Journal of Korean Society of Occupational and Environmental Hygiene
/
v.3
no.2
/
pp.152-165
/
1993
This study was performed at eleven small-sized plating factories located in Seoul, Incheon, Ansan, and Taejeon from July 21 to October 6, 1992. The major objectives of this study were to evaluate worker exposure to hexavalent chromium and local exhaust ventilation (L.E.V.) systems at the chromium plating operations. The most suitable L.E.V. systems for chromium plating tanks were designed as examples for recommendation to the industry. The results are summarized as follows. The range of chromium plating operations investigated included decorative, hard, and black chromium plating on several kinds of parts. Most of plating tanks were not equipped with proper control methods against emission of hexavalent chromium mists and workers were not wearing appropriate personal protectives. The ariborne hexavalent chromium concentrations showed an approximate lognormal distribution. The geometric means of both personal and area samples were within the Korean and ACGIH standards, $50{\mu}g/m^3$. However, in comparison with the NIOSH criterion, $1{\mu}g/m^3$, the geometric means of personal samples at two factories and the geometric means of area samples at two factories exceeded it. The geometric means of personal and area samples of high exposure groups (above the NIOSH criterion) were 7 and 27 times higher than those of low exposure groups (below the NIOSH criterion), respectively. The L.E.V. systems of high exposure groups were improperly designed, and the factory with the highest exposure level had no L.E.V. systems at all on chemical etching process. Whereas at factories of low exposure groups, mist control methods such as mist suppressants, tank cover, and/or auxillary L.E.V. systems were added to L.E.V systems. The evaluation of L.E.V. systems showed that there was no chromium plating operation satisfying the ACGIH criteria for capture velocity, slot velocity, and exhaust rate simultaneously. To increase performance of L.E.V. systems, it must be designed to minimize the impact of boundary layer separation. Push-pull ventilation hood and downward plenum ventilation hood were suggested for the Korean industry.
This study was performed to evaluate chromium in air and chromium concentrations in whole blood and urine of workers at chrome plating factories, and to determine the correlation between environmental and biological chromium levels. This study involved 29 workers as study group and 24 undergraduate students as control group. The geometric means(GM) of airborne hexavalent chromium and total chromium concentrations in the plating factories were 3.4 $\mu\textrm{g}$/㎥ and 10.8 $\mu\textrm{g}$/㎥, respectively. Hexavalent chromium levels in two of total 29 measurements exceeded the korean occupational exposure limit and the American Conference of Governmental Industrial Hygienists Threshold Limit Value(ACGIH-TLV) of 50$\mu\textrm{g}$/㎥. Only one sample for total chromium exceeded the Korea occupational exposure limits, the ACGIH-TLV, and the National Institute for Occupational Safety and Health Recommended Exposure Limits(NIOSH-REL) of 500 $\mu\textrm{g}$/㎥. The GM of chromium concentrations in blood and urine of workers exposed to chromium were 8.4 $\mu\textrm{g}$/L and 11.9 $\mu\textrm{g}$/L. The GM of chromium concentrations in blood and urine of workers exposed to chromium were 8.4 $\mu\textrm{g}$/L and 11.9 $\mu\textrm{g}$/L, respectively, whereas the chromium concentrations in blood and urine of the controls were 1.6 $\mu\textrm{g}$/L and 3.8 $\mu\textrm{g}$/L, respectively. There were statistically significant differences of blood and urine concentrations between study group and control group (p<0.01). The chromium concentrations in urine were most highly related to hexavalent chromium, concentration in air(r=0.642, p<0.01). Also, there was a relatively high correlation between the hexavalent chromium concentrations in air and chromium concentrations in whole blood(r=0.557, p<0.05). These results indicate that whole-blood chromium with urinary chromium could be an indicator of chromium body burden caused by exposure to chromic acid mist in plating operation.
Decorative properties of chromium depositions from oxalic acid bath containing chromium oxide and ammonium sulfate have been examined over a wide range of bath compositions and plating conditions. The obtained results from this experiment are summarized as follow: The followings were determined as a optimum conditions, bath compositions; $CrO_3\;200{\sim}250\;g/{\ell},\;H_2C_2O_4{\cdot}2H_2O\;500{\sim}700\;g/{\ell},\;(NH_4)_2SO_4\;40{\sim}120\;g/{\ell}$, and operation conditions; pH $2.0{\sim}2.5$, current density $15{\sim}250\;A/dm^2$ at bath temperature range of $30{\sim}80^{\circ}C$. Bright chromium deposits were obtained over a wide range of ammonium sulfate concentration and bath temperature. Decorative property for chromium deposition was adopted to apply stoichiometric ratio of $CrO_3$ concentration and $H_2C_2O_4{\cdot}2H_2O$.
