Article pubs.acs.org/est
Contamination History of Lead and Other Trace Metals Reconstructed from an Urban Winter Pond in the Eastern Mediterranean Coast (Israel) I. Zohar,*,†,‡ R. Bookman,† N. Levin,§ H. de Stigter,∥ and N. Teutsch‡ †
Department of Marine Geosciences, University of Haifa, Haifa 31905, Israel Geological Survey of Israel, Jerusalem 95501, Israel § Department of Geography, Hebrew University of Jerusalem, Jerusalem 91905, Israel ∥ Royal Netherlands Institute for Sea Research (NIOZ), NL-1790 AB Den Burg, Texel, Netherlands ‡
S Supporting Information *
ABSTRACT: Pollution history of Pb and other trace metals was reconstructed for the first time for the Eastern Mediterranean, from a small urban winter pond (Dora, Netanya), located at the densely populated coastal plain of Israel. An integrated approach including geochemical, sedimentological, and historical analyses was employed to study sediments from the center of the pond. Profiles of metal concentrations (Pb, Zn, V, Ni, Cu, Cr, Co, Cd, and Hg) and Pb isotopic composition denote two main eras of pre- and post-19th century. The deeper sediment is characterized by low concentrations and relatively constant 206Pb/207Pb (around 1.20), similar to natural Pb sources, with slight indications of ancient anthropogenic activity. The upper sediment displays an upward increase in trace metal concentrations, with the highest enrichment factor for Pb (18.4). Lead fluxes and isotopic composition point to national/regional petrol-Pb emissions as the major contributor to Pb contamination, overwhelming other potential local and transboundary sources. Traffic-related metals are correlated with Pb, emphasizing the polluting inputs of traffic. The Hg profile, however, implies global pollution rather than local sources.
■
INTRODUCTION Since the start of the Industrial Revolution, levels of lead (Pb) and other trace metals have increased dramatically in atmospheric, terrestrial, and aquatic environments.1 The introduction of petrol additives (alkyl-Pb compounds) in the 1920s, immensely increased Pb emissions on a global scale.2 The presence of other trace metals may also be traffic-related3 or originate from other anthropogenic activities.1,4 Regional atmospheric pollution of trace metals can be recorded in aquatic sediments, which may serve as excellent archives,5 provided that no diagenetic processes (e.g., following reducing conditions) leading to metal mobility have taken place. A short residence time in the watershed and in the water and strong sequestration by the sediment constituents [e.g., fine grains and organic matter (OM)] may ensure that the sedimentary record is synchronized with the atmospheric contaminant content.6,7 Wetlands and swamps were very abundant in the Mediterranean semi-arid Israeli coastal plain (about 550 mm year−1) prior to the major demographic changes in the late-19th century. The wetlands were extensively drained by the mid20th century to increase urban, agricultural, and industrial land resources8 in the area, now the most populated in Israel, encompassing 34.7% of the Israel population [Central Bureau of Statistics (CBS)]. However, the residual wetlands may serve © 2014 American Chemical Society
as archives for anthropogenic activity, introducing trace metals along the regional history, since ancient times (e.g., Byzantine and Islamic eras), until the modern era of drastic population and Industrial growth. Among all trace metals, Pb has the highest fraction of anthropogenic components,9,10 mostly contributed by leaded petrol11 (consistent with other countries).12 Petrol consumption in Israel increased from less than 0.5 million tons in 1970 to over 2.6 million tons in 2010.13 Unleaded petrol was introduced in Israel in 1991 and gradually became more dominant (ca. 50% in 1997) until the absolute phase out of leaded petrol in 2010.13 Lead isotopic composition was previously employed to investigate Pb in the Israeli environment, including in aerosols (local and transboundary contributions),11,14−16 natural and contaminated soils,17 and aquatic sediments.18,19 Geochronology of metal contamination can be achieved by combining Pb isotopic composition and other trace metal data with 210Pb dating of sediment profiles (e.g., refs 5 and 20). In Israel, such Received: Revised: Accepted: Published: 13592
February 5, 2014 September 9, 2014 October 16, 2014 October 16, 2014 dx.doi.org/10.1021/es500530x | Environ. Sci. Technol. 2014, 48, 13592−13600
Environmental Science & Technology
Article
Figure 1. Dora winter pond in (A) map of Israel, showing night lights (as of January 2013) acquired by Visible Infrared Imaging Radiometer Suite (VIIRS) sensor on-board the Suomi National Polar-orbiting Partnership (NPP) sensor, (B) 2013 aerial photo with location of the sediment core collection, (C) aerial photo from 2009 with marking of the built area based on data from 2003, and (D) map from 1880. The watershed of the Dora pond is marked in red in all panels.
