efsa-opinion-chromium-food-drinking-water

efsa-opinion-chromium-food-drinking-water efsa-opinion-chromium-food-drinking-water

damienvanherp
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Chromium in food and drinking water Cr(VI) compounds are reduced to the trivalent form in the presence of oxidizable substances (reductants). In natural waters, often characterized by a fair degree of acidity (Kotaś and Stasicka, 2000), Cr(VI) compounds are generally more stable as the concentration of reducing materials is relatively low. However, Fe(II) in solution or Fe(II)-bearing minerals, sulphides, and/or oxidizable organic matter may cause a reduction of Cr(VI) to Cr(III) (Schroeder and Lee, 1975; Fendorf, 1995; Loyaux-Lawniczak et al., 2001). Figure 4: Dichromate ion Conclusion In conclusion, in aqueous media chromium generally occurs in the form of its two most stable oxidation states, Cr(III) and Cr(VI), both existing as complex groups of interrelated chemical species. As described, the distribution of species containing Cr(III) and Cr(VI) depends on the redox potential, the pH, the presence of oxidizing or reducing substances, the kinetics of redox reactions, the formation of Cr(III) complexes or insoluble Cr(III) compounds, and the total chromium concentration. In the environment, and specifically in aqueous media, the two forms are involved in rather complex equilibria, which may be easily altered if the ambient chemico-physical conditions are modified (for the technical problems in Cr(VI) analysis, see Section 3). 1.2. Environmental fate and sources of food and drinking water contamination 1.2.1. Environmental fate In the atmosphere, chromium occurs from natural sources (e.g. volcanic emissions) as well as from many anthropogenic activities, including burning of fossil fuels and wood; the most important industrial sources of airborne chromium are associated with ferrochrome production. Both Cr(III), and Cr(VI) can be released into the air, although the latter to a lesser extent (WHO, 2003): due to analytical difficulties, chromium speciation data in air are very limited. In air, chromium is present in the form of aerosols that are removed by wet and dry deposition. Chromium particles of small aerodynamic diameter (< 10 µm) may remain airborne for long periods and undergo long-range transport. Under normal conditions, airborne Cr(0) and Cr(III) forms do not undergo any reaction, whereas Cr(VI) eventually reacts with dust particles or other pollutants to yield Cr(III) (U.S. EPA, 1998a, b). As observed in the preceding Section, in the aquatic environment Cr(III) and Cr(VI) occur mostly as Cr(OH) n (3 – n)+ and as CrO 4 2− or HCrO 4 − . In water, Cr(III) may form positive or negative ionic species at low or high pH values, respectively, whereas at intermediate pH values the neutral hydroxide form, Cr(OH) 3 0 , is predominant. In surface waters, relatively high concentrations of Cr(VI) forms can be found locally (WHO, 2003). Surface runoff, deposition from air, and release of municipal and industrial waste waters are sources of chromium in surface waters. Cr(III) is lost from the aquatic environment primarily due to precipitation of hydrated Cr 2 O 3 followed by sedimentation. The Cr(VI) anion species can persist in aquatic media, possibly for long periods, as water-soluble complexes; however, they will react with organic matter or other reducing agents to form Cr(III). Therefore, in surface waters rich in organic content, Cr(VI) will have a much shorter lifetime (U.S. EPA, 1998a, b). EFSA Journal 2014;12(3):3595 16