Decorative property of chromium deposition from oxalic acid bath containing chromium oxide and ammonium sulfate, has been examined over a wide range of bath compositions and plating conditions. The followings were determined as optimum bath composition, $CrO_3\;200{\sim}250g/{\ell},\;H_2C_2O_4{\cdot}2H_2O\;500{\sim}700g/{\ell},\;(NH_4){_2}SO_4\;40{\sim}120g/{\ell}$, and operation conditions; pH $2.0{\sim}2.5$, current density of $15{\sim}250Adm^2 $ at the bath temperatures of $30{\sim}80^{\circ}C$. Bright chromium deposits were obtained over a wide range of ammonium sulfate concentration, bath temperature, and current density. The current efficiency decreased with increasing current density and bath pH, and increased with Increasing bath temperature. The highest current efficiency was obtained in the bath containing $80g/{\ell}$ of ammonium sulfate. Bright chromium deposits were not obtained at conditions of all the highest current efficiencies.
Hexavalent chromium may reduce on polyvinyl chloride (PVC) filter during sampling and storage of sample. Recently, new or modified filters for preventing Cr(VI) from the reduction has been introduced. Thus, this study was performed to compare the reduction behaviors of Cr(VI) on several sampling filters and to find the most appropriate filter for airborne Cr(VI) sampling in plating operation. The results were as follows. 1. There were statistically significant differences among PVC, polytetrafluoroethylene (PTFE). glass fiber (GF) and polyvinylidene fluoride (PVDF) filters in recovery rates of spiked Cr(VI) samples by storage time(p<0.05). There was no significant difference between PVC and PTFE filters(p>0.05). The PVC and PTFE filters showed higher recoveries than GF and PVDF filters(p<0.05). 2. The quartz fiber(QF) filter treated with an alkali solution(2% NaOH/3% Na$_2$CO$_3$, 1% NaOH) showed a significantly higher recovery of Cr(VI) by storage time than other filters(GF and QF filter)(p<0.05). There was no difference in recovery of Cr(VI) between alkali-treated and untreated GF it filters(p>0.05). But the QF filters treated with two alkali solution showed a significantly higher recovery than the untreated QF filter(p<0.05). There was no significant difference in recovery of Cr(VI) between QF filters treated with 1% NaOH and 2% NaOH/3% Na$_2$CO$_3$(p>0.05). In conclusion, treatment of QF fillers with alkali solution was most effective in protecting from the reduction of Cr(VI).
Chromium exists at various valences, including elemental, trivalent, and hexavalent chromium, and undergoes reduction-oxidation reactions in the environment. Since hexavalent chromium is known as a human carcinogen, it is most important to evaluate the oxidationreduction characteristics of the hexavalent chromium species. Although hexavalent chromium can be reduced to trivalent state, the detailed information on this in workplace environments is limited. The purpose of this study was to investigate hexavalent chromium reduction in time in various conditions. A pilot chrome plating operation was prepared and operated in a laboratory for this study. There was evidence that the hexavalent chromium was reduced by time after mist generation. The percentage ratio (with 95% confidence intervals in parentheses) of hexavalent chromium to total chromium was almost 100% (99.1 ; 102.3) immediately after mist generation, and was reduced to 87.4% (84.8 ; 89.9) at 1 hour and 81.0% (78.3 ; 83.5) at 2 hours, respectively. Another test indicated that hexavalent chromium collected on PVC filters was also reduced by time after sampling. Hexavalent chromium was reduced to 90.8% (88.2 ; 93.3) at 2 hours after sampling. It also was found that hexavalent chromium was reduced during storage in air. It is recommended that air samples of hexavalent chromium be protected against reduction during storage.
Journal of Korean Society of Occupational and Environmental Hygiene
/
v.11
no.1
/
pp.48-55
/
2001
The purpose of this study was to evaluate the analytical accuracy and precision of microwave oven digestion/atomi absorption spectrophotometry (AAS) for analyzing airborne chromium collected on mixed cellulose ester membrane (M filter from the work environment, and to compare the accuracy and the precision with those of the National Institute for Occupational Safety and Health (NIOSH) Method #7024 hot plate digestion/AAS method. For this study, field air sample pairs were collected from a electroplating process, and spiked samples in a laboratory were prepared and using these samples. Two digestion methods were comp; and evaluated in terms of recovery rate and bias as indices of accuracy and coefficient of variation as a index of precision. The results and conclusions are as follows. In spiked samples, the accuracies (% mean recoveries) of hot plate/AAS and microwave oven/AAS method were 97.19%, 97.1%, respectively, and the precisions (pooled respectively, and the precisions (pooled coefficient of variance, $CV_{pooled}$) 6.93% and 3.88%, respectively. The biases of hot plate ani microwave oven methods were 4.56 - 14.7% and 2.22 - 7.42% respectively. There was no statistically significant difference between hot plate and microwave oven methods recovery rates of spiked samples (p>0,05). Also, no statistically significant difference was shown among the concentrations of air samples determined by two method (p>0.05). In conclusion, microwave oven/AAS method h excellent accuracy and precision, and advantages such as time-saving and simple procedure in comparison with the classical NIOSH method. Therefore, this method can be use widely to analyze airborne chromium collected on MCE filter from the work environments.
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.
Proceedings of the Korean Environmental Health Society Conference
/
2002.04a
/
pp.40.1-43
/
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.
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