and dilute acid leachates (leach) of trace and major metals were determined as well as Pb isotopic composition of the leach fraction. The particle size and OM content were analyzed, and the profile dating was determined by 210Pb activity decay. The deepest part of an additional core retrieved from the Dora center on another occasion verified the metal background levels.
an approach has been applied previously for deciphering Pb sources in the watershed of the Sea of Galilee.18 In the current study, we attempt to reconstruct a broad-region metal pollution history using sediment from a residual wetland (Dora pond, Netanya, Israel) in the coastal plain. The Dora winter pond has an area of ca. 0.055 km2, while its watershed area is 1.5 km2 (Figure 1). The regional prevailing wind direction is southwest. Eucalyptus trees at its perimeter are already observed in a 1929 map.8 Winter flooding with a typical water depth of 30−80 cm allows growth of wetland vegetation, which wilts by late summer. In late summer 2008, a wildfire occurred in all of the area of the dry pond. While the Dora pond was kept roughly the same state at least since 1880,8 land uses have changed dramatically in its surrounding area over the years (Figure 1). The immediate surrounding (a recreational park) is drained by runoff waters entering from its northern margin. Since 2010, drainage water has entered the pond also from the eastern part of the watershed, including from a built area, following changes in management policy (A. Avisar, personal communication). The very small watershed and its apparent undisturbed area make Dora pond a potential archive for atmospheric pollution fluxes. The geochemical, sedimentary, and geographical data from the pond were integrated with the historical data of the region to reveal the impact of regional−global dispersal of pollutants on the Eastern Mediterranean basin, for the first time.
■
RESULTS Sedimentological and Mineralogical Characterizations. The texture of the core is relatively homogeneous, consisting of fine grains with over 99% Cr > V > Ni > Cu (see Table S5 of the Supporting Information), demonstrating the relative anthropogenic effect for each metal. The Pb L/T from a depth of 4.5 cm increased 5 times the background value (0.11; depth of 40.5 cm), being the highest raise among all studied metals (see Table S2 of the Supporting Information). Fluxes of Pb and Other Metals. Sedimentation rates can affect the metal concentration by dilution with increased deposition or metal enrichment in periods of reduced sedimentation. Therefore, regional exposure to metals is better assessed by their fluxes into the sediment rather than concentrations alone. Fluxes for depths of 0−12 cm were calculated by multiplying the leach concentrations with sediment accumulation rates, determined from the 210Pb dating (Figure 4).
Figure 5. 208Pb/206Pb versus 206Pb/207Pb plot of Dora samples and potential end members. Superscript numbers represent references for the feasible sources. Cairo represents the North African−Arabian source. Further details can be found in Tables S3 and S4 of the Supporting Information.
uncontaminated Israeli soils,11,17 Saharan dust,15 aerosols from Cairo15 and eastern Europe,16 and the petrol used in Israel: pre1992 (American) petrol and post-1992 (European) petrol.11 Contamination sources may be elucidated by plotting the isotopic signatures of the sources and the in situ samples together.7,26 In a 208Pb/206Pb versus 206Pb/207Pb plot (Figure 5), Dora samples are generally aligned on two mixing lines according to their depth: the lower part of the profile corresponds to natural Pb sources, while samples from the upper part of the profile (0−12 cm) plot on a petrol source line. The close association between the sample chronology and the isotopic shift between pre- and post-1992 Pb indicates petrol Pb as the predominating polluting source to the upper sediment in Dora, consistent with other studies in Israel.17−19 The slight offset of the sediment Pb isotopic values from the petrol line, however, implies inputs from other potential end members, in particular, polluting aerosols and the natural soil Pb (recycled through plant−sediment processes).27 Coal combustion is a potential polluting source of Pb to the atmosphere.7,28,29 A power plant using coal (containing ca. 11 mg of Pb kg−1)30 is located 20 km north of the pond. Coal combustion began in this plant only in 1980, significantly
Figure 4. Metal fluxes in Dora pond. Metal fluxes were determined for the time span of calculated 210Pb age.
