• 한국환경보건학회지
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• 제28권2호
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• pp.109-116
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• 2002

The purpose of this study was to evaluate a new sampling and analytical method for the determination of airborne hexavalent chromium, Cr(Ⅵ), in a field plating operation. The procedures of this new method (Shin & Paik's Method) are as the following: Airborne hexavalent chromium is collected on polyvinyl chloride (PVC) filter according to the National Institute iota Occupational Safety and Health (NIOSH) Method 7600, and the filler sample is placed in a screw-capped vial and soaked with 2% NaOH/3% Na₂CO₃ solution immediately after sampling. The Cr(Ⅵ) sample is analyzed by ion chromatography/visible spectrophotometry (IC/VS) according to the U.S. Environmental Protection Agency (EPA) Method 218.6. The airborne Cr(Ⅵ) concentrations measured by this method were compared with those determined by three reference methods: One (NIOSH/EPA Method) consisted of sampling airborne Cr(Ⅵ) on PVC filters and storing the sample filters in strew-capped vials according to the NIOSH method, and analyzing Cr(Ⅵ) in samples using IC/VS according to the EPA method. The second method (Impinger Method/NaHCO₃) consisted of absorbing airborne Cr(Ⅵ) into 0.02 M NaHCO₃ solution in midget impinger, and analyzing the Cr(Ⅵ) in samples using IC/VS. The third method was the OSHA Method ID-215. Using these four different methods, lour replicates of air samples were collected at an electroplating process and analyzed simultaneously. Two-way ANOVA and paired t-test were used to test difference among values determined by the methods. There was no significant difference and a strong correlation (r²:0.99) between Cr(Ⅵ) concentrations measured by the Shin & Paik's Method and an impinger method (p>0.05). However, Cr(Ⅵ) concentrations determined by Shin & Paik's Method were significant1y different from those by the NIOSH/EPA Method (p<0.05) or the OSHA method (p<0.05). The Cr(Ⅵ) concentrations of Shin & Paik's Method were significantly higher than those of the NIOSH/EPA Method or the OSHA method. This result indicated that the Shin & Paik's Method may prevent Cr(Ⅵ) losses caused by reduction and give more reliable results of airborne Cr(Ⅵ) concentrations in work environments.

• 한국환경보건학회:학술대회논문집
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• 한국환경보건학회 2002년도 춘계 국제 학술대회
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• pp.40.1-43
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• 2002

The purpose of this study was to evaluate a new sampling and analytical method for the determination of hexavalent chromium, Cr(VI) in mist from field plating operation. The Procedures of this new method (Shin & Paik's Method) are as the following: Airborne hexavalent chromium is collected on polyvinyl chloride (PVC) filter according to the National Institute for Occupational Safety and Health (NIOSH) Method 7600, and the filter sample is placed in a screw-capped vial and soaked with 2％ NaOH/3％ Na₂CO₃ solution immediately after sampling. The Cr(VI) sample is analyzed by ion chromatography/visible spectrophotometry (IC/VS) according to the U.S. Environmental Protection Agency (EPA) Method 218.6. The airborne Cr(VI) concentrations measured by this method were compared with those determined by three reference methods: One (NIOSH/EPA Method) consisted of sampling airborne Cr(VI) on PVC filters and storing the sample filters in screw-capped vials according to the NIOSH method, and analyzing Cr(VI) in samples using IC/VS according to the EPA method. The second method (Impinger Method/NaHCO₃) consisted of absorbing airborne Cr(VI) into 0.02 MN/sub a/Hco₃ solution in midget impinger, and analyzing the Cr(VI) in samples using IC/VS. The third method was the OSHA Method Id-215. Using these four different methods, four replicates of air samples were collected at an electroplating process and analyzed simultaneously. Two-way ANOVA and Paired t-test were used to test difference among values determined by the methods. There was no significant difference and a strong correlation (r/sup 2/=0.99) between Cr(VI) concentrations measured by the shin & Paik's Method and an impinger method (p＞0.05). However, Cr(VI) concentrations determined by Shin & Paik's Method were Significantly different form those by the NIOSH/EPA Method (p＜0.05) or the OSHA method (p＜0.05). The Cr(VI) concentrations of Shin & Paik's Method were Significantly higher than those of the NIOSH/EPA Method or the OSHA method. We concluded that the Shin & Paik's Method could prevent Cr(VI) losses caused by reduction and give more reliable results of airborne Cr(VI) concentrations in work environments.

