaces: Quarterly report, January 1987-April 1987

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hercules, D.M.

1987-04-01

The work has focused on exploration of ambient temperature in-situ derivatization of aldehydes and ketones on carbon surfaces. 2,4-Dinitrophenylhydrazine, bisulfite, -ylium dichloro-iodate, and iminium perchlorate derivatizations were performed on a set of model aldehydes and ketones. Positive and negative ion laser mass spectra (LMS) of the 2,4-dinitrophenylhydrazine derivatives were obtained on zinic which is a common metal support used for LMS analysis. Although positive ion spectra were informative, negative ion spectra were more satisfactory as most compounds yielded molecular ion species in negative ion analysis. Spectra of selected preformed derivatives placed on charcoal and of benzaldehyde derivatized on charcoal weremore » also obtained. Molecular ion species that can be distinguished readily from carbon background ions were observed. Thus, the results established that in-situ derivatization followed by analysis is indeed possible. 3 refs., 8 figs.« less

Preparation and evaluation of a silica-based 1-alkyl-3-(propyl-3-sulfonate) imidazolium zwitterionic stationary phase for high-performance liquid chromatography.

PubMed

Qiu, Hongdeng; Jiang, Qiong; Wei, Zheng; Wang, Xusheng; Liu, Xia; Jiang, Shengxiang

2007-09-07

A new zwitterionic stationary phase based on silica bonded with 1-alkyl-3-(propyl-3-sulfonate) imidazolium was synthesized and characterized in this paper. The materials have been confirmed and evaluated by elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. Potassium and calcium were separated simultaneously with several common inorganic anions including an iodate, chloride, bromide, nitrate and iodide on the phase. The effects of the concentration, organic solvent and pH of the eluent on the separation of anions were studied. Operated in the anion-exchange mode, this new stationary phase shows considerable promise for the separation of anions. Bases, vitamins and three imidazolium ionic liquids with different alkyl chains are also separated successfully on this column. The stationary phase has multiple retention mechanisms, such as anion-exchange, electrostatic attraction and repulsion interactions, and hydrophobic interaction between the zwitterionic stationary phase and specimens.

Determination of trace level bromate and perchlorate in drinking water by ion chromatography with an evaporative preconcentration technique.

PubMed

Liu, Yongjian; Mou, Shifen; Heberling, Shawn

2002-05-17

A simple sample preconcentration technique employing microwave-based evaporation for the determination of trace level bromate and perchlorate in drinking water with ion chromatography is presented. With a hydrophilic anion-exchange column and a sodium hydroxide eluent in linear gradient, bromate and perchlorate can be determined in one injection within 35 min. Prior to ion chromatographic analysis, the drinking water sample was treated with an OnGuard-Ag cartridge to remove the superfluous chloride and concentrated 20-fold using a PTFE beaker in a domestic microwave oven for 15 min. The recoveries of the anions ranged from 94.6% for NO2- to 105.2% for F-. The detection limits for bromate, perchlorate, iodate and chlorate were 0.1, 0.2, 0.1 and 0.2 microg/l, respectively. The developed method is applicable for the quantitation of bromate and perchlorate in drinking water samples.

Simultaneous detection of iodine and iodide on boron doped diamond electrodes.

PubMed

Fierro, Stéphane; Comninellis, Christos; Einaga, Yasuaki

2013-01-15

Individual and simultaneous electrochemical detection of iodide and iodine has been performed via cyclic voltammetry on boron doped diamond (BDD) electrodes in a 1M NaClO(4) (pH 8) solution, representative of typical environmental water conditions. It is feasible to compute accurate calibration curve for both compounds using cyclic voltammetry measurements by determining the peak current intensities as a function of the concentration. A lower detection limit of about 20 μM was obtained for iodide and 10 μM for iodine. Based on the comparison between the peak current intensities reported during the oxidation of KI, it is probable that iodide (I(-)) is first oxidized in a single step to yield iodine (I(2)). The latter is further oxidized to obtain IO(3)(-). This technique, however, did not allow for a reasonably accurate detection of iodate (IO(3)(-)) on a BDD electrode. Copyright © 2012 Elsevier B.V. All rights reserved.

Iodide-ion-induced oscillations of the ferroin-catalyzed Belousov—Zhabotinskii reaction

NASA Astrophysics Data System (ADS)

Melicherčík, Milan; Treindl, Ľudovít

1992-08-01

Contrary to "classical" Belousov—Zhabotinskii (BZ) oscillatory systems, consisting of malonic acid, Ce(IV)—Ce(III) or Mn(III)—Mn(II) redox catalyst and KBrO 3 in solutions of H 2SO 4, where in an interval of added iodide initial concentrations 10 -4 mol dm -3 < [I -] 0 < 10 -3 mol dm -3 the oscillations have the same frequency and amplitude as in the absence of iodide, the effect of added iodide on the ferroin-catalyzed BZ system with methyl ester of 3-oxobutanoic acid leads to an increase in the number of oscillations and in the time of their duration. The dependence of this effect on substrate, bromate, iodide, sulfuric acid and ferroin concentrations has been studied. The observations may be explained by a mechanism involving direct reduction of ferroin by iodide, oxidation of iodide to iodate by bromate with a bromide production and eventual faster bromination and iodination of methyl ester of 3-oxobutanoic acid in relation to malonic acid.

Thyrotoxicosis induced by iodine contamination of food--a common unrecognised condition?

PubMed Central

Stewart, J C; Vidor, G I

1976-01-01

The incidence of thyrotoxicosis in northern Tasmania rose significantly in 1964, two years before an epidemic of iodine-induced thyrotoxicosis was precipitated by the addition of iodate to bread to prevent goitre. Each time older patients accounted for most of the increase. The 1964 increase was probably iodine-induced as the use of iodophor disinfectants on dairy farms, which causes iodine residues in milk, began in 1963 and a fall in the prevalence of goitre in young children suggested an increase in dietary iodine at about that time. A further small increase in thyrotoxicosis in 1971 may also have been iodine-induced as it followed an extension of the use of iodophors. Dietary iodine is rising substantially in many places because of high iodine levels in milk and the use of iodine compounds in automated bread making, and this may be causing unsuspected iodine-induced thyrotoxicosis. Dietary iodine should be monitored regularly and clinicans alerted to any rise. Contamination of common foods with iodine should be more strictly controlled. PMID:946162

Temperature Dependences of Dielectric, Elastic and Piezoelectric Properties of KIO 3 Single Crystals Associated with the Successive Phase Transitions

NASA Astrophysics Data System (ADS)

Maeda, Masaki; Takagi, Masayoshi; Suzuki, Ikuo

2000-01-01

Pottasium iodate, KIO3, belongs to the perovskite structure and undergoes successive phase transitions at T1= 212°C, T2= 72.5°C, T3=-15°C, T4=-160°C and T5=-240°C, respectively. The temperature dependences of the dielectric, elastic and piezoelectic properties have been measured in the temperature range from -263°C to 330°C.The superionic conductivity was found in the temperature range above T2. Pronounced dielectric dispersions in the frequency range below 10 kHz were observed around -160°C and -240°C and the data were analyzed by fitting to the Davidson-Cole and Havriliak-Negami dispersion formulas, respectively. Both dielectric anomalies are ascribed to the orientaional glass-transitions. The piezoelectric and elastic properties have been investigsated by the resonance-antiresonance method. The piezoelectric and elastic anomalies were observed at T2 and T3.

Microbial Transformation of Iodine: From Radioisotopes to Iodine Deficiency.

PubMed

Yeager, Chris M; Amachi, Seigo; Grandbois, Russell; Kaplan, Daniel I; Xu, Chen; Schwehr, Kathy A; Santschi, Peter H

2017-01-01

Iodine is a biophilic element that is important for human health, both as an essential component of several thyroid hormones and, on the other hand, as a potential carcinogen in the form of radioiodine generated by anthropogenic nuclear activity. Iodine exists in multiple oxidation states (-1, 0, +1, +3, +5, and +7), primarily as molecular iodine (I 2 ), iodide (I - ), iodate [Formula: see text] , or organic iodine (org-I). The mobility of iodine in the environment is dependent on its speciation and a series of redox, complexation, sorption, precipitation, and microbial reactions. Over the last 15years, there have been significant advances in iodine biogeochemistry, largely spurred by renewed interest in the fate of radioiodine in the environment. We review the biogeochemistry of iodine, with particular emphasis on the microbial processes responsible for volatilization, accumulation, oxidation, and reduction of iodine, as well as the exciting technological potential of these fascinating microorganisms and enzymes. Copyright © 2017 Elsevier Inc. All rights reserved.

The impact of disulfide bond dynamics in wheat gluten protein on the development of fermented pastry crumb.

PubMed

Ooms, Nand; Jansens, Koen J A; Pareyt, Bram; Reyniers, Stijn; Brijs, Kristof; Delcour, Jan A

2018-03-01

Gluten proteins functionality during pastry production was examined by including redox agents in the ingredient bill. Addition of reducing and oxidizing agents respectively increased and decreased dough height during fermentation. The presence of large gas bubbles in the samples with oxidizing agents may have caused a 'stacking'-effect and a more effective dough lift. During baking, the level of extractable proteins decreased to comparable values for all samples, except when potassium iodate (KIO 3 ) was used in the recipe. As a result of its use, a lower level of gliadin was incorporated into the gluten polymer and dough layers tended to 'slide' apart during baking, thereby causing collapse. Most likely, KIO 3 caused glutenin oxidation within each individual dough layer to such extent during the dough stage that insufficient thiol groups were available for forming dough layer interconnections during baking, after margarine melting. Furthermore, addition of redox agents impacted the product's crumb structure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uptake of different species of iodine by water spinach and its effect to growth.

PubMed

Weng, Huan-Xin; Yan, Ai-Lan; Hong, Chun-Lai; Xie, Lin-Li; Qin, Ya-Chao; Cheng, Charles Q

2008-08-01

A hydroponic experiment has been carried out to study the influence of iodine species [iodide (I(-)), iodate (IO(-)(3)), and iodoacetic acid (CH(2)ICOO(-))] and concentrations on iodine uptake by water spinach. Results show that low levels of iodine in the nutrient solution can effectively stimulate the growth of biomass of water spinach. When iodine levels in the nutrient solution are from 0 to 1.0 mg/l, increases in iodine levels can linearly augment iodine uptake rate by the leafy vegetables from all three species of iodine, and the uptake effects are in the following order: CH(2)ICOO(-) >I(-)>IO(-)(3). In addition, linear correlation was observed between iodine content in the roots and shoots of water spinach, and their proportion is 1:1. By uptake of I(-), vitamin C (Vit C) content in water spinach increased, whereas uptake of IO(-)(3) and CH(2)ICOO(-) decreased water spinach Vit C content. Furthermore, through uptake of I(-) and IO(-)(3). The nitrate content in water spinach was increased by different degrees.

Silver-functionalized silica aerogels and their application in the removal of iodine from aqueous environments

DOE PAGES

Asmussen, R. Matthew; Matyas, Josef; Qafoku, Nikolla P.; ...

2018-05-01

Here, one of the key challenges for radioactive waste management is the efficient capture and immobilization of radioiodine, because of its radiotoxicity, high mobility in the environment, and long half-life (t 1/2 = 1.57 × 10 7 years). Silver-functionalized silica aerogel (AgAero) represents a strong candidate for safe sequestration of radioiodine from various nuclear waste streams and subsurface environments. Batch sorption experiments up to 10 days long were carried out in oxic and anoxic conditions in both deionized water (DIW) and various Hanford Site Waste Treatment Plant (WTP) off-gas condensate simulants containing from 5 to 10 ppm of iodide (Imore » –) or iodate (IO 3 –). Also tested was the selectivity of AgAero towards I – in the presence of other halide anions. AgAero exhibited fast and complete removal of I – from DIW, slower but complete removal of I – from WTP off-gas simulants, preferred removal of I – over Br – and Cl –, and it demonstrated ability to remove IO 3 – through reduction to I –.« less

Impact of impurities on the α-LiIO{sub 3} crystal growth: Technique for measuring the “dead zone”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noskova, A. N., E-mail: anna-13.08@mail.ru; Rubakha, V. I.; Prokhorov, A. P.

Lithium iodate (α-LiIO{sub 3}) single crystal is a promising nonlinear optical material, which used for efficient laser radiation conversion in the visible and near-IR regions. A technique for measuring the “dead zone” (ΔТ{sub dz}) of LiIO{sub 3} solutions has been developed; data on the impact of Fe(IO{sub 3}){sub 2}, AgIO{sub 3}, CsOH, H{sub 3}PO{sub 4}, and methyl methacrylate on the growth of the (100) face of α-LiIO{sub 3} crystals have been presented; and the dependences of the nucleation and motion of single steps on the degree of supersaturation have been measured. It is shown that the ΔТ{sub dz} value makesmore » it possible to estimate the validity of solutions for growing α-LiIO{sub 3} crystals. The results of measuring the face growth rates and step velocities for KDP and α-LiIO{sub 3} crystals are compared.« less

Iodine-Mediated Etching of Gold Nanorods for Plasmonic ELISA Based on Colorimetric Detection of Alkaline Phosphatase.

PubMed

Zhang, Zhiyang; Chen, Zhaopeng; Wang, Shasha; Cheng, Fangbin; Chen, Lingxin

2015-12-23

Here, we propose a plasmonic enzyme-linked immunosorbent assay (ELISA) based on highly sensitive colorimetric detection of alkaline phosphatase (ALP), which is achieved by iodine-mediated etching of gold nanorods (AuNRs). Once the sandwich-type immunocomplex is formed, the ALP bound on the polystyrene microwells will hydrolyze ascorbic acid 2-phosphate into ascorbic acid. Subsequently, iodate is reduced to iodine, a moderate oxidant, which etches AuNRs from rod to sphere in shape. The shape change of AuNRs leads to a blue-shift of longitudinal localized surface plasmon resonance. As a result, the solution of AuNRs changes from blue to red. Benefiting from the highly sensitive detection of ALP, the proposed plasmonic ELISA has achieved an ultralow detection limit (100 pg/mL) for human immunoglobulin G (IgG). Importantly, the visual detection limit (3.0 ng/mL) allows the rapid differential diagnosis with the naked eye. The further detection of human IgG in fetal bovine serum indicates its applicability to the determination of low abundance protein in complex biological samples.

Silver-functionalized silica aerogels and their application in the removal of iodine from aqueous environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asmussen, R. Matthew; Matyas, Josef; Qafoku, Nikolla P.

Here, one of the key challenges for radioactive waste management is the efficient capture and immobilization of radioiodine, because of its radiotoxicity, high mobility in the environment, and long half-life (t 1/2 = 1.57 × 10 7 years). Silver-functionalized silica aerogel (AgAero) represents a strong candidate for safe sequestration of radioiodine from various nuclear waste streams and subsurface environments. Batch sorption experiments up to 10 days long were carried out in oxic and anoxic conditions in both deionized water (DIW) and various Hanford Site Waste Treatment Plant (WTP) off-gas condensate simulants containing from 5 to 10 ppm of iodide (Imore » –) or iodate (IO 3 –). Also tested was the selectivity of AgAero towards I – in the presence of other halide anions. AgAero exhibited fast and complete removal of I – from DIW, slower but complete removal of I – from WTP off-gas simulants, preferred removal of I – over Br – and Cl –, and it demonstrated ability to remove IO 3 – through reduction to I –.« less

Optimized and Validated Spectrophotometric Methods for the Determination of Enalapril Maleate in Commercial Dosage Forms

PubMed Central

Rahman, Nafisur; Haque, Sk Manirul

2008-01-01

Four simple, rapid and sensitive spectrophotometric methods have been proposed for the determination of enalapril maleate in pharmaceutical formulations. The first method is based on the reaction of carboxylic acid group of enalapril maleate with a mixture of potassium iodate (KIO3) and iodide (KI) to form yellow colored product in aqueous medium at 25 ± 1°C. The reaction is followed spectrophotometrically by measuring the absorbance at 352 nm. The second, third and fourth methods are based on the charge transfer complexation reaction of the drug with p-chloranilic acid (pCA) in 1, 4-dioxan-methanol medium, 2, 3-dichloro 5, 6-dicyano 1, 4-benzoquinone (DDQ) in acetonitrile-1,4 dioxane medium and iodine in acetonitrile-dichloromethane medium. Under optimized experimental conditions, Beer’s law is obeyed in the concentration ranges of 2.5–50, 20–560, 5–75 and 10–200 μg mL−1, respectively. All the methods have been applied to the determination of enalapril maleate in pharmaceutical dosage forms. Results of analysis are validated statistically. PMID:19609388

[Determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry].

PubMed

Lin, Li; Chen, Guang; Chen, Yuhong

2011-07-01

A method was established for the determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP/ MS). Alkaline extraction and IC-ICP/MS were applied as the sample pre-treatment method and the detection technique respectively, for iodate and iodide determination. Moreover, high-temperature pyrolysis absorption was adopted as the pre-treatment method for total iodine analysis, which finally converted all the iodine species into iodide and measured the iodide by IC-ICP/MS. The recoveries of iodine for alkaline extraction and high-temperature pyrolysis absorption were 89.6%-97.5% and 95.2%-111.2%, respectively. The results were satisfactory. The detection limit of iodine was 0.010 mg/kg. The iodine and its speciation contents in several kinds of plant samples such as seaweeds, kelp, cabbage, tea leaf and spinach were investigated. It was shown that the iodine in seaweeds mainly existed as organic iodine; while the ones in kelp, cabbage, tea leaf and spinach mainly existed as inorganic iodine.

