Field evaluation of a sampling and analytical method for environmental levels of airborne hexavalent chromium.

Hexavalent chromium, Cr(VI), has been classified as a human respiratory carcinogen. Airborne Cr(VI) emissions are associated with a number of industrial sources including metal plating, tanning, chromite ore processing, and spray painting operations; combustion sources such as automobiles and incinerators; and fugitive dusts from contaminated soil. There has been considerable interest within industry and the regulatory community to assess the potential cancer risks of workers exposed to Cr(VI) at levels substantially below the threshold limit value (TLV) of 50 micrograms/m3. To date, only the workplace sampling and analytical method (National Institute for Occupational Safety and Health [NIOSH] Method 7600) has been validated for measuring airborne Cr(VI), and it can accurately measure concentrations only as low as 500 ng/m3. This paper describes the field evaluation of a sampling and analytical method for the quantitation of airborne Cr(VI) at concentrations 5000 times lower than the current standard method (as low as 0.1 ng/m3). The collection method uses three 500-mL Greenberg-Smith impingers in series, operated at 15 Lpm for 24 hr. All three impingers are filled with 200 mL of a slightly alkaline (pH approximately 8) sodium bicarbonate buffer solution. The results of validation tests showed that both Cr(VI) and trivalent chromium, Cr(III), were stable in the collection medium and that samples may be stored for up to 100 days without appreciable loss of Cr(VI). Method precision based on the pooled coefficient of variation for replicate samples was 10.4%, and method accuracy based on the mean percent recovery of spiked samples was 94%. Both the precision and accuracy of the impinger method were within NIOSH criteria. This method could be used to measure ambient concentrations of Cr(VI) in the workplace caused by fugitive emissions from manufacturing processes or chromium-contaminated soils at workplace concentrations well below the current TLV (50 micrograms/m3) or permissible exposure limit (100 micrograms/m3).     

Airborne exposure to inhalable hexavalent chromium in welders and other occupations: Estimates from the German MEGA database

This study aimed to estimate occupational exposure to inhalable hexavalent chromium (Cr(VI)) using the exposure database MEGA. The database has been compiling Cr(VI) concentrations and ancillary data about measurements at German workplaces. We analysed 3659 personal measurements of inhalable Cr(VI) collected between 1994 and 2009. Cr(VI) was determined spectrophotometrically at 540 nm after reaction with diphenylcarbazide. We assigned the measurements to pre-defined at-risk occupations using the information provided about the workplaces. Two-thirds of the measurements were below the limit of quantification (LOQ) and multiply imputed according to the distribution above LOQ. The 75th percentile value was 5.2 μg/m³ and the 95th percentile was 57.2 μg/m³. We predicted the geometric mean for 2 h sampling in the year 2000, and the time trend of Cr(VI) exposure in these settings with and without adjustment for the duration of measurements. The largest dataset was available for welding (N = 1898), which could be further detailed according to technique. The geometric means were above 5 μg/m³ in the following situations: spray painting, shielded metal arc welding, and flux-cored arc welding if applied to stainless steel. The geometric means were between 1 μg/m³ and 5 μg/m³ for gas metal arc welding of stainless steel, cutting, hard-chromium plating, metal spraying and in the chemical chromium industry. The exposure profiles described here are useful for epidemiologic and industrial health purposes. Exposure to Cr(VI) varies not only between occupations, but also within occupations as shown for welders. In epidemiologic studies, it would be desirable to collect exposure-specific information in addition to the job title.     

Biochemical and spectroscopic studies of the response of Convolvulus arvensis L. to chromium(III) and chromium(VI) stress