• 한국대기환경학회지
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• 제18권1호
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• pp.39-49
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• 2002

In this study, limits of detection (LOD), accuracy and precision of four sampling/ analytical methods were evaluated and compared for the determination of airborne hexavalent chromium, Cr (VI). The methods include : (1) a combination of the National Institute for Occupational Safety and Health (NIOSH) Method 7600/U. S. Environmental Protection Agency (EPA) Method 218.6 (NIOSH/EPA Method) proposed by Shin and Paik, 2) two impinger methods using 2% NaOH/3% Na$_2$CO$_3$. (3) same as (2) but with 0.02 N NaHCO$_3$absorbing solution, and (4) the Occupational Safety and Health (OSHA) Method ID-215. An ion chromatograph/visible absorbance detector was used for the analysis of Cr (VI) in sample solution. Limit of detection (LOD) , analytical accuracy, and precision were also tested using Cr (VI) spike samples. Recoveries (as index of accuracy) and coefficient of variation (CV) (as a index of precision) were determined. Two-way ANOVA and Turkey's test were performed to test the significance in differences among recoveries and CVs of the methods. In all the methods, the peaks of Cr (VI) were separated sharply on chromatograms and exhibited a strong linearity with Cr (VI) concentrations in solution. The correlation coefficients of calibration curves typically ranged from 0.9997 to 0.9999, and the analytical LODs from 0.025 to 0.1$\mu\textrm{g}$/sample. All the method had good sensitivities and linearities between Cr (VI) levels and peak areas. The accuracies (% mean recoveries) of the methods ranged from 80.1 to 104.2%, while the precisions (pooled coefficient of variation) ranged from 3.16 to 4.43%. The impinger methods showed higher recoveries ( > 95%) than those of the PVC filter methods (the OSHA Method and the NIOSH/EPA Method). It was assumed that Cr (VI) on PVC filter was exposed to air and reduced to trivalent chromium, Cr (III), whereas it was stabilized in alkali solution contained in impinger. Thus, a special treatment of Cr (VI) samples collected on PVC filters may be required.

• 분석과학
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• 제12권5호
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• pp.447-459
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• 1999

용접 흄에 존재하는 6가 크롬의 분석방법을 평가하기 위하여 깨끗한 PVC여과지와 용접 흄 매트릭스의 여과지에 일정량의 6가 크롬과 3가 크롬을 첨가한 후 NIOSH 7600 및 7604의 알카리 추출방법, 마그네슘 첨가방법, 아세트산 나트륨 완충액 추출로 전처리를 하여 분광광도계(DPC), 유도결합플라스마-광학발광분석법(ICP-OES), 이온크로마토그래피(IC)로 분석하였다. 위 전처리 방법은 모두 부적절하여 새로운 방법으로 알카리 용액상에서 초음파 추출하는 방법을 제안하였다. NIOSH에서 추천하는 2% NaOH/3% $Na_2CO_3$ 추출방법은 6가 크롬만 있을 때 적합하고 3가 크롬이 있으면 일부가 6가 크롬으로 산화된다. 산화 경향은 용접 흄이 있을 때 크게 나타났다. 분광광도계를 이용한 diphenylcarbazide방법은 저농도와 고농도의 6가 크롬이 있을 때 부적합하고 알카리 추출을 하면 ICP-OES분석방법이나 IC분석방법이 적합하다. 용접 흄 중 6가 크롬을 전처리하는 방법으로 NIOSH 방법의 $135^{\circ}C$로 가열하는 대신 초음파처리를 하면 3가의 6가로의 산화를 훨씬 억제할 수 있다. 즉, 2% NaOH/3% $Na_2CO_3$로 초음파처리를 60분 이내에 실시하여 IC 또는 ICP-OES(또는 AAS)로 측정하면 된다.