Bi2(IO3)(IO6): First combination of [IO3]- and [IO6]5- anions in three-dimensional framework

NASA Astrophysics Data System (ADS)

Sun, Chuanling; Wu, Yuandong; Mei, Dajiang; Doert, Thomas

2018-03-01

A new bismuth (III) iodate periodate, Bi2(IO3)(IO6) was obtained from hydrothermal reactions using Bi(NO3)3·5H2O, and H5IO6 as starting materials. Bi2(IO3)(IO6) crystallizes in the monoclinic space group P21/c (No. 14) with lattice parameters ɑ = 8.1119(6), b = 5.4746(4), c = 16.357(1) Å, β = 99.187(2)°, V = 717.07(9) Å3, Z = 4. The structure of Bi2(IO3)(IO6) features a three-dimensional framework which is a combination of [Bi(1)O5] tetragonal pyramids, [Bi(2)O8] bicapped trigonal prisms and [IO3]- and [IO6]5- anions. Thermal analysis shows that the compound is thermally stable up to about 350 °C. The solid state UV-vis-NIR diffuse reflectance spectrum indicates that Bi2(IO3)(IO6) is a semiconductor with a band gap of 2.76 eV.

Silver-functionalized silica aerogels and their application in the removal of iodine from aqueous environments.

PubMed

Asmussen, R Matthew; Matyáš, Josef; Qafoku, Nikolla P; Kruger, Albert A

2018-05-01

One of the key challenges for radioactive waste management is the efficient capture and immobilization of radioiodine, because of its radiotoxicity, high mobility in the environment, and long half-life (t 1/2  = 1.57 × 10 7 years). Silver-functionalized silica aerogel (AgAero) represents a strong candidate for safe sequestration of radioiodine from various nuclear waste streams and subsurface environments. Batch sorption experiments up to 10 days long were carried out in oxic and anoxic conditions in both deionized water (DIW) and various Hanford Site Waste Treatment Plant (WTP) off-gas condensate simulants containing from 5 to 10 ppm of iodide (I - ) or iodate (IO 3 - ). Also tested was the selectivity of AgAero towards I - in the presence of other halide anions. AgAero exhibited fast and complete removal of I - from DIW, slower but complete removal of I - from WTP off-gas simulants, preferred removal of I - over Br - and Cl - , and it demonstrated ability to remove IO 3 - through reduction to I - . Copyright © 2018 Elsevier B.V. All rights reserved.

Implementing large-scale food fortification in Ghana: lessons learned.

PubMed

Nyumuah, Richard Odum; Hoang, Thuy-Co Caroline; Amoaful, Esi Foriwa; Agble, Rosanna; Meyer, Marc; Wirth, James P; Locatelli-Rossi, Lorenzo; Panagides, Dora

2012-12-01

Food fortification began in Ghana in 1996 when legislation was passed to enforce the iodization of salt. This paper describes the development of the Ghanaian fortification program and identifies lessons learned in implementing fortification initiatives (universal salt iodization, fortification of vegetable oil and wheat flour) from 1996 to date. This paper identifies achievements, challenges, and lessons learned in implementing large scale food fortification in Ghana. Primary data was collected through interviews with key members of the National Food Fortification Alliance (NFFA), implementation staff of the Food Fortification Project, and staff of GAIN. Secondary data was collected through desk review of documentation from the project offices of the National Food Fortification Project and the National Secretariat for the Implementation of the National Salt Iodization in Ghana. Reduction of the prevalence of goiter has been observed, and coverage of households with adequately iodized salt increased between 1996 and 2006. Two models were designed to increase production of adequately iodized salt: one to procure and distribute potassium iodate (KIO3) locally, and the second, the salt bank cooperative (SBC) model, specifically designed for small-scale artisanal salt farmers. This resulted in the establishment of a centralized potassium iodate procurement and distribution system, tailored to local needs and ensuring competitive and stable prices. The SBC model allowed for nearly 157 MT of adequately iodized salt to be produced in 2011 in a region where adequately iodized salt was initially not available. For vegetable oil fortification, implementing quantitative analysis methods for accurate control of added fortificant proved challenging but was overcome with the use of a rapid test device, confirming that 95% of vegetable oil is adequately fortified in Ghana. However, appropriate compliance with national standards on wheat flour continues to pose challenges due to adverse sensory effects, which have led producers to reduce the dosage of premix in wheat flour. Challenges to access to premix experienced by small producers can be overcome with a central procurement model in which the distributor leverages the overall volume by tendering for a consolidated order. The SBC model has the potential to be expanded and to considerably increase the coverage of the population consuming iodized salt in Ghana. Successful implementation of the cost-effective iCheck CHROMA rapid test device should be replicated in other countries where quality control of fortified vegetable oil is a challenge, and extended to additional food vehicles, such as wheat flour and salt. Only a reduced impact on iron deficiency in Ghana can be expected, given the low level of fortificant added to the wheat flour. An integrated approach, with complementary programs including additional iron-fortified food vehicles, should be explored to maximize health impact.

Sensitive monitoring of iodine species in sea water using capillary electrophoresis: vertical profiles of dissolved iodine in the Pacific Ocean.

PubMed

Huang, Zhuo; Ito, Kazuaki; Morita, Isamu; Yokota, Kuriko; Fukushi, Keiichi; Timerbaev, Andrei R; Watanabe, Shuichi; Hirokawa, Takeshi

2005-08-01

Using a novel high-sensitivity capillary electrophoretic method, vertical distributions of iodate, iodide, total inorganic iodine, dissolved organic iodine and total iodine in the North Pacific Ocean (0-5500 m) were determined without any sample pre-treatment other than UV irradiation before total iodine analysis. An extensive set of data demonstrated that the iodine behaviour in the ocean water collected during a cruise in the North Pacific Ocean in February-March 2003 was not conservative but correlated with variations in concentrations of dissolved oxygen and nutrient elements such as silicon, nitrogen and phosphorus. This suggests that the vertical distribution of iodine is associated with biological activities. The dissolved organic iodine was found in the euphotic zone in accord with observations elsewhere in the oceans. The vertical profile of dissolved organic iodine also appears to be related to biogeochemical activity. The concentrations of all measured iodine species vary noticeably above 1000 m but only minor latitudinal changes occur below 1000 m and slight vertical alterations can be observed below 2400 m. These findings are thought to reflect the stratification of nutrients and iodine species with different biological activities in the water column.

Delayed near-infrared analysis permits visualization of rodent retinal pigment epithelium layer in vivo

NASA Astrophysics Data System (ADS)

Pankova, Natalie; Zhao, Xu; Liang, Huiyuan; Baek, David Sung Hyeon; Wang, Hai; Boyd, Shelley

2014-07-01

Patches of atrophy of the retinal pigment epithelium (RPE) have not been described in rodent models of retinal degeneration, as they have the clinical setting using fundus autofluorescence. We hypothesize that prelabeling the RPE would increase contrast and allow for improved visualization of RPE loss in vivo. Here, we demonstrate a new technique termed "delayed near-infrared analysis (DNIRA)" that permits ready detection of rat RPE, using optical imaging in the near-infrared (IR) spectrum with aid of indocyanine green (ICG) dye. Using DNIRA, we demonstrate a fluorescent RPE signal that is detected using confocal scanning laser ophthalmoscopy up to 28 days following ICG injection. This signal is apparent only after ICG injection, is dose dependent, requires the presence of the ICG filters (795/810 nm excitation/emission), does not appear in the IR reflectance channel, and is eliminated in the presence of sodium iodate, a toxin that causes RPE loss. Rat RPE explants confirm internalization of ICG dye. Together with normal retinal electrophysiology, these findings demonstrate that DNIRA is a new and safe noninvasive optical imaging technique for in vivo visualization of the RPE in models of retinal disease.

Spectroscopic analysis of the powdery complex chitosan-iodine

NASA Astrophysics Data System (ADS)

Gegel, Natalia O.; Babicheva, Tatyana S.; Belyakova, Olga A.; Lugovitskaya, Tatyana N.; Shipovskaya, Anna B.

2018-04-01

A chitosan-iodine complex was obtained by modification of polymer powder in the vapor of an iodine-containing sorbate and studied by electron and IR spectroscopy, optical rotation dispersion. It was found that the electronic spectra of an aqueous solution of the modified chitosan (the source one and that stored for a year) showed intense absorption bands of triiodide and iodate ions, and also polyiodide ions, bound to the macromolecule by exciton bonding with charge transfer. Analysis of the IR spectra shows destruction of the network of intramolecular and intermolecular hydrogen bonds in the iodinated chitosan powder in comparison with the source polymer and the formation of a new chemical substance. E.g., the absorption band of deformation vibrations of the hydroxyl group disappears in the modified sample, and that of the protonated amino group shifts toward shorter wavelengths. The intensity of the stretching vibration band of the glucopyranose ring atoms significantly reduces. Heating of the modified sample at a temperature below the thermal degradation point of the polymer leads to stabilization of the chitosan-iodine complex. Based on our studies, the hydroxyl and amino groups of the aminopolysaccharide have been recognized as the centers of retention of polyiodide chains in the chitosan matrix.

Abatement of waste gases and water during the processes of semiconductor fabrication.

PubMed

Wen, Rui-mei; Liang, Jun-wu

2002-10-01

The purpose of this article is to examine the methods and equipment for abating waste gases and water produced during the manufacture of semiconductor materials and devices. Three separating methods and equipment are used to control three different groups of electronic wastes. The first group includes arsine and phosphine emitted during the processes of semiconductor materials manufacture. The abatement procedure for this group of pollutants consists of adding iodates, cupric and manganese salts to a multiple shower tower (MST) structure. The second group includes pollutants containing arsenic, phosphorus, HF, HCl, NO2, and SO3 emitted during the manufacture of semiconductor materials and devices. The abatement procedure involves mixing oxidants and bases in an oval column with a separator in the middle. The third group consists of the ions of As, P and heavy metals contained in the waste water. The abatement procedure includes adding CaCO3 and ferric salts in a flocculation-sedimentation compact device equipment. Test results showed that all waste gases and water after the abatement procedures presented in this article passed the discharge standards set by the State Environmental Protection Administration of China.

Determination of total sulfur content of sedimentary rocks by a combustion method

USGS Publications Warehouse

Coller, M.E.; Leininger, R.K.

1955-01-01

Total sulfur has been determined in common sedimentary rocks by a combustion method. Sulfur contents range from 0.001 to 5.0%. Experiments show that the combustion method can be used in analyzing sedimentary rocks in which sulfur is present as sulfide, sulfate, or both. Pulverized samples from 0.100 to 0.500 gram in weight are used in this method. Each sample is placed in a No. 6 Leco combustion boat and covered with two fluxes: 0.50 gram of standard ingot iron and approximately 1.0 gram of 30-mesh granular tin. The boat with sample then is placed in the combustion tube of a Burrell Unit Package Model T29A tube furnace which is controlled at a temperature of 1310?? to 1320?? C. After the sample has been heated for 1 minute, oxygen is admitted at a rate of about 1 liter per minute. The sulfur dioxide formed is absorbed in a starch solution and is titrated with standard potassium iodate in a Leco sulfur determinator. Thirteen values obtained for National Bureau of Standards standard sample 1a, argillaceous limestone, range from 0.273 to 0.276% sulfur (certificate value 0.27% by calculation).

Redox transformations and transport of cesium and iodine (-1, 0, +5) in oxidizing and reducing zones of a sand and gravel aquifer

USGS Publications Warehouse

Fox, P.M.; Kent, D.B.; Davis, J.A.

2010-01-01

Tracer tests were performed in distinct biogeochemical zones of a sand and gravel aquifer in Cape Cod, MA, to study the redox chemistry (I) and transport (Cs, I) of cesium and iodine in a field setting. Injection of iodide (I -) into an oxic zone of the aquifer resulted in oxidation of I - to molecular iodine (I2) and iodate (IO3-) over transport distances of several meters. Oxidation is attributed to Mn-oxides present in the sediment. Transport of injected IO 3- and Cs+ was retarded in the mildly acidic oxic zone, with retardation factors of 1.6-1.8 for IO3- and 2.3-4.4for Cs. Cs retardation was likely due to cation exchange reactions. Injection of IO3- into a Fe-reducing zone of the aquifer resulted in rapid and complete reduction to I- within 3 m of transport. The nonconservative behavior of Cs and I observed during the tracer tests underscores the necessity of taking the redox chemistry of I as well as sorption properties of I species and Cs into account when predicting transport of radionuclides (e.g., 129I and 137Cs) in the environment.

Fluorescence turn-on detection of iodide, iodate and total iodine using fluorescein-5-isothiocyanate-modified gold nanoparticles.

PubMed

Chen, Yi-Ming; Cheng, Tian-Lu; Tseng, Wei-Lung

2009-10-01

Selective turn-on fluorescence detection of I(-) was accomplished using fluorescein isothiocyanate-decorated gold nanoparticles (FITC-AuNPs). FITC molecules, which fluoresce strongly in an alkaline solution, were severely quenched when they were attached to the surface of AuNPs through their isothiocyanate group. Upon the addition of I(-), FITC molecules were detached because of I(-) adsorption on the surface of AuNPs. As a result, released FITC molecules were restored to their original fluorescence intensity. Because I(-) has a higher binding affinity to the surface of Au than do Br(-), Cl(-), or F(-), the FITC-AuNPs obviously have a higher selectivity toward I(-) than toward these other anions. Meanwhile, after IO(3)(-) was reduced to I(-) with ascorbic acid, the detection of IO(3)(-) was successfully achieved using the FITC-AuNPs. Under an optimum pH and AuNP concentration, the lowest detectable concentrations of I(-) and IO(3)(-) using this probe were 10.0 and 50.0 nM, respectively. The FITC-AuNPs provide a number of advantages, including easy preparation, selectivity, sensitivity, and low cost. This unique probe was applied to an analysis of the total iodine in edible salt and seawater.

Indirect spectrophotometric determination of arbutin, whitening agent through oxidation by periodate and complexation with ferric chloride

NASA Astrophysics Data System (ADS)

Barsoom, B. N.; Abdelsamad, A. M. E.; Adib, N. M.

2006-07-01

A simple and accurate spectrophotometric method for the determination of arbutin (glycosylated hydroquinone) is described. It is based on the oxidation of arbutin by periodate in presence of iodate. Excess periodate causes liberation of iodine at pH 8.0. The unreacted periodate is determined by measurement of the liberated iodine spectrophotometrically in the wavelength range (300-500 nm). A calibration curve was constructed for more accurate results and the correlation coefficient of linear regression analysis was -0.9778. The precision of this method was better than 6.17% R.S.D. ( n = 3). Regression analysis of Bear-Lambert plot shows good correlation in the concentration range 25-125 ug/ml. The identification limit was determined to be 25 ug/ml a detailed study of the reaction conditions was carried out, including effect of changing pH, time, temperature and volume of periodate. Analyzing pure and authentic samples containing arbutin tested the validity of the proposed method which has an average percent recovery of 100.86%. An alternative method is also proposed which involves a complexation reaction between arbutin and ferric chloride solution. The produced complex which is yellowish-green in color was determined spectophotometrically.

The formation and control of emerging disinfection by-products of health concern.

PubMed

Krasner, Stuart W

2009-10-13

When drinking water treatment plants disinfect water, a wide range of disinfection by-products (DBPs) of health and regulatory concern are formed. Recent studies have identified emerging DBPs (e.g. iodinated trihalomethanes (THMs) and acids, haloacetonitriles, halonitromethanes (HNMs), haloacetaldehydes, nitrosamines) that may be more toxic than some of the regulated ones (e.g. chlorine- and bromine-containing THMs and haloacetic acids). Some of these emerging DBPs are associated with impaired drinking water supplies (e.g. impacted by treated wastewater, algae, iodide). In some cases, alternative primary or secondary disinfectants to chlorine (e.g. chloramines, chlorine dioxide, ozone, ultraviolet) that minimize the formation of some of the regulated DBPs may increase the formation of some of the emerging by-products. However, optimization of the various treatment processes and disinfection scenarios can allow plants to control to varying degrees the formation of regulated and emerging DBPs. For example, pre-disinfection with chlorine, chlorine dioxide or ozone can destroy precursors for N-nitrosodimethylamine, which is a chloramine by-product, whereas pre-oxidation with chlorine or ozone can oxidize iodide to iodate and minimize iodinated DBP formation during post-chloramination. Although pre-ozonation may increase the formation of trihaloacetaldehydes or selected HNMs during post-chlorination or chloramination, biofiltration may reduce the formation potential of these by-products.

Chemical-mechanical planarization of aluminum and copper interconnects with magnetic liners

NASA Astrophysics Data System (ADS)

Wang, Bin

2000-10-01

Chemical Mechanical Planarization (CMP) has been employed to achieve Damascene patterning of aluminum and copper interconnects with unique magnetic liners. A one-step process was developed for each interconnect scheme, using a double-layered pad with mesh cells, pores, and perforations on a top hard layer. In a hydrogen peroxide-based slurry, aluminum CMP was a process of periodic removal and formation of a surface oxide layer. Cu CMP in the same slurry, however, was found to be a dissolution dominant process. In a potassium iodate-based slurry, copper removal was the result of two competing reactions: copper dissolution and a non-native surface layer formation. Guided by electrochemistry, slurries were developed to remove nickel in different regimes of the corrosion kinetics diagram. Nickel CMP in a ferric sulfate-based slurry resulted in periodic removal and formation of a passive surface layer. In a potassium permanganate-based slurry, nickel removal is a dissolution dominant process. Visible Al(Cu) surface damages obtained with copper-doped aluminum could be eliminated by understanding the interactions between the substrate, the pad, and the abrasive agglomerate. Increasing substrate hardness by annealing prior to CMP led to a surface finish free of visible scratches. A similar result was also obtained by preventing formation of abrasive agglomerates and minimizing their contact with the substrate.

