S C I E N C E ’ S C O M PA S S gists and statisticians, as well as the goodwill of researchers who have invested many years of their careers in collecting detailed data. Our ability to make generalizations about population dynamics will facilitate conservation efforts, and so benefit future generations. References 1. 2. 3. 4. 5. 6. 7. 8. 9. G. M. Mace, R. Lande, Conserv. Biol. 5, 148 (1991). N. Owen-Smith, J. Anim. Ecol. 59, 893 (1990). T. Coulson et al., Science 292, 1528 (2001). B.-E. Sæther, S. Engen, E. Matthysen, Science 295, 2070 (2002). S. C. Stearns, The Evolution of Life Histories (Oxford Univ. Press, Oxford, 1992). B. E. Sæther et al., Proc. R. Soc. London Ser. B 267, 621 (2000). H. Leirs et al., Nature 389, 176 (1997). M. Lima, J. E. Keymer, F. M. Jaksic, Am. Nat. 153, 467 (1999). B. R. Grant, P. R. Grant, Proc. R. Soc. London Ser. B 251, 111 (1993). Downloaded from www.sciencemag.org on August 28, 2012 in short-lived bird Sæther et al. demonspecies the population strate that generalizadynamics are more tions might exist. The Image not strongly influenced by next step will be to atavailable for the recruitment of new tempt to confirm these individuals into the generalizations with online use. population, whereas in more data sets from a long-lived birds the wider range of populadynamics are more tions and species. strongly influenced by the survival rates of Sæther et al. show that there are prethe adults that are already present in the dictable differences between the populapopulation. Understanding the association tion dynamics of species with different life between population dynamics and birth, histories. They present a benchmark study death, and dispersal rates requires that de- in the relatively new field of comparative tailed data be collected from marked indi- population dynamics. However, the enorviduals. This knowledge is crucial for mous potential of this field can only be rewildlife managers, as it identifies the key alized if data sets of sufficient length and demographic rate that should be targeted to quality continue to be collected and anareverse population declines or to prevent lyzed. Achieving this goal will require inpopulation eruptions. The f indings of ternational collaboration between ecoloP E R S P E C T I V E S : E N V I R O N M E N TA L C H E M I S T R Y Tracking Hexavalent Cr in Groundwater David Blowes hroughout the world, groundwater is used extensively as a source of drinking water. In the United States, 56% of the population rely on groundwater for their drinking water (1). Much of the groundwater extracted in North America and elsewhere is supplied by shallow aquifers, which are susceptible to the release of contaminants from industrial, agricultural, and domestic activities. A common groundwater contaminant is chromium, which is widely used for electroplating, leather tanning, and corrosion protection (2). Chromium is the second most abundant inorganic groundwater contaminant at hazardous waste sites (3). On page 2060 of this issue, Ellis et al. present a technique for determining the abundance ratio of stable chromium isotopes and apply it to samples from chromium-contaminated sites (4). The technique provides an important tool for assessing the migration of chromium from contaminant sources and evaluating the effectiveness of chromium removal systems. The oxidized, hexavalent state of Cr, Cr(VI), forms chromate (CrO 4 2– ) or bichromate (HCrO4–). Chromate-containing minerals are very soluble and, because the chromate ion has a negative charge, chromate adsorption on aquifer minerals is T The author is in the Department of Earth Sciences, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada. E-mail: [email protected] 2024 limited (2). As a result, chromate may be present at concentrations well above water quality guidelines and may move with the flowing groundwater in aquifers. In contrast, the reduced state, Cr(III), forms insoluble precipitates under slightly acidic and neutral conditions, limiting Cr(III) to very low concentrations in most aquifers (2). The reduction of Cr(VI) to Cr(III) thus limits both the concentration and mobility of dissolved chromium. This difference is very important because chromate is toxic and carcinogenic (5–7), whereas Cr(III) is a nutrient at trace levels. Variations in the isotopic ratios of light elements are sensitive indicators of chemical processes that occur in natural systems. For example, the 34S/32S ratio in dissolved sulfate increases when bacteria reduce sulfate to sulfide. Ellis et al. (4) now show that the 53Cr/52Cr ratio also changes during reduction of Cr(VI) to Cr(III). They show that abiotic