Exposure profiles of workers from indium tin oxide target manufacturing and recycling factories in Taiwan.

Indium tin oxide exposure poses a potential health risk, but the exposure assessment in occupational setting remains incomplete and continues to be a significant challenge. To this end, we investigated the association of work type, airborne indium concentration, respirable fraction of total indium, and cumulative indium exposure index (CEI) with the levels of plasma indium (P-In) and urinary indium (U-In) among 302 indium tin oxide target manufacturing and recycling workers in Taiwan. We observed that recycling-crushing produced the highest concentrations of total indium (area: 2084.8 µg/m3; personal: 3494.5 µg/m3) and respirable indium (area: 533.4 µg/m3; personal: 742.0 µg/m3). Powdering produced the highest respirable fraction of total indium (area: 58.6%; personal: 81.5%), where the workers had the highest levels of P-In (geometric mean: 2.0 µg/L) and U-In (1.0 µg/g creatinine). After adjusting for the confounder, the CEIs of powdering (ßPR = 0.78; ßPR = 0.44), bonding (ßPT = 0.61; ßPT = 0.37), and processing workers (ßPT = 0.43; ßPT = 0.28) showed significant associations with P-In and U-In, validating its utility in monitoring the exposure. Also, the respirable fraction of total indium significantly contributed to the increased levels of P-In and U-In among workers. The varying levels of relationship noted between indium exposure and the levels of P-In and U-In among workers with different work types suggested that setting the exposure limits among different work types is warranted.

Indium concentration in serum is an excellent predictor for assessing accumulated indium concentration in the lungs.

OBJECTIVE: To clarify whether indium in serum (In-S) is an appropriate parameter for assessing accumulated indium concentration in the lungs (In-L). METHODS: During our approximately 15-year Japanese cohort follow-up, five male indium-tin oxide (ITO) or/and indium trioxide-exposed workers underwent lung surgical procedures to treat lung diseases or to confirm a diagnosis of lung impairments. We measured In-L of these Cases 1-5 and were able to assess the relationship between In-L and the most recent In-S. Another 1 Japanese case (Case 6) exposed to indium trioxide and indium hydroxide was referred from an article. RESULTS: Cases 1 and 3 had lung cancer, Case 2 suffered from recurrent pneumothorax, and Case 4 had interstitial pneumonia with mild emphysema. Case 5 had severe emphysema with pulmonary hypertension and underwent bilateral lung transplantation. In Cases 1-5, In-L and In-S ranged from 3.4 to 161.2 µg/g wet weight and 0.7 to 60.4 ng/mL, respectively, and In-L/In-S ratios ranged from 2484 to 4857. The slope of the single regression equation with zero intercept was 2767 and the correlation coefficient was 0.995. In contrast, Case 6 was extraordinarily outlying, but the reason is unclear. CONCLUSIONS: In-S is an excellent predictor for assessing indium load in the lungs in ITO or/and indium trioxide-exposed workers. However, number of cases was only five and not enough to authorize definite conclusion. It is desirable to add more cases to confirm our conclusion.

Liquid-Liquid Extraction of Indium(III) from the HCl Medium by Ionic Liquid A327H+Cl- and Its Use in a Supported Liquid Membrane System.

Ionic liquid A327H+Cl- was generated by reaction of tertiary amine A327 and HCl, and the liquid-liquid extraction of indium(III) from the HCl medium by this ionic liquid dissolved in Solvesso 100 was investigated. The extraction reaction is exothermic. The numerical analysis of indium distribution data suggests the formation of A327H+InCl4- in the organic phase. The results derived from indium(III) extraction have been implemented in a supported liquid membrane system. The influence of the stirring speed (600-1200 min-1), carrier concentration (2.5-20% v/v) in the membrane phase, and indium concentration (0.01-0.2 g/L) in the feed phase on metal transport have been investigated.

Selective ratiometric red-emission detection of In3+ in aqueous solutions and in live cells using a fluorescent peptidyl probe and metal chelating agent.

