Fluorine contamination, mobility, and risks in soils at a phosphate-gypsum waste landfill: a new analytical method and comparison with previous methods.

This study used a new X-ray fluorescence (XRF)-based analytical method with better precision and sensitivity to evaluate the fluorine concentrations in soil. It was hypothesized that the XRF method with a pellet-synthesizing procedure may effectively analyze the fluorine concentrations in soil with ease and reliability. The total fluorine concentrations determined using XRF were compared with those determined using three different types of analytical protocols-incineration/distillation, alkaline fusion, and aqua regia extraction procedures. Among the three procedures, the incineration/distillation procedure did not show reliable precision and reproducibility. In contrast, the total fluorine concentrations determined using the XRF analysis were linearly correlated with those determined using the alkaline fusion and aqua regia extraction procedures. Based on the results of the Korean waste leaching procedure and toxicity characteristics leaching procedure, the leachability of fluorine from soil and waste was not directly related to total fluorine concentrations in soil. Risk assessment also revealed that the fluorine-rich soils did not show non-carcinogenic toxic effects, despite exceeding the regulation level (800 mg/kg) in South Korea for total fluorine concentrations in soil. Our results suggest that XRF analysis in combination with the newly developed pretreatment method may be a promising alternative procedure for easily and rapidly determining the total fluorine concentration in soil. However, further efforts are needed to evaluate fluorine leachability and its associated risks in fluorine-contaminated soils.

Adsorption Characteristics of Dimethylated Arsenicals on Iron Oxide-Modified Rice Husk Biochar.

In this study, the adsorption characteristics of dimethylated arsenicals to rice husk biochar (BC) and Fe/biochar composite (FeBC) were assessed through isothermal adsorption experiments and X-ray absorption spectroscopy analysis. The maximal adsorption capacities (qm) of inorganic arsenate, calculated using the Langmuir isotherm equation, were 1.28 and 6.32 mg/g for BC and FeBC, respectively. Moreover, dimethylated arsenicals did not adsorb to BC at all, and in the case of FeBC, qm values of dimethylarsinic acid (DMA(V)), dimethylmonothioarsinic acid (DMMTA(V)), and dimethyldithioarsinic acid (DMDTA(V)) were calculated to be 7.08, 0.43, and 0.28 mg/g, respectively. This was due to the formation of iron oxide (i.e., two-line ferrihydrite) on the surface of BC. Linear combination fitting using As K-edge X-ray absorption near edge structure spectra confirmed that all chemical forms of dimethylated arsenicals adsorbed on the two-line ferrihydrite were DMA(V). Thus, FeBC could retain highly mobile and toxic arsenicals such as DMMTA(V) and DMDTA(V)) in the environment, and transform them into DMA(V) with relatively low toxicity.

New insights into surface behavior of dimethylated arsenicals on montmorillonite using X-ray absorption spectroscopy.

Although recent studies have revealed the occurrence of dimethylated arsenicals, little is known about their behavior in environment. This study investigates the adsorption behavior of dimethylarsinic acid (DMAV), dimethyldithioarsinic acid (DMDTAV), and dimethylmonothioarsinic acid (DMMTAV) on montmorillonite. Complicated transformations among arsenicals under normal environmental conditions were also considered. Our results clearly demonstrate that DMDTAV was oxidized to DMMTAV, which was relatively stable but partially transformed to DMAV when exposed to air during adsorption. The transformed DMAV exhibited high adsorption affinities for montmorillonite, while DMMTAV and DMDTAV were not appreciably retained by montmorillonite for 48 h. This is the first study to provide insights into DMDTAV oxidation under environmental conditions. X-ray absorption near edge structure and extended X-ray absorption fine structure studies confirmed that most of the adsorbed arsenicals on montmorillonite were DMAV. The significantly different bonding characteristics of each adsorbed DMAV provide direct evidence for the transformation of DMAV from DMDTAV and DMMTAV. Our study suggests the importance of incorporating the DMMTAV in the realistic risk management for soil environments because it is highly toxic, easily transformed from DMDTAV, and stable in the environment.

Dimethylmonothioarsinic acid and dimethyldithioarsinic acid in the environment: Sorption characteristics on 2-line ferrihydrite and acute toxicity to Daphnia magna.