At the late 19th century, the Dora Pb flux starts to increase from a relatively low level ( 0.85; see Table S8 of the Supporting Information) of Pb with Cd, V, Zn, Ni, Cr, and Co (by order of decreasing correlation with Pb). Mercury and Cu are highly associated with each other but not with the other metals. When only the time interval of leaded petrol usage in Israel is inspected (encompassing the sediment layers of 2−9 cm, dated to 1924−1996), an even better correlation of Pb with most metals is observed, especially with Cd and Zn (see Table S8 of the Supporting Information). Lead and Cd have the highest correlation coefficients (R2 of 0.93 and 0.99 in the two time spans, respectively; see Table S8 of the Supporting Information) reflected in their very similar concentration profiles (see Figure S2 of the Supporting Information), including the ca. 40% decline toward the sediment surface. Similarly, Pb and Cd coupling is reported in mosses across Europe,36 where Cd major contributors were identified as waste incineration (in 1990) and metal production (2003), exceeding oil combustion input. Because atmospheric Cd may originate from multiple sources,36 the exact sources of Cd to the studied pond are not yet fully identified. High correlation of Zn (attributed mainly to tire wear)37,38 with Pb during 1924−1996 (R2 = 0.99) manifests the growth in vehicle use in Israel. After the mid-1990s, Pb fluxes showed a decline following the phasing out of leaded petrol, while Zn and other vehicle-related metal fluxes increase continuously with vehicle usage. This is expressed in lower correlations in the broader
Figure 6. Lead indices: Dora Pb flux, national petrol Pb, and Highway 2 petrol Pb. Indices are calculated from data in Tables S6 and S7 of the Supporting Information, and their formulation is explained in the Supporting Information. The national petrol Pb and Highway 2 petrol Pb are presented as a percentage of the lowest value, attained in 2011. Lead flux is multiplied by 15 to be shown on the same scale. The Highway 2 index is discontinued because of the lack of complete road count data. The emphasized area shows increasing trends in the Pb flux index and the national petrol-Pb index, starting as early as 1970 (beginning of the national petrol consumption record), while the increase in the trend of Highway 2 starts only during the 1980s. This points to the importance of the national source rather than the local source.
described here). The national index is based on the yearly national leaded and unleaded petrol consumption and the allowed Pb content (see Table S6 of the Supporting Information). The Highway 2 index is based on the yearly mean traffic density of the adjacent Highway 2 (1.2 km distant; Figure 1C) and the national trends in leaded and unleaded petrol usage (see Table S7 of the Supporting Information). The lead flux index correlates strongly with both the national and Highway 2 indices (R2 of 0.932 and 0.925, respectively). However, only the national and flux indexes share similar smaller scale variability (Figure 6); both simultaneously increase since 1970 (first traffic record) and peak in the late 1980s, whereas the Highway 2 index starts to increase only in the 1980s. Although Highway 2 was first opened in the mid1960s and since the mid-1980s has had a high traffic density 13596
dx.doi.org/10.1021/es500530x | Environ. Sci. Technol. 2014, 48, 13592−13600
Environmental Science & Technology
Article
time span. In the 1970s, the fluxes of most trace metals (excluding Pb and Cd) peaked, suggesting a temporal impact of another non-traffic source, possibly augmented construction activity in the watershed of the pond during this time span. Coal combustion is a known source of the trace metals Zn, V, Cu, Cr, Ni, Pb, Co, Cd, and Hg (by order of decreasing average concentrations in the range of 53−0.2 μg g−1).30 However, as discussed above for Pb, coal usage record in Israel13 does not fit any of these trace metal profiles, including Hg, which is often attributed to coal combustion emissions.39,40 Mercury, a very toxic metal,41 was enriched in the region in the modern era, according to the Dora sedimentary record (see Tables S2 and S5 of the Supporting Information), including a substantial increase in Hg flux since the 1960s, peaking in the 1970s, strongly declining from the 1980s to the 1990s, and present incline (Figure 4). Mercury has an atmospheric lifetime of ca. 1 year, allowing for its transportation on a global scale.6 The global emissions of Hg peaked in the 1970s,42 as observed in sediments worldwide.25,43,44 Specifically, the Hg general flux profile resembles trends of Hg emissions in eastern Europe, Africa, and the Middle East,42,45 which are potential source areas of transboundary aerosols to the coastal plain.15,16,34 The recent increase in Hg flux in the sediment (2005−2011) might correspond to the significant increase in coal combustion in Asia.42 Copper smelting (e.g., in eastern Europe),42 is another potential source to Hg emissions42 and possibly explains their close association in the sediment, considering that Cu is also a global pollutant.46 To conclude, Hg in the Dora sediment appears to be mostly derived from global sources rather than the local sources, including the coal power plant (the temporal source impacting most other trace metals may have also contributed to the Hg peak in the 1970s, although low association to the other metals). In the 1970s, electricity generation in Israeli power plants relied almost exclusively on the use of heavy fuel oil (“Mazut”), which gradually declined to ca. 5% in the late 2000s.13 Mazut combustion may have introduced trace metals, such as Zn, Ni, V, and Co (IEC, A. Mezger, personal communication), and therefore, possibly contributed to their inventory in the Dora sediment. Reconstructing the Pollution History of Pb and Other Metals. The pollution chronology of Pb and other trace metals is presented by emphasis on principle temporal periods from antiquity until present (numbers in parentheses correspond to Figure 3): Ancient Era. (1 in Figure 3; ending in Palestine