Indium has been regarded as one of the most rarely used metal ions; however, the consumption of indium has increased intensively due to its increasing use in electrodes of liquid crystal displays (LCDs). In recent years, warnings have been issued about the toxicity of indium to aquatic ecosystems and humans. Thus, the development of efficient and selective detection methods for In3+ in aquatic environments as well as in live cells is highly required. However, the selective and sensitive detection of In3+ in the presence of trivalent metal ions and other metal ions is highly challenging. In the present study, we synthesized a fluorescent probe (1) for In3+ and Al3+ based on an unnatural peptide receptor and an aggregation-induced emission fluorophore and developed a selective fluorescent detection method for In3+ in aqueous solutions and live cells using the probe and a metal chelating agent. 1 recognized In3+ and Al3+ selectively among 19 metal ions in aqueous solutions depending on pH by the enhancement of the red emission at 600 nm and decrease in the green emission at 530 nm. 1 sensitively detected In3+ and Al3+ by ratiometric response in a wide pH range (3.5-7.4), and the ratiometric response was complete within 20 seconds in an aqueous buffered solution at pH 5.0. Interestingly, the addition of EDTA to the complex of 1 with In3+ or Al3+ did not induce the Al3+-free spectrum but instead induced the In3+-free spectrum; thus, In3+ and Al3+ could be easily differentiated. The detection limit of 1 for In3+ ions was 211 nM (R2 = 0.981) in purely aqueous solutions. The fluorescence ratiometric detection method using 1 could quantify low concentrations of In3+ in ground water and tap water. Fluorescence cell image studies revealed that the probe was cell-permeable, and low concentrations of In3+ inside the cells could be recognized by the enhancement of the red emission at 600 nm. The binding mode study via NMR, IR, and CD spectroscopy revealed how the peptide receptor of 1 interacted with In3+ and resulted in the enhancement of the red emission in an aqueous solution.

A sieve-conducted two-syringe-based pressurized liquid-phase microextraction for the determination of indium by slotted quartz tube-flame atomic absorption spectrometry.

In this study, a new liquid-phase microextraction method termed sieve-conducted two-syringe-based pressurized liquid-phase microextraction (SCTS-PLPME) was developed as a preconcentration tool for indium. Here, two syringes were connected to each other by an apparatus to produce an environment subject to pressure. The pressure created between the two syringes by simultaneous movements of the syringe plungers (to and fro) generated an efficient dispersion and this eliminated the need for dispersive solvents. Determination of indium after preconcentration was carried out with a slotted quartz tube attached flame atomic absorption spectrometer (SQT-FAAS). The detection limit (LOD) and quantification limit (LOQ) of the developed method were calculated as 19.2 and 72.2 µg L-1, respectively. The reliability and accuracy of the developed method was tested by performing recovery studies on lake water spiked at different concentrations and the obtained percent recoveries were between 101.2 and 106.9%.

Work Tasks as Determinants of Respirable and Inhalable Indium Exposure among Workers at an Indium-Tin Oxide Production and Reclamation Facility.

Increased global demand for touch screens, photovoltaics, and optoelectronics has resulted in an increase in the production of indium-tin oxide (ITO). Occupational exposure to indium compounds is associated with the development of indium lung disease. Although many previous epidemiologic investigations highlight an excess of lung abnormalities in workplaces where ITO is produced, few assessments of occupational exposure to respirable and inhalable indium are reported to date. The objective of this study was to identify the determinants of respirable and inhalable indium at an ITO production facility to target exposure interventions. In 2012 and 2014, we conducted exposure assessments at an ITO production facility and collected full-shift personal respirable (n = 159) and inhalable (n = 57) indium samples. We also observed workers and recorded information on task duration and location, materials used, and use of personal protective equipment (PPE). Tasks (n = 121) recorded in task diaries were categorized into 40 similar task groups using the Advanced REACH Tool and process-related information. Mixed-effects models were fit separately for log-transformed respirable and inhalable indium, with random effect of subject and fixed effects of task groups. Overall, respirable and inhalable indium measurements ranged from 0.1 to 796.6 µg m-3 and 1.6 to 10 585.7 µg m-3, respectively, and were highly correlated with Spearman correlation coefficient of 0.90. The final model for respirable indium explained 36.3% of total variance and identified sanding, powder transfer tasks in reclaim, powder transfer tasks in refinery, handling indium materials, and liquid transfer tasks in ITO production as tasks associated with increased respirable indium exposure. The final model for inhalable indium explained 24.6% of total variance and included powder transfer tasks in ITO production, cleaning cylinder or tile, and handling indium material tasks. Tasks identified as strong predictors of full-shift exposure to respirable and inhalable indium can guide the use of engineering, administrative, and PPE controls designed to mitigate occupational exposure to indium. Moreover, since the tasks were aligned with REACH activities, results from this study can also be used to inform REACH activity scenarios.

Quantifying indium with ion chromatography in hydro- and biohydrometallurgical leaching solutions.

