Preparation of DMMTAV and DMDTAV Using DMAV for Environmental Applications: Synthesis, Purification, and Confirmation

Dimethylated thioarsenicals such as dimethylmonothioarsinic acid (DMMTAV) and dimethyldithioarsinic acid (DMDTAV), which are produced by the metabolic ...

Korea Basic Science Institute, Seoul Center

Lithium manganese oxide-based adsorbents have been developed for the recovery of lithium from seawater. To maximize the recovery efficiency, it is important to prevent microfouling of lithium adsorbents by marine bacteria. To identify the marine bacteria that cause biofouling against the lithium adsorbents, lithium adsorbents were installed into a non-coated frame or a frame coated with an antifouling agent soaked in seawater. Microorganisms from the surface of lithium adsorbents were collected for 30 days at 10-day intervals, cultured in marine broth, isolated, and identified by 16S rDNA sequencing. Pseudoalteromonas and Vibrio were constituted to 35.6 and 28.8 % of total isolates, respectively, and were predominant in the non-coated frame, whereas Vibrio was poorly isolated (2.3 %) from the antifouling agent-coated frame. In this study, antifouling strategy for maximum lithium recovery efficiency in the marine area takes account of Pseudoalteromonas and Vibrio.

Identification of marine bacteria affecting lithium adsorbents in seawater.

Dimethylarsinic acid (DMA(V)) was pre-concentrated from water samples using a strong cation exchange (SCX) disk functionalized with sulfonic groups, before being analyzed by wavelength dispersive X-ray fluorescence spectrometry (WDXRF). The adsorption of DMA(V) occurred preferentially on the surface of the SCX disk, regardless of pH levels, probably due to interactions with the sulfonic functional groups. However, no other arsenic species, such as arsenate (iAs(V)), arsenite (iAs(III)), and monomethylarsonic acid (MMA(V)), were retained. The SCX-WDXRF method produced a strongly linear calibration curve (R(2)=0.9996) with its limit of detection at 0.218 μgL(-1) when a one-liter water sample was used for pre-concentration. The As intensity of the system was sensitive to the Pb content retained on the SCX disk owing to the proximity of the As-Kα and Pb-Lα lines. To compensate for this interference, a correction factor was developed by considering the calibration slope ratio between the X-ray intensity measured at a Bragg angle of 48.781° and the Pb content of the SCX disks. The results of spike tests for iAs(V), iAs(III), MMA(V), and DMA(V) with and without the addition of Pb in synthetic landfill leachate exhibited reasonable recoveries (i.e., 98-105%) after the spectral adjustment for the Pb interference.

A simplified analysis of dimethylarsinic acid by wavelength dispersive X-ray fluorescence spectrometry combined with a strong cation exchange disk.

This study assessed the status of fluorine (F) in soil in the vicinity of a spillage of anhydrous hydrofluoric acid in Korea. Gaseous hydrogen fluoride dispersed was suspected to have contaminated the surrounding soil environment. Total and water soluble F concentrations in soil within a 1 km radius of the spillage were determined. Total F concentrations (mean=222±70.1 mg kg(-1)) were lower than the Korean limit value (i.e., 400 mg kg(-1)) and several reported measurements of background F concentrations in soils except for a single outlying case. Soluble F concentrations ranged from 0.111 to 6.40 mg kg(-1) (mean=2.20±1.80 mg kg(-1)). A negative correlation between the soluble F concentration of soil and distance from the spillage was observed. This indicates that the soluble F concentration has a crucial role in fractionating the F concentration arising from a 'non natural input' i.e., the spillage. The F content of rice samples seemed to be significantly influenced by the soluble F concentrations of soils. Rice samples collected from the control and affected areas contained 41 mg kg(-1) and 578 mg kg(-1) of total F, respectively.

Fluorine distribution in soil in the vicinity of an accidental spillage of hydrofluoric acid in Korea.

In this study, facilitated extraction with enzyme was employed for the first time to extract fluorine (F) from plants. Feasibility of the proposed method for F analysis was assessed by comparing with the alkali fusion-ion selective electrode (ISE) method. In the extraction procedure, 30 mg of a protease and 0.1 g of a plant sample were added in 10 mL of deionized water. In the absence of sonication, the solution was mechanically shaken for 10 s. A variety of parameters (i.e., the amounts of enzymes used, physical treatment conditions applied, extraction time, temperature, and pH) were optimized to enhance the extraction efficiency of the proposed method. The suitability of the proposed method for various plant samples (i.e., grass, perilla, peanut, hot pepper, and eggplant) was also evaluated. The proposed method involves decreased operation time, simplified extraction procedures, and minimal consumption of hazardous reagents and solvents in comparison with other existing methods. Experimental results demonstrated that facilitated extraction with enzyme is appropriate for the rapid determination of F content in plant samples.

Determination of fluorine contents in plant samples by means of facilitated extraction with enzyme.