at the early 19th century) The ancient era is characterized by fairly constant Pb concentrations and isotopic compositions, following a slight increase from background levels. The concentrations of other trace metals also increased from background levels (see Figure S2 of the Supporting Information). The sedimentary record may imply on continuous settlement in the coastal region, consistent with archeological observations.47 Anthropogenic activities in the ancient era, such as manufacturing and usage of ceramic Pb glazeware in important cities in Palestine48 during the Islamic period,49,50 might have left their mark on the sediment lower profile. Early to Mid-19th Century. (2 in Figure 3) The early to mid-19th century represents a transitional period between the pre- and post-industrial eras. The drastic shift of Pb isotopic composition into anthropogenic values (Figure 3B) seems to precede the introduction of petrol-Pb additive in the 1920s2 and might be explained by (a) input of European-polluted
aerosols,15,16,34 possibly marking the onset of the Industrial Revolution in Europe in the Dora sediment, and (b) imprint of early demographic changes in Palestine,51 including coalburning steamships, reported harboring in Jaffa Port since the mid-19th century.52 Similar Pb isotopic trends in the U.K. were explained by coal combustion and other industrial activities, before the turn of the 20th century.53 Cobalt and Ni appear to peak at this period, possibly expressing global emissions; however, there is not enough information to determine this. The Late 19th Century. (3 in Figure 3) Since the late 19th century, new trends of Pb and other trace metal (V, Zn, Hg, Cu, and Cd) concentrations and fluxes and Pb isotopic composition are perceived (Figures 3 and 4 and Figure S3 of the Supporting Information). This time corresponds to the commencement of Jewish immigration from Europe to Palestine. Along the coastal plain, population growth was accompanied by intensification and change in land use and enhanced industrialization,51 likely marking the beginning of the anthropogenic metal pollution era in Palestine, preceding the petrol-Pb additive usage. The 1920s−1930s. (4 in Figure 3) In the 1920s−1930s, the sediment was first exposed to petrol-Pb additive along with its global introduction,2 while the population of Palestine increased significantly since the 1930s (see Figure S3 of the Supporting Information). The combined effect of these two factors has probably contributed to an increase in Pb fluxes, since the late 1930s (7−8 cm; Figure 4). The increased fluxes of other metals (Zn and V; Figure 4) are probably also related to the population growth at that time. Interestingly, the introduction of petrol-Pb additive is not marked in the Pb isotopic profile (Figure 3B). The 1970s. (5 in Figure 3) In the 1970s, maximum sediment accumulation rate (Figure S1 of the Supporting Information) was attained, while fluxes of several trace metals (e.g., Zn, V, and Cu; Figure 4) also reached peak values and a slight change in Pb isotopic trend was observed (Figure 3B). These features may suggest temporary input from another contamination source than petrol Pb, possibly construction activity in the Dora watershed at this time frame, adding up to high pollution levels in Israel54 and on a global scale.1 Mercury flux peaks in the 1960s−1970s, coinciding with global trends of Hg emission,42 thus possibly manifesting transboundary pollution. The Late 1980s−Early 1990s. (6 in Figure 3) In the late 1980s−early 1990s, maximum petrol-Pb emissions in Israel are manifested in the Dora sediment (2−3 cm; 1987−1996) in the highest fluxes of Israeli petrol Pb compared to other layers (Figure 6), the highest leach and total Pb concentrations (Figure 3A), and the highest peak ratio (see Table S5 of the Supporting Information). The L/T Pb ratio was 0.42, growing 4-fold from the bottom. A slight shift of Pb isotopic composition (Figures 3B and 5) indicates the highest contribution of post-1992 petrol Pb. Recent Decades. (7 in Figure 3) In recent decades, lower levels of Pb concentrations and fluxes are recorded in the sediment (Figure 4 and Figure S2 of the Supporting Information), probably reflecting the phasing out of leaded petrol in Israel since the early 1990s,13 also documented previously.17,18 The declining trend of Pb is in accordance with other parts of the world, where leaded petrol was phased out several decades ago.1 Nonetheless, the data imply that polluting petrol Pb lingers in the Israeli environment, as observed recently for the Israeli coastal environment.19 This prolonged Pb occurrence is probably the result of resuspension of past 13597
dx.doi.org/10.1021/es500530x | Environ. Sci. Technol. 2014, 48, 13592−13600
Environmental Science & Technology
Article
AD), following the Pb pollution peak, representing the culmination of the Greek−Roman industry (about 0 AD). (2) While the Industrial Revolution has triggered widespread exposure to Pb and other trace metals in Europe at the mid19th century, this was postponed in Palestine to the late 19th century, when major immigration initiated industrialization. (3) The peak in Pb emissions in the coastal plain lagged approximately 1 decade after Europe, where it is usually found in 1960−1980, because of phasing out of leaded petrol in Israel only since the 1990s. Earlier reduction of Pb usage could have prevented the major part of the exposure to Pb, because traffic density has made a pronounced growth since the 1980s (see Tables S6 and S7 of the Supporting Information). In this study, we combined Pb and other metal concentrations and Pb isotopic composition with sedimentological, geochronological, historical, and geographical tools to identify contamination sources and reconstruct the pollution history in the Israeli coastal plain. The regional trace metal data set, presented in the current study, emphasizes the metals with the present environmental significance. Further isotopic research of the enriched trace metals (e.g., Zn and Hg) may facilitate source identification and restriction of environmental exposure.