A methodology has been developed to chromatographically quantify indium in polymetallic (bio)hydrometallurgical processing solutions using the Dionex IonPac CS5A column and pyridine-2,6-dicarboxylic acid eluent. Cu(II) and In(III) could be separated by elevating the column temperature to 45°C. The comparatively low stability constant of the In-eluent complex (log K2  = 3.8) required typical leaching samples to be diluted in the eluent rather than acid or water to overcome ligand competition between components of the sample solution and the eluent. The methodology was applied to leachates from (bio)hydrometallurgical processing of oxidic flue dust residues and sulfidic zinc ores, where both are promising candidates for the recovery of indium from low grade ores and metallurgical wastes. Indium, ferrous iron, ferric iron, copper, zinc, nickel, and manganese concentrations could be simultaneously quantified. The method was found suitable for samples containing at least 0.25 mg/L indium and an iron to indium ratio of up to 100:1.

Emerging investigator series: atmospheric cycling of indium in the northeastern United States.

Indium is critical to the global economy and is used in an increasing number of electronics and new energy technologies. However, little is known about its environmental behavior or impacts, including its concentrations or cycling in the atmosphere. This study determined indium concentrations in air particulate matter at five locations across the northeastern United States over the course of one year, in 1995. Historical records from a Massachusetts bog core showed that indium atmospheric concentrations in this region changed only modestly between 1995 and 2010. Atmospheric indium concentrations varied significantly both geographically and temporally, with average concentrations in PM3 of 2.1 ± 1.6 pg m-3 (1 standard deviation), and average particle-normalized concentrations of 0.2 ± 0.2 µg In per g PM3. Peaks in the particle-normalized concentrations in two New York sites were correlated with wind direction; air coming from the north contributed higher concentrations of indium than air coming from the west. This correlation, along with measurements of indium in zinc smelter emissions and coal fly ash, suggests that indium in the atmosphere in the northeastern United States comes from a relatively constant low-level input from coal combustion in the midwest, and higher but more sporadic contributions from the smelting of lead, zinc, copper, tin, and nickel north of the New York sample sites. Understanding the industrial sources of indium to the atmosphere and how they compare with natural sources can lead to a better understanding of the impact of human activities on the indium cycle, and may help to establish a baseline for monitoring future impacts as indium use grows.

Evaluation of personal exposure of workers to indium concentrations in total dust and its respirable fraction at three Japanese indium plants.

This study aimed to evaluate personal exposures of 27 workers to indium compounds as "total" dust and its "respirable" fraction in their breathing zones at 3 Japanese indium plants. Eight-hour time-weighted average (TWA) indium concentrations of personal exposure to dust collected in sampling periods of 6 h or longer were determined by ICP-MS. The arithmetic means of exposure concentrations were 0.095 mg indium (In)/m3, when sampled as total dust, and 0.059 mg In/m3, as respirable fraction. ACGIH's TLV-TWA of 0.1 mg In/m3 for total particulate matter and Acceptable Exposure Concentration Limit (AECL) of 3×10-4 mg In/m3 for the respirable fraction notified by the Japanese Ministry of Health, Labour and Welfare were used to evaluate the exposure concentrations. Twenty-five out of 27 workers were exposed to indium concentrations lower than TLV-TWA, while all of the workers were exposed to the indium concentrations higher than AECL. We noted that there was a large discrepancy between the two occupational exposure limits referred to in this report, and these differences were attributed to the sampling strategies and health effects used as the prevention targets. Carcinogenicity of the respirable fraction of indium-containing particulates was considered in setting AECL, whereas it was not in ACGIH's TLV.

A field evaluation of a single sampler for respirable and inhalable indium and dust measurements at an indium-tin oxide manufacturing facility.

Indium-tin oxide production has increased greatly in the last 20 years subsequent to increased global demand for touch screens and photovoltaics. Previous studies used measurements of indium in blood as an indicator of indium exposure and observed associations with adverse respiratory outcomes. However, correlations between measurements of blood indium and airborne respirable indium are inconsistent, in part because of the long half-life of indium in blood, but also because respirable indium measurements do not incorporate inhalable indium that can contribute to the observed biological burden. Information is lacking on relationships between respirable and inhalable indium exposure, which have implications for biological indicators like blood indium. The dual IOM sampler includes the foam disc insert and can simultaneously collect respirable and inhalable aerosol. Here, the field performance of the dual IOM sampler was evaluated by comparing performance with the respirable cyclone and traditional IOM for respirable and inhalable indium and dust exposure, respectively. Side-by-side area air samples were collected throughout an indium-tin oxide manufacturing facility. Cascade impactors were used to determine particle size distribution. Several statistical methods were used to evaluate the agreement between the pairs of samplers including calculating the concordance correlation coefficient and its accuracy and precision components. One-way ANOVA was used to evaluate the effect of dust concentration on sampler differences. Respirable indium measurements showed better agreement (concordance correlation coefficient: 0.932) compared to respirable dust measurements (concordance correlation coefficient: 0.777) with significant differences observed in respirable dust measurements. The dual IOM measurements had high agreement with the traditional IOM for inhalable indium (concordance correlation coefficient: 0.997) but lower agreement for inhalable dust (concordance correlation coefficient: 0.886 and accuracy: 0.896) with a significantly large mean bias (-146.9 µg/m3). Dust concentration significantly affected sampler measurements of inhalable dust and inhalable indium. Results from this study suggest that the dual IOM is a useful single sampler for simultaneous measurements of occupational exposure to respirable and inhalable indium.