Impact of redox agents on the extractability of gluten proteins during bread making.

PubMed

Lagrain, Bert; Thewissen, Bert G; Brijs, Kristof; Delcour, Jan A

2007-06-27

The gluten proteins gliadin and glutenin are important for dough and bread characteristics. In the present work, redox agents were used to impact gluten properties and to study gliadin-glutenin interactions in bread making. In control bread making, mixing increased the extractability of glutenin. The level of SDS-extractable glutenin decreased during fermentation and then further in the oven. The levels of extractable alpha- and gamma-gliadin also decreased during bread baking due to gliadin-glutenin polymerization. Neither oxidizing nor reducing agents had an impact on glutenin extractabilities after mixing. The redox additives did not affect omega-gliadin extractabilities during bread making due to their lack of cysteine residues. Potassium iodate (0.82-2.47 micromol/g of protein) and potassium bromate (1.07-3.17 micromol/g of protein) increased both alpha- and gamma-gliadin extractabilities during baking. Increasing concentrations of glutathione (1.15-3.45 micromol/g of protein) decreased levels of extractable alpha- and gamma-gliadins during baking. The work not only demonstrated that, during baking, glutenin and gliadin polymerize through heat-induced sulfhydryl-disulfide exchange reactions, but also demonstrated for the first time that oxidizing agents, besides their effect on dough rheology and hence bread volume, hinder gliadin-glutenin linking during baking, while glutathione increases the degree of covalent gliadin to glutenin linking.

Purification and Characterization of (Per)Chlorate Reductase from the Chlorate-Respiring Strain GR-1

PubMed Central

Kengen, Servé W. M.; Rikken, Geoffrey B.; Hagen, Wilfred R.; van Ginkel, Cees G.; Stams, Alfons J. M.

1999-01-01

Strain GR-1 is one of several recently isolated bacterial species that are able to respire by using chlorate or perchlorate as the terminal electron acceptor. The organism performs a complete reduction of chlorate or perchlorate to chloride and oxygen, with the intermediate formation of chlorite. This study describes the purification and characterization of the key enzyme of the reductive pathway, the chlorate and perchlorate reductase. A single enzyme was found to catalyze both the chlorate- and perchlorate-reducing activity. The oxygen-sensitive enzyme was located in the periplasm and had an apparent molecular mass of 420 kDa, with subunits of 95 and 40 kDa in an α3β3 composition. Metal analysis showed the presence of 11 mol of iron, 1 mol of molybdenum, and 1 mol of selenium per mol of heterodimer. In accordance, quantitative electron paramagnetic resonance spectroscopy showed the presence of one [3Fe-4S] cluster and two [4Fe-4S] clusters. Furthermore, two different signals were ascribed to Mo(V). The Kmvalues for perchlorate and chlorate were 27 and <5 μM, respectively. Besides perchlorate and chlorate, nitrate, iodate, and bromate were also reduced at considerable rates. The resemblance of the enzyme to nitrate reductases, formate dehydrogenases, and selenate reductase is discussed. PMID:10542172

Removal efficiency of water purifier and adsorbent for iodine, cesium, strontium, barium and zirconium in drinking water.

PubMed

Sato, Itaru; Kudo, Hiroaki; Tsuda, Shuji

2011-01-01

The severe incident of Fukushima Daiichi Nuclear Power Station has caused radioactive contamination of environment including drinking water. Radioactive iodine, cesium, strontium, barium and zirconium are hazardous fission products because of the high yield and/or relatively long half-life. In the present study, 4 pot-type water purifiers and several adsorbents were examined for the removal effects on these elements from drinking water. Iodide, iodate, cesium and barium were removed by all water purifiers with efficiencies about 85%, 40%, 75-90% and higher than 85%, respectively. These efficiencies lasted for 200 l, which is near the recommended limits for use of filter cartridges, without decay. Strontium was removed with initial efficiencies from 70% to 100%, but the efficiencies were slightly decreased by use. Zirconium was removed by two models, but hardly removed by the other models. Synthetic zeolite A4 efficiently removed cesium, strontium and barium, but had no effect on iodine and zirconium. Natural zeolite, mordenite, removed cesium with an efficiency as high as zeolite A4, but the removal efficiencies for strontium and barium were far less than those of zeolite A4. Activated carbon had little removal effects on these elements. In case of radioactive contamination of tap water, water purifiers may be available for convenient decontamination of drinking water in the home.

Nutritional composition and vitamin C stability in stored camu-camu (Myrciaria dubia) pulp.

PubMed

Justi, K C; Visentainer, J V; Evelázio de Souza, N; Matsushita, M

2000-12-01

Camu-camu (Myrciaria dubia), a native fruit of the Amazon region, is one of the richest sources of vitamin C (2.4 to 3.0 g/100 g in the pulp) found in Brazil. The purpose of this work was the physical-chemical characterization of some nutrients and the valuation of vitamin C stability in stored camu-camu pulp, produced by the Agronomic Institute of Paraná (IAPAR), Paraná State, Brazil. The vitamin C determination was made by titration with potassium iodate. The fruit produced in Paraná State, presented a lower content of vitamin C than the one native of the amazon region, possibly due to the different development conditions of the plant, and consequently of the fruit, as well as the climatic variation, the humidity and the characteristics of the soil. Regarding the vitamin C stability in stored (-18 degrees C) camu-camu pulp, a considerable decrease in its concentration until the 28th day was observed lost 23% (from 1.57 to 1.21 g/100 g), staying approximately the same until the end of the experiment. After 335 days of storage, the content found was of approximately 1.16 g/100 g of pulp, the ascorbic acid losses amounted to 26%. This content was still higher than the one found for most fruits that are good sources of this vitamin.

Chemical state and distribution of iodine deposits on 17% Cr/12% Ni steel oxidised in CO 2/CH 3I gas mixtures

NASA Astrophysics Data System (ADS)

Allen, G. C.; Tyler, J. W.

1990-03-01

Iodine-131 is one of the most important volatile fission product elements with respect to radiobiological impact, and the characterisation of its chemical state and distribution on reactor surfaces is required for reactor safety assessments. To this end, duplicate samples of Type 316 (17%Cr/12% Ni) stainless steel oxidised in {CO 2}/{CH 3}I gas mixtures and previously characterised using X-ray photoelectron spectroscopy have been examined using Raman spectroscopy. The aim is to improve our understanding of the way in which iodine is distributed throughout the oxide scale and to identify its chemical state. In this paper we present Raman spectra recorded from a series of stainless steel specimens together with spectra recorded from a number of standard iodine compounds. It is demonstrated that the technique is well suited as a fingerprint method of species identification, can differentiate between the chemical state of iodine as iodide and iodate and can analyse thin oxide films (5-50 nm). Identification of iodine deposits in these oxide films at concentrations of ⩽ 2 at% was not achieved however, there being insufficient iodine present to distinguish any peaks present from the background signal. It is concluded that local concentrations of iodine in oxide inclusions of different composition/morphology on the steel surface does not occur to any extent.

Biofortification of lettuce (Lactuca sativa L.) with iodine: the effect of iodine form and concentration in the nutrient solution on growth, development and iodine uptake of lettuce grown in water culture.

PubMed

Voogt, Wim; Holwerda, Harmen T; Khodabaks, Rashied

2010-04-15

Iodine is an essential trace element for humans. Two billion individuals have insufficient iodine intake. Biofortification of vegetables with iodine offers an excellent opportunity to increase iodine intake by humans. The main aim was to study the effect of iodine form and concentration in the nutrient solution on growth, development and iodine uptake of lettuce, grown in water culture. In both a winter and summer trial, dose rates of 0, 13, 39, 65, and 90 or 129 microg iodine L(-1), applied as iodate (IO(3)(-)) or iodide (I(-)), did not affect plant biomass, produce quality or water uptake. Increases in iodine concentration significantly enhanced iodine content in the plant. Iodine contents in plant tissue were up to five times higher with I(-) than with IO(3)(-). Iodine was mainly distributed to the outer leaves. The highest iodide dose rates in both trials resulted in 653 and 764 microg iodine kg(-1) total leaf fresh weight. Biofortification of lettuce with iodine is easily applicable in a hydroponic growing system, both with I(-) and IO(3)(-). I(-) was more effective than IO(3)(-). Fifty grams of iodine-biofortified lettuce would provide, respectively, 22% and 25% of the recommended daily allowance of iodine for adolescents and adults. (c) 2010 Society of Chemical Industry.

129I and its species in the East China Sea: level, distribution, sources and tracing water masses exchange and movement

PubMed Central

Liu, Dan; Hou, Xiaolin; Du, Jinzhou; Zhang, Luyuan; Zhou, Weijian

2016-01-01

Anthropogenic 129I as a long-lived radioisotope of iodine has been considered as an ideal oceanographic tracer due to its high residence time and conservative property in the ocean. Surface water samples collected from the East China Sea (ECS) in August 2013 were analyzed for 129I, 127I and their inorganic chemical species in the first time. The measured 129I/127I ratio is 1–3 orders of magnitude higher than the pre-nuclear level, indicating its dominantly anthropogenic sources. Relatively high 129I levels were observed in the Yangtze River and its estuary, as well as in the southern Yellow Sea, and 129I level in seawater declines towards the ECS shelf. In the open sea, 129I and 127I in surface water exists mainly as iodate, while in Yangtze River estuary and some locations, iodide is dominated. The results indicate that the Fukushima nuclear accident has no detectable effects in the ECS until August 2013. The obtained results are used for investigation of interaction of various water masses and water circulation in the ECS, as well as the marine environment in this region. Meanwhile this work provides essential data for evaluation of the possible influence of the increasing NPPs along the coast of the ECS in the future. PMID:27849026

Dried powder of corn stalk as a potential biosorbent for the removal of iodate from aqueous solution.

PubMed

Zhang, Kui; Chen, Tao

2018-10-01

Removal of IO 3 - from environmental samples with low-cost methods and materials is very useful approach for especially large-scale applications. Corn stalk is highly abundant agriculture residual, which is employed as useful biosorbent in many studies. In the present work, dried powder of corn stalk is applied for the removal of IO 3 - under various conditions. The results indicate that the K d is 49.73 ml g -1 under general conditions (m/V = 8 g L -1 , t = 5 day, equilibrium pH = 7 ± 0.3, T = 298 K and C 0  = 15 mg L -1 ). The sorption kinetics follows the pseudo-second-order equation, and the isotherm is well described by the Langmuir model. The sorption reaction was non-spontaneous and endothermic. Hydroxyl and carbonyl groups of the corn stalk contribute to IO 3 - sorption by ion-exchange, electrostatic attraction and redox reactions. Spectroscopic analyses and the effect of equilibrium pH prove that corn stalk was not only removed IO 3 - from aqueous solution but also reduced IO 3 - into I 2 and I - . These results demonstrate that corn stalk is a promising biosorbent for the environmental remediation of radioactive iodine pollution. Copyright © 2018 Elsevier Ltd. All rights reserved.

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

USGS Publications Warehouse

Fox, P.M.; Davis, J.A.; Luther, G. W.

2009-01-01

The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Photorefraction in the ultraviolet: Materials and effects

NASA Astrophysics Data System (ADS)

Laeri, F.; Jungen, R.; Angelow, G.; Vietze, U.; Engel, T.; Würtz, M.; Hilgenberg, D.

1995-10-01

Doped as well as nominally pure crystals of Lithium Niobate (LiNbO3), ι-Arginine Phosphate (LAP), Lithium Iodate (LiIO3), Potassium Dihydrogen Phosphate (KDP), Lithium Formate (LFM), Beta-Barium Borate (BBO), and lithium tetra borate were grown and investigated for photorefractive effects at ultraviolet wavelengths down to 333 nm. In nominally undoped LiNbO3 crystals strong beam coupling effects were observed. In contrast to the visible we revealed a diffusion-dominated charge transport mechanism based on holes, and a low photovoltaic field in the order of 550 V/cm. With such a crystal we investigated the modulation transfer function of a lensless image projection system based on a phase conjugation scheme. A spatial frequency response beyond 2800 line pairs per millimeter was observed. Photorefractive beam coupling was also obtained in LiIO3. Light-induced scattering was detected in iron-doped LiIO3 whereas as-grown LAP material did not exhibit any observable photorefractive effects. However, 100 kV X-ray irradiation seems to induce material defects which can lead to weak light-induced scattering at 351 nm. In all other above-mentioned materials, doped as well as undoped, light-induced scattering could not be observed. On the other hand, this is appreciated in all the applications where the crystals are used as nonlinear material for optical frequency conversion.

Hydrophobic Organic Compounds in Hydraulic Fracturing Flowback Waters: Identification and Source Apportionment

NASA Astrophysics Data System (ADS)

Plata, D.; Shregglman, K.; Elsner, M.; Getzinger, G.; Ferguson, L.; Drollette, B.; Karatum, O.; Nelson, R. K.; Reddy, C. M.

2014-12-01

Current hydraulic fracturing technologies rely on organic chemicals to serve multiple critical functions, including corrosion inhibition, in situ gel formation, and friction reduction. While industrial users have disclosed several hundreds of compound and mixture identities, it is unclear which of these are used and where, in what proportion, and with what frequency. Furthermore, while flowback and production waters contain both fracturing additive and geogenic compounds, they may contain potential reaction byproducts as well. Here, we identified several hundred organic compounds present in six hydraulic fracturing flowback waters over the Fayetteville shale. Identifications were made via non-target analysis using two-dimensional gas chromatography with time of flight mass spectrometry for hydrophobic organic compounds and liquid chromatography- orbitrap mass spectrometry. Compound identities were confirmed using purchased standards when available. Using the SkyTruth database and the Waxman list of disclosed compounds, we assigned compounds as either fracturing-fluid-derived or geogenic (or both), or a putative transformation products thereof. Several unreported halogenated compounds were detected, including chlorinated, brominated, and iodated species that have no known natural sources. Control studies indicated that these could not be formed under typical laboratory or field storage conditions, suggesting that halogenation reactions may give rise to novel compounds in the subsurface, presumably via reaction between fracturing fluid additives and shale-derived brines. Further, the six samples were strikingly heterogeneous, reflecting the diversity in fracturing fluid composition and flowback handling procedures at the time of the study.

Subretinal transplantation of rat MSCs and erythropoietin gene modified rat MSCs for protecting and rescuing degenerative retina in rats.

PubMed

Guan, Y; Cui, L; Qu, Z; Lu, L; Wang, F; Wu, Y; Zhang, J; Gao, F; Tian, H; Xu, L; Xu, G; Li, W; Jin, Y; Xu, G-T

2013-11-01

For degenerative retinal diseases, like the acquired form exemplified by age-related macular degeneration (AMD), there is currently no cure. This study was to explore a stem cell therapy and a stem cell based gene therapy for sodium iodate (SI)-induced retinal degeneration in rats. Three cell types, i.e., rat mesenchymal stem cells (rMSCs) alone, erythropoietin (EPO) gene modified rMSCs (EPO-rMSCs) or doxycycline (DOX) inducible EPO expression rMSCs (Tet-on EPO-rMSCs), were transplanted into the subretinal spaces of SI-treated rats. The rMSCs were prepared for transplantation after 3 to 5 passages or modified with EPO gene. During the 8 weeks after the transplantation, the rats treated with rMSCs alone or with two types of EPO-rMSCs were all monitored with fundus examination, fundus fluorescein angiography (FFA) and electroretinogram. The transplantation efficiency of donor cells was examined for their survival, integration and differentiation. Following the transplantation, labeled donor cells were observed in subretinal space and adopted RPE morphology. EPO concentration in vitreous and retina of SI-treated rats which were transplanted with EPO-rMSCs or Tet-on EPO-rMSCs was markedly increased, in parallel with the improvement of retinal morphology and function. These findings suggest that rMSCs transplantation could be a new therapy for degenerative retinal diseases since it can protect and rescue RPE and retinal neurons, while EPO gene modification to rMSCs could be an even better option.

Identification of Key Factors Involved in the Biosorption of Patulin by Inactivated Lactic Acid Bacteria (LAB) Cells.

PubMed

Wang, Ling; Wang, Zhouli; Yuan, Yahong; Cai, Rui; Niu, Chen; Yue, Tianli

2015-01-01

The purpose of this study was to identify the key factors involved in patulin adsorption by heat-inactivated lactic acid bacteria (LAB) cells. For preventing bacterial contamination, a sterilization process was involved in the adsorption process. The effects of various physical, chemical, and enzymatic pre-treatments, simultaneous treatments, and post-treatments on the patulin adsorption performances of six LAB strains were evaluated. The pre-treated cells were characterized by scanning electron microscopy (SEM). Results showed that the removal of patulin by viable cells was mainly based on adsorption or degradation, depending on the specific strain. The adsorption abilities were widely increased by NaOH and esterification pre-treatments, and reduced by trypsin, lipase, iodate, and periodate pre-treatments. Additionally, the adsorption abilities were almost maintained at pH 2.2-4.0, and enhanced significantly at pH 4.0-6.0. The effects of sodium and magnesium ions on the adsorption abilities at pH 4 were slight and strain-specific. A lower proportion of patulin was released from the strain with higher adsorption ability. Analyses revealed that the physical structure of peptidoglycan was not a principal factor. Vicinal OH and carboxyl groups were not involved in patulin adsorption, while alkaline amino acids, thiol and ester compounds were important for patulin adsorption. Additionally, besides hydrophobic interaction, electrostatic interaction also participated in patulin adsorption, which was enhanced with the increase in pH (4.0-6.0).

Conversion of iodide to hypoiodous acid and iodine in aqueous microdroplets exposed to ozone.