inputs, industrial activity, and present traffic-related pollution. The continuous increase in traffic-related pollution (as inferred from the continuous increase in petrol consumption; Table S6 of the Supporting Information) is likely a major contributor to a significant rise in Zn fluxes (Figure 4). The apparent strong decline in Hg flux around the early 2000s might be the result of a wildfire in the pond in 2008 (S. Gafni, personal communication), possibly releasing Hg to the atmosphere, including Hg present at a few millimeters below the surface.55,56 If indeed this was the case, then the recent increase in Hg flux may have been even stronger than represented by the sediment, reflecting a bigger impact of potential sources, such as the Asian emissions.42 A further study (e.g., isotopic composition) of Hg in the Dora sediment may shed light on its sources and postdepositional behavior. The new management practices at Dora pond since 2010 included entry of urban runoff to the north of the pond (A. Avisar, personal communication), which may have contributed to the recent enhanced trace metal fluxes (Figure 4). As discussed earlier, impact on older sediment is not expected in the absence of signs for sediment interference, including desiccation cracks below the wilted coverage. The modern and ancient eras (post- and pre-19th century, respectively) and the intermediate mid-19th century period are clearly distinguished in a 206Pb/207Pb versus 1/Pb plot (Figure 7). Furthermore, this type of plot may reveal end members.
■
ASSOCIATED CONTENT
* Supporting Information S
Further information, including sediment sample collection, processing, and analyses, sedimentary characteristics, major chemical composition and trace metal concentrations in the sediment, Pb isotopic ratios of the sediment sub-samples and those of feasible end members, Pb index formulation procedure, correlation coefficients of trace metal in the sediment, and sediment accumulation rate. This material is available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Telephone: 972-4-8288792. Fax: 972-4-8288267. E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
■
Figure 7. 206Pb/207Pb versus 1/leach Pb and 1/leach normalized Pb (normalization to total percent TiO2). The data are plotted by chronological groups (asterisk represents extrapolated age). EFs of normalized leach Pb of each time period were calculated relative to the background level.
ACKNOWLEDGMENTS The authors thank the Ministry of National Infrastructure, Energy and Water Resources for funding the research. The authors thank the Geological Survey of Israel staff, S. Ashkenazi, M. Kitin, H. Lutzkyl, and Y. Mizrahi, for help in the field work and N. Toplyakov and O. Yoffe for laboratory assistance. The authors thank Wim Boer and Piet van Gaever from the Royal Netherlands Institute for Sea Research (NIOZ) for running the 210 Pb activity measurements and assisting in interpretation and Dr. Nimer Taha from the Sedimentology Laboratory, University of Haifa. The authors thank Y. Harlavan for useful comments and S. Gafni, A. Avisar, and A. Mezger for helpful information. The authors thank the Geographic Information Systems (GIS) Center of the Hebrew University of Jerusalem for providing us access to GIS layers and orthophotos from the survey of Israel. The authors thank three anonymous reviewers and the editor Prof. Xiang-dong Li for providing valuable comments, which greatly improved the manuscript.