The objective of the present study was to determine the oxidative stress caused by hexavalent chromium (Cr[VI]), the chromium (Cr) uptake, and the Cr speciation in Convolvulus arvensis L. plants grown in hydroponics media containing either Cr(VI) or Cr(III). The results demonstrated that C. arvensis plants exposed to Cr(VI) concentrations ranging from 0 to 40 mg/L expressed higher ascorbate peroxidase specific activity in roots than in shoots. On the other hand, catalase activity monitored in plants exposed to 2 mg/L of Cr(VI) for 24 h increased in roots after a few hours of exposure. However, catalase activity in shoots revealed a decrement almost immediately after treatment was initiated. The results from x-ray absorption spectroscopic studies indicated that the oxidation state of the supplied Cr(III) remained the same in plant tissues. The supplied Cr(VI), however, was reduced to the trivalent form in plant tissues. The results of inductively coupled plasma/optical emission spectroscopy demonstrated that after 5 d, the roots of plants exposed to 40 mg/L of Cr(III) or Cr(VI) accumulated approximately 25,000 and 3,500 mg/kg dry weight of Cr, respectively. Nevertheless, shoots concentrated 1,500 and 2,000 mg/kg dry weight of Cr from Cr(III) and Cr(VI), respectively, which indicated that Cr moved faster into C. arvensis plants when supplied as Cr(VI).     

Chromium bond detection in isolated erythrocytes: a new principle of biological monitoring of exposure to hexavalent chromium

Summary Internal stress to chromium is only relevant in occupational medicine if it is due to the handling of hexavalent chromium. Cr(VI) ions, after uptake by inhalation or percutaneously are carried in the blood plasma and penetrate—depending on the concentration—into the erythrocytes. Due to the intracellular reduction to Cr(III) and the concurrent intracellular protein binding, the erythrocytes represent an easily accessible target organ for quantitative chromium determination after occupational exposure to Cr(VI) compounds. The results of an earlier experimental study indicate that human plasma too is capable of spontaneous reduction of Cr(VI) ions of up to 2 ppm to Cr(III). This plasma reduction capacity (PRC) can be increased and accelerated considerably by adding ascorbic acid (AA). These findings were supported in this investigation by proving a decreased binding of Cr(VI) inside the erythrocytes under the effect of AA. This leads to the assumption that only those Cr(VI) concentrations can penetrate the membrane of the erythrocytes and enter the cell which either come into contact with the membrane during the reduction process or exceed this limit concentration of 2 ppm. Only in these two instances can corresponding chromium findings be analyzed in isolated and washed erythrocytes. These results are compared with those obtained by conventional methods, such as Cr determination in the blood and/or urine. Our findings indicate that a single determination of chromium concentration in the erythrocytes will permit the monitoring of critical cases of Cr(VI) exposure. This is a new type of biological monitoring in the sense of a condensed longitudinal study, in order to find out whether threshold concentrations have been respected over a given period.     

Phytotoxicity and phytoaccumulation of trivalent and hexavalent chromium in brake fern

A recently recognized hyperaccumulator plant, Chinese brake fern (Pteris vittata), has been found to extract very high concentration of arsenic from arsenic-contaminated soil. Chromium usually is a coexisting contaminant with arsenic in most contaminated soils. The potential application of ferns for phytoremediation of chromium(III)- and chromium(VI)-contaminated soils and their phytotoxicity to ferns has not been studied before. In this study, chromium distribution and phytotoxicity at the plant and cellular levels of brake ferns were studied using chemical analyses and scanning electron microscopy. The results show a higher phytotoxicity of Cr from Cr(VI)-contaminated soil to Chinese brake fern than from Cr(III)-contaminated soil. Phytotoxicity symptoms included significant decreases both in fresh biomass weight and relative water content (RWC), and also in leaf chlorosis during the late stage of growing. At higher concentrations (500 mg/kg Cr[VI] and 1,000 mg/kg Cr[III] addition), plants showed reduction in the number of palisade and spongy parenchyma cells in leaves. Compared with other plant species reported for phytoremediation of Cr(VI)-contaminated soil, brake fern took up and accumulated significant amounts of Cr (up to 1,145 mg/kg in shoots and 5,717 mg/kg in roots) and did not die immediately from phytotoxicity. Our study suggests that Chinese brake fern is a potential candidate for phytoremediation of Cr(VI)-contaminated soils, even though plants showed severe phytotoxic symptoms at higher soil Cr concentrations.     

A study of chromium induced allergic contact dermatitis with 54 volunteers: implications for environmental risk assessment.