• 한국산업보건학회지
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• 제25권1호
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• pp.89-94
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• 2015

Objectives: The objective of this study was to determine characteristics of workers' exposures to airborne total and hexavalent chromium by job title in electroplating processes. Methods: Total Cr was determined through a modified method based on NIOSH Method 7024. Airborne hexavalent Cr, Cr(VI), was sampled and extracted according to NIOSH Method 7600 and analyzed at 520 nm using an ion chromatograph/visible detector. Results: The geometric mean(GM) of total Cr concentrations from all factories was $11.2{\mu}g/m^3$(GSD=4.9). The GM of Cr(VI) concentrations from all factories was $2.84{\mu}g/m$ (GSD=5.2), and the concentrations among factories were significantly different (p<0.05). The Cr(VI) levels were lower than total Cr levels. Total Cr exposure levels were highest among buffing workers ($21.6{\mu}g/m^3$), but Cr(VI) levels were highest among plating workers($4.15{\mu}g/m^3$). The concentrations of Cr(VI) and total Cr from plating tasks was highly correlated(r=0.91). Conclusions: In the electroplating industry, plating workers were mainly exposed to Cr(VI), but others were not. Oxidation-reduction states of Cr and job titles should be considered in the exposure or risk assessments of chrome electroplating factories.

• 한국산업보건학회지
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• 제7권2호
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• pp.223-232
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• 1997

The accuracy and precision of a modified method of NIOSH Method 7600 and EPA method 218.6 was determined for analyzing hexavalent chromium, Cr(VI), collected on PVC filter from workplace air. The method was designed to extract from Cr(VI) on PVC filter with a alkali solution, 2% NaOH/3% $Na_2CO_3$, and to analyze it using ion chromatography/visible absorbance detection(IC/VAD). The results and conclusion are as the following. 1. The peak of Cr(VI) was separated sharply on chromatogram and was linearly related with Cr(VI) concentration in sloution. The correlation coefficient was 0.9999 in a calibration curve. The limit of detection was 0.25 $0.25{\mu}g/sample$. 2. The accuracy(% recovery) was 93.3% in a set of sample($9-50{\mu}g$) stored for a day, and 100.1%($10-60{\mu}g$) in another set of samples stored for 2 hours. It is assumed that the difference in recovery by storage time was due to reduction of Cr(VI) to Cr(III). 3. The precision(coefficient of variation, CV) of the method was 0.015 in spiked samples with Cr(VI) standard solution, and 0.010 in spiked samples with plating solution from a chrome electroplating factory. The overall CV in all types of samples was 0.0013. 4. The Cr(VI) was stable in 2% NaOH/3% $Na_2CO_3$ at least for 10 hours. In conclusion, the IC/VAD method is appropriate for determining low-level Cr(VI) in workplace air containing various interferences.

• 한국산업보건학회지
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• 제4권2호
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• pp.189-197
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• 1994

Analytic methods for Cr(VI) level in industrial hygienic field were suggested by the National Institute for Occupational Safety and Health(NIOSH method 7600, 7604). There were growing needs for measurement of Cr(III) and Cr(VI) levels simultaneously. Two analytical methods were suggested to determine Cr(III) and Cr(VI) levels simultaneously. The one is method by using reversed phase high peformance liquid chromatography(HPLC) and the other is by using ion exchange HPLC. The purpose of this work was to evaluate the usefulness of these two analytic methods. For the difference of ionic charges of Cr(III)-ethylendiamine tetraacetic acid(EDTA) chelate and $CrO_4{^-2}$, we could detect them simultaneously by ion exchange HPLC. Also, we attempted to determine the levels of Cr(III) and Cr(VI) chelated with sodium diethyldithiocarbamate(NaDDTC) by using reversed phase HPLC. The confirmation of Cr(III) and Cr(VI) were checked by fraction collector and nameless atomic absorption spectrometer. The optimal conditions for the formation of Cr(III)-EDTA chelate were two hours incubation period with pH 5. Cr(III)-EDTA and Cr(VI) in EDTA solution were successfully separated by anion exchange column using $Na_2CO_3/NaOH$ mixture as mobile phase. Peaks of Cr(III)-EDTA and Cr(VI) in EDTA were identified at 5 minutes and 7 minutes of retention time respectively by the ion exchange HPLC. The formation of Cr(III)-NaDDTC and Cr(VI)-NaDDTC chelates were twelve hours incubation period. Cr(III)-NaDDTC and Cr(VI)-NaDDTC chelates were separated by reversed phase column using methanol and water mixture as mobile phase. Peaks of Cr(VI)NaDDTC and Cr(III)-NaDDTC chelates were identified at 13 minutes and 26 minutes of retention time respectively by the reversed phase HPLC. Due to reduction of Cr(VI) to Cr(III), it seems to be not suitable for simultaneous determination of Cr(III)-NaDDTC and Cr(VI)-NaDDTC chelates by reversed phase HPLS. Simultaneos determination of Cr(III) and Cr(VI) by ion exchange HPLC was more accurate and simple method.