Interestingly, the ancient era appears to encompass an anthropogenic imprint, distinct from the background level, which, together with the petrol-Pb end member, forms a triangle diagram (rather than the expected mixing line between two end members). The Pb pollution history reconstructed from the Dora sediment is generally in agreement with similar trends found in other parts of the industrialized world (e.g., refs 5 and 57−59), but local history differs in three aspects. (1) Most of the ancient period in the Dora sediment is characterized by constant values (after the slight increase from the bottom), probably manifesting the prolonged human activity in the region, whereas European profiles show a declining trend (400−900 13598
dx.doi.org/10.1021/es500530x | Environ. Sci. Technol. 2014, 48, 13592−13600
Environmental Science & Technology
■
Article
(23) Walraven, N.; van Os, B. J. H.; Klaver, G. Th.; Middleburg, J. J.; Davis, G. R. Reconstruction of historical atmospheric Pb using Dutch urban lake sediments: A Pb isotope study. Sci,. Total Environ. 2014, 484, 185−195. (24) Pienitz, R.; Roberge, K.; Vincent, W. F. Three hundred years of human-induced change in an urban lake: Paleolimnological analysis of Lac Saint-Augustin, Québec City, Canada. Can. J. Bot. 2006, 84 (2), 303−320. (25) Bookman, R.; Driscoll, C. T.; Effler, S. W.; Engstrom, D. R. Anthropogenic impacts recorded in recent sediments from Otisco Lake, New York, USA. J. Paleolimnol. 2010, 43, 449−462. (26) Cheng, H.; Hu, Y. Lead (Pb) isotopic fingerprinting and its applications in lead pollution studies in China: A review. Environ. Pollut. 2010, 158, 1134−1146. (27) Weis, J. S.; Weis, P. Metal uptake, transport and release by wetland plants: Implications for phytoremediation and restoration. Environ. Int. 2004, 30, 685−700. (28) Díaz-Somoano, M.; Kylander, M. E.; López-Antón, M. A.; Suárez-Ruiz, I.; Martínez-Tarazona, M. R.; Ferrat, M.; Kober, B.; Weiss, D. J. Stable lead isotope compositions in selected coals from around the world and implications for present day aerosol source tracing. Environ. Sci. Technol. 2009, 43, 1078−1085. (29) Komárek, M.; Ettler, V.; Chrastný, V.; Mihaljevic, M. Lead isotopes in environmental sciences: A review. Environ. Int. 2008, 34, 562−577. (30) National Coal Ash Board (NCAB). http://www.coal-ash.co.il/ english/env_heavy.html. (31) National Coal Ash Board (NCAB). http://www.coal-ash.co.il/ docs/EferDa1_PreambleLeafletMay2011.pdf (in Hebrew). (32) Jaffe, D.; McKendry, I.; Anderson, T.; Price, H. Six “new” episodes of trans-Pacific transport of air pollutants. Atmos. Environ. 2003, 37, 391−404. (33) Karner, A. A.; Eisinger, D. S.; Niemeier, D.A. Near-roadway air quality: Synthesizing the findings from real-world data. Environ. Sci. Technol. 2010, 44, 5334−5344. (34) Herut, B.; Nimmo, M.; Medway, A. Dry atmospheric inputs of trace metals at the Mediterranean coast of Israel (SE Mediterranean): Sources and fluxes. Atmos. Environ. 2001, 35, 803−813. (35) Lough, G. C.; Schauer, J. J.; Park, J. S.; Shafer, M. M.; Deminter, J. T.; Weinstein, J. P. Emissions of metals associated with motor vehicles roadways. Environ. Sci. Technol. 2005, 39, 826−836. (36) Harmens, H.; Norris, D. A.; Koerber, G. R.; Buse, A.; Steinnes, E.; Rühling, A. Temporal trends (1990−2000) in the concentration of cadmium, lead and mercury in mosses across Europe. Environ. Pollut. 2008, 151, 368−376. (37) Councell, T. B.; Duckenfield, K. U.; Landa, E. R.; Callender, E. Tire-wear particles as a source of zinc to the environment. Environ. Sci. Technol. 2004, 38, 4206−4214. (38) Thapalia, A.; Borrok, D. M.; Van Metre, P. C.; Musgrove, M.; Landa, E. R. Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake. Environ. Sci. Technol. 2010, 44, 1544−1550. (39) Pai, P.; Niemi, D.; Powers, B. A North American inventory of anthropogenic mercury emissions. Fuel Process. Technol. 2000, 65−66, 101−115. (40) Pacyna, E. G.; Pacyna, J. M.; Steenhuisen, F.; Wilson, S. Global anthropogenic mercury emission inventory for 2000. Atmos. Environ. 2006, 40, 4048−4063. (41) Pirrone, N.; Cinnirella, S.; Feng, X.; Finkelman, R. B.; Friedli, H. R.; Leaner, J.; Mason, R.; Mukherjee, A. B.; Stracher, G. B.; Streets, D. G. Global mercury emissions to the atmosphere from anthropogenic and natural sources. Atmos. Chem. Phys. 2010, 10, 5951−5964. (42) Streets, D. G.; Devane, M. K.; Lu, Z.; Bond, T. C.; Sunderland, E. M.; Jacob, D. J. All-time releases of mercury to the atmosphere from human activities. Environ. Sci. Technol. 2011, 45, 10485−10491. (43) Perry, E.; Norton, S. A.; Kamman, N. C.; Lorey, P. M.; Driscoll, C. T. Deconstruction of historic mercury accumulation in lake sediments, northeastern United States. Ecotoxicology 2005, 14, 85−99.
