Vapor exposure of 459 ppm concentration (Table 2) showed dimmed vision and nasal irritation by Kawai et al. [26]. In the case of this concentration, it was estimated carefully the lowest concentration indicated optic nerve disorder among the previous reports. The subject was mainly workers who use MeOH in their workshop and were exposed chronically to MeOH vapor as single chemical, not a solvent mixture. This exposure concentration was important because of adjacent to 200 ppm of TLV-TWA and 250 ppm of STEL by ACGIH. The exposure concentration 459 ppm was near the TLV-TWA and STEL which was 2.3 folds higher than the TLV-TWA and 1.8 folds higher than the STEL. Then, blurred vision and eye irritation related to optic nerve disorder were identified at 1025 ppm of Table 3. About the concentration range of 459 to 1025 ppm, the author, unfortunately, couldn’t identify reports of methanol exposure worker and their symptoms. Vapor exposure range of 1025 ppm to 1755.5 ppm had clearly occurred the MeOH symptoms of optic nerve disorders and central nerve disorders. For the assistance to this exposure range, the exposure concentration of 1625.3 ppm could play a pivotal role in proving symptom occurrence. These 1625. 3 ppm exposure had a range of 1030.1 to 2220.5 ppm. And symptoms showed amblyopia, binocular optic neuritis, visual dimness, blindness, vomiting, difficulty breathing, loss of pupillary reflex, metabolic encephalopathy, vomiting, and decreased consciousness. These were involved in almost representative MeOH exposure symptoms. At that focus, these Korean reports had somewhat more special findings than previous reports. 1025 ppm had very close to 1030.1 ppm (in minimum exposure concentration of 1625.3 ppm) of the median of Korean MeOH accident reports[3, 18, 19]. And 1707.5 ppm MeOH exposure report[4] was very near to 1625.3 ppm and was thought to be a reference value to assist the Korean MeOH accident report. 1722.5 ppm had 365–3080 ppm of wide exposure concentration range[32]. The symptoms of the exposure concentration (1722.5 ppm) were also related symptoms with the Korean MeOH accident report.
For a more precise exposure condition, the working records of the two workers were identified. The two workers in Table 4 had mainly worked overtime for 12 hours of working at the companies and were exposed to 99.9% of extra-pure grade MeOH [14, 19]. The two workers were formally reported by the Ministry of Employment of Labor in Korea that their neurological symptom was from MeOH vapor exposure at the workplace. Worker 1, worked for 3 months and 17 days from Sep. 21, 2015, to Jan 16, 2016. She showed vomiting before to shiftwork at 21 pm on Jan. 15, 2016, then went to the hospital for consulting and had blood tests. However, the cause for the symptoms could not be found. When woke up the next day, she had no eyesight and difficulty breathing. She was transferred to the emergency room in another university hospital and received care such as hemodialysis. She was diagnosed with binocular optic neuritis from an eye examination on Jan 16, 2016, She checked symptoms and urinary MeOH concentration for biological monitoring and was judged to be blindness finally from the physician of the Department of Occupational and Environmental Medicine on Jan. 22, 2016 [19]. Clear diagnosis from the outbreaks of symptoms took 7 days in Worker 1 case. Worker 2, worked for 4 months and 20 days on Sep. 02, 2015-Jan. 22, 2016. He couldn’t see after the end of work. He went to the hospital but the cause for the symptoms could not be found. Then he went to another second hospital with an ophthalmologist and underwent various tests but the cause for the symptoms also could not be found. After that the same day, the third consulting the other hospital he was diagnosed with MeOH poisoning by the physician of the Department of Occupational and Environmental Medicine on Jan. 22, 2016. Symptoms of the two workers (Worker 1 and 2) showed blindness, decreased consciousness, and vomiting. Exposed MeOH concentration in the workroom air was 1103 to 2220 ppm. Biological monitoring tests were accomplished on only 1 worker (Worker 1; Women). She had 7.632 mg/L in urinary MeOH and 31.320 mg/g cre. in urinary aluminum after 72 hours from work shift [19].
Table 4
Exposure status of workers to MeOH intoxication in aluminum CNC cutting process of Korean experience[3, 18, 19]
|
Worker 1a
|
Worker 2
|
Sex
|
Women
|
Man
|
Employment condition
|
Illegally dispatched workers
|
Illegally dispatched workers
|
Affiliated Company
|
Third-tier subcontractor
|
Third-tier subcontractor
|
Age
|
27
|
27
|
MeOH in workroom air (mg/l)
|
1661.5 as median
(1103–2220)
|
Exposure period for symptoms
|
119 days
(3 Months 27 Days)
|
142days
(4 Months 20 Days)
|
Symptoms from exposure
|
Vomiting
Difficulty breathing
Decreased consciousness
Binocular optic neuritis
Blindness
|
Vomiting
Decreased consciousness
Visual dimness
Blindness
|
TLV-TWA of MeOH in South Korea is 200 ppm and STEL is 250 ppm.
a 72 hours later after work-shift, urinary MeOH was 7.632 mg/L and 31.320 mg/g urinary creatinine.
All workers had 12 hours work a day and shiftwork and exposed to 99.9% extra-pure grade MeOH.
|
This study did not confirm whether long-term exposure (for example, continuous exposure by work for more than a year) caused symptoms that did not appear in low-concentration exposure due to the short exposure period of study participants. In addition, the subject of methanol vapor exposure was limited to humans (workers), and the simple dose-response relationship between exposure concentration and symptoms was confirmed. Most of the research data collected in this process were related to chronic exposure, and short-term exposure was used for volunteers. Indeed, the accident of exposure to methanol vapor by Korean workers was sub-chronic. To date, the relationship between the exposure period and the concentration of exposed steam has not been sufficiently explained in this study. In the future, clearer research on these focuses should be conducted.