reduction of Cr(VI) resulting from reaction with the mineral magnetite, estuarine sediments, and freshwater sediments leads to a consistent 53Cr/52Cr shift. This observation indicates that 53Cr/52Cr ratios increase systematically with progressive Cr(VI) reduction in groundwater. The conventional approach to groundwater remediation is to install a series of pumping wells, extract the water from the aquifer, and treat it with techniques previously developed for surface waters. A series of studies in the late 1980s and early 15 MARCH 2002 VOL 295 SCIENCE A B C D Groundwater remediation strategies. (A) No attenuation. (B) Contaminant removal by natural attenuation processes. (C) Contaminant removal using a permeable reactive barrier. (D) Injection of a reductant to attenuate the contaminant. www.sciencemag.org CREDIT: (TOP) MARK CHAPPELL/ANIMALS ANIMALS/EARTH SCENES 65 64 63 62 61 60 59 58 57 56 55 54 53 52 51 50 49 48 47 46 45 44 43 42 41 40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 S C I E N C E ’ S C O M PA S S 1990s indicated, however, that able reactive barriers. A strong 10,000,000 this “pump-and-treat” approach reductant such as sodium 9,000,000 was expensive and in many cases dithionate can be injected di8,000,000 ineffective (8). There are three rectly into the plume of contamPump and treat 7,000,000 reasons for this. First, the system inated water (see the first fig6,000,000 extracts and treats clean water ure) to promote the reduction of 5,000,000 along with the contaminated wachromate and precipitation of ter. Second, full remediation typchromium hydroxide. Sodium 4,000,000 ically takes longer than predicted dithionate solutions also can be 3,000,000 because contaminants are often injected into the path of a chro2,000,000 Permeable reactive barrier (10 year cycle) retained in fine-grained zones. mate-containing plume to re1,000,000 Third, contaminants that were duce natural ferric iron-bearing Natural attenuation 0 previously precipitated or adminerals, generating a reservoir 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 sorbed to mineral surfaces reof ferrous iron-bearing minerals Time (years) lease slowly. (15). These minerals then reSince the late 1980s, research The costs of different groundwater remediation strategies. Natural duce the chromate as it migrates has focused on how to overcome attenuation, a permeable reactive barrier, and a pump-and-treat sys- through the aquifer. the limitations of the convention- tem are considered (14). This comparison focuses on a halogenated hyThe new finding that 53Cr/52Cr al pump-and-treat approach. One drocarbon plume, but the material used in the reactive barrier was ze- ratios reveal the extent of abiotic possibility is to use the natural ro-valent iron, the same material used to treat hexavalent chromium. reduction suggests that 53Cr/52Cr measurements can assist in the ability of aquifers to attenuate The costs are therefore probably similar for a chromate plume. evaluation of the effectiveness of contaminants without intervention (9). This research has resulted in the curred, and there is thus no need to see all these approaches to chromate reduction development and approval of “monitored whether Cr(VI) mass decreases over time. in groundwater. natural attenuation” remedies for contami- (ii) The measurement of reduction inteReferences and Notes nated groundwater. An alternative ap- grates spatially over a flow path, whereas 1. F. van der Leeden, F. L. Troise, D. K. Todd, The Water proach focuses on the development of in analyses of aquifer solids give information Encyclopedia (Lewis, Chelsea, MI, 1990). situ treatment systems that clean the con- on a much smaller spatial scale. 2. C. D. Palmer, P. R. Wittbrodt, Environ. Health Perspect. 53Cr/52Cr measurements can also help 92, 25 (1991). taminated groundwater within the aquifer 3. National Academy of Sciences Committee on to evaluate in situ approaches, which have (10, 11). Ground Water Cleanup Alternatives, Alternatives for Ground Water Cleanup (National Academy Press, Chromate is attenuated naturally be- been developed for sites where natural atWashington, DC, 1994). cause minerals containing reduced forms tenuation is insufficient to prevent chro4. A. S. Ellis, T. M. Johnson, T. D. Bullen, Science 295, of iron and sulfur are abundant in many mate migration. In situ approaches include 2060 (2002). 5. E. Nieboer, S. L. Shaw, in Chromium in the Natural aquifers. These minerals reduce hexavalent permeable reactive barriers, injection of and Human Environments, vol. 20 of Advances in Enchromium to trivalent chromium and pro- chemical reactants to reduce chromate, vironmental Science and Technology, J. O. Nriagu, E. mote the precipitation of insoluble solids and injection of a reductant to react with Nieboer, Eds. (Wiley, New York, 1988), pp. 399–442. 