REFERENCES
(1) Nriagu, J. O. A history of global metal pollution. Science 1996, 272, 223−224. (2) Nriagu, J. O. Tales told in lead. Science 1998, 281, 1622−1623. (3) Ward, N. I. Multielement contamination of British motorway environments. Sci. Total Environ. 1990, 93, 393−401. (4) Center for Ecology and Hydrology (CEH). Heavy Metals in European Mosses: 2000/2001 Survey. UNECE ICP Vegetation Coordination Centre, CEH: Bangor, U.K., 2003. (5) Weiss, D.; Shotyk, W.; Appleby, P. G.; Kramers, J. D.; Cheburkin, A. K. Atmospheric Pb deposition since the Industrial Revolution recorded by five Swiss peat profiles: Enrichment factors, fluxes, isotopic composition, and sources. Environ. Sci. Technol. 1999, 33, 1340−1352. (6) Fitzgerald, W. F.; Engstrom, D. R.; Mason, R. P.; Nater, E. A. The case for atmospheric mercury contamination in remote areas. Environ. Sci. Technol. 1998, 32, 1−7. (7) Kober, B.; Wessels, M.; Bollhöfer, A.; Mangini, A. Pb isotopes in sediments of Lake Constance, Central Europe constrain the heavy metal pathways and the pollution history of the catchment, the lake and the regional atmosphere. Geochim. Cosmochim. Acta 1999, 63, 1293−1303. (8) Levin, N.; Elron, E.; Gasith, A. Decline of wetland ecosystems in the coastal plain of Israel during the 20th century: Implications for wetland conservation and management. Landsc. Urban Plan. 2009, 92, 220−232. (9) Shirav, M.; Ilani, S.; Halicz, L.; Yoffe, O. Identification of Trace Metal Pollution Foci in the Emek Zevulun Area Using Geochemical Techniques; Israel Geological Survey: Jerusalem, Israel, 2009. (10) Shirav, M.; Ilani, S.; Halicz, L.; Yoffe, O. Geochemistry of Sediment in Streams and Soils in the Western Galilee−Caramel; Israel Geological Survey: Jerusalem, Israel, 2009. (11) Erel, Y.; Veron, A.; Halicz, L. Tracing the transport of anthropogenic lead in the atmosphere and in soils using isotopic ratios. Geochim. Cosmochim. Acta 1997, 61, 4495−4505. (12) Rubio, B.; Nombela, M.; Vilas, F. Geochemistry of major and trace elements in sediments of the Ria de Vigo (NW Spain): An assessment of metal pollution. Mar. Pollut. Bull. 2000, 40, 968−980. (13) Central Bureaue of Statistics (CBS). Energy Balance of Israel; CBS: Jerusalem, Israel, 2014; http://www1.cbs.gov.il/energy/new_ energy/new_enr_nach_eng_new_huz.html. (14) Erel, Y.; Axelrod, T.; Veron, A.; Mahrer, Y.; Katsafados, P.; Dayan, U. Transboundary atmospheric lead pollution. Environ. Sci. Technol. 2002, 36, 3230−3233. (15) Erel, Y.; Dayan, U.; Rabi, R.; Rudich, Y.; Stein, M. Trans boundary transport of pollutants by atmospheric mineral dust. Environ. Sci. Technol. 2006, 40, 2996−3005. (16) Erel, Y.; Kalderon-Asael, B.; Dayan, U.; Sandler, A. European atmospheric pollution imported by cooler air masses to the Eastern Mediterranean during the summer. Environ. Sci. Technol. 2007, 41, 5198−5203. (17) Teutsch, N.; Erel, Y.; Halicz, L.; Banin, A. Distribution of natural and anthropogenic lead in Mediterranean soils. Geochim. Cosmochim. Acta 2001, 65, 2853−2864. (18) Erel, Y.; Dubowski, Y.; Halicz, L.; Erez, J.; Kaufman, A. Lead concentrations and isotopic ratios in the sediments of the Sea of Galilee. Environ. Sci. Technol. 2001, 35, 292−299. (19) Harlavan, Y.; Almogi-Labin, A.; Herut, B. Tracing natural and anthropogenic Pb in sediments along the Mediterranean Coast of Israel using Pb isotopes. Environ. Sci. Technol. 2010, 44, 6576−6582. (20) Townsend, A. T.; Seen, A. J. Historical lead isotope record of a sediment core from the Derwent River (Tasmania, Australia): A multiple source environment. Sci. Total Environ. 2012, 424, 153−161. (21) Zalasiewicz, J.; Williams, M.; Steffen, W.; Crutzen, P. The new world of the Anthropocene. Environ. Sci. Technol. 2010, 44, 2228− 2231. (22) Bookman, R.; Driscoll, C. T.; Engstrom, D. R.; Effler, S. W. Local to regional emission sources affecting mercury fluxes to New York lakes. Atmos. Environ. 2008, 42, 6088−6097. 13599