Chromium in food and drinking water In soil, Cr(III) predominates, likely as insoluble hydrated Cr 2 O 3 forms: in addition to a direct release as a result of anthropogenic activities, trivalent chromium can easily arise from reduction of Cr(VI) species due to the presence of reductants. Chromium is lost from soil primarily due to physical processes. For instance, chromium-containing soil particles can be raised by air draughts and dispersed over long distances; likewise, runoff can remove from topsoil chromium ions and bulk precipitates of the metal. Flooding of soils and the subsequent decomposition of vegetal matter may also increase dissolution of soil-borne Cr 2 O 3 through the formation of water-soluble chromium complexes which will possibly leach and percolate through soil (U.S. EPA, 1998a, b; WHO, 2003). A study was conducted in 1991 to determine the levels of heavy metals and polycyclic aromatic hydrocarbons (PAHs) in soil along a busy road that runs through the Aplerbecker forest near the German town of Dortmund. Background concentrations of the metals were reached some 5-10 m away from the road. The concentration of chromium in the soil at the edge of the road showed a two- to four-fold increase relative to background levels, reaching up to 64 mg/kg (Münch, 1993). The thick vegetation structure of the forest and its barrier effect was discussed as a reason for the heavy accumulation of the metals and PAHs detected in the roadside soil. The bioconcentration factor (BCF) for chromium in rainbow trout (Salmo gairdneri) was reported as 1. In bottom-feeder bivalves, such as the oyster (Crassostrea virginica), blue mussel (Mytilus edulis), and soft shell clam (Mya arenaria), chromium BCF values were found to be in the order of 10 2 . Based on experimental observations, chromium is not expected to biomagnify in the aquatic food chain (U.S. EPA, 1998a, b; OEHHA, 2011; ATSDR, 2012). Higher chromium concentrations were found in plants growing in soils with high chromium contents compared with plants growing in normal soils: however, as only a small fraction of chromium is translocated from soil to the epigeal parts of edible plants, bioaccumulation of chromium from soil to the aforesaid plant parts is unlikely. There is no indication of chromium biomagnification along the terrestrial food chain. 1.2.2. Sources of food and drinking water contamination Chromium can enter the food chain via the different environmental compartments, either as a result of natural presence or emission from anthropogenic activities. Food preparation with stainless steel containers, processors and utensils could represent an additional source for the presence of chromium in food (Stoewsand et al., 1979; Offenbacher and Pi-Sunyer, 1983; Kumpulainen, 1992). Environmental levels According to studies from the late 1970s onwards (WHO, 2000, 2003), air chromium concentrations in the range of 0.005-1.1 ng/m 3 were detected in various remote locations such as the Arctic and Antarctic poles, north Atlantic ocean, Shetland Islands, Norway, and northwest Canada; in remote European areas, concentrations up to 3 ng/m 3 were measured. Health Canada (1986) reported chromium concentrations in air samples from five remote areas in Canada between 0.32 and 25 ng/m 3 , while in the USA chromium concentrations in urban air were reported from less than 10 to 50 ng/m 3 . Most environment monitoring stations in the USA detected average chromium levels in ambient air of rural and urban areas below 300 ng/m 3 (median, < 20 ng/m 3 ), although occasional measurements could be higher (WHO, 2000, 2003). The mean concentration of chromium in air in the Netherlands appeared to vary in the range of 2 to 5 ng/m 3 ; in continental Europe, air chromium concentrations were found to span 1-140 ng/m 3 , a range comprising urban area values (4-70 ng/m 3 ). In industrial European settings, air chromium concentrations were in the range 5-200 ng/m 3 . The air chromium levels in Japan and Hawaii were found to be in the range 20-70 ng/m 3 (WHO, 2000). In general, in nonindustrialized areas concentrations above 10 ng/m 3 were uncommon whereas in urban areas they were two to four times higher than regional background concentrations (WHO, 2003; OEHHA, 2011). As a result of smoking, chromium concentrations in indoor air (≈ 1000 ng/m 3 ) may be 10-400 times greater than outdoor concentrations (WHO, 2003). Chromium concentrations in rainwater showed a marked variability (for example, see: van Daalen, 1991; Neal et al., 1996; Kaya and Tuncel, 1997); however, on average they were found to be in the range 0.2-1 µg/L (WHO, 2003). Cr(VI) forms may be present in rainwater (Seigneur and Constantinou, 1995): for instance, chromium species were determined in several rainwater samples collected in North Carolina in 1999 through 2001 (Kieber et al., 2002). The EFSA Journal 2014;12(3):3595 17

Chromium in <strong>food</strong> and <strong>drinking</strong> <strong>water</strong><br />

In soil, Cr(III) predominates, likely as insoluble hydrated Cr 2 O 3 forms: in addition to a direct release<br />

as a result of anthropogenic activities, trivalent <strong>chromium</strong> can easily arise from reduction of Cr(VI)<br />

species due to the presence of reductants. Chromium is lost from soil primarily due to physical<br />

processes. For instance, <strong>chromium</strong>-containing soil particles can be raised by air draughts and dispersed<br />

over long distances; likewise, runoff can remove from topsoil <strong>chromium</strong> ions and bulk precipitates of<br />

the metal. Flooding of soils and the subsequent decomposition of vegetal matter may also increase<br />

dissolution of soil-borne Cr 2 O 3 through the formation of <strong>water</strong>-soluble <strong>chromium</strong> complexes which<br />

will possibly leach and percolate through soil (U.S. EPA, 1998a, b; WHO, 2003).<br />

A study was conducted in 1991 to determine the levels of heavy metals and polycyclic aromatic<br />

hydrocarbons (PAHs) in soil along a busy road that runs through the Aplerbecker forest near the<br />