PubMed

Pillar, Elizabeth A; Guzman, Marcelo I; Rodriguez, Jose M

2013-10-01

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O3) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O3 and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O3 at variable iodide (I(-)) concentration (0.010-100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates and products expected in sea spray for low tropospheric [O3]. The ultrafast oxidation of I(-) by O3 at the air-water interface of microdroplets is evidenced by the appearance of hypoiodous acid (HIO), iodite (IO2(-)), iodate (IO3(-)), triiodide (I3(-)), and molecular iodine (I2). Mass spectrometry measurements reveal an enhancement (up to 28%) in the dissolution of gaseous O3 at the gas-liquid interface when increasing the concentration of NaI or NaBr from 0.010 to 100 μM. The production of iodine species such as HIO and I2 from NaI aerosolized solutions exposed to 50 ppbv O3 can occur at the air-water interface of sea spray, followed by their transfer to the gas-phase, where they contribute to the loss of tropospheric ozone.

K2 Au(IO3)5 and β-KAu(IO3)4: Polar Materials with Strong SHG Responses Originating from Synergistic Effect of AuO4 and IO3 Units.

PubMed

Xu, Xiang; Hu, Chun-Li; Li, Bing-Xuan; Mao, Jiang-Gao

2016-01-26

Two new polar potassium gold iodates, namely, K2 Au(IO3)5 (Cmc21) and β-KAu(IO3)4 (C2), have been synthesized and structurally characterized. Both compounds feature zero-dimensional polar [Au(IO3)4](-) units composed of an AuO4 square-planar unit coordinated by four IO3(-) ions in a monodentate fashion. In β-KAu(IO3)4, isolated [Au(IO3)4](-) ions are separated by K(+) ions, whereas in K2 Au(IO3)5, isolated [Au(IO3)4](-) ions and non-coordinated IO3(-) units are separated by K(+) ions. Both compounds are thermally stable up to 400 °C and exhibit high transmittance in the NIR region (λ=800-2500 nm) with measured optical band gaps of 2.65 eV for K2 Au(IO3 )5 and 2.75 eV for β-KAu(IO3)4. Powder second-harmonic generation measurements by using λ=2.05 μm laser radiation indicate that K2 Au(IO3)5 and β-KAu(IO3)4 are both phase-matchable materials with strong SHG responses of approximately 1.0 and 1.3 times that of KTiOPO4, respectively. Theoretical calculations based on DFT methods confirm that such strong SHG responses originate from a synergistic effect of the AuO4 and IO3 units. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Singlet-Oxygen Generation in Alkaline Periodate Solution.

PubMed

Bokare, Alok D; Choi, Wonyong

2015-12-15

A nonphotochemical generation of singlet oxygen ((1)O2) using potassium periodate (KIO4) in alkaline condition (pH > 8) was investigated for selective oxidation of aqueous organic pollutants. The generation of (1)O2 was initiated by the spontaneous reaction between IO4(-) and hydroxyl ions, along with a stoichiometric conversion of IO4(-) to iodate (IO3(-)). The reactivity of in-situ-generated (1)O2 was monitored by using furfuryl alcohol (FFA) as a model substrate. The formation of (1)O2 in the KIO4/KOH system was experimentally confirmed using electron spin resonance (ESR) measurements in corroboration with quenching studies using azide as a selective (1)O2 scavenger. The reaction in the KIO4/KOH solution in both oxic and anoxic conditions initiated the generation of superoxide ion as a precursor of the singlet oxygen (confirmed by using superoxide scavengers), and the presence of molecular oxygen was not required as a precursor of (1)O2. Although hydrogen peroxide had no direct influence on the FFA oxidation process, the presence of natural organic matter, such as humic and fulvic acids, enhanced the oxidation efficiency. Using the oxidation of simple organic diols as model compounds, the enhanced (1)O2 formation is attributed to periodate-mediated oxidation of vicinal hydroxyl groups present in humic and fulvic constituent moieties. The efficient and simple generation of (1)O2 using the KIO4/KOH system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral and near-alkaline conditions.

Effect of iodide on transformation of phenolic compounds by nonradical activation of peroxydisulfate in the presence of carbon nanotube: Kinetics, impacting factors, and formation of iodinated aromatic products.

PubMed

Guan, Chaoting; Jiang, Jin; Pang, Suyan; Luo, Congwei; Yang, Yi; Ma, Jun; Yu, Jing; Zhao, Xi

2018-06-04

Our recent study has demonstrated that iodide (I - ) can be easily and almost entirely oxidized to hypoiodous acid (HOI) but not to iodate by nonradical activation of peroxydisulfate (PDS) in the presence of a commercial carbon nanotube (CNT). In this work, the oxidation kinetics of phenolic compounds by the PDS/CNT system in the presence of I - were examined and potential formation of iodinated aromatic products was explored. Experimental results suggested that I - enhanced the transformation of six selected substituted phenols, primarily attributed to the generation of HOI that was considerably reactive toward these phenolic compounds. More significant enhancement was obtained at higher I - concentrations or lower pH values, while the change of PDS or CNT dosages exhibited a slight impact on the enhancing effect of I - . Product analyses with liquid chromatography tandem mass spectrometry clearly revealed the production of iodinated aromatic products when p-hydroxybenzoic acid (p-HBA, a model phenol) was treated by the PDS/CNT/I - system in both synthetic and real waters. Their formation pathways probably involved the substitution of HOI on aromatic ring of p-HBA, as well as the generation of iodinated p-HBA phenoxyl radicals and subsequent coupling of these radicals. Given the considerable toxicity and harmful effects of these iodinated aromatic products, particular attention should be paid when the novel PDS/CNT oxidation technology is applied for treatment of phenolic contaminants in iodide-containing waters. Copyright © 2018 Elsevier Ltd. All rights reserved.

Accounting for changes in particle charge, dry mass and composition occurring during studies of single levitated particles.

PubMed

Haddrell, Allen E; Davies, James F; Yabushita, Akihiro; Reid, Jonathan P

2012-10-11

The most used instrument in single particle hygroscopic analysis over the past thirty years has been the electrodynamic balance (EDB). Two general assumptions are made in hygroscopic studies involving the EDB. First, it is assumed that the net charge on the droplet is invariant over the time scale required to record a hygroscopic growth cycle. Second, it is assumed that the composition of the droplet is constant (aside from the addition and removal of water). In this study, we demonstrate that these assumptions cannot always be made and may indeed prove incorrect. The presence of net charge in the humidified vapor phase reduces the total net charge retained by the droplet over prolonged levitation periods. The gradual reduction in charge limits the reproducibility of hygroscopicity measurements made on repeated RH cycles with a single particle, or prolonged experiments in which the particle is held at a high relative humidity. Further, two contrasting examples of the influence of changes in chemical composition changes are reported. In the first, simple acid-base chemistry in the droplet leads to the irreversible removal of gaseous ammonia from a droplet containing an ammonium salt on a time scale that is shorter than the hygroscopicity measurement. In the second example, the net charge on the droplet (<100 fC) is high enough to drive redox chemistry within the droplet. This is demonstrated by the reduction of iodic acid in a droplet made solely of iodic acid and water to form iodine and an iodate salt.

pH-regulated chemical oscillators.

PubMed

Orbán, Miklós; Kurin-Csörgei, Krisztina; Epstein, Irving R

2015-03-17

The hydrogen ion is arguably the most ubiquitous and important species in chemistry. It also plays a key role in nearly every biological process. In this Account, we discuss systems whose behavior is governed by oscillations in the concentration of hydrogen ion. The first chemical oscillators driven by changes in pH were developed a quarter century ago. Since then, about two dozen new pH oscillators, systems in which the periodic variation in pH is not just an indicator but an essential prerequisite of the oscillatory behavior, have been discovered. Mechanistic understanding of their behavior has grown, and new ideas for their practical application have been proposed and, in some cases, tested. Here we present a catalog of the known pH oscillators, divide them into mechanistically based categories based on whether they involve a single oxidant and reductant or an oxidant and a pair of reductants, and describe general mechanisms for these two major classes of systems. We also describe in detail the chemistry of one example from each class, hydrogen peroxide-sulfide and ferricyanide-iodate-sulfite. Finally, we consider actual and potential applications. These include using pH oscillators to induce oscillation in species that would otherwise be nonoscillatory, creating novel spatial patterns, generating periodic transitions between vesicle and micelle states, stimulating switching between folded and random coil states of DNA, building molecular motors, and designing pulsating drug delivery systems. We point out the importance for future applications of finding a batch pH oscillator, one that oscillates in a closed system for an extended period of time, and comment on the progress that has been made toward that goal.

Multiple metabolisms constrain the anaerobic nitrite budget in the Eastern Tropical South Pacific

NASA Astrophysics Data System (ADS)

Babbin, Andrew R.; Peters, Brian D.; Mordy, Calvin W.; Widner, Brittany; Casciotti, Karen L.; Ward, Bess B.

2017-02-01

The Eastern Tropical South Pacific is one of the three major oxygen deficient zones (ODZs) in the global ocean and is responsible for approximately one third of marine water column nitrogen loss. It is the best studied of the ODZs and, like the others, features a broad nitrite maximum across the low oxygen layer. How the microbial processes that produce and consume nitrite in anoxic waters interact to sustain this feature is unknown. Here we used 15N-tracer experiments to disentangle five of the biologically mediated processes that control the nitrite pool, including a high-resolution profile of nitrogen loss rates. Nitrate reduction to nitrite likely depended on organic matter fluxes, but the organic matter did not drive detectable rates of denitrification to N2. However, multiple lines of evidence show that denitrification is important in shaping the biogeochemistry of this ODZ. Significant rates of anaerobic nitrite oxidation at the ODZ boundaries were also measured. Iodate was a potential oxidant that could support part of this nitrite consumption pathway. We additionally observed N2 production from labeled cyanate and postulate that anammox bacteria have the ability to harness cyanate as another form of reduced nitrogen rather than relying solely on ammonification of complex organic matter. The balance of the five anaerobic rates measured—anammox, denitrification, nitrate reduction, nitrite oxidation, and dissimilatory nitrite reduction to ammonium—is sufficient to reproduce broadly the observed nitrite and nitrate profiles in a simple one-dimensional model but requires an additional source of reduced nitrogen to the deeper ODZ to avoid ammonium overconsumption.

Visible light water oxidation using a co-catalyst loaded anatase-structured Ti(1-(5x/4))Nb(x)O(2-y-δ)N(y) compound.

PubMed

Breault, Tanya M; Brancho, James J; Guo, Ping; Bartlett, Bart M

2013-08-19

The photocatalytic activity of anatase-structured Ti(1-(5x/4))Nb(x)O(2-y-δ)N(y) (x = 0.25, y = 0.02; NbN-25) was examined for water oxidation under UV and visible light irradiation. The semiconductor was prepared by sol-gel processing followed by nitridation in flowing ammonia and exhibits an indirect optical gap of 2.2 eV. Ti(1-(5x/4))Nb(x)O(2-y-δ)N(y) was loaded with RuO2 by an impregnation technique, and optimized conditions reveal that 1 wt % RuO2 generates 16 μmol O2 from water with concomitant IO3(-) reduction after 3 h of illumination under simulated solar radiation at a flux of 600 mW/cm(2) illumination, which corresponds to 6-sun AM1.5G illumination (compared to no detectible O2 without the RuO2 cocatalyst). A series of cut-on filters shows that the catalyst-loaded semiconductor evolves O2 for λ ≤ 515 nm, and a gas-phase mass spectrometry isotope labeling experiment shows that irradiating an iodate solution in H2(18)O in the presence of 1 wt % RuO2 loaded on NbN-25 gives rise to catalytic water oxidation: both (36)O2 and (34)O2 are observed. It is unclear whether (16)O arises from IO3(-) or surface reconstruction on the photocatalyst, but ICP-AES analysis of the postirradiated solution shows no dissolved metal ions.

A new technique for the rapid screening and selection of large pieces of tissue for ultrastructural evaluation.

PubMed

Dalley, B K; Seliger, W G

1980-05-01

A simple and rapid technique is described for the screening of Epon embedded organ slices for the location, isolation, and removal of small specific sites for ultrastructural study with the transmission electron microscope. This procedure consists of perfusion fixation followed by making 1 to 21/2 mm thick slices of relatively large pieces of the organs, control of the degree and evenness of the osmium staining by addition of 3% sodium iodate, and infiltration with a fluorescent dye prior to embedment in Epon. Tissue slices are embedded in wafer-shaped blocks, generally with several slices in one "wafer", and are examined in a controlled manner using a rapid form of serial surface polishing. Each level of the polished wafer is examined using an epi-illuminated fluorescence microscope, and selected sites are chosen at each level for ultrastructural study. Methods are also described for marking each selected site using a conventional slide marker, and for the removal of the selected site in the form of a small disc of Epon, after which the Epon wafer can be further serially polished and the examination continued. Areas to be thin-sectioned are removed using a core drill mounted on a model-maker's drill press. The technique is simple, does not require the destruction of remaining tissues to evaluate more critically a single small site, allows for the easy maintenance of tissue orientation, and the most time-consuming portions of the technique can be quickly taught to a person with no previous histological training.

Perspectives on Proterozoic surface ocean redox from iodine contents in ancient and recent carbonate

NASA Astrophysics Data System (ADS)

Hardisty, Dalton S.; Lu, Zunli; Bekker, Andrey; Diamond, Charles W.; Gill, Benjamin C.; Jiang, Ganqing; Kah, Linda C.; Knoll, Andrew H.; Loyd, Sean J.; Osburn, Magdalena R.; Planavsky, Noah J.; Wang, Chunjiang; Zhou, Xiaoli; Lyons, Timothy W.

2017-04-01

The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today's, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene-Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene-Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic-anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.

Simultaneous Analyses and Applications of Multiple Fluorobenzoate and Halide Tracers in Hydrologic Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Q; Moran, J E

2004-01-22

An analytical method that employs ion chromatography has been developed to more fully exploit the use of fluorobenzoic acids (FBAs) and halides as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g., nitrate and sulfate). The usefulness of this ion chromatographic (IC) analytical method is demonstrated in both field and laboratory tracer experiments. Field experiments in unsaturated tuff featuring fractures or a fault show that this efficient and cost-effective method helps achieve the objectives ofmore » tracer studies that use multiple FBAs and/or diffusivity tracers (simultaneous use of one or more FBA and halide). The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the United States--mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need--reveal several insights about tracer transport behavior: (1) Bromide and FBAs are not always transported conservatively. (2) The delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy. (3) Any use of iodine as a hydrologic tracer should take into account the different sorption behaviors of iodide and iodate and the possible conversion of iodine's initial chemical form. (4) The transport behavior of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large-scale field tracer experiments.« less

Marine redox structure at the culmination of the Great Oxidation Event: Insights from the Zaonega Formation, Karelia, Russia

NASA Astrophysics Data System (ADS)

Kipp, M.; Lepland, A.; Buick, R.

2017-12-01

The availability of dissolved oxygen is thought to have been the dominant throttle on the evolution and diversification of eukaryotic life during the Proterozoic Eon [1]. In the mid-Proterozoic, during the interval that presaged the rise of eukaryotes to ecological dominance, oxygen scarcity is thought to have relegated eukaryotic organisms to slivers of oxygenated shallow oceans [2]. However, recent work has suggested that oxygen levels rose dramatically during the early Paleoproterozoic Great Oxidation Event before crashing to the low levels of the mid-Proterozoic [3]. Evidence from selenium isotopes in shales [4] and iodate concentrations in carbonates [5] has even suggested that wide swathes of continental shelves were oxic enough to support eukaryotic organisms at this time. How oxic though, and for how long, remain poorly constrained. Here we present new selenium geochemical data from the Zaonega Formation of Karelia, Russia that can help resolve those questions. Previous work has proposed that the Zaonega Formation, and correlative Francevillian Series of Gabon, record the establishment of an oxygen-rich atmosphere at the culmination of the GOE [6]. Our selenium isotope dataset provides a test for this hypothesis, and can also be used to assess the preservation of the geochemical signatures in the Zaonega Formation. These data point to regional redox fluctuations, but due to the short marine residence time of selenium, extrapolating these results to global phenomena remains difficult. 1. Reinhard, et al (2016) PNAS 2. Planavsky, et al (2014) Science 3. Bekker and Holland (2012) EPSL 4. Kipp, et al (2017) PNAS 5. Hardisty, et al (2014) Geology 6. Kump, et al (2011) Science

Formation of regulated and unregulated disinfection byproducts during chlorination of algal organic matter extracted from freshwater and marine algae.

PubMed

Liu, Chao; Ersan, Mahmut S; Plewa, Michael J; Amy, Gary; Karanfil, Tanju

2018-05-29

Seasonal algal blooms in freshwater and marine water can increase the input of algal organic matter (AOM) to the pool of dissolved organic matter. The impact of bromide (Br - ) and iodide (I - ) on the formation of regulated and unregulated disinfection byproducts (DBPs) was studied from chlorination of AOM solutions extracted from three species of cultured isolates of freshwater and marine algae (Microcystis aeruginosa (MA), Synechococcus (SYN), and Alexandrium tamarense (AT)). Comparable concentrations of DBPs were formed from three types of AOM. In the absence of Br - , trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetaldehydes (HALs) were the main groups of DBP formed, and haloacetonitriles (HANs) were formed at lower concentrations. In contrast, the formation of iodinated THMs was <8 nM (1.7 μg/L) since most of initial I - was oxidized to iodate. Increasing initial Br - concentrations increased the formation of THMs and HANs, while concentrations of total organic halogen and HAA remained stable. On the contrary, total HAL concentrations decreased due to the instability of bromated HALs. Decreasing the specific UV absorbance (SUVA) value of AOM favours bromine substitution since bromine more preferentially reacts with low reactivity organic matter than chlorine. Increasing the pH enhanced the formation of THMs but decreased the formation of HANs. Concentrations of HANs and HALs decreased at high pH (e.g., 9.0), high initial chlorine concentration and long reaction time due to the decomposition. Based on the cytotoxicity calculations, unregulated HANs and HALs were the main contributors for the total toxicity of DBPs measured, even though based on the weight regulated THMs and HAAs predominated. Copyright © 2018 Elsevier Ltd. All rights reserved.