Over the past 60 years, dose-response patch test studies by various methods have been conducted in an attempt to identify the minimum elicitation threshold (MET) concentration of hexavalent chromium (Cr(VI)) that produces an allergic response in Cr(VI) sensitive subjects. These data are not adequate, however, to provide an accurate estimate of the MET because of the variability in the patch testing techniques and the variability in diagnostic criteria used. Furthermore, the data were not reported in terms of mass of allergen per surface area of skin (mg Cr/cm2-skin), which is necessary for conducting occupational or environmental health risk assessments. Thus the purpose of this study was to determine the MET (mg allergen/cm2) for Cr(VI) and trivalent chromium (Cr(III)) by patch testing techniques. A patch test method that delivers a controlled amount of allergen per surface area of skin was used. A group of 54 Cr(VI) sensitised volunteers were patch tested with serial dilutions of Cr(VI) and Cr(III) to determine the cumulative response rate at several concentrations. The results indicate that the 10% MET for Cr(VI) based on the cumulative response was 0.089 micrograms Cr(VI)/cm2-skin. Only one of the 54 volunteers may have responded to 33 micrograms Cr(III)/cm2-skin, otherwise Cr(III) was unable to produce allergic contact dermatitis in these highly sensitive volunteers. Two supplemental studies were also conducted to assess whether the surface area of the patch and the concentration of Cr(VI) in the patch (related to patch thickness) were likely to influence the results. The data from these studies were used to assess the risk of developing allergic contact dermatitis due to contact with Cr(VI) and Cr(III) in soil. The findings indicated that soil concentrations at least as high as 450 ppm Cr(VI) and 165,000 ppm Cr(III) should not pose an allergic contact dermatitis hazard for at least 99.99% of the people in the community who might be exposed.     

The simultaneous detection of trivalent & hexavalent chromium in exhaled breath condensate: A feasibility study comparing workers and controls

The analytical method outlined in this feasibility study has been used to show that trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) can be detected and measured in exhaled breath condensate (EBC) samples. EBC samples and urine samples were collected from a cohort of 58 workers occupationally exposed to hexavalent chromium compounds and 22 unexposed volunteers (control group). Levels of Cr(III) and Cr(VI) were determined in EBC samples and total chromium levels were determined in urine samples. Pre and post working week samples for both EBC and urine were collected in tandem. Total chromium in urine samples was analysed by inductively coupled plasma mass spectrometry (ICP-MS). Analysis of Cr(III) and Cr(VI) in EBC samples used a hyphenated micro liquid chromatography (μLC) system coupled to an ICP-MS. Separation was achieved using an anion exchange micro-sized column. The results showed that the occupationally exposed workers had significantly higher levels of Cr(III) and Cr(VI) in their EBC samples than the control group, as well as higher levels of total chromium in their urine samples. However, for the exposed workers no significant difference was found between pre and post working week EBC samples for either Cr(III) or Cr(VI). This study has established that Cr(III) and Cr(VI) can simultaneously be detected and measured in ‘real’ EBC samples and will help in understanding inhalation exposure.     

Occupational exposure to Cr(VI): comparison between chromium levels in lymphocytes,erythrocytes, and urine

 The relationships between chromium (Cr) levels in lymphocytes, erythrocytes, urine, and ambient air were compared among 14 chrome-platers from a metallurgic plant in Bulgaria and two groups of local controls, one from the same heavily polluted industrial town as the chrome-platers (n=11) and one from a seaside resort town 100 km away (n=6). Among the chrome-platers, the Cr concentration in peripheral lymphocytes was positively correlated with total Cr and Cr(VI) levels in ambient air and with Cr excretion in urine. As compared to the controls, the chrome-platers had mean Cr levels in lymphocytes twice as high, in erythrocytes ninefold higher, and in urine fourfold to eightfold higher. Although Cr levels in urine and lymphocytes were similar between the two control groups, levels in erythrocytes were 3 times higher among subjects from the industrial area than among those from the seaside town. The study suggests that lymphocyte Cr could be a good indicator of the Cr body burden caused by high exposures to Cr(VI), such as in electroplating operations. In these conditions, erythrocyte Cr may be less useful, possibly owing to increased toxicity due to the high affinity of erythrocytes for Cr. However, when exposure is lower, such as in most environmental situations, erythrocyte Cr should provide a better and more sensitive index than lymphocyte Cr. By contrast, urinary Cr, which provides information on total Cr exposure, including Cr(III) from dietary and environmental sources, does not seem to be of value for studying occupational exposure to Cr(VI). Received: 22 September 1995/Accepted: 2 January 1996     