dx.doi.org/10.1021/es500530x | Environ. Sci. Technol. 2014, 48, 13592−13600
Environmental Science & Technology
Article
(44) Yang, H.; Battarbee, R. W.; Turner, S. D.; Rose, N. L.; Derwent, R. G.; Wu, G.; Yang, R. Historical reconstruction of mercury pollution across the Tibetan Plateau using lake sediments. Environ. Sci. Technol. 2010, 44, 2918−2924. (45) United Nations Economic Commission for Europe. Hemispheric Transport of Air Pollution 2010. Part B: Mercury. Air Pollution Studies Number 18; United Nations Economic Commission for Europe: Geneva, Switzerland, 2011; http://www.unece.org/fileadmin/DAM/ env/lrtap/Publications/11-22145-Part-B.pdf. (46) Hong, S.; Candelone, J.-P.; Soutif, M.; Boutron, C. F. A reconstruction of changes in copper production and copper emissions to the atmosphere during the past 7000 years. Sci. Total Environ. 1996, 188, 183−193. (47) Ad, U. Netanya final report. Hadashot Arkheologiyot; Israel Antiquities Authority: Jerusalem, Israel, 2009; Vol. 121. (48) Gutfeld, O. RamlaFinal Report on the Excavations North of the White Mosque; The Hebrew University of Jerusalem: Jerusalem, Israel, 2010; Monographs of the Institute of Archaeology. (49) Mason, R. B.; Tite, M. S. The begining of tin-opacification of pottery glazes. Archaeometry 1997, 39, 41−58. (50) Tite, M. S.; Freestone, I.; Mason, R. B.; Molera, J.; Vendrell-Saz, M.; Wood, N. Lead glazes in antiguityMethods of production and reasons for use. Archaeometry 1998, 40, 241−260. (51) Kark, R.; Levin, N. The environment in Palestine in the late Ottoman period, 1798−1918. In Israel’s Environmental History; Miller, C., Tal, A., Orenstein, D., Eds.; University of Pittsburgh Press: Pittsburgh, PA. 2012; p 1. (52) Avitsur, S. Ha’Kitor Magi’a (The steam is coming). Et-mol 1991, 16, 96 (in Hebrew). (53) Bacon, J. R.; Jones, K. C.; McGrath, S. P.; Johnston, A. E. Isotopic character of lead deposited from the atmosphere at a grassland site in the United Kingdom since 1860. Environ. Sci. Technol. 1996, 30, 2511−2518. (54) Tal, A. Israel’s urban environment, 1948−1988. In Pollution in a Promised Land; University of California Press: Oakland, CA, 2002; pp 243−281. (55) Brunke, G.; Labuschagne, C.; Slemr, F. Gaseous mercury emissions from a fire in the Cape Peninsula, South Africa, during January 2000. Geophys. Res. Lett. 2001, 28, 1483−1486. (56) Engle, M. A.; Sexauer Gustin, M.; Johnson, D. W.; Murphy, J. F.; Miller, W. W.; Walker, R. F.; Wright, J.; Markee, M. Mercury distribution in two Sierran forest and one desert sagebrush steppe ecosystems and the effects of fire. Sci. Total Environ. 2006, 367, 222− 233. (57) Shotyk, W.; Weiss, D.; Appleby, P. G.; Cheburkin, A. K.; Frei, R.; Gloor, M.; Kramers, J. D.; Reese, S.; Van der Knaap, W. O. History of atmospheric lead deposition since 12,370 14C yr BP from a Peat Bog, Jura Mountains, Switzerland. Science 1998, 281, 1635−1640. (58) Brännvall, M.; Bindler, R.; Emteryd, O.; Renberg, I. Four thousand years of atmospheric lead pollution in northern Europe: A summary from Swedish lake sediments. J. Paleolimnol. 2001, 25, 421− 435. (59) Sherrell, R. M.; Boyle, E. A.; Hamelin, B. Isotopic equilibration between dissolved and suspended particulate lead in the Atlantic Ocean: Evidence from 210Pb and stable Pb isotopes. J. Geophys. Res. 1992, 97, 11257−11268.
13600
dx.doi.org/10.1021/es500530x | Environ. Sci. Technol. 2014, 48, 13592−13600