Development, validation, and application of a novel LC-MS/MS trace analysis method for the simultaneous quantification of seven iodinated X-ray contrast media and three artificial sweeteners in surface, ground, and drinking water.

PubMed

Ens, Waldemar; Senner, Frank; Gygax, Benjamin; Schlotterbeck, Götz

2014-05-01

A new method for the simultaneous determination of iodated X-ray contrast media (ICM) and artificial sweeteners (AS) by liquid chromatography-tandem mass spectrometry (LC-MS/MS) operated in positive and negative ionization switching mode was developed. The method was validated for surface, ground, and drinking water samples. In order to gain higher sensitivities, a 10-fold sample enrichment step using a Genevac EZ-2 plus centrifugal vacuum evaporator that provided excellent recoveries (90 ± 6 %) was selected for sample preparation. Limits of quantification below 10 ng/L were obtained for all compounds. Furthermore, sample preparation recoveries and matrix effects were investigated thoroughly for all matrix types. Considerable matrix effects were observed in surface water and could be compensated by the use of four stable isotope-labeled internal standards. Due to their persistence, fractions of diatrizoic acid, iopamidol, and acesulfame could pass the whole drinking water production process and were observed also in drinking water. To monitor the fate and occurrence of these compounds, the validated method was applied to samples from different stages of the drinking water production process of the Industrial Works of Basel (IWB). Diatrizoic acid was found as the most persistent compound which was eliminated by just 40 % during the whole drinking water treatment process, followed by iopamidol (80 % elimination) and acesulfame (85 % elimination). All other compounds were completely restrained and/or degraded by the soil and thus were not detected in groundwater. Additionally, a direct injection method without sample preparation achieving 3-20 ng/L limits of quantification was compared to the developed method.

Electrochemical treatment of iopromide under conditions of reverse osmosis concentrates--elucidation of the degradation pathway.

PubMed

Lütke Eversloh, C; Henning, N; Schulz, M; Ternes, T A

2014-01-01

Application of reverse osmosis for the reuse of treated wastewater on the one hand offers a way to provide high quality effluent waters. On the other hand reverse osmosis concentrates exhibiting highly concentrated contaminants are produced simultaneously. Electrochemical treatment of those concentrates is regarded as one possible answer to the problem of their disposal into surface waters. Nevertheless, due to the diversity of direct and indirect degradation processes during electrolysis, special care has to be taken about the formation of toxic transformation products (TPs). In this study the electrochemical transformation of the X-ray contrast medium iopromide was investigated as a representative of biologically persistent compounds. For this purpose, anodic oxidation at boron doped diamond as well as cathodic reduction using a platinum electrode were considered. Kinetic analyses revealed a transformation of 100 μM iopromide with first order kinetic constants between 0.6 and 1.6 × 10(-4) s(-1) at the beginning and a subsequent increase of the reaction order due to the influence of secondary oxidants formed during electrolysis. Mineralization up to 96% was achieved after about 7.5 h. At shorter treatment times several oxidatively and reductively formed transformation products were detected, whereas deiodinated iopromide represented the major fraction. Nevertheless, the latter exhibited negligible toxicological relevance according to tests on vibrio fisheri. Additional experiments utilizing a divided cell setup enabled the elucidation of the transformation pathway, whereas emerging TPs could be identified by means of high resolution mass spectrometry and MS(n)-fragmentations. During electrolysis the iodine released from Iopromide was found to 90% as iodide and to 10% as iodate even in the open cell experiments, limiting the potential formation of toxic iodo-disinfection by-products. Chlorinated TPs were not found. Copyright © 2013. Published by Elsevier Ltd.

Speciation of Bio-Available Iodine in Abalone (Haliotis discus hannai) by High-Performance Liquid Chromatography Hyphenated with Inductively Coupled Plasma-Mass Spectrometry Using an In Vitro Method.

PubMed

Doh, Han Sol; Park, Hyun Jin

2018-06-01

Abalone is one of the most valuable marine products found in East Asia because it is rich in nutritious substances including iodine. In this study, the in vitro dialyzability approach was used to assess the bio-available iodine species in abalone. Iodide, iodate, 3-iodo-L-tyrosine (MIT), and 3,5-diiodo-L-tyrosine (DIT) were separated by high-performance liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). To assure the consistency, reliability, and accuracy of the data, the method was validated. Comparison of the total iodine in abalone muscle and viscera indicated that abalone muscle showed greater digestion/absorption efficiency than abalone viscera (digestion efficiency: 68.13 ± 2.59% and 47.88 ± 5.76% and absorption efficiency: 59.78 ± 2.93% and 35.12 ± 1.43% for abalone viscera and muscle, respectively). However, evaluation of the sum of the analyzed iodine species targeted in this study by HPLC-ICP-MS indicated that abalone muscle showed lower digestion efficiency and similar absorption efficiency compared to that of abalone viscera (digestion efficiency: 35.52 ± 5.41% and 28.84 ± 1.83%; absorption efficiency: 23.56 ± 4.38% and 27.56 ± 1.51% for abalone viscera and muscle, respectively). The main forms of iodine detected in abalone muscle were iodide and MIT, whereas iodide was the major form in abalone viscera. The bio-available iodine in abalone was quantified via an in vitro method employing HPLC-ICP-MS. The results of this study indicated that abalone is feasible as a new iodine source and may prospectively find application in iodine-fortified foods. © 2018 Institute of Food Technologists®.

An investigation into the effects of maternal supplementation with excess iodine on the mechanisms and impacts of reduced IgG absorption in the lamb postpartum.

PubMed

McGovern, F M; Sweeney, T; Ryan, M T; Lott, S; Campion, F P; Boland, T M

2017-04-01

An experiment was conducted to determine: (1) the effect of excess maternal I supplementation on the thyroid hormone status of the ewe and her progeny; (2) potential mechanisms underpinning the failure of passive transfer associated with excess I and (3) the growing lambs' response to natural gastrointestinal infection. Twin-bearing ewes received one of two treatments (n 32/treatment group): basal diet (C) or C plus 26·6 mg of iodine/ewe per d (I), supplied as calcium iodate. Ewes were individually fed from day 119 of gestation to parturition. Progeny of I ewes had lower (P<0·01) serum IgG concentrations from 24 h to 28 d postpartum but higher serum IgG concentrations at day 70 postpartum (P<0·05). I supplementation increased the relative expression of Fc receptor, IgA, IgM high affinity and polymeric Ig receptor in the ileum of the lamb at 24 h postpartum; however, thyroid hormone receptor-β (THRB) and β-2-microglobulin (B2M) expression declined (P<0·05). Progeny of I ewes had higher growth rates to weaning (P<0·05) and lower faecal egg count (FEC) for Nematodirus battus (P<0·05) between weeks 6 and 10 postpartum. In conclusion, excess maternal I supplementation negatively affected the thyroid hormone status, serum IgG concentration, ileal morphology and the gene expression of THRB and B2M in the ileum and ras-related protein (RAB) RAB25 and the mucin gene (MUC) MUC1 in the duodenum of the lamb postpartum. These effects were followed by an enhancement of average daily gain and lower N. battus FEC in the pre-weaning period of I-supplemented lambs.

New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Daria L.; Beltrán-Suito, Rodrigo; Thomsen, Julianne M.

2016-02-05

This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation processmore » requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.« less

Measuring In Vivo Free Radical Production by the Outer Retina

PubMed Central

Berkowitz, Bruce A.; Bredell, Bryce X.; Davis, Christopher; Samardzija, Marijana; Grimm, Christian; Roberts, Robin

2015-01-01

Purpose Excessive and continuously produced free radicals in the outer retina are implicated in retinal aging and the pathogenesis of sight-threatening retinopathies, yet measuring outer retinal oxidative stress in vivo remains a challenge. Here, we test the hypothesis that continuously produced paramagnetic free radicals from the outer retina can be measured in vivo using high-resolution (22-μm axial resolution) 1/T1magnetic resonance imaging (MRI) without and with a confirmatory quench (quench-assisted MRI). Methods Low-dose sodium iodate–treated and diabetic C57Bl6/J mice (and their controls), and rod-dominated (129S6) or cone-only R91W;Nrl−/− mice were studied. In dark-adapted groups, 1/T1 was mapped transretinally in vivo without or with (1) the antioxidant combination of methylene blue (MB) and α-lipoic acid (LPA), or (2) light exposure; in subgroups, retinal superoxide production was measured ex vivo (lucigenin). Results In the sodium iodate model, retinal superoxide production and outer retina-specific 1/T1 values were both significantly greater than normal and corrected to baseline with MB+LPA therapy. Nondiabetic mice at two ages and 1.2-month diabetic mice (before the appearance of oxidative stress) had similar transretinal 1/T1 profiles. By 2.3 months of diabetes, only outer retinal 1/T1 values were significantly greater than normal and were corrected to baseline with MB+LPA therapy. In mice with healthy photoreceptors, a light quench caused 1/T1 of rods, but not cones, to significantly decrease from their values in the dark. Conclusions Quench-assisted MRI is a feasible method for noninvasively measuring normal and pathologic production of free radicals in photoreceptors/RPE in vivo. PMID:26670830

The role of glutathione in DNA damage by potassium bromate in vitro.

PubMed

Parsons, J L; Chipman, J K

2000-07-01

We have investigated the role of reduced glutathione (GSH) in the genetic toxicity of the rodent renal carcinogen potassium bromate (KBrO(3)). A statistically significant increase in the concentration of 8-oxodeoxyguanosine (8-oxodG) relative to deoxyguanosine was measured following incubation of calf thymus DNA with KBrO(3) and GSH or N-acetylcysteine (NACys). This was dependent on these thiols and was associated with the loss of GSH and production of oxidized glutathione. A short-lived (<6 min) intermediate was apparent which did not react with the spin trap dimethylpyrroline N-oxide. DNA oxidation was not evident when potassium chlorate (KClO(3)) or potassium iodate (KIO(3)) were used instead of KBrO(3), though GSH depletion also occurred with KIO(3), but not with KClO(3). Other reductants and thiols in combination with KBrO(3) did not cause a significant increase in DNA oxidation. DNA strand breakage was also induced by KBrO(3) in human white blood cells (5 mM) and rat kidney epithelial cells (NRK-52E, 1.5 mM). This was associated with an apparent small depletion of thiols in NRK-52E cells at 15 min and with an elevation of 8-oxodG at a delayed time of 24 h. Depletion of intra-cellular GSH by diethylmaleate in human lymphocytes decreased the amount of strand breakage induced by KBrO(3). Extracellular GSH, however, protected against DNA strand breakage by KBrO(3), possibly due to the inability of the reactive product to enter the cell. In contrast, membrane-permeant NACys enhanced KBrO(3)-induced DNA strand breakage in these cells. DNA damage by KBrO(3) is therefore largely dependent on access to intracellular GSH.

Iodine binding to humic acid.

PubMed

Bowley, H E; Young, S D; Ander, E L; Crout, N M J; Watts, M J; Bailey, E H

2016-08-01

The rate of reactions between humic acid (HA) and iodide (I(-)) and iodate (IO3(-)) have been investigated in suspensions spiked with (129)I at concentrations of 22, 44 and 88 μg L(-1) and stored at 10 °C. Changes in the speciation of (129)I(-), (129)IO3(-) and mixed ((129)I(-) + (129)IO3(-)) spikes were monitored over 77 days using liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS). In suspensions spiked with (129)I(-) 25% of the added I(-) was transformed into organic iodine (Org-(129)I) within 77 days and there was no evidence of (129)IO3(-) formation. By contrast, rapid loss of (129)IO3(-) and increase in both (129)I(-) and Org-(129)I was observed in (129)IO3(-)-spiked suspensions. However, the rate of Org-(129)I production was greater in mixed systems compared to (129)IO3(-)-spiked suspensions with the same total (129)I concentration, possibly indicating IO3(-)I(-) redox coupling. Size exclusion chromatography (SEC) demonstrated that Org-(129)I was present in both high and low molecular weight fractions of the HA although a slight preference to bond with the lower molecular weight fractions was observed indicating that, after 77 days, the spiked isotope had not fully mixed with the native (127)I pool. Iodine transformations were modelled using first order rate equations and fitted rate coefficients determined. However, extrapolation of the model to 250 days indicated that a pseudo-steady state would be attained after ∼200 days but that the proportion of (129)I incorporated into HA was less than that of (127)I indicating the presence of a recalcitrant pool of (127)I that was unavailable for isotopic mixing. Copyright © 2016 Elsevier Ltd. All rights reserved.

Efficacy of wheat-based biscuits fortified with microcapsules containing ferrous sulfate and potassium iodate or a new hydrogen-reduced elemental iron: a randomised, double-blind, controlled trial in Kuwaiti women.

PubMed

Biebinger, Ralf; Zimmermann, Michael B; Al-Hooti, Suad N; Al-Hamed, Nawal; Al-Salem, Ebtehal; Zafar, Tasleem; Kabir, Yearul; Al-Obaid, I'nam; Petry, Nicolai; Hurrell, Richard F

2009-11-01

Adverse sensory changes prevent the addition of highly bioavailable ferrous sulfate (FeSO4) to most wheat flours. Poorly absorbable reduced Fe powders are commonly used. Encapsulation of FeSO4 can overcome these sensory changes, but the particle size of commercial compounds is too large to be used by flour mills. The first objective of the study was to measure the efficacy in wheat flour of two newly developed Fe compounds, an H-reduced Fe powder (NutraFine RS; North America Höganäs High Alloys LLC, Johnstown, PA, USA) and small particle-sized (40 microm) encapsulated FeSO4. As a second objective, the microcapsules were evaluated as a vehicle for iodine fortification. A randomised, double-blind controlled intervention trial was conducted in Kuwaiti women (n 279; aged 18-35 years) with low body Fe stores (serum ferritin (SF) < 25 microg/l) randomly assigned to one of three groups (20 mg Fe as NutraFine RS, 10 mg Fe as encapsulated FeSO4 and 150 microg iodine, or no fortification Fe) who consumed wheat-based biscuits 5 d per week. At baseline and 22 weeks, Hb, SF, transferrin receptor, urinary iodine and body Fe stores were measured. Relative to control, mean SF in the encapsulated FeSO4 group increased by 88 % (P < 0.001) and body Fe stores increased from - 0.96 to 2.24 mg/kg body weight (P < 0.001), while NutraFine RS did not significantly increase SF or body Fe stores. The median urinary iodine concentration increased from 140 to 213 microg/l (P < 0.01). NutraFine RS added at double the amount of Fe as FeSO4 was not efficacious in improving Fe status. The newly developed microcapsules were highly efficacious in improving both Fe stores and iodine status.

An animal model of marginal iodine deficiency during development: the thyroid axis and neurodevelopmental outcome.

PubMed

Gilbert, Mary E; Hedge, Joan M; Valentín-Blasini, Liza; Blount, Benjamin C; Kannan, Kurunthachalam; Tietge, Joseph; Zoeller, R Thomas; Crofton, Kevin M; Jarrett, Jeffrey M; Fisher, Jeffrey W

2013-03-01

Thyroid hormones (THs) are essential for brain development, and iodine is required for TH synthesis. Environmental chemicals that perturb the thyroid axis result in modest reductions in TH, yet there is a paucity of data on the extent of neurological impairments associated with low-level TH disruption. This study examined the dose-response characteristics of marginal iodine deficiency (ID) on parameters of thyroid function and neurodevelopment. Diets deficient in iodine were prepared by adding 975, 200, 125, 25, or 0 µg/kg potassium iodate to the base casein diet to produce five nominal iodine levels ranging from ample (Diet 1: 1000 μg iodine/kg chow, D1) to deficient (Diet 5: 25 µg iodine/kg chow, D5). Female Long Evans rats were maintained on these diets beginning 7 weeks prior to breeding until the end of lactation. Dams were sacrificed on gestational days 16 and 20, or when pups were weaned on postnatal day (PN) 21. Fetal tissue was harvested from the dams, and pups were sacrificed on PN14 and PN21. Blood, thyroid gland, and brain were collected for analysis of iodine, TH, and TH precursors and metabolites. Serum and thyroid gland iodine and TH were reduced in animals receiving two diets that were most deficient in iodine. T4 was reduced in the fetal brain but was not altered in the neonatal brain. Neurobehavior, assessed by acoustic startle, water maze learning, and fear conditioning, was unchanged in adult offspring, but excitatory synaptic transmission was impaired in the dentate gyrus in animals receiving two diets that were most deficient in iodine. A 15% reduction in cortical T4 in the fetal brain was sufficient to induce permanent reductions in synaptic function in adults. These findings have implications for regulation of TH-disrupting chemicals and suggest that standard behavioral assays do not readily detect neurotoxicity induced by modest developmental TH disruption.

Protective effect of KI in mtDNA in porcine thyroid: comparison with KIO₃ and nDNA.