6. A. Yassi, E. Nieboer, in Chromium in the Natural and such as chromium hydroxide (9). Organic the aquifer materials to form reduced minHuman Environments, vol. 20 of Advances in Envicarbon-rich materials, such as wetland erals in the aquifer. ronmental Science and Technology, J. O. Nriagu, E. Nieboer, Eds. (Wiley, New York, 1988), pp. 443–496. Permeable reactive barriers are consediments and peat, can also reduce hex7. E. Nieboer, A. A. Jusys, in Chromium in the Natural avalent chromium. In aquifers where these structed by excavating a portion of the and Human Environments, vol. 20 of Advances in Enreduced sediments are abundant and the aquifer. The aquifer material is replaced vironmental Science and Technology, J. O. Nriagu, E. Nieboer, Eds. (Wiley, New York, 1988), pp. 21–80. concentrations of hexavalent chromium with a permeable mixture designed to re8. D. M. Mackay, J. A. Cherry, Environ. Sci. Technol. 23, are low, the attenuation capacity of the act with the contaminant (12). For inor630 (1989). aquifer may be suff icient to prevent ganic contaminants such as chromium, the 9. C. D. Palmer, R. W. Puls, Natural Attenuation of Hexavalent Chromium in Ground Water and Soils, U.S. reactive material is selected to retain the chromium migration (see the first figure). EPA Ground Water Issue Paper, EPA/540/S-94/505 The appropriateness of monitored natu- contaminant within the barrier (10). Per(U.S. EPA, Office of Research and Development, Washington, October 1994). ral attenuation depends on the groundwa- meable reactive barriers containing zeroW. Blowes et al ., J. Contam. Hydrol. 45, 121 ter flow system, the rate of chromium mi- valent iron (iron filings) have been used to 10. D. (2000). gration, and the ability of the aquifer ma- treat hexavalent chromium (10, 13). 11. G. Hocking, S. L. Wells, R. I. Ospina, in Chemical Oxidation and Reactive Barriers: Remediation of ChloriLandis (14) has compared the costs asterials to reduce chromate. It can be diffinated and Recalcitrant Compounds, G. B. Wickracult, however, to distinguish measured sociated with three groundwater remediamanyake, A. R. Gavaskar, A. S. C. Chen, Eds. (Battelle, Columbus, OH, 2000), pp. 307–314. chromate decreases caused by attenuation tion options for a 400-feet wide and 80permeable reactive barriers are installed in reactions from those caused by mixing or foot deep contaminant plume: pump-and- 12. Typically trenches, but barriers also have been constructed by dispersion in the aquifer. At some sites, it treat, managed natural attenuation, and the jetting reactive materials into the ground, or by generating fractures within the aquifer and filling the is therefore useful to test samples of use of a permeable reactive barrier (see the fracture with reactive materials (11). aquifer materials for the products of chro- second figure). The comparison suggests 13. D. W. Blowes et al., An in situ permeable reactive barthat monitored natural attenuation is least mate reduction. rier for the treatment of hexavalent chromium and trichloroethylene in groundwater. Volume 2, PerforThe measurement of chromium isotope expensive, followed by permeable reactive mance Monitoring, U.S. EPA Report EPA/600/rratios provides a new tool for evaluating barrier systems, particularly if the reactive 99/095b (U.S. EPA, Office of Research and Development, Washington, September 1999). the extent of chromate natural attenuation barrier is augmented by natural attenuaR. Landis, Section 11 in In Situ Permeable Reactive and estimating the rate of chromium atten- tion. The pump-and-treat system is much 14. Barriers: Application and Deployment, U.S. EPA uation. Relative to conventional methods, more expensive. Training Manual EPA/542/B-00/001 (U.S. EPA, Solid 53Cr/52Cr Waste Management and Emergency Response, WashInjection of solutions containing it has two advantages: (i) Each January 2000). determination provides a measure of the strong reductants into aquifers provides 15. ington, J. S. Fruchter et al., Ground Water Monit. Remed. Spring (no. 2), 66 (2000). amount of reduction that has already oc- in situ treatment alternatives to permewww.sciencemag.org SCIENCE VOL 295 15 MARCH 2002 Downloaded from www.sciencemag.org on August 28, 2012 Cumulative net present cost ($) CREDIT: ADAPTED FROM (14) 65 64 63 62 61 60 59 58 57 56 55 54 53 52 51 50 49 48 47 46 45 44 43 42 41 40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 2025
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