Quantitative assessment of occupational exposure to total indium dust in Japanese indium plants.

This study quantitatively assessed personal exposure of 86 workers to indium compounds as total dust at 11 Japanese indium plants. The personal exposures to indium concentrations in the breathing zone during an 8 h work-shift were determined by ICP-MS. The arithmetic mean indium concentration of all the workers was 0.098 mg Indium (In)/m3, with individual values ranging from 0.0001 to 1.421 mg In/m3. There were 11 workers whose exposure to indium concentrations exceeded the American Conference of Governmental Industrial Hygienists' Threshold Limit Value-Time Weighted Average (TLV-TWA) of 0.1 mg In/m3. Based on the condition TLV-TWA

Control banding assessment of workers' exposure to indium and its compounds in 13 Japanese indium plants.

OBJECTIVES: This study aimed to assess workers' exposure to indium and its compounds in 55 indium-handling operations among 13 Japanese plants. The surveyed plants were selected from indium-manufacturing plants whose annual indium production exceeded 500 kg. METHODS: The Control of Substances Hazardous to Health (COSHH) Essentials control banding toolkit, which contains simple scales for hazard levels, quantities in daily use, and "dustiness" characteristics, was used to assess generic risks of indium-handling operations. The operations were then classified into one of four Control Approaches (CAs). RESULTS: There were 35 indium-handling operations classified into CA4 (requires expert advice) and 16 grouped into CA3 (requires containment). There were three operations classified into CA2 (requires engineering controls) and only one into CA1 (requires good general ventilation (GV) and working practices). Of the 51 operations classified as CA4 and CA3, 36 were found to be improperly equipped with local exhaust ventilation, and the remaining 15 operations solely relied on GV practices. Respiratory protective equipment (RPE) used in the 13 indium plants was examined with reference to the recommendations of the COSHH Essentials and Japan's Technical Guidelines. CONCLUSIONS: Our findings suggest that stringent engineering control measures and respiratory protection from indium dust are needed to improve indium-handling operations. Our results show that the most common control approach for Japanese indium-handling operations is to require expert advice, including worker health checks for respiratory diseases and exposure measurement by air sampling.

Spiropyran-Isoquinoline Dyad as a Dual Chemosensor for Co(II) and In(III) Detection.

Spiropyran derivatives have been studied as light-regulated chemosensors for a variety of metal cations and anions, but there is little research on chemosensors that simultaneously detect multiple metal cations. In this study, a spiropyran derivative with isoquinoline, SP-IQ, was prepared and it functions investigated as a light-regulated sensor for both Co2+ and In3+ cations. A colorless nonfluorescent SP-IQ converts to a pink-colored fluorescent MC-IQ by UV irradiation or standing in the dark, and MC-IQ returns to SP-IQ with visible light. Upon UV irradiation with the Co2+ cation for 7 min, the stronger absorption at 540 nm and the similar fluorescence intensity at 640 nm are observed, compared to when no metal cation is added, due to the formation of a Co2+ complex with pink color and pink fluorescence. When placed in the dark with the In3+ cation for 7 h, the colorless solution of SP-IQ changes to the In3+ complex with yellow color and pink fluorescence, which shows strong absorption at 410 nm and strong fluorescence at 640 nm. Selective detection of the Co2+ cation with UV irradiation and the In3+ cation in the dark could be possible with SP-IQ by both absorption and fluorescence spectroscopy or by the naked eye.

Dispersion and solubility of In, Tl, Ta and Nb in the aquatic environment and intertidal sediments of the Scheldt estuary (Flanders, Belgium).