PubMed

Karbownik-Lewinska, Malgorzata; Stepniak, Jan; Milczarek, Magdalena; Lewinski, Andrzej

2015-03-01

Iodine, bivalent iron (Fe²⁺), and hydrogen peroxide (H₂O₂), all significantly affecting the red-ox balance, are required for thyroid hormone synthesis. Intracellular iodine excess (≥10⁻³ M) transiently blocks thyroid hormonogenesis (an adaptive mechanism called Wolff-Chaikoff effect). The aim of the study was to evaluate the effects of iodine, used as potassium iodide (KI) or potassium iodate (KIO₃), in concentrations corresponding to those typical for Wolff-Chaikoff effect, on the level of oxidative damage to nuclear DNA (nDNA) and mitochondrial DNA (mtDNA) isolated from porcine thyroid under basal conditions and in the presence of Fenton reaction (Fe²⁺+H₂O₂ → Fe³⁺+(·)OH + OH⁻) substrates. Thyroid nDNA and mtDNA were incubated in the presence of either KI or KIO₃ (2.5-50 mM), without/with FeSO₄ (30 µM) + H₂O₂ (0.5 mM). Index of DNA damage, i.e., 8-oxo-7,8-dihydro-2'-deoxyguanosine, was measured by HPLC. Neither KI nor KIO₃ increased the basal level of 8-oxodG in both nDNA and mtDNA. KI-in all used concentrations-completely prevented the damaging effect of Fenton reaction substrates in mtDNA, and it partially prevented this damage in nDNA. KIO₃ partially prevented Fe²⁺+H₂O₂-induced oxidative damage in both DNA only in its highest used concentrations (≥25 mM). Without additional prooxidative abuse, both iodine compounds, i.e., KI and KIO₃, seem to be safe in terms of their potential oxidative damage to DNA in the thyroid. The superiority of KI over KIO₃ relies on its stronger protective effects against oxidative damage to mtDNA, which constitutes an argument for its preferential utility in iodine prophylaxis.

Radioiodine concentrated in a wetland.

PubMed

Kaplan, Daniel I; Zhang, Saijin; Roberts, Kimberly A; Schwehr, Kathy; Xu, Chen; Creeley, Danielle; Ho, Yi-Fang; Li, Hsiu-Ping; Yeager, Chris M; Santschi, Peter H

2014-05-01

Most subsurface environmental radioactivity contamination is expected to eventually resurface in riparian zones, or wetlands. There are a number of extremely sharp biogeochemical interfaces in wetlands that could alter radionuclide speciation and promote accumulation. The objective of this study was to determine if a wetland concentrated (129)I emanating from a former waste disposal basin located on the Savannah River Site (SRS) in South Carolina, USA. Additionally, studies were conducted to evaluate the role of sediment organic matter in immobilizing the radioiodine. Groundwater samples were collected along a 0.7-km transect away from the seepage basin and in the downstream wetlands. The samples were analyzed for (129)I speciation (iodide (I(-)), iodate (IO3(-)), and organo-I). Groundwater (129)I concentrations in many locations in the wetlands (as high as 59.9 Bq L(-1)(129)I) were greatly elevated with respect to the source term (5.9 Bq L(-1)(129)I). (129)I concentration profiles in sediment cores were closely correlated to organic matter concentrations (r(2) = 0.992; n = 5). While the sediment organic matter promoted the uptake of (129)I to the wetland sediment, it also promoted the formation of a soluble organic fraction: 74% of the wetland groundwater (129)I could pass through a 1 kDa (<1 nm) membrane and only 26% of the (129)I was colloidal. Of that fraction that could pass through a 1 kDa membrane, 39% of the (129)I was organo-I. Therefore, while wetlands may be highly effective at immobilizing aqueous (129)I, they may also promote the formation of a low-molecular-weight organic species that does not partition to sediments. This study provides a rare example of radioactivity concentrations increasing rather than decreasing as it migrates from a point source and brings into question assumptions in risk models regarding continuous dilution of released contaminants. Copyright © 2013 Elsevier Ltd. All rights reserved.

Simultaneous determination of free and total glycerol in biodiesel by capillary electrophoresis using multiple short-end injection.

PubMed

Spudeit, Daniel Alfonso; Piovezan, Marcel; Dolzan, Maressa D; Vistuba, Jacqueline Pereira; Azevedo, Mônia Stremel; Vitali, Luciano; Leal Oliveira, Marcone Augusto; Oliveira Costa, Ana Carolina; Micke, Gustavo Amadeu

2013-12-01

A rapid method for the simultaneous determination of free glycerol (FG) and total glycerol (TG) in biodiesel by CE using a short-end multiple injection (SE/MI) configuration system is described. The sample preparation for FG involves the extraction of glycerol with water and for TG a saponification reaction is carried out followed by extraction as in the case of FG. The glycerol extracted in both cases is submitted to periodate oxidation and the iodate ions formed are measured on a CE-SE/MI system. The relevance of this study lies in the fact that no analytical procedure has been previously reported for the determination of TG (or of FG and TG simultaneously) by CE. The optimum conditions for the saponification/extraction process were 1.25% KOH and 25°C, with a time of only 5 min, and biodiesel mass in the range of 50.0-200.0 mg can be used. Multiple injections were performed hydrodynamically with negative pressure as follows: 50 mbar/3s (FG sample); 50 mbar/6s (electrolyte spacer); 50 mbar/3s (TG sample). The linear range obtained was 1.55-46.5 mg/L with R(2) > 0.99. The LOD and LOQ were 0.16 mg/L and 0.47 mg/L, respectively for TG. The method provides acceptable throughput for application in quality control and monitoring biodiesel synthesis process. In addition, it offers simple sample preparation (saponification process), it can be applied to a variety biodiesel samples (soybean, castor, and waste cooking oils) and it can be used for the determination of two key parameters related to the biodiesel quality with a fast separation (less than 30 s) using an optimized CE-SE/MI system. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring strategies to remove contaminants from subsurface plumes: iron-bearing materials and calcite

NASA Astrophysics Data System (ADS)

Lawter, A.; Qafoku, N. P.; Garcia, W.; Lee, B.; Freedman, V. L.

2017-12-01

At the Hanford site in eastern Washington, depending on the particular waste site, radionuclide (Tc99/I129) laden liquid waste was not of a sufficient volume to carry the contamination through the vadose zone to the groundwater. Contaminants are therefore retained in the vadose zone, which represents a continuous source of these contaminants to groundwater through flux created by precipitation recharge. Deployment of treatment technologies in the vadose zone that will intercept flow from vadose zone recharge and sequester contaminants is needed for future groundwater protection. In this study, first we tested zero valent iron (ZVI) and sulfur modified iron (SMI) to determine the feasibility of using these materials to intercept Tc migrating from the vadose zone into the groundwater. Secondly, this study focused on testing the ZVI and SMI in conjunction with several potential amendments needed for capture of additional contaminants present (e.g., IO3) to immobilize contaminants both individually and combined. Previous testing has shown removal of IO3 by incorporation into calcite; these experiments test the effect of ZVI/SMI on the efficiency of the removal of IO3 by calcite and vice versa. Preliminary results have shown strong removal of high Tc concentrations (i.e., 22 ppm or 44 ppm) at solid to solution ratios of 1 g to 100 mL, but when the solid and the Tc concentration was scaled down to more field relevant conditions (i.e., 0.42 ppm), the Tc removal was slower and the amount of Tc removed (per gram of Fe solid) was decreased. In some tests, results indicated that there is no interference from IO3 on Tc removal, but presence of ZVI/SMI has a negative impact on the removal of IO3 by calcite incorporation, likely due to the fast reduction of iodate to iodide by the ZVI/SMI (iodide is usually not incorporated into calcite).

Etude de l'halogénation de EuBa2Cu3O6

NASA Astrophysics Data System (ADS)

Tshimanga Kabeya, D.; Mokhtari, M.; Perrin, C.; Sergent, M.; Grushko, Yu.; Kokovina, L.; Rozhniakova, N.

1994-11-01

Sintered samples of EuBa2Cu3O6 have been halogenated at low temperature (t < 300 ^circC) by treatments under NF3 or CCl4 flow diluted in nitrogen, or by reaction with iodine in sealed tubes. Such mild conditions of synthesis allowed to avoid the decomposition of the material during the reactions. The incorporation of the halogen in the sample has been evidenced by the weight gain, by the evolution of the unit-cell parameters and by SEM and EDS analyses. After fluorination and chlorination, the samples become superconducting, but no superconducting behaviour is observed after iodination. These results are compared to the ones previously obtained during the halogenation of YBa2Cu3O6. Des échantillons frittés de EuBa2Cu3O6 ont été halogénés à basse température (t < 300 ^circC) par traitement sous courant de NF3 ou de CCl4 dilué dans de l'azote, ou par réaction avec de l'iode en tube scellé. De telles conditions de synthèse ont permis de limiter la décomposition du matériau au cours de la réaction. L'incorporation de l'halogène dans l'échantillon est mise en évidence par variation de masse, par l'évolution des paramètres de maille, par observations au MEB et analyses EDS. Après fluoration et chloration l'échantillon devient supraconducteur, tandis qu'aucun comportement supraconducteur n'est observé après iodation. Ces résultats sont comparés avec ceux qui avaient été obtenus préalablement lors de l'halogénation de YBa2Cu3O6.

Effects of varying dietary iodine supplementation levels as iodide or iodate on thyroid status as well as mRNA expression and enzyme activity of antioxidative enzymes in tissues of grower/finisher pigs.

PubMed

Li, Qimeng; Mair, Christiane; Schedle, Karl; Hellmayr, Isabella; Windisch, Wilhelm

2013-02-01

The objective of this study was to investigate the influence of high dietary iodine supply and different iodine sources on thyroid status and oxidative stress in target tissues of the thyroid hormones in fattening pigs. Eighty castrates (body weight: 33.3 ± 0.4 kg) were randomly allotted into five different treatments: The control diet contained 150 μg I/kg as KI, the other feeding groups were supplemented with 4,000 μg I/kg (as KI and KIO(3)) and 10,000 μg I/kg (as KI and KIO(3)), respectively. The mRNA expression levels of sodium/iodide symporter (NIS) and key antioxidant enzymes (Cu/Zn SOD, CAT, GPx) were analyzed in thyroid gland, liver, kidney, muscle, and adipose tissue sampled during slaughter. Furthermore, antioxidant enzyme activities and the effect on lipid peroxidation (MDA) were determined in liver and muscle. In thyroid gland, a significant downregulation of NIS and Cu/Zn SOD mRNA expression was observed in high-iodine groups. In liver, a source effect on the mRNA expression of Cu/Zn SOD between KI and KIO(3) at 4,000 μg I/kg was shown. In contrast, not SOD but GPx activity was affected by iodine source with strongest downregulation in high KIO(3) group. In muscle, GPx activity was affected by both iodine source and dose, showing stronger downregulation in KI groups. In kidney and adipose tissue, oxidative stress parameters showed no or only unsystematic changes. However, variation in iodine supply had no effect on MDA concentrations. NIS expression was significantly decreased with increased iodine supplementation, which is to ensure the thyroid gland function. However, the alleviating effect of iodine supplementation observed in antioxidant enzyme mRNA expression and activity did not reflect on the lipid peroxide level.

Development of anion-exchange/reversed-phase high performance liquid chromatography-inductively coupled plasma-mass spectrometry methods for the speciation of bio-available iodine and bromine from edible seaweed.

PubMed

Romarís-Hortas, Vanessa; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

2012-05-04

Anion exchange high performance liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry has been novelly applied to assess inorganic (iodide and iodate) and organic (3-iodotyrosine - MIT, and 3,5-diiodotyrosine - DIT) iodine species in a single chromatographic run. The optimized operating conditions (Dionex IonPac AS7, gradient elution with 175 mM ammonium nitrate plus 15% (v/v) methanol, pH 3.8, as a mobile phase and flow rates within the 0.5-1.5 mL min(-1) range) have also been used to perform inorganic bromine speciation analysis (bromide and bromate). The developed method has been applied for determining the bio-available contents of iodine and bromine species in dialyzates from edible seaweed. Reverse phase high performance liquid chromatography (Zorbax Eclipse XDB-C8, gradient elution with 0.2% (m/m) acetic acid, and 0.2% (m/m) acetic acid in methanol, as mobile phases, and a constant flow rate of 0.75 mL min(-1)) also hyphenated with inductively coupled plasma-mass spectrometry was used to confirm the presence of organic iodine species (MIT and DIT) in the dialyzates. The verification of the presence of iodinated amino acids (MIT and DIT) in the extracts was also performed by reverse phase high performance liquid chromatography-electrospray ionization-mass spectrometry (LTQ Orbitrap). The developed methods have provided good repeatability (RSD values lower than 10% for both anion exchange and reverse phase separations) and analytical recoveries within the 90-105% range for all cases. The in vitro bio-availability method consisted of a simulated gastric and an intestinal digestion/dialysis (10 kDa molecular weight cut-off - MWCO) two-stage procedure. Iodide and MIT were the main bio-available species quantified, whereas bromide was the major bromine species found in the extracts. Copyright © 2012 Elsevier B.V. All rights reserved.

Assessment of spatial variation in drinking water iodine and its implications for dietary intake: a new conceptual model for Denmark.

PubMed

Voutchkova, Denitza Dimitrova; Ernstsen, Vibeke; Hansen, Birgitte; Sørensen, Brian Lyngby; Zhang, Chaosheng; Kristiansen, Søren Munch

2014-09-15

Iodine is essential for human health. Many countries have therefore introduced universal salt iodising (USI) programmes to ensure adequate intake for the populations. However, little attention has been paid to subnational differences in iodine intake from drinking water caused by naturally occurring spatial variations. To address this issue, we here present the results of a Danish nationwide study of spatial trends of iodine in drinking water and the relevance of these trends for human dietary iodine intake. The data consist of treated drinking water samples from 144 waterworks, representing approx. 45% of the groundwater abstraction for drinking water supply in Denmark. The samples were analysed for iodide, iodate, total iodine (TI) and other major and trace elements. The spatial patterns were investigated with Local Moran's I. TI ranges from <0.2 to 126 μg L(-1) (mean 14.4 μg L(-1), median 11.9 μg L(-1)). Six speciation combinations were found. Half of the samples (n = 71) contain organic iodine; all species were detected in approx. 27% of all samples. The complex spatial variation is attributed both to the geology and the groundwater treatment. TI >40 μg L(-1) originates from postglacial marine and glacial meltwater sand and from Campanian-Maastrichtian chalk aquifers. The estimated drinking water contribution to human intake varies from 0% to >100% of the WHO recommended daily iodine intake for adults and from 0% to approx. 50% for adolescents. The paper presents a new conceptual model based on the observed clustering of high or low drinking-water iodine concentrations, delimiting zones with potentially deficient, excessive or optimal iodine status. Our findings suggest that the present coarse-scale nationwide programme for monitoring the population's iodine status may not offer a sufficiently accurate picture. Local variations in drinking-water iodine should be mapped and incorporated into future adjustment of the monitoring and/or the USI programmes. Copyright © 2014 Elsevier B.V. All rights reserved.

Intra-vitreal αB crystallin fused to elastin-like polypeptide provides neuroprotection in a mouse model of age-related macular degeneration.

PubMed

Sreekumar, Parameswaran G; Li, Zhe; Wang, Wan; Spee, Christine; Hinton, David R; Kannan, Ram; MacKay, J Andrew

2018-05-18

Age-related macular degeneration (AMD) is the leading cause of severe and irreversible central vision loss, and the primary site of AMD pathology is the retinal pigment epithelium (RPE). Geographic atrophy (GA) is an advanced form of AMD characterized by extensive RPE cell loss, subsequent degeneration of photoreceptors, and thinning of retina. This report describes the protective potential of a peptide derived from the αB crystallin protein using a sodium iodate (NaIO 3 ) induced mouse model of GA. Systemic NaIO 3 challenge causes degeneration of the RPE and neighboring photoreceptors, which have similarities to retinas of GA patients. αB crystallin is an abundant ocular protein that maintains ocular clarity and retinal homeostasis, and a small peptide from this protein (mini cry) displays neuroprotective properties. To retain this peptide for longer in the vitreous, mini cry was fused to an elastin-like polypeptide (ELP). A single intra-vitreal treatment by this crySI fusion significantly inhibits retinal degeneration in comparison to free mini cry. While mini cry is cleared from the eye with a mean residence time of 0.4 days, crySI is retained with a mean residence time of 3.0 days; furthermore, fundus photography reveals evidence of retention at two weeks. Unlike the free mini cry, crySI protects the RPE against NaIO 3 challenge for at least two weeks after administration. CrySI also inhibits RPE apoptosis and caspase-3 activation and protects the retina from cell death up to 1-month post NaIO 3 challenge. These results show that intra-ocular ELP-linked peptides such as crySI hold promise as protective agents to prevent RPE atrophy and progressive retinal degeneration in AMD. Copyright © 2018 Elsevier B.V. All rights reserved.

Effects of oxidizing adulterants on detection of 11-nor-delta9-THC-9-carboxylic acid in urine.