Hexavalent chromium-induced DNA damage and repair mechanisms

Hexavalent chromium is a commonly used industrial metal that has been shown to induce lung cancer in workers having long term exposure. In the particulate form, Cr(VI) dissolves slowly in vivo, leading to an extended exposure of lung cells. Hexavalent chromium is taken into the cell and rapidly reduced to Cr(V), Cr(IV), Cr(III), and reactive oxygen species. Cells treated with Cr(VI) are subject to several types of DNA damage resulting from this reduction, including base modification, single-strand breaks, double-strand breaks, Cr-DNA adducts, DNA-Cr-DNA adducts, and protein-Cr-DNA adducts. These types of damage, if left unrepaired or are misrepaired, can lead to growth arrest, cytotoxicity, and apoptosis, as well as mutations leading to neoplastic transformation and ultimately tumorigenesis. Here we review the current literature on Cr-induced DNA damage and its repair.     

Relation between various chromium compounds and some other elements in fumes from manual metal arc stainless steel welding.

For the years 1987-1990 160 individual samples of manual metal arc stainless steel (MMA/SS) welding fumes from the breathing zone of welders in four industrial plants were collected. Concentrations of soluble and insoluble chromium (Cr) III and Cr VI compounds as well as of some other welding fume elements (Fe, Mn, Ni, F) were determined. Concentration of welding fumes in the breathing zone ranged from 0.2 to 23.4 mg/m3. Total Cr amounted to 0.005-0.991 mg/m3 (including 0.005-0.842 mg/m3 Cr VI). Total Cr content of fumes varied from 0.1 to 7.4%. The distribution of particular Cr compounds was: 52.6% soluble Cr (including 50.7% Cr VI), 65.5% total Cr VI, and 11.4% insoluble Cr VI. The results obtained indicate that MMA/SS welding is a process that could be highly hazardous to human health. Evaluation of occupational exposure has shown that MMA/SS welders may exceed the admissible concentrations of soluble and insoluble Cr VI forms as well as of Mn and Ni. In the plants investigated the sum of the ratios of concentrations of particular welding fumes in the breathing zone of welders exceeded corresponding maximum allowable concentration values by 24 times (including 17 times for total Cr VI). Due to the variety and changeability of particular parameters occurring in the working environment, the composition of MMA/SS welding fumes (in the welder's breathing zone) is so variable that it is not possible to assess the exposure by means of one universal exposure indicator (maximum additive hygienic limit value). The evaluation should be based on the results of measurements of concentrations of particular elements in welding fumes.     

Removal of Chromium from Soils Cultivated with Maize (<Emphasis Type="Italic">Zea Mays</Emphasis>) After the Addition of Natural Minerals as Soil Amendments

The efficiency of natural minerals, i.e. zeolite, bentonite and goethite, regarding the retention of chromium, from maize was examined. Specifically, 1.0 kg of soil, 1.0 g of soil amendment and either 50 mg L^?1 Cr(III) or 1 mg L^?1 Cr(VI) were added in plant pots. Then, seeds of maize were cultivated. Each treatment was repeated three times. The statistical results of the experiments were analyzed by LSD test. Cr(III) addition in soil has shown that zeolite was the only amendment that increased the dry weight. Zeolite and bentonite reduced significantly the total chromium in plants after the addition of 50 mg L^?1 Cr(III). The addition of Cr(VI) in soil has shown that bentonite was the only amendment that increased the dry weight of biomass and the plants’ height. All soil amendments reduced to zero the total chromium concentration measured to plants after the addition of 1 mg L^?1 Cr(VI).     