Dimethyldithioarsinic acid (DMDTA(V)), present in such intense sources as municipal landfill leachate, has drawn a great deal of attention due to its abundant occurrence and different aspect of toxicity. The hydrosulfide (HS(-)) concentration in leachate was studied as a major variable affecting the formation of DMDTA(V). To this end, the HPLC-ICPMS system equipped with the reversed-phase C18 column was used to determine DMDTA(V). Simulated landfill leachates (SLLs) were prepared to cover a mature landfill condition with the addition of sodium sulfate and sulfide at varying concentrations in the presence of dimethylarsinic acid (DMA(V)). The concentration of sodium sulfide added in the SLLs generally exhibited a strong positive correlation with the concentration of DMDTA(V). As such, the formation of DMDTA(V) in the SLLs is demonstrated to be controlled by the interactive relationship between DMA(V) and the HS(-).

Formation of dimethyldithioarsinic acid in a simulated landfill leachate in relation to hydrosulfide concentration.

A novel approach using wavelength dispersive X-ray fluorescence (WDXRF) spectrometry combined with an activated carbon (AC) disk was developed for the determination of total iodine concentrations in water samples. Dissolved iodine species (i.e., I(-) and IO3(-)) in water samples were preconcentrated on the AC disk and directly analyzed by WDXRF spectrometry. The adsorption behavior of I(-) and IO3(-) on the AC disk was assessed at varying pH levels (4, 6, and 8). The AC disks completely retained the I(-) and IO3(-) for all the pH levels tested. The calibration curve obtained from the iodine concentrations (i.e., 0, 20, 200, and 400 μg) of AC disks and the measured X-ray intensity from the WDXRF analysis showed a good linearity (R(2)=0.9960), with a relatively low limit of detection (0.575 μg). The durability of the AC disk for repeatable measurements was also assessed to validate the sustainability of the proposed method and consequently the measured X-ray intensity for the AC disks was constant until 8d of analysis time. The accuracy of the proposed AC-WDXRF method was confirmed by measuring iodine concentration spiked in drinking water using inductively coupled plasma-mass spectrometry (ICP-MS). The proposed method is simple, rapid, efficient, and environmental friendly for iodine analysis in water samples. As a precursor of disinfection by products (DBPs), it is important to determine the total iodine concentrations in raw water.

Effectiveness of activated carbon disk for the analysis of iodine in water samples using wavelength dispersive X-ray fluorescence spectrometry.

Dimethylmonothioarsinic acid (DMMTA) is a highly toxic, thiolated analogue of dimethylarsinic acid (DMA). In comparison, a further thiolated analogue, dimethyldithioarsinic acid (DMDTA), and DMAboth exhibit lower toxicity. To understand the environmental conditions responsible for forming DMMTA, the kinetics of DMAthiolation are examined. The thiolation of DMAis pH-dependent and consists of two consecutive first-order reactions under excess sulfide conditions. The first thiolation of DMAto form DMMTAis faster than the second one to DMDTA. DMMTAis therefore an intermediate. The first reaction is first-order in HS at pH 6.0 and 20 °C; therefore, the overall reaction is second-order and the rate coefficient in this condition is 0.0780 Ms. The rate coefficient significantly decreases at pH 8.0, indicating that HS(aq) triggers the thiolation of DMA. The second reaction rate is significantly decreased at pH 2.5; therefore, reaction under strongly acidic conditions leads to accumulation of highly toxic DMMTAin the early stages of thiolation. The transformation of DMDTAto DMMTAis catalyzed in the presence of ferric iron. Formation of DMMTAshould be considered when assessing risk posed by arsenic under sulfidic or sulfate reducing conditions.

Kinetics of Dimethylated Thioarsenicals and the Formation of Highly Toxic Dimethylmonothioarsinic Acid in Environment.

The existence of arsenic in the environment poses severe global health threats. Considering its toxicity, the sensing of arsenic is extremely important. Due to the complexity of environmental and biological samples, many of the available detection methods for arsenic have serious limitations on selectivity and sensitivity. To improve sensitivity and selectivity and to circumvent interferences, different electrode systems have been developed based on surface modification with nanomaterials including carbonaceous nanomaterials, metallic nanoparticles (MNPs), metal nanotubes (MNTs), and even enzymes. Despite the progress made in electrochemical sensing of arsenic, some issues still need to be addressed to realize cost effective, portable, and flow-injection type sensor systems. The present review provides an in-depth evaluation of the nanoparticle-modified electrode (NME) based methods for the electrochemical sensing of arsenic. NME based sensing systems are projected to become an important option for monitoring hazardous pollutants in both environmental and biological media.

Hye-On Yoon

Korea Basic Science Institute, Seoul Center

Preparation of DMMTA^V and DMDTA^V Using DMA^V for Environmental Applications: Synthesis, Purification, and Confirmation