PubMed

Paul, Buddha D; Jacobs, Aaron

2002-10-01

Bleach, nitrite, chromate, and hydrogen peroxide-peroxidase are effective urine adulterants used by the illicit drug users to conceal marijuana-positive results. Methods for detecting nitrite and chromate are available. Effects of other oxidizing agents that could possibly be used as adulterants and are difficult to detect or measure are presented in this report. Urine samples containing 40 ng/mL of 11-nor-delta9-THC-9-carboxylic acid (THC-acid) were treated with 10 mmol/L of commonly available oxidizing agents. Effects of horseradish peroxidase of activity 10 unit/mL and extracts from 2.5 g of red radish (Raphanus sativus, Radicula group), horseradish (Armoracia rusticana), Japanese radish (Raphanus sativus, Daikon group), and black mustard seeds (Brassica nigra), all with 10 mmol/L of hydrogen peroxide, were also examined. After 5 min, 16 h and 48 h of exposure at room temperature (23 degrees C) the specimens were tested by a gas chromatographic-mass spectrometric method for THC-acid. A control group treated with sodium hydrosulfite to reduce the oxidants, was also tested to investigate the effect of oxidizing agents on THC-acid in the extraction method. THC-acid was lost completely in the extraction method when treated with chromate, nitrite, oxone, and hydrogen peroxide/ferrous ammonium sulfate (Fenton's reagent). Some losses were also observed with persulfate and periodate (up to 25%). These oxidants, and other oxidizing agents like permanganate, periodate, peroxidase, and extracts from red radish, horseradish, Japanese radish and black mustard seeds destroyed most of the THC-acid (> 94%) within 48 h of exposure. Chlorate, perchlorate, iodate, and oxychloride under these conditions showed little or no effect. Complete loss was observed when THC-acid was exposed to 50 mmol/L of oxychloride for 48 h. Several oxidizing adulterants that are difficult to test by the present urine adulterant testing methods showed considerable effects on the destruction of THC-acid. The time and temperature for these effects were similar to those used by most laboratories to collect and test specimens. In several cases, the loss of THC-acid was > 94%.

Effect of pharmacologically induced retinal degeneration on retinal autofluorescence lifetimes in mice.

PubMed

Dysli, Chantal; Dysli, Muriel; Zinkernagel, Martin S; Enzmann, Volker

2016-12-01

Fluorescence lifetime imaging ophthalmoscopy (FLIO) was used to investigate retinal autofluorescence lifetimes in mouse models of pharmacologically induced retinal degeneration over time. Sodium iodate (NaIO 3 , 35 mg/kg intravenously) was used to induce retinal pigment epithelium (RPE) degeneration with subsequent loss of photoreceptors (PR) whereas N-methyl-N-nitrosourea (MNU, 45 mg/kg intraperitoneally) was employed for degeneration of the photoreceptor cell layer alone. All mice were measured at day 3, 7, 14, and 28 after the respective injection of NaIO 3 , MNU or NaCl (control). Fluorescence lifetime imaging was performed using a fluorescence lifetime imaging ophthalmoscope (Heidelberg Engineering, Heidelberg, Germany). Fluorescence was excited at 473 nm and fluorescence lifetimes were measured in a short and a long spectral channel (498-560 nm and 560-720 nm). Corresponding optical coherence tomography (OCT) images were consecutively acquired and histology was performed at the end of the experiments. Segmentation of OCT images and histology verified the cell type-specific degeneration process over time. Retinal autofluorescence lifetimes increased from day 3 to day 28 in mice after NaIO 3 treatment. Finally, at day 28, fluorescence lifetimes were prolonged by 8% in the short and 61% in the long spectral channel compared to control animals (p = 0.21 and p = 0.004, respectively). In mice after MNU treatment, the mean retinal autofluorescence lifetimes were already decreased at day 3 and retinal lifetimes were finally shortened by 27% in the short and 51% in the long spectral channel at day 28 (p = 0.0028). In conclusion, degeneration of the RPE with subsequent photoreceptor degeneration by NaIO 3 lead to longer mean fluorescence lifetimes of the retina compared to control mice, whereas during specific degeneration of the photoreceptor layer induced by MNU shorter lifetimes were measured. Therefore, short retinal fluorescence lifetimes may originate from the RPE and may be modified by the overlaying retinal layers. Copyright © 2016 Elsevier Ltd. All rights reserved.

Exploiting genotypic variation in plant nutrient accumulation to alleviate micronutrient deficiency in populations.

PubMed

Genc, Yusuf; Humphries, Julia M; Lyons, Graham H; Graham, Robin D

2005-01-01

More than 2 billion people consume diets that are less diverse than 30 years ago, leading to deficiencies in micronutrients, especially iron (Fe), zinc (Zn), selenium (Se), iodine (I), and also vitamin A. A strategy that exploits genetic variability to breed staple crops with enhanced ability to fortify themselves with micronutrients (genetic biofortification) offers a sustainable, cost-effective alternative to conventional supplementation and fortification programs. This is more likely to reach those most in need, has the added advantages of requiring no change in current consumer behaviour to be effective, and is transportable to a range of countries. Research by our group, along with studies elsewhere, has demonstrated conclusively that substantial genotypic variation exists in nutrient (e.g. Fe, Zn) and nutrient promotor (e.g. inulin) concentrations in wheat and other staple foods. A rapid screening technique has been developed for lutein content of wheat and triticale, and also for pro-vitamin A carotenoids in bread wheat. This will allow cost-effective screening of a wider range of genotypes that may reveal greater genotypic variation in these traits. Moreover, deeper understanding of genetic control mechanisms and development of molecular markers will facilitate breeding programs. We suggest that a combined strategy utilising plant breeding for higher micronutrient density; maximising the effects of nutritional promoters (e.g. inulin, vitamin C) by promoting favourable dietary combinations, as well as by plant breeding; and agronomic biofortification (e.g. adding iodide or iodate as fertiliser; applying selenate to cereal crops by spraying or adding to fertiliser) is likely to be the most effective way to improve the nutrition of populations. Furthermore, the importance of detecting and exploiting beneficial interactions is illustrated by our discovery that in Fe-deficient chickens, circulating Fe concentrations can be restored to normal levels by lutein supplementation. Further bioavailability/bioefficacy trials with animals and humans are needed, using varying dietary concentrations of Fe, Zn, carotenoids, inulin, Se and I to elucidate other important interactions in order to optimise delivery in biofortification programs.

Buoyancy-driven convection around chemical fronts traveling in covered horizontal solution layers.

PubMed

Rongy, L; Goyal, N; Meiburg, E; De Wit, A

2007-09-21

Density differences across an autocatalytic chemical front traveling horizontally in covered thin layers of solution trigger hydrodynamic flows which can alter the concentration profile. We theoretically investigate the spatiotemporal evolution and asymptotic dynamics resulting from such an interplay between isothermal chemical reactions, diffusion, and buoyancy-driven convection. The studied model couples the reaction-diffusion-convection evolution equation for the concentration of an autocatalytic species to the incompressible Stokes equations ruling the evolution of the flow velocity in a two-dimensional geometry. The dimensionless parameter of the problem is a solutal Rayleigh number constructed upon the characteristic reaction-diffusion length scale. We show numerically that the asymptotic dynamics is one steady vortex surrounding, deforming, and accelerating the chemical front. This chemohydrodynamic structure propagating at a constant speed is quite different from the one obtained in the case of a pure hydrodynamic flow resulting from the contact between two solutions of different density or from the pure reaction-diffusion planar traveling front. The dynamics is symmetric with regard to the middle of the layer thickness for positive and negative Rayleigh numbers corresponding to products, respectively, lighter or heavier than the reactants. A parametric study shows that the intensity of the flow, the propagation speed, and the deformation of the front are increasing functions of the Rayleigh number and of the layer thickness. In particular, the asymptotic mixing length and reaction-diffusion-convection speed both scale as square root Ra for Ra>5. The velocity and concentration fields in the asymptotic dynamics are also found to exhibit self-similar properties with Ra. A comparison of the dynamics in the case of a monostable versus bistable kinetics is provided. Good agreement is obtained with experimental data on the speed of iodate-arsenous acid fronts propagating in horizontal capillaries. We furthermore compare the buoyancy-driven dynamics studied here to Marangoni-driven deformation of traveling chemical fronts in solution open to the air in the absence of gravity previously studied in the same geometry [L. Rongy and A. De Wit, J. Chem. Phys. 124, 164705 (2006)].

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, Kent E.; Golovich, Elizabeth C.; Wellman, Dawn M.

Iodine sorption onto seven resins and six carbon materials was evaluated using water from well 299-W19-36 on the Hanford Site. These materials were tested using a range of solution-to-solid ratios. The test results are as follows. The efficacy of the resin and granular activated carbon materials was less than predicted based on manufacturers’ performance data. It is hypothesized that this is due to the differences in speciation previously determined for Hanford groundwater. The sorption of iodine is affected by the iodine species in the source water. Iodine loading on resins using source water ranged from 1.47 to 1.70 µg/g withmore » the corresponding K d values from 189.9 to 227.0 mL/g. The sorption values when the iodine is converted to iodide ranged from 2.75 to 5.90 µg/g with the corresponding K d values from 536.3 to 2979.6 mL/g. It is recommended that methods to convert iodine to iodide be investigated in fiscal year (FY) 2015. The chemicals used to convert iodine to iodate adversely affected the sorption of iodine onto the carbon materials. Using as-received source water, loading and K d values ranged from 1.47 to 1.70 µg/g and 189.8 to 226.3 mL/g respectively. After treatment, loading and K d values could not be calculated because there was little change between the initial and final iodine concentration. It is recommended the cause of the decrease in iodine sorption be investigated in FY15. In direct support of CH2M HILL Plateau Remediation Company, Pacific Northwest National Laboratory has evaluated samples from within the 200W pump and treat bioreactors. As part of this analysis, pictures taken within the bioreactor reveal a precipitate that, based on physical properties and known aqueous chemistry, is hypothesized to be iron pyrite or chalcopyrite, which could affect iodine adsorption. It is recommended these materials be tested at different solution-to-solid ratios in FY15 to determine their effect on iodine sorption.« less

Population living in the Red Sea State of Sudan may need urgent intervention to correct the excess dietary iodine intake.

PubMed

Izzeldin, H S; Crawford, M A; Jooste, P L

2007-01-01

Both inadequate and high intakes of iodine are associated with thyroid disease and associated abnormalities. Consumption of foods deficient in iodine induces hypothyroidism. Conversely, excessive intake of the nutrient precipitates hyperthyroidism. Iodine deficiency causes impairment of thyroid hormonogenesis resulting in goiter (struma), cretinism which is associated with increased prenatal and infant mortality, deafness, motor disabilities and mental retardation due to damage during fetal and neonatal brain development. We have assessed the iodine status of school children from the locality of Port Sudan, Red Sea State of Eastern Sudan. The primary sources of iodine of the children are mainly iodized salt and rations supplied by local donors and various aid agencies operating in the Sudan. Male and female children (n=141), aged 6 to 12 years (median age 9.8 years), were selected for the survey using a multistage random sampling technique, between May 22 and August 25, 2006. All the children were assessed for urinary iodine and visible goiter. In addition, the iodine content of twenty salt samples was determined using the lodometric titration method and spot test kits. The components of other foods that are routinely consumed by the children and households were noted using a questionnaire form. Urinary iodine concentration exceeded 300 microg/l and 1000 microg/l in 65% and 9.9% of the children, respectively. The highest urinary iodine level was 1470 microg/l. The prevalence of visible goiter was 17%. All the salt samples collected from the schools had more than 150mg potassium iodate per kg of salt. The results of this pilot survey reveal that excessive intake of iodine in children exists in Port Sudan. Inappropriate and unregulated local fortification of salt and lack of monitoring of the imported and donated salt is the primary reason for the excessive intake. There is an urgent need for a regulatory mechanism during the process of iodine fortification and at the point of entry of imported and donated iodized salt as well as the mode of delivery in order to avoid hyperthyroidism and associated disorders. In addition, independent professionals should critically evaluate the health impact of excessive consumption of the nutrient.

Halogens in oil and gas production-associated wastewater.

NASA Astrophysics Data System (ADS)

Harkness, J.; Warner, N. R.; Dwyer, G. S.; Mitch, W.; Vengosh, A.

2014-12-01

Elevated chloride and bromide in oil and gas wastewaters that are released to the environment are one of the major environmental risks in areas impacted by shale gas development [Olmstead et al.,2013]. In addition to direct contamination of streams, the potential for formation of highly toxic disinfection by-products (DBPs) in drinking water in utilities located downstream from disposal sites poses a serious risk to human health. Here we report on the occurrence of iodide in oil and gas wastewater. We conducted systematic measurements of chloride, bromide, and iodide in (1) produced waters from conventional oil and gas wells from the Appalachian Basin; (2) hydraulic fracturing flowback fluids from unconventional Marcellus and Fayetteville shale gas, (3) effluents from a shale gas spill site in West Virginia; (4) effluents of oil and gas wastewater disposed to surface water from three brine treatment facilities in western Pennsylvania; and (5) surface waters downstream from the brine treatment facilities. Iodide concentration was measured by isotope dilution-inductively coupled plasma-mass spectrometry, which allowed for a more accurate measurement of iodide in a salt-rich matrix. Iodide in both conventional and unconventional oil and gas produced and flowback waters varied from 1 mg/L to 55 mg/L, with no systematic enrichment in hydraulic fracturing fluids. The similarity in iodide content between the unconventional Marcellus flowback waters and the conventional Appalachian produced waters clearly indicate that the hydraulic fracturing process does not induce additional iodide and the iodide content is related to natural variations in the host formations. Our data show that effluents from the brine treatment facilities have elevated iodide (mean = 20.9±1 mg/L) compared to local surface waters (0.03± 0.1 mg/L). These results indicate that iodide, in addition to chloride and bromide in wastewater from oil and gas production, poses an additional risk to downstream surface water quality and drinking water utilities given the potential of formation of iodate-DBPs in drinking water. Olmstead, S.M. et al. (2013). Shale gas development impacts on surface water quality in Pennsylvania, PNAS, 110, 4962-4967.

Isotope excursions and shifting oxidation states recorded in the Paleoproterozoic Franceville Basin

NASA Astrophysics Data System (ADS)

Wang, V.; Junium, C. K.; Lu, Z.; Préat, A.

2014-12-01

Geochemical studies of Paleoproterozoic rocks have revealed that the initial rise of oxygen was protracted and that Earth's surface environments fluctuated between oxic and anoxic states over hundreds of millions of years. Marine sediments of the 2.1 Gyr-old Franceville Basin of west central Africa are only lightly metamorphosed, and their geochemistry may thus reveal unique insights into the environmental and metabolic conditions during the history of rising oxygen levels. In the Franceville Basin stratigraphic variation totaling 10‰ in δ13Ccarb was previously documented. This contribution builds on this work and characterizes changes in C, N, and S cycles using stable isotope values. The results from systematic analysis of several biologically mediated redox proxies preserved in carbonates from the Franceville Basin will be presented, including δ34S values of pyrite and δ13C and δ15N values of bulk organic carbon and kerogens. Consistent with independent reports of an excursion in δ13Corg in the Franceville Basin and elsewhere, we find ~20‰ stratigraphic variation in δ13C of bulk organic carbon. Initial results for δ15N of bulk organic matter range from -6 to 6 ‰, a wider distribution of values than previously reported for the Franceville Basin and more negative than values reported for the similarly aged Onega Basin in Fennoscandia. I/Ca ratios range from near zero to near Phanerozoic levels and are consistent with the presence of iodate. Chromium reducible sulfide has been extracted from all but one sample, confirming the presence of pyrite. δ34S of pyrite as well as δ13C and δ15N of kerogen will also be presented. The biochemically diverse array of proxy analyses presented here have varying thresholds of sensitivity to oxygen levels and hence will allow detailed reconstruction of the redox history of basin waters. As minimum O2 thresholds are often needed for certain biochemical processes, the resulting data will also have implications for key steps in the evolution of biochemical pathways.

Technetium, Iodine, and Chromium Adsorption/Desorption Kd Values for Vadose Zone Pore Water, ILAW Glass, and Cast Stone Leachates Contacting an IDF Sand Sequence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Last, George V.; Snyder, Michelle M.V.; Um, Wooyong

Performance and risk assessments of immobilized low-activity waste (ILAW) at the Integrated Disposal Facility (IDF) have shown that risks to groundwater are quite sensitive to adsorption-desorption interactions occurring in the near- and far-field environment. These interactions between the underlying sediments and the contaminants present in the leachates that descend from the buried glass, secondary waste grouts, and potentially Cast Stone low-activity waste packages have been represented in these assessments using the contaminant distribution coefficient (Kd) construct. Some contaminants (99Tc, 129I, and Cr) present in significant quantities in these wastes have low Kd values and tend to drive risk to publicmore » health and the environment. Relatively small changes in the Kd value can cause relatively large changes in the retardation factor. Thus, even relatively small uncertainty in the Kd value can result in a relatively large uncertainty in the risk determined through performance assessment modeling. The purpose of this study is to further reduce the uncertainty in Kd values for 99Tc, iodine (iodide and iodate), and Cr (chromate; CrO42-) by conducting systematic adsorption-desorption experiments using actual sand-dominated Hanford formation sediments from beneath the IDF and solutions that closely mimic Hanford vadose zone pore water and leachates from Cast Stone and ILAW glass waste forms. Twenty-four batch and 21 flow-through column experiments were conducted, yielding 261 Kd measurements for these key contaminants, and contributing to our understanding for predicting transport from wastes disposed to the IDF. While the batch Kd methodology is not well-suited for measuring Kd values for non-sorbing species (as noted by the U.S. Environmental Protection Agency), the batch Kd results presented here are not wholly inconsistent with the column Kd results, and could be used for sensitivity purposes. Results from the column experiments are consistent with the best estimate and lower range of Kd values reported by Krupka et al. and Cantrell et al.« less

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS.

PubMed

Eklund, Lars; Hofer, Tomas S; Persson, Ingmar

2015-01-28

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2(-), chlorate, ClO3(-), and perchlorate, ClO4(-). In addition, the structures of the hydrated hypochlorite, ClO(-), bromate, BrO3(-), iodate, IO3(-) and metaperiodate, IO4(-), ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO6(3-), ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01-0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.

Identification of transformation products during advanced oxidation of diatrizoate: Effect of water matrix and oxidation process.