Toxicity of chromium(III) and chromium(VI) to the earthworm Eisenia fetida

The effects of Cr(III) and Cr(VI) on the survival, behavior, and morphology of the earthworm, Eisenia fetida, in water at pH 6, 7, and 8 and their toxicity in 10 different soils and an organic substrate have been assessed. A decrease in the pH of water resulted in increased toxicity of Cr to the earthworm. In water, both Cr species produced behavioral changes and morphological symptoms. The 48-h LC(50) values of Cr(III) at pH 6, 7, and 8 were 1.93, 2.55, and 2.78 mg/L, and those of Cr(VI) were 0.47, 0.61, and 0.63 mg/L, respectively. The 14-day median lethal concentrations (LC(50)) of Cr(III) and Cr(VI) for earthworm range from 1656 to 1902 mg/kg for Cr(III) and from 222 to 257 mg/kg for Cr(VI) in soil. In the organic substrate, the LC(50) values of Cr(III) and Cr(VI) were 1635 and 219 mg/kg, respectively. Stepwise multiple regression analysis predicted that clay content of soils accounted for 92% and 88% of the variation in the LC(50) values of Cr(III) and Cr(VI), respectively.     

Estimating historical occupational exposure to airborne hexavalent chromium in a chromate production plant: 1940--1972

This article presents a retrospective exposure assessment for 493 workers who were occupationally exposed to airborne hexavalent chromium, Cr(VI), at a Painesville, Ohio, chromate production plant from 1940-1972. Exposure estimates were reconstructed using a job-exposure matrix approach that related job titles with area monitoring data from 21 industrial hygiene surveys conducted from 1943 to 1971. No personal monitoring data were collected. Specifically, airborne Cr(VI) concentration profiles for 22 areas of the plant, termed job-exposure group (JEG) areas, were constructed for three distinct time periods (1940-1949, 1950-1964, and 1965-1972), with cut points based on known major plant and process changes. Average airborne Cr(VI) concentrations were the highest for the bridge crane operators (5.5 mg/m3) prior to 1965, although only four cohort members held this job title. Airborne concentrations for the rest of the production areas of the plant ranged from 1.9 mg/m3 for packers in the 1940s to 0.012 mg/m3 for ore mill operators after 1964. For nearly all JEG areas, exposures decreased over time, particularly after 1964. For example, average airborne concentrations in production areas of the plant decreased from 0.72 mg/m3 in the 1940s to 0.27 mg/m3 from 1950 to 1964, and the average was 0.039 mg/m3 after 1964. Former workers were interviewed to determine activity patterns in the plant by job title. This information was combined with Cr(VI) monitoring data to calculate cumulative occupational exposure for each worker. Cumulative exposures ranged from 0.003 to 23 (mg/m3) x years. The highest monthly 8-hour average exposure concentration for each worker ranged from 0.003 to 4.1 mg/m3. These exposure estimates have been combined with mortality data for this cohort to assess the lung cancer risk associated with inhaled Cr(VI), and a positive dose-response relationship was observed for increases in lung cancer mortality with measures of cumulative exposure and highest monthly exposure.     

Assessment of EDTA in Chromium (III–VI) Toxicity on Marine Intertidal Crab (Petrolisthes laevigatus)

Chromium poses a potential threat to coastal ecosystems. We used standard toxicity bioassays (semi-static, chronic) to evaluate EDTA as a chelating agent for reducing trivalent and hexavalent chromium toxicity on Petrolisthes laevigatus. Crab survival decreased linearly with increased chromium concentrations and dropped significantly beginning at 40 mg/L Cr (VI) and 80 mg/L Cr (III). No significant differences were observed with Cr (III) + EDTA as compared with untreated controls. Cr (VI) toxicity was greater than that of Cr (III), with low individual survival rates. The protective effect of EDTA in the medium increased crab survival by 41%-48%.     

Evaluation of Aquatic Toxicities of Chromium and Chromium-Containing Effluents in Reference to Chromium Electroplating Industries

This study evaluated aquatic toxicities of chromium and chromium-containing laboratory samples representative of effluents from chromium electroplating industries, and compared the aquatic environmental risks of hexavalent and trivalent chromium electroplating operations. Trivalent chromium electroplating has emerged as an acceptable alternative to hazardous hexavalent chromium electroplating. This process substitution has reduced the human health impact in the workplace and minimized the production of hazardous sludge regulated under the Resource Conservation and Recovery Act (RCRA). The thrust behind this research was to investigate whether trivalent chromium electroplating operations have lower adverse impacts on standardized toxicity test organisms. Ceriodaphnia dubia and Pimephales promelas were used to investigate toxicities of trivalent chromium (Cr (III)), hexavalent chromium (Cr (VI)), and industrial effluents. In agreement with previous studies, Cr (III) was found to be less toxic than Cr (VI). Despite having several organic and inorganic constituents in the effluents obtained from trivalent chromium plating baths, they exhibited less adverse effects to C. dubia than effluents obtained from hexavalent chromium electroplating baths. Thus, transition from hexavalent to trivalent chromium electroplating processes may be justified. However, because of the presence of organic constituents such as formate, oxalate, and triethylene glycol in effluents, trivalent chromium electroplating operations may face additional regulatory requirements for removal of total organic carbon.     