Certain specialty elements are indispensable in modern technologies for their particular properties. Yet, potential risks associated to the release of these elements at any stage, remains unknown. Therefore, the dispersion of indium (In), thallium (Tl), tantalum (Ta) and niobium (Nb) in the aquatic environment of the Scheldt estuary (Flanders, Belgium) was studied. Maximum concentrations in intertidal sediments of 101 ± 15 µg kg-1 for In, 481 ± 37 µg kg-1 for Tl, 88 ± 19 µg kg-1 for Ta and 1162 ± 4 µg kg-1 for Nb appeared on the sampling location closest to the river mouth, i.e. 57.5 km upstream. Their distribution in the intertidal sediments depends on the physicochemical sediment characteristics along the flow of the river Scheldt. The same was the case for most other metals and aluminum as their occurrence also correlated (p < 0.05) with the occurrence of In, Tl and Nb. While in general, studied elements correlate to the OM content and sulfur and phosphorus herein included, a relative enrichment of In, Tl and Nb was seen at Rupelmonde (92.0 km from the river mouth). Mainly the intertidal sediment silt fraction is capable of retaining the elements by exchanging with other ions in the mineral interlayer. Increasing salinity towards the river mouth can furthermore induce the formation of insoluble chloride species. Overall, the solubility of In, Tl, Ta and Nb appeared extremely low upon extraction of pore water from intertidal sediments saturated to 100% field capacity.

Ecotoxicity assessment of ionic As(III), As(V), In(III) and Ga(III) species potentially released from novel III-V semiconductor materials.

III-V materials such as indium arsenide (InAs) and gallium arsenide (GaAs) are increasingly used in electronic and photovoltaic devices. The extensive application of these materials may lead to release of III-V ionic species during semiconductor manufacturing or disposal of decommissioned devices into the environment. Although arsenic is recognized as an important contaminant due to its high toxicity, there is a lack of information about the toxic effects of indium and gallium ions. In this study, acute toxicity of As(III), As(V), In(III) and Ga(III) species was evaluated using two microbial assays testing for methanogenic activity and O2 uptake, as well as two bioassays targeting aquatic organisms, including the marine bacterium Aliivibrio fischeri (bioluminescence inhibition) and the crustacean Daphnia magna (mortality). The most noteworthy finding was that the toxicity is mostly impacted by the element tested. Secondarily, the toxicity of these species also depended on the bioassay target. In(III) and Ga(III) were not or only mildly toxic in the experiments. D. magna was the most sensitive organism for In(III) and Ga(III) with 50% lethal concentrations of 0.5 and 3.4mM, respectively. On the other hand, As(III) and As(V) caused clear inhibitory effects, particularly in the methanogenic toxicity bioassay. The 50% inhibitory concentrations of both arsenic species towards methanogens were about 0.02mM, which is lower than the regulated maximum allowable daily effluent discharge concentration (2.09mg/L or 0.03mM) for facilities manufacturing electronic components in the US. Overall, the results indicate that the ecotoxicity of In(III) and Ga(III) is much lower than that of the As species tested. This finding is important in filling the knowledge gap regarding the ecotoxicology of In and Ga.

The growth and uptake of Ga and In of rice (Oryza sative L.) seedlings as affected by Ga and In concentrations in hydroponic cultures.

Limited information is available on the effects of gallium (Ga) and indium (In) on the growth of paddy rice. The Ga and In are emerging contaminants and widely used in high-tech industries nowadays. Understanding the toxicity and accumulation of Ga and In by rice plants is important for reducing the effect on rice production and exposure risk to human by rice consumption. Therefore, this study investigates the effect of Ga and In on the growth of rice seedlings and examines the accumulation and distribution of those elements in plant tissues. Hydroponic cultures were conducted in phytotron glasshouse with controlled temperature and relative humidity conditions, and the rice seedlings were treated with different levels of Ga and In in the nutrient solutions. The growth index and the concentrations of Ga and In in roots and shoots of rice seedlings were measured after harvesting. A significant increase in growth index with increasing Ga concentrations in culture solutions (<10mgGaL-1) was observed. In addition, the uptake of N, K, Mg, Ca, Mn by rice plants was also enhanced by Ga. However, the growth inhibition were observed while the In concentrations higher than 0.08mgL-1, and the nutrients accumulated in rice plants were also significant decreased after In treatments. Based on the dose-response curve, we observed that the EC10 (effective concentration resulting in 10% growth inhibition) value for In treatment was 0.17mgL-1. The results of plant analysis indicated that the roots were the dominant sink of Ga and In in rice seedlings, and it was also found that the capability of translocation of Ga from roots to shoots were higher than In. In addition, it was also found that the PT10 (threshold concentration of phytotoxicity resulting in 10% growth retardation) values based on shoot height and total biomass for In were 15.4 and 10.6µgplant-1, respectively. The beneficial effects on the plant growth of rice seedlings were found by the addition of Ga in culture solutions. In contrast, the In treatments led to growth inhibition of rice seedlings. There were differences in the phytotoxicity, uptake, and translocation of the two emerging contaminants in rice seedlings.