PubMed

Azerrad, Sara P; Lütke Eversloh, Christian; Gilboa, Maayan; Schulz, Manoj; Ternes, Thomas; Dosoretz, Carlos G

2016-10-15

Removal of micropollutants from reverse osmosis (RO) brines of wastewater desalination by oxidation processes is influenced by the scavenging capacity of brines components, resulting in the accumulation of transformation products (TPs) rather than complete mineralization. In this work the iodinated contrast media diatrizoate (DTZ) was used as model compound due to its relative resistance to oxidation. Identification of TPs was performed in ultrapure water (UPW) and RO brines applying nonthermal plasma (NTP) and UVA-TiO2 as oxidation techniques. The influence of main RO brines components in the formation and accumulation of TPs, such as chloride, bicarbonate alkalinity and humic acid, was also studied during UVA-TiO2. DTZ oxidation pattern in UPW resulted similar in both UVA-TiO2 and NTP achieving 66 and 61% transformation, respectively. However, DTZ transformation in RO brines was markedly lower in UVA-TiO2 (9%) than in NTP (27%). These differences can be attributed to the synergic effect of RO brines components during NTP. Moreover, reactive species other than hydroxyl radical contributed to DTZ transformation, i.e., direct photolysis in UVA-TiO2 and direct photolysis + O3 in NTP accounted for 16 and 23%, respectively. DTZ transformation led to iodide formation in both oxidation techniques but it further oxidized to iodate by ozone in NTP. In total 14 transformation products were identified in UPW of which 3 were present only in UVA-TiO2 and 2 were present exclusively in NTP; 5 of the 14 TPs were absent in RO brines. Five of them were new and were denoted as TP-474A/B, TP-522, TP-586, TP-602, TP-628. TP-522 (mono-chlorinated) was elucidated only in presence of high chloride titer-synthetic water matrix in NTP, most probably formed by active chlorine species generated in situ. TPs accumulation in RO brines was markedly different in comparison to UPW. This denotes the influence of RO brines components in the formation of reactive species that could further attack DTZ/TPs and/or scavenging performed by these brine components that could limit further TPs degradation. Five plausible degradation pathways are proposed for DTZ transformation in UPW. Copyright © 2016 Elsevier Ltd. All rights reserved.

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

PubMed Central

Eklund, Lars; Hofer, Tomas S.

2014-01-01

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2−, chlorate, ClO3−, and perchlorate, ClO4−. In addition, the structures of the hydrated hypochlorite, ClO−, bromate, BrO3−, iodate, IO3− and metaperiodate, IO4−, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO63−, ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5=1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5=2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions. PMID:25473816

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

DOE PAGES

Eklund, Lars; Hofer, Tomas S.; Persson, Ingmar

2014-11-26

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO 2 –, chlorate, ClO 3 –, and perchlorate, ClO 4 –. In addition, the structures of the hydrated hypochlorite, ClO –, bromate, BrO 3 –, iodate, IO 3 – and metaperiodate, IO 4 –, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H 2IO 6 3–, ions have been determinedmore » by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl–O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. Here, the water exchange rate for the perchlorate ion is significantly faster, τ 0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ 0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.« less

Effect of various sources and levels of iodine, as well as the kind of diet, on the performance of young laying hens, iodine accumulation in eggs, egg characteristics, and morphotic and biochemical indices in blood.

PubMed

Słupczyńska, M; Jamroz, D; Orda, J; Wiliczkiewicz, A

2014-10-01

Young hens were fed over a period of 150 d with 2 kinds of diets including corn and soybean meal or corn, soybean, and rapeseed meal. Diets were enriched with potassium iodide (KI) or potassium iodate (KIO3) as an I source in amounts equal to 1, 3, or 5 mg of supplemented I/kg of feed. The hen performance, egg quality, hematological and morphotic indices in blood, hepatic enzyme activity, lipid indices in blood serum as well as I accumulation in wet egg content were determined. Introduction of 00-variety rapeseed meal into the diet improved the laying rate and feed conversion (P < 0.05); however, better egg weight was noted by feeding the hens with a diet without rapeseed meal. Use of KI as an I source enhanced the egg weight. The increased I level in the diet had an equivocal influence on egg weight, improved the feed conversion per 1 kg of eggs, and decreased the proportion of damaged eggs. The use of corn, soybean, and rapeseed meal in hen diets significantly improved yolk color; similar results were noted after an increase in I levels in the diets after 3 mo of feeding. Hematological indices of hen blood demonstrated significantly higher red blood cells numbers and hemoglobin concentrations with the use of KI. The use of a diet containing rapeseed meal led to an enhancement of hepatic enzyme activity, especially of alkaline phosphatase (P = 0.007). Lipid metabolism indices were not influenced by the kind of diet or the I source or level. The accumulation of I in wet egg content was negatively influenced by the use of a diet containing rapeseed meal (P = 0.000). The application of KI as an I source enhanced (P = 0.003) the accretion of I in eggs after 5 mo of treatment. Enhanced I supply significantly increased accumulation of I in eggs (P = 0.000) after 3 and 5 mo of the experiment from 260 and 310 to 1,011 and 1,256 µg/kg of wet egg content, respectively. ©2014 Poultry Science Association Inc.

RedOx-controlled sorption of iodine anions by hydrotalcite composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levitskaia, Tatiana G.; Chatterjee, Sayandev; Arey, Bruce W.

2016-01-01

The radioactive contaminant iodine-129 (I-129) is one of the top risk drivers at radiological waste disposal and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. Currently there are very few options available to treat I-129 in the groundwater, which is partially related to its complex biogeochemical behavior in the subsurface and occurrence in the multiple chemical forms. We hypothesize that layered hydrotalcite materials containing redox active transition metal ions offer a potential solution, benefiting from the simultaneous adsorption of iodate (IO3-) and iodide (I-) anions, which exhibit different electronic and structural properties and therefore may require dissimilarmore » hosts. To test this hypothesis, Cr3+- based materials were selected based on the rationale that Cr3+ readily reduces IO3- in solution. It was combined with either redox-active Co2+ or redox-inactive Ni2+ so that two model materials were prepared by hydrothermal synthesis including Co2+-Cr3+ and Ni2+-Cr3+(M-Cr). Obtained M-Cr materials comprised of Co2+-Cr3+ or Ni2+-Cr3+ layered hydrotalcite and small fractions of Co3O4 spinel or Ni(OH)2 theophrastite phases were structurally characterized before and after uptake of periodate (IO4-), IO3-, and I- anions. It was found that the IO3- uptake is driven by its chemical reduction to I2 and I-. Interestingly, in the Co2+-Cr3+ hydrotalcite, Co2+ and not Cr3+ serves as a reductant while in the Ni2+-Cr3+ hydrotalcite Cr3+ is responsible for the reduction of IO3-. A different uptake mechanism was identified for the IO4- anion. The Co2+-Cr3+ hydrotalcite phase efficiently uptakes IO4- by a diffusion-limited ion exchange mechanism and is not accompanied by the redox process, while Cr3+ in the Ni2+-Cr3+ hydrotalcite reduces IO4- to IO3-, I2 and I-. Iodide exhibited high affinity only to the Co-Cr material. The Co-Cr material performed remarkably well for the removal of IO3-, I- and total iodine from the groundwater collected from the US DOE Hanford site, WA, USA outperforming non-redox active hydrotalcites (e.g., Mg2+-Al3+) reported previously. This work demonstrates that redox-controlled sorption can be a highly effective method for the treatment of anions based on elements with mobile oxidation states. Further, multiple anions of interest could be simultaneously removed through combination of approaches.« less

Speciation of 127I and 129I in atmospheric aerosols at Risø, Denmark: insight into sources of iodine isotopes and their species transformations

NASA Astrophysics Data System (ADS)

Zhang, Luyuan; Hou, Xiaolin; Xu, Sheng

2016-02-01

Speciation analysis of iodine in aerosols is a very useful approach for understanding geochemical cycling of iodine in the atmosphere. In this study, overall iodine species, including water-soluble iodine species (iodide, iodate and water-soluble organic iodine), NaOH-soluble iodine, and insoluble iodine have been determined for 129I and 127I in the aerosols collected at Risø, Denmark, during March and May 2011 (shortly after the Fukushima nuclear accident) and in December 2014. The measured concentrations of total iodine are in the range of 1.04-2.48 ng m-3 for 127I and (11.3-97.0) × 105 atoms m-3 for 129I, corresponding to 129I / 127I atomic ratios of (17.8-86.8) × 10-8. The contribution of Fukushima-derived 129I (peak value of 6.3 × 104 atoms m-3) is estimated to be negligible (less than 6 %) compared to the total 129I concentration in northern Europe. The concentrations and species of 129I and 127I in the aerosols are found to be strongly related to their sources and atmospheric pathways. Aerosols that were transported over the contaminated seas contained higher concentrations of 129I than aerosols transported over the European continent. The high 129I concentrations of the marine aerosols are attributed to secondary emission of marine discharged 129I in the contaminated seawater in the North Sea, North Atlantic Ocean, English Channel, Kattegat, etc., rather than direct gaseous release from the European nuclear reprocessing plants (NRPs). Water-soluble iodine was found to be a minor fraction to the total iodine for both 127I (7.8-13.7 %) and 129I (6.5-14.1 %) in ocean-derived aerosols, but accounted for 20.2-30.3 % for 127I and 25.6-29.5 % for 129I in land-derived aerosols. Iodide was the predominant form of water-soluble iodine, accounting for more than 97 % of the water-soluble iodine. NaOH-soluble iodine seems to be independent of the sources of aerosols. The significant proportion of 129I and 127I found in NaOH-soluble fractions is likely bound with organic substances. In contrast to water-soluble iodine, the sources of air masses exerted distinct influences on insoluble iodine for both 129I and 127I, with higher values for marine air masses and lower values for terrestrial air masses.

Physico-Chemical Research on the Sounding Rocket Maser 13

NASA Astrophysics Data System (ADS)

Lockowandt, Christian; Kemi, Stig; Abrahamsson, Mattias; Florin, Gunnar

MASER is a sounding rocket platform for short-duration microgravity experiments, providing the scientific community with an excellent microgravity tool. The MASER programme has been running by SSC from 1987 and has up to 2012 provided twelve successful flights for microgravity missions with 6-7 minutes of microgravity, the g-level is normally below 1x10-5 g. The MASER 13 is planned to be launched in spring 2015 from Esrange Space Center in Northern Sweden. The rocket will carry four ESA financed experiment modules. The MASER 13 vehicle will be propelled by the 2-stage solid fuel VSB-30 rocket motor, which provided the 390 kg payload with an apogee of 260 km and 6 and a half minutes of microgravity. Swedish Space Corporation carries out the MASER missions for ESA and the program is also available for other customers. The payload comprise four different experiment modules of which three could be defined as physic-chemical research; XRMON-SOL, CDIC-3, MEDI. It also comprises the Maser Service Module and the recovery system. The Service Module provided real-time 5 Mbps down-link of compressed experiment digital video data from the on-board cameras, as well as high-speed housekeeping telemetry data. XRMON-SOL In this experiment the influence of gravity on the formation of an equiaxed microstructure will be investigated. Special attention will be put on the aspect of nucleation, segregation and impingement. The experiment scope is to melt and solidify an AlCu-alloy sample in microgravity. The solidification will be performed in an isothermal environment. The solidification process will be monitored and recorded with X-ray image during the whole flight, images will also be down-linked to ground for real-time monitoring and possible interaction. CDIC-3 The goal is to study in migrogravity the spatio-temporal dynamics of a chemical front travelling in a thin solution layer open to the air and specifically the respective role of Marangoni and density-related hydrodynamic instabilities. The model reaction is the autocatalytic iodate oxidation of arsenous acid, where surface tension changes due to the change in composition. The experiment will be performed by injecting the fluids into an experiment cell and the reaction will be triggered by an electrical pulse. The chemical reaction front and the dynamics of the liquid will be monitored by different optical systems. MEDI The general objective of the investigation is to improve the understanding of the physical phenomena that govern the formation of the columnar-to-equiaxed transition (CET) in alloy solidification and its consequences for casting soundness. In the frame of the experiment MEDI on MASER 13 the goal is to investigate the formation of an equiaxed microstructure under low gravity conditions.

Iodine-to-calcium ratios in carbonates suggest a primary origin for the Precambrian Lomagundi and Shuram carbon isotope excursions

NASA Astrophysics Data System (ADS)

Hardisty, D. S.; Lu, Z.; Planavsky, N. J.; Osburn, M. R.; Bekker, A.; Lyons, T. W.

2013-12-01

Systematic increases in iodine-to-calcium ratios (I/Ca) in carbonates from both the Precambrian Lomagundi and Shuram carbonate carbon isotope (δ13Ccarb) excursion intervals suggest primary origins for these events. Iodate (IO3-), the oxidized iodine species, is the exclusive species incorporated into carbonates. The high redox sensitivity of IO3- to deoxygenation requires highly oxidizing fluids for IO3- production, making I/Ca in platform carbonates a simple indicator of the presence of oxidizing fluids in the surface ocean. Similarly, redox sensitivity makes the proxy host susceptible to diagenetic iodine loss during carbonate recrystallization in reducing pore fluids. Recent work has shown carbonates to experience near-complete iodine loss during dolomitization in the Permian, and work from our group evaluating modern and recent carbonates demonstrate the potential for diagenetic iodine loss during carbonate recrystallization. In some cases, however, such as meteoric aragonite-to-calcite transitions, oxidizing pore fluids have the potential to buffer IO3- concentrations, causing negligible alteration to primary I/Ca despite negative shifts in δ13Ccarb. These results highlight that diagenetic alterations to I/Ca and δ13Ccarb need not always be coupled, but importantly, no observed scenario promotes post-depositional addition of iodine to carbonates. This means that, independent of δ13Ccarb, systematic, stratigraphic increases in I/Ca ratios observed in the carbonate record are most easily interpreted as resulting from depositional controls such as surface ocean redox or shifts in the total marine iodine reservoir. From this, increasing I/Ca ratios coincident with rising and falling δ13Ccarb trends for the Paleoproterozic Lomagundi and Neoproterozoic Shuram events, respectively, support suggestions of a primary origin for the δ13Ccarb excursions. Significant increase in I/Ca in dolomites deposited during the Lomagundi excursion, rising from blank values in the Archean, suggest very early dolomitization in an oxidizing surface ocean promoting aerobic iodine cycling. This interpretation is consistent with earlier suggestions relating a >+10 ‰ δ13Ccarb shift to substantial organic carbon burial and associated oxygen production. Extremely negative δ13Ccarb (down to <-10 ‰) observed during the Shuram event have been linked to both diagenetic and primary mechanisms. We propose, however, that a marked increase in I/Ca ratios associated with the negative δ13Ccarb excursion in the Khufai Formation of Oman provides evidence for a primary origin for the Shuram. Such an increase could be interpreted as enhanced delivery of IO3- or total iodine from the deep ocean, perhaps driven by deep ocean ventilation and/or oxidation of a large pool of marine-derived organic matter. Overall, regardless of the individual primary controls driving increases in carbonate I/Ca during the Lomagundi and Shuram events, authigenic/diagenetic controls allowing for increased I/Ca are unlikely, suggesting a primary origin for the two largest δ13Ccarb excursions in Earth history.

Chemical-mechanical polishing of metal and dielectric films for microelectronic applications

NASA Astrophysics Data System (ADS)

Hegde, Sharath

The demand for smaller, faster devices has led the integrated circuit (IC) industry to continually increase the device density on a chip while simultaneously reducing feature dimensions. Copper interconnects and multilevel metallization (MLM) schemes were introduced to meet some of these challenges. With the employment of MLM in the ultra-large-scale-integrated (ULSI) circuit fabrication technology, repeated planarization of different surface layers with tolerance of a few nanometers is required. Presently, chemical-mechanical planarization (CMP) is the only technique that can meet this requirement. Damascene and shallow trench isolation processes are currently used in conjunction with CMP in the fabrication of multilevel copper interconnects and isolation of devices, respectively, for advanced logic and memory devices. These processes, at some stage, require simultaneous polishing of two different materials using a single slurry that offers high polish rates, high polish selectivity to one material over the other and good post-polish surface finish. Slurries containing one kind of abrasive particles do not meet most of these demands due mainly to the unique physical and chemical properties of each abrasive. However, if a composite particle is formed that takes the advantages of different abrasives while mitigating their disadvantages, the CMP performance of resulting abrasives would be compelling. It is demonstrated that electrostatic interactions between ceria and silica particles at pH 4 can be used to produce composite particles with enhanced functionality. Zeta potential measurement and TEM images used for particle characterization show the presence of such composite particles with smaller shell particles attached onto larger core particles. Slurries containing ceria (core)/silica (shell) and silica (core)/ceria (shell) composite particles when used to polish metal and dielectric films, respectively, yield both enhanced metal and dielectric film removal rates and better post-polish surface roughness values compared to those containing single kind of particles. Several arguments are proposed to explain the enhanced CMP performance with the composite abrasives. The effect of surface charge of the composite abrasive and the hardness of the core particles in the composite abrasives contained in the polishing slurry on polish rates of different films is discussed. Also, as a part of this thesis, several issues related to CMP were addressed. The planarization ability of Cu CMP slurry containing alumina coated silica particles was studied to elucidate the role of pattern geometry in affecting polish rate and also generating pattern dependent defects like dishing and erosion. Additionally, a polishing process was devised which, when viewed with the optical profilometer, eliminated surface defects including shallow and deep scratches and pits already present in a copper film. Also, molybdenum dioxide (MoO2) was evaluated as a potential abrasive for a highly reactive copper CMP slurry with potassium iodate as the oxidizing agent. Finally, the interaction of amino acid additives in ceria slurries with the silicon nitride film during STI CMP is discussed. Directions for future work have been presented at the end of the thesis.