Rabbit alveolar macrophages after inhalation of hexa- and trivalent chromium

Rabbits inhaled aerosols of hexavalent chromium (Na2CrO4) and trivalent chromium (Cr(NO3)3) at concentrations of 0.9 and 0.6 mg/m3 of the metal, respectively, for 4-6 weeks (5 days/week and 6 hr/day). Significantly more macrophages were obtained from the lungs of rabbits exposed to Cr(VI) but not from rabbits exposed to Cr(III) as compared with the controls. Macrophages from rabbits exposed to Cr(III) showed several conspicuous changes. About one-third of the macrophages contained round dark inclusions, 0.5-1.5 micron diameter, rich in chromium. Most cells had very large lysosomes which contained membranous fragments of different sizes surrounded by a more homogeneous matrix. Laminated inclusions similar to the lamellar bodies in the type II cells increased in number as did the percentage of cells with a smooth cell surface. Also macrophages from rabbits exposed to Cr(VI) showed morphological changes. The most pronounced one was enlarged lysosomes which contained short lamellae and electron-dense patchy inclusions. Only Cr(III) produced functional changes of the macrophages. The metabolic activity measured by reduction of nitroblue tetrazolium was increased and the phagocytic activity reduced.     

Experimental bases for ascorbic acid therapy of poisoning by hexavalent chromium compounds

Summary The most frequent outcome of the usually transdermal absorption of hexavalent chromium compounds is uraemia due to tubular necrosis. We have confirmed earlier observations that this can be prevented by the immediate application of ascorbic acid (AA) with the aim of reducing Cr(VI) to Cr(III). The spontaneous reducing capacity of samples of serum and plasma for Cr(VI) compounds was polarographically determined to be about 2 ppm. Addition of AA in doses of 50 to 1000 ppm led to a rapid and dose-dependent reduction of chromium(VI), which was studied on the concentration level of 5 ppm. For example in the presence of 1000 ppm AA, five ppm chromium(VI) fade to 0.7 ppm within 20 min and to undetectable concentrations after 40 min. These experiments demonstrate the effectiveness of AA for the treatment of Cr(VI) poisoning. Reduction is increased and accelerated by AA and the resulting Cr(III)-protein complexes are non-toxic and can be excreted with the urine. Early and repeated high i.v. doses of AA are recommended as the therapy of choice for Cr(VI) poisoning. In cases of delayed medical treatment, AA should be immediately applied orally.     

Location-specific ecotoxicological risk assessment of metal-polluted soils

When chemical analysis indicates metal pollution, a second-tier method is needed to evaluate whether toxic effects occur at the polluted sites. A method based on pollution-induced community tolerance (PICT) was developed using samples taken from locations polluted with sewage more than 20 years ago. Microorganisms extracted from soil samples were exposed to a concentration range of zinc, nickel, copper, chromium (III), or chromium (VI) salts in a buffer suspension. The remaining activity of the intoxicated microorganisms was determined by color formation with 31 different organic substrates in microtiter plates. Microorganisms from moderately Zn-polluted sites (>45 mg/kg) showed an increased tolerance for zinc. Nickel tolerance was observed at 51 mg Ni/kg soil, chromium (VI) tolerance at 923 mg Cr/kg. In most cases, tolerance also was observed at higher concentrations. High concentrations of 1,494 mg Cu/kg or 3,935 mg Cr/kg did not show PICT, indicating a limited bioavailability of Cu and Cr at these sites. The benefits of our method are its greater sensitivity compared to other tests used at these sites, and its specificity for those metals that exceed allowable levels.