German town of Dortmund. Background concentrations of the metals were reached some 5-10 m away<br />

from the road. The concentration of <strong>chromium</strong> in the soil at the edge of the road showed a two- to<br />

four-fold increase relative to background levels, reaching up to 64 mg/kg (Münch, 1993). The thick<br />

vegetation structure of the forest and its barrier effect was discussed as a reason for the heavy<br />

accumulation of the metals and PAHs detected in the roadside soil.<br />

The bioconcentration factor (BCF) for <strong>chromium</strong> in rainbow trout (Salmo gairdneri) was reported<br />

as 1. In bottom-feeder bivalves, such as the oyster (Crassostrea virginica), blue mussel (Mytilus<br />

edulis), and soft shell clam (Mya arenaria), <strong>chromium</strong> BCF values were found to be in the order of<br />

10 2 . Based on experimental observations, <strong>chromium</strong> is not expected to biomagnify in the aquatic <strong>food</strong><br />

chain (U.S. EPA, 1998a, b; OEHHA, 2011; ATSDR, 2012). Higher <strong>chromium</strong> concentrations were<br />

found in plants growing in soils with high <strong>chromium</strong> contents compared with plants growing in<br />

normal soils: however, as only a small fraction of <strong>chromium</strong> is translocated from soil to the epigeal<br />

parts of edible plants, bioaccumulation of <strong>chromium</strong> from soil to the aforesaid plant parts is unlikely.<br />

There is no indication of <strong>chromium</strong> biomagnification along the terrestrial <strong>food</strong> chain.<br />

1.2.2. Sources of <strong>food</strong> and <strong>drinking</strong> <strong>water</strong> contamination<br />

Chromium can enter the <strong>food</strong> chain via the different environmental compartments, either as a result of<br />

natural presence or emission from anthropogenic activities. Food preparation with stainless steel<br />

containers, processors and utensils could represent an additional source for the presence of <strong>chromium</strong><br />

in <strong>food</strong> (Stoewsand et al., 1979; Offenbacher and Pi-Sunyer, 1983; Kumpulainen, 1992).<br />

Environmental levels<br />

According to studies from the late 1970s onwards (WHO, 2000, 2003), air <strong>chromium</strong> concentrations<br />

in the range of 0.005-1.1 ng/m 3 were detected in various remote locations such as the Arctic and<br />

Antarctic poles, north Atlantic ocean, Shetland Islands, Norway, and northwest Canada; in remote<br />

European areas, concentrations up to 3 ng/m 3 were measured. Health Canada (1986) reported<br />

<strong>chromium</strong> concentrations in air samples from five remote areas in Canada between 0.32 and 25 ng/m 3 ,<br />

while in the USA <strong>chromium</strong> concentrations in urban air were reported from less than 10 to 50 ng/m 3 .<br />

Most environment monitoring stations in the USA detected average <strong>chromium</strong> levels in ambient air of<br />

rural and urban areas below 300 ng/m 3 (median, < 20 ng/m 3 ), although occasional measurements could<br />

be higher (WHO, 2000, 2003). The mean concentration of <strong>chromium</strong> in air in the Netherlands<br />

appeared to vary in the range of 2 to 5 ng/m 3 ; in continental Europe, air <strong>chromium</strong> concentrations were<br />

found to span 1-140 ng/m 3 , a range comprising urban area values (4-70 ng/m 3 ). In industrial European<br />

settings, air <strong>chromium</strong> concentrations were in the range 5-200 ng/m 3 . The air <strong>chromium</strong> levels in<br />

Japan and Hawaii were found to be in the range 20-70 ng/m 3 (WHO, 2000). In general, in nonindustrialized<br />

areas concentrations above 10 ng/m 3 were uncommon whereas in urban areas they were<br />

two to four times higher than regional background concentrations (WHO, 2003; OEHHA, 2011). As a<br />

result of smoking, <strong>chromium</strong> concentrations in indoor air (≈ 1000 ng/m 3 ) may be 10-400 times greater<br />

than outdoor concentrations (WHO, 2003). Chromium concentrations in rain<strong>water</strong> showed a marked<br />

variability (for example, see: van Daalen, 1991; Neal et al., 1996; Kaya and Tuncel, 1997); however,<br />

on average they were found to be in the range 0.2-1 µg/L (WHO, 2003). Cr(VI) forms may be present<br />

in rain<strong>water</strong> (Seigneur and Constantinou, 1995): for instance, <strong>chromium</strong> species were determined in<br />

several rain<strong>water</strong> samples collected in North Carolina in 1999 through 2001 (Kieber et al., 2002). The<br />

EFSA Journal 2014;12(3):3595 17

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