Dimethylmonothioarsinic acid (DMMTA(V)) and dimethyldithioarsinic acid (DMDTA(V)), which are commonly found in landfill leachate and pore water of rice paddy soil, have attracted considerable attention for their high toxicity. This study aims to evaluate the behavior and potential risks of DMMTA(V) and DMDTA(V) in the environment by conducting an equilibrium sorption test using 2-line ferrihydrite and acute toxicity (immobilization) test using Daphnia magna. The overall maximum sorption capacity (qm) derived by the Langmuir isotherm model showed an increase in the order of inorganic arsenate (As(V)) > dimethylarsinic acid (DMA(V)) > DMMTA(V) > DMDTA(V), which was likely due to steric hindrance due to the presence of methyl and thiol groups. Moreover, DMMTA(V) and DMDTA(V) showed no or negligible change in qm with pH change, while qm decreased rapidly with increasing pH in As(V) and DMA(V). The 50% inhibition concentrations (IC50) for As(V), DMA(V), DMMTA(V), and DMDTA(V), which were measured after 48 h exposure to D. magna, were 9.5, > 30, 1.7, and 6.5 mg/L, respectively. Overall, the results demonstrated that DMMTA(V) and DMDTA(V) have high mobility and eco-toxicity in the environment and that methylated thioarsenicals should be accurately monitored and controlled.

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 pathway of dimethylarsinic acid (DMAV) thiolation, have been recently found in the environment as well as human organs. DMMTAV and DMDTAV can be quantified to determine the ecological effects of dimethylated thioarsenicals and their stability in environmental media. The synthesis method for these compounds is unstandardized, making replicating previous studies challenging. Furthermore, there is a lack of information about storage techniques, including storage of compounds without species transformation. Moreover, because only limited information about synthesis methods is available, there may be experimental difficulties in synthesizing standard chemicals and performing quantitative analysis. The protocol presented herein provides a practically modified synthesis method for the dimethylated thioarsenicals, DMMTAV and DMDTAV, and will help in the quantification of species separation analysis using high performance liquid chromatography in conjunction with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The experimental steps of this procedure were modified by focusing on the preparation of chemical reagents, filtration methods, and storage.

Nanomaterial-based electrochemical sensors for arsenic - A review.

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.

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

Dimethylmonothioarsinic acid (DMMTAV) is a highly toxic, thiolated analogue of dimethylarsinic acid (DMAV). In comparison, a further thiolated analogue, dimethyldithioarsinic acid (DMDTAV), and DMAV both exhibit lower toxicity. To understand the environmental conditions responsible for forming DMMTAV, the kinetics of DMAV thiolation are examined. The thiolation of DMAV is pH-dependent and consists of two consecutive first-order reactions under excess sulfide conditions. The first thiolation of DMAV to form DMMTAV is faster than the second one to DMDTAV. DMMTAV is therefore an intermediate. The first reaction is first-order in H2S at pH 6.0 and 20 °C; therefore, the overall reaction is second-order and the rate coefficient in this condition is 0.0780 M-1 s-1. The rate coefficient significantly decreases at pH 8.0, indicating that H2S(aq) triggers the thiolation of DMAV. The second reaction rate is significantly decreased at pH 2.5; therefore, reaction under strongly acidic conditions leads to accumulation of highly toxic DMMTAV in the early stages of thiolation. The transformation of DMDTAV to DMMTAV is catalyzed in the presence of ferric iron. Formation of DMMTAV should be considered when assessing risk posed by arsenic under sulfidic or sulfate reducing conditions.

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

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.

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

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(-).

Experimental approach to the fundamental limit of the extinction coefficients of ultra-smooth and highly spherical gold nanoparticles.

The theoretical extinction coefficients of gold nanoparticles (AuNPs) have been mainly verified by the analytical solving of the Maxwell equation for an ideal sphere, which was firstly founded by Mie (generally referred to as Mie theory). However, in principle, it has not been directly feasible with experimental verification especially for relatively large AuNPs (i.e., >40 nm), as conventionally proposed synthetic methods have inevitably resulted in a polygonal shaped, non-ideal Au nanosphere. Here, mono-crystalline, ultra-smooth, and highly spherical AuNPs of 40-100 nm were prepared by the procedure reported in our recent work (ACS Nano, 2013, 7, 11064). The extinction coefficients of the ideally spherical AuNPs of 40-100 nm were empirically extracted using the Beer-Lambert law, and were then compared with the theoretical limits obtained by the analytical and numerical methods. The obtained extinction coefficients of the ideally spherical AuNPs herein agree much more closely with the theoretical limits, compared with those of the faceted or polygonal shaped AuNPs. In addition, in order to further elucidate the importance of being spherical, we systematically compared our ideally spherical AuNPs with the polygonal counterparts; effectively addressing the role of the surface morphology on the spectral responses in both theoretical and experimental manners.

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

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.

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

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.

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

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.

Evaluation of the memory effect on gold-coated silica adsorption tubes used for the analysis of gaseous mercury by cold vapor atomic absorption spectrometry.

In an effort to reduce the experimental bias involved in the analysis of gaseous elemental mercury (Hg(o)), the blank response from gold-coated adsorption tubes has been investigated using cold vapor atomic absorption spectrometry (CVAAS). Our study has been compared with our recent investigation on memory effect in a cold vapour atomic fluorescence spectrometry (CVAFS). The pattern of blank responses was quantified after loading different amounts of mercury and after different time intervals of 1, 14, and 45 days. In case of the one day interval, the result of five to six instant blank heating cycles confirmed successful liberation of mercury following the second and third blank heating cycles. The results of 14 or 45 days generally suggest that liberation of excess mercury is affected by both the initial loading amount and the length of storage time prior to analysis. We have demonstrated a possibly effective way to reduce memory effects. Some similarities of these results with those from CVAFS experiment suggests that the blank response is caused by a combination of mercury absorbed within the bulk gold and micro- and nanoparticles liberated during heating and not from coabsorbing interfering gaseous species.

Identification of marine bacteria affecting lithium adsorbents in seawater.

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.

A simple approach for measuring emission patterns of vapor phase mercury under temperature-controlled conditions from soil.

In an effort to study the possible effects of climate change on the behavior of atmospheric mercury (Hg), we built a temperature-controlled microchamber system to measure its emission from top soils. To this end, mercury vapour emission rates were investigated in the laboratory using top soil samples collected from an urban area. The emissions of Hg, when measured as a function of soil temperature (from ambient levels up to 70°C at increments of 10°C), showed a positive correlation with rising temperature. According to the continuous analyses of the Hg vapor given off by the identical soil samples, evasion rate diminished noticeably with increasing number of repetitions. The experimental results, if examined in terms of activation energy (Ea), showed highly contrasting patterns between the single and repetitive runs. Although the results of the former exhibited Ea values smaller than the vaporization energy of Hg (i.e., <14 Kcal mol(-1)), those of the latter increased systematically with increasing number of repetitions. As such, it is proposed that changes in the magnitude of Ea values can be used as a highly sensitive criterion to discriminate the important role of vaporization from other diverse (biotic/abiotic) processes occurring in the soil layer.

Current status of trace metal pollution in soils affected by industrial activities.

There is a growing public concern over the potential accumulation of heavy metals in soil, owing to rapid industrial development. In an effort to describe the status of the pollutions of soil by industrial activities, relevant data sets reported by many studies were surveyed and reviewed. The results of our analysis indicate that soils were polluted most significantly by metals such as lead, zinc, copper, and cadmium. If the dominant species are evaluated by the highest mean concentration observed for different industry types, the results were grouped into Pb, Zn, Ni, Cu, Fe, and As in smelting and metal production industries, Mn and Cd in the textile industry, and Cr in the leather industry. In most cases, metal levels in the studied areas were found to exceed the common regulation guideline levels enforced by many countries. The geoaccumulation index (I(geo)), calculated to estimate the enrichment of metal concentrations in soil, showed that the level of metal pollution in most surveyed areas is significant, especially for Pb and Cd. It is thus important to keep systematic and continuous monitoring of heavy metals and their derivatives to manage and suppress such pollution.

Effect of incineration on the removal of key offensive odorants released from a landfill leachate treatment station (LLTS).

As a basic means to control odorants released from a landfill leachate treatment station (LLTS), effluents venting from this station were treated via incineration with methane rich landfill gas (at 750°C). A list of the key offensive odorants covering 22 chemicals was measured by collecting those gas samples both before and after the treatment. Upon incineration, the concentration levels of most odorants decreased drastically below threshold levels. The sum of odorant intensities (SOIs), if compared between before and after incineration, decreased from 6.94 (intolerable level) to 3.45 (distinct level). The results indicate that the thermal incineration method can be used as a highly efficient tool to remove most common odorants (e.g., reduced sulfur species), while it is not so for certain volatile species (e.g., carbonyls